CA2230199C - Pyridazin-3-one derivatives, their use as a herbicide, and intermediates for their production - Google Patents
Pyridazin-3-one derivatives, their use as a herbicide, and intermediates for their production Download PDFInfo
- Publication number
- CA2230199C CA2230199C CA002230199A CA2230199A CA2230199C CA 2230199 C CA2230199 C CA 2230199C CA 002230199 A CA002230199 A CA 002230199A CA 2230199 A CA2230199 A CA 2230199A CA 2230199 C CA2230199 C CA 2230199C
- Authority
- CA
- Canada
- Prior art keywords
- compound
- alkyl
- methyl
- compound according
- chloro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/72—Hydrazones
- C07C251/74—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/76—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
- C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D237/14—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
Abstract
The present invention is directed to novel pyridazin-3-one derivatives of formula (see formula I) wherein R1 is haloalkyl; R2 and R3 are the same or different and are hydroge n, alkyl, haloalkyl, or alkoxyalkyl; and Q is [Q-1], [Q-2], [Q-3], [Q-4] or [Q-5]. The compounds of the present invention are useful as active ingredients of herbicides. Also provided are their use and intermediates for their production.
Description
1~1 PYRIDAZIN-3-ONE DERIVATIVES, THEIR USE AS A HERBICIDE, AND INTERMEDIATES FOR THEIR PRODUCTION
The present invention relates to pyridazin-3 -one derivatives, their use as herbicides, and intermediates for their production.
EP-A-0029123 discloses a process for the preparation of substituted anilines and novel substituted anilines. In particular, it teaches that certain substituted anilines obtained by this process are useful as important starting materials for the preparation of novel substituted pyridazin-3-one derivatives having herbicidal activity in postemergence application. These pyridazin-3-one derivatives are, however, different from those of the present invention in that they have a substituted phenoxyphenyl group as an essential structural element at position 2 of the pyridazinone ring and further have quite distinct substituents on the pyridazinone ring.
The present inventors have studied intensively to find a compound having excellent herbicidal activity. As a result, 'they have found that pyridazin-3-one derivatives represented by formula [1] as depicted below have excellent herbicidal activity.
Thus the present invention provides a compound of the formula:
Q-N " Ri [1]
~
N-wherein R' is C1-C3 haloalkyl; RZ and R3 are the same or different and are hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, or C1-C3 alkoxy C1-C3 alkyl; and Q is [Q-1], [Q-2], [Q-31, [Q-41, or (Q-5] of the formula:
X X
Zt y ~ \
Y f ' (R4 n Z2 ~
N
(Q-1] (Q-21 [Q-3]
X X
Y ~ ~ //
N- , R7 Rg [Q-4] [Q-5]
wherein X is hydrogen or halogen;
Y is halogen, nitro, cyano, or trifluoromethyl;
ZI is oxygen, sulfur, or NH;
Z2 is oxygen or sulfur;
nis0or1;
B is hydrogen, halogen, nitro, cyano, chlorosulfonyl, ORiO, SR10, SO2-OR10, N(R1')R12, SO2N(R11)R12, NR1I(COR13), NRiI(S02R14), N(S02R14)-(S02R15), N(SO2R14)(COR13), NHCOOR 13, COOR10, CON(R11)R12, CSN(R11)R12' COR 16, CR 17=CR 18COR 16, CR 17=CR 1 gCOOR 13, CR 17=CR 18CON(R I 1)R 12, WCOOR13, CH2CHWCON(R11)R12, CR17=NOR33, CR17=NN(Ril)R12, CR17(Z2-R34)2, OC02R19, or OCORig;
R't is hydrogen or C1-C3 alkyl;
R5 is hydrogen, C1-C6 alkyl, Cl-C6 haloalkyl, C3-C8 cycloalkylalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, cyano C1-C6 alkyl, C2-C8 alkoxyalkyl, C3-C8 alkoxyalkoxyalkyl, carboxy CI-C6 alkyl, (C1-C6 alkoxy)-carbonyl C 1-C6 alkyl, {(C I-Ca alkoxy) C 1-C4 alkoxy } carbonyl C i-C6 alkyl, (C3-C8 cycloalkoxy)carbonyl Ci-C6 alkyl, CH2CON(RI I)R12, CH2COON(RI i)R12, CH(Ci-C4 alkyl)CON(R11)R12, CH(CI-C4 alkyl)COON(R11)R12, C2-C8 alkylthioalkyl, or hydroxy C I -C6 alkyl; R6 is C I-C6 alkyl, C 1-C6 haloalkyl, formyl, cyano, carboxyl, hydroxy C i-C6 alkyl, C I-C6 alkoxy C I-C6 alkyl, C I-C6 alkoxy C I-C6 alkoxy C 1-C6 alkyl, (C I-C6 alkyl)carbonyloxy C I-C6 alkyl, (C i-C6 haloalkyl)carbonyloxy C 1-C6 alkyl, WO 97/07104 PCT/.TP96/02311 (C1-C6 alkoxy)carbonyl, or (Ci-C6 alkyl)carbonyl;
= R7 is hydrogen or CI-C6 alkyl; and R8 is hydrogen, CI -C6 alkyl, C I -C6 haloalkyl, hydroxy C I -C6 alkyl, C2-C8 = alkoxyalkyl, C3-Clp alkoxyalkoxyalkyl, (C1-C5 alkyl)carbonyloxy CI-C6 alkyl, (C1-C6 haloalkyl)carbonyloxy C1-C6 alkyl, carboxyl, carboxy CI-C6 alkyl, (Ct-C8 alkoxy)-carbonyl, (C1-C6 haloalkoxy)carbonyl, (C3-Cip cycloalkoxy)carbonyl, (C3-C8 alkenyl-oxy)carbonyl, (C3-C8 alkynyloxy)carbonyl, aminocarbonyl, (C1-C6 alkyl)amino-carbonyl, di(Ci-C6 alkyl)aminocarbonyl, (C1-C5 alkyl)arninocarbonyloxy CI -C6 alkyl, or di(CI -C6 alkyl)aminocarbonyloxy CI -C6 alkyl;
wherein RIO is hydrogen, CI-C6 alkyl, CI-C6 haloalkyl, C3-C8 cycloalkyl, benzyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, cyano CI-C6 alkyl, C2-C8 alkoxyalkyl, C2-C8 alkylthioalkyl, carboxy C1-C6 alkyl, (Ci-Cg alkoxy)carbonyl C1-C6 alkyl, (C1-C6 haloalkoxy)carbonyl CI-C6 alkyl, {(C1-Cq.
alkoxy) C 1-Cq. alkoxy } carbonyl C 1-C5 alkyl, (C3-C8 cycloalkoxy)carbonyl C I-C6 alkyl, (C I -C6 alkyl)carbonyl CI -C6 alkyl, (C1-C6 haloalkyl)carbonyl C1-C6 alkyl, {(C1-C4 alkoxy) CI-C4 alkyl}carbonyl C1-C6 alkyl, (C3-C8 cycloalkyl)carbonyl C1-C6 alkyl, (R11)R12, CH2COON(RI 1)R12, CH(CI -C4 alkyl)CON(R1i)RI2, CH(CI -C4 alkyl)-COON(R 11)R 12, {(C 1-C6 alkoxy)carbonyl C i-C6 alkyl }oxycarbonyl C I -C6 alkyl, or hydroxy C I -C6 alkyl;
RI 1 and R 12 are independently hydrogen, C 1-C6 alkyl, C i-C6 haloalkyl, C3-C6 alkenyl, C3-C6 alkynyl, cyano CI-C6 alkyl, C2-C8 alkoxyalkyl, C2-C8 alkylthio-alkyl, carboxy C1-C6 alkyl, (CI -C6 alkoxy)carbonyl C1-C6 alkyl, (C3-C8 cycloalkoxy)-carbonyl CI -C6 alkyl, {(CI -C4 alkoxy) CI -C4 alkoxy}carbonyl C1-C6 alkyl, or R11 and R 12 are combined together to form tetramethylene, pentamethylene, or ethyleneoxy-ethylene;
= R13 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, or C3-C6 alkenyl;
R1't and R 15 are independently C I -C6 alkyl, C I-C6 haloalkyl, or phenyl optionally substituted with methyl or nitro;
R16 is hydrogen, C 1-C6 alkyl, C 1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C8 alkoxyalkyl, or hydroxy alkyl;
R17 and R18 are independently hydrogen or C i-C6 alkyl;
R19 is C I -C6 alkyl;
R33 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, cyano Ci-C6 alkyl, or (C1-C6 alkoxy)carbonyl CI-C6 alkyl;
R34 is C1-C6 alkyl, or two R34's are combined together to form (CH2)2 or (CH2)3; and W is hydrogen, chlorine, or bromine, (hereinafter referred to as the present compound(s)); and a herbicide containing it as an active ingredient.
The present invention also provides a compound of the formula:
Ql-NHN=~
~~CF3 [2]
wherein R3 is as defined above, and Qi is [Qi-1], [Q-2], [Q1-3], [Q-4], or [Q-5] of the formula:
X X
X
Zt 0 1.
Y _ tR4 ~n N Z' B~ 0 R5 Ry IQ'-1 ] IQ-2] IQ'-3]
X X
Y ~ ~
- ,' _ O N- ' S
R
R7 Rg [Q-4] [Q-5]
wherein X, Y, Z1, Z2, n, R4, R5, R7, and R8 are as defined above; B1 is hydrogen, halogen, nitro, cyano, OR27, SR27, S020R27, NR11(R12), SO2NR11(R12), NR11-(COR13), NR11(S02R14)> N(S02R14)(S02R15), N(S02R14)(COR13), NHCOOR13, COOR27, CONR11(R12), CSNR11(R12), CR17=CR18COOR13, CR17=CR18CONR11-(R12), CH2CHWCOOR13, CH2CHWCONRII(R12), CR17=NOR33, CR17=NNR11-(R12), CR]7(Z2R34)2, OCO2R19, or OCOR19; R9 is C1-C6 alkyl, C1-C6 haloalkyl, cyano, carboxyl, hydroxy C1-C6 alkyl, C1-C6 alkoxy Ci-C6 alkyl, Ci-C6 alkoxy Ci-C6 alkoxy Ci-C6 alkyl, (C1-C6 alkyl)carbonyloxy C1-C6 alkyl, (C1-C6 haloalkyl)carbonyl-oxy C1-C6 alkyl, (C1-C6 alkoxy)carbonyl, or (C1-C6 alkyl)carbonyl; R27 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, benzyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, cyano C1-C6 alkyl, C2-C8 alkoxyalkyl, CZ C$
alkylthioalkyl, carboxy CI-C6 alkyl, (C1-C8 alkoxy)carbonyl C1-C6 alkyl, (C1-haloalkoxy)carbonyl CX6 alkyl, {(C1-C4 alkoxy) CI-C4 alkoxy}carbonyl C1-C6 alkyl, (C3-C8 cycloalkoxy)carbonyl C1-C6 alkyl, CHZCON(R")R'', CH2COON(R")R12, CH(Cl-C4 alkyl)CON(R")R12, CH(Ci-C4 alkyl)COON(R")Rt2, {(C1-C6 alkoxy)carbonyl Cj-C6 alkyl}oxycarbonyl C1-C6 alkyl, or hydroxy C1-C6 alkyl; and R", R12, R13, R14, R'', R", R18, R19, R33' R34' and Z2 are as defined above.
In the above definition of the present compounds, the respective substituents are exemplified as follows:
Examples of the Ci-C3 haloalkyl represented by R' include trifluoromethyl and chlorodifluoromethyl.
The present invention relates to pyridazin-3 -one derivatives, their use as herbicides, and intermediates for their production.
EP-A-0029123 discloses a process for the preparation of substituted anilines and novel substituted anilines. In particular, it teaches that certain substituted anilines obtained by this process are useful as important starting materials for the preparation of novel substituted pyridazin-3-one derivatives having herbicidal activity in postemergence application. These pyridazin-3-one derivatives are, however, different from those of the present invention in that they have a substituted phenoxyphenyl group as an essential structural element at position 2 of the pyridazinone ring and further have quite distinct substituents on the pyridazinone ring.
The present inventors have studied intensively to find a compound having excellent herbicidal activity. As a result, 'they have found that pyridazin-3-one derivatives represented by formula [1] as depicted below have excellent herbicidal activity.
Thus the present invention provides a compound of the formula:
Q-N " Ri [1]
~
N-wherein R' is C1-C3 haloalkyl; RZ and R3 are the same or different and are hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, or C1-C3 alkoxy C1-C3 alkyl; and Q is [Q-1], [Q-2], [Q-31, [Q-41, or (Q-5] of the formula:
X X
Zt y ~ \
Y f ' (R4 n Z2 ~
N
(Q-1] (Q-21 [Q-3]
X X
Y ~ ~ //
N- , R7 Rg [Q-4] [Q-5]
wherein X is hydrogen or halogen;
Y is halogen, nitro, cyano, or trifluoromethyl;
ZI is oxygen, sulfur, or NH;
Z2 is oxygen or sulfur;
nis0or1;
B is hydrogen, halogen, nitro, cyano, chlorosulfonyl, ORiO, SR10, SO2-OR10, N(R1')R12, SO2N(R11)R12, NR1I(COR13), NRiI(S02R14), N(S02R14)-(S02R15), N(SO2R14)(COR13), NHCOOR 13, COOR10, CON(R11)R12, CSN(R11)R12' COR 16, CR 17=CR 18COR 16, CR 17=CR 1 gCOOR 13, CR 17=CR 18CON(R I 1)R 12, WCOOR13, CH2CHWCON(R11)R12, CR17=NOR33, CR17=NN(Ril)R12, CR17(Z2-R34)2, OC02R19, or OCORig;
R't is hydrogen or C1-C3 alkyl;
R5 is hydrogen, C1-C6 alkyl, Cl-C6 haloalkyl, C3-C8 cycloalkylalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, cyano C1-C6 alkyl, C2-C8 alkoxyalkyl, C3-C8 alkoxyalkoxyalkyl, carboxy CI-C6 alkyl, (C1-C6 alkoxy)-carbonyl C 1-C6 alkyl, {(C I-Ca alkoxy) C 1-C4 alkoxy } carbonyl C i-C6 alkyl, (C3-C8 cycloalkoxy)carbonyl Ci-C6 alkyl, CH2CON(RI I)R12, CH2COON(RI i)R12, CH(Ci-C4 alkyl)CON(R11)R12, CH(CI-C4 alkyl)COON(R11)R12, C2-C8 alkylthioalkyl, or hydroxy C I -C6 alkyl; R6 is C I-C6 alkyl, C 1-C6 haloalkyl, formyl, cyano, carboxyl, hydroxy C i-C6 alkyl, C I-C6 alkoxy C I-C6 alkyl, C I-C6 alkoxy C I-C6 alkoxy C 1-C6 alkyl, (C I-C6 alkyl)carbonyloxy C I-C6 alkyl, (C i-C6 haloalkyl)carbonyloxy C 1-C6 alkyl, WO 97/07104 PCT/.TP96/02311 (C1-C6 alkoxy)carbonyl, or (Ci-C6 alkyl)carbonyl;
= R7 is hydrogen or CI-C6 alkyl; and R8 is hydrogen, CI -C6 alkyl, C I -C6 haloalkyl, hydroxy C I -C6 alkyl, C2-C8 = alkoxyalkyl, C3-Clp alkoxyalkoxyalkyl, (C1-C5 alkyl)carbonyloxy CI-C6 alkyl, (C1-C6 haloalkyl)carbonyloxy C1-C6 alkyl, carboxyl, carboxy CI-C6 alkyl, (Ct-C8 alkoxy)-carbonyl, (C1-C6 haloalkoxy)carbonyl, (C3-Cip cycloalkoxy)carbonyl, (C3-C8 alkenyl-oxy)carbonyl, (C3-C8 alkynyloxy)carbonyl, aminocarbonyl, (C1-C6 alkyl)amino-carbonyl, di(Ci-C6 alkyl)aminocarbonyl, (C1-C5 alkyl)arninocarbonyloxy CI -C6 alkyl, or di(CI -C6 alkyl)aminocarbonyloxy CI -C6 alkyl;
wherein RIO is hydrogen, CI-C6 alkyl, CI-C6 haloalkyl, C3-C8 cycloalkyl, benzyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, cyano CI-C6 alkyl, C2-C8 alkoxyalkyl, C2-C8 alkylthioalkyl, carboxy C1-C6 alkyl, (Ci-Cg alkoxy)carbonyl C1-C6 alkyl, (C1-C6 haloalkoxy)carbonyl CI-C6 alkyl, {(C1-Cq.
alkoxy) C 1-Cq. alkoxy } carbonyl C 1-C5 alkyl, (C3-C8 cycloalkoxy)carbonyl C I-C6 alkyl, (C I -C6 alkyl)carbonyl CI -C6 alkyl, (C1-C6 haloalkyl)carbonyl C1-C6 alkyl, {(C1-C4 alkoxy) CI-C4 alkyl}carbonyl C1-C6 alkyl, (C3-C8 cycloalkyl)carbonyl C1-C6 alkyl, (R11)R12, CH2COON(RI 1)R12, CH(CI -C4 alkyl)CON(R1i)RI2, CH(CI -C4 alkyl)-COON(R 11)R 12, {(C 1-C6 alkoxy)carbonyl C i-C6 alkyl }oxycarbonyl C I -C6 alkyl, or hydroxy C I -C6 alkyl;
RI 1 and R 12 are independently hydrogen, C 1-C6 alkyl, C i-C6 haloalkyl, C3-C6 alkenyl, C3-C6 alkynyl, cyano CI-C6 alkyl, C2-C8 alkoxyalkyl, C2-C8 alkylthio-alkyl, carboxy C1-C6 alkyl, (CI -C6 alkoxy)carbonyl C1-C6 alkyl, (C3-C8 cycloalkoxy)-carbonyl CI -C6 alkyl, {(CI -C4 alkoxy) CI -C4 alkoxy}carbonyl C1-C6 alkyl, or R11 and R 12 are combined together to form tetramethylene, pentamethylene, or ethyleneoxy-ethylene;
= R13 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, or C3-C6 alkenyl;
R1't and R 15 are independently C I -C6 alkyl, C I-C6 haloalkyl, or phenyl optionally substituted with methyl or nitro;
R16 is hydrogen, C 1-C6 alkyl, C 1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C8 alkoxyalkyl, or hydroxy alkyl;
R17 and R18 are independently hydrogen or C i-C6 alkyl;
R19 is C I -C6 alkyl;
R33 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, cyano Ci-C6 alkyl, or (C1-C6 alkoxy)carbonyl CI-C6 alkyl;
R34 is C1-C6 alkyl, or two R34's are combined together to form (CH2)2 or (CH2)3; and W is hydrogen, chlorine, or bromine, (hereinafter referred to as the present compound(s)); and a herbicide containing it as an active ingredient.
The present invention also provides a compound of the formula:
Ql-NHN=~
~~CF3 [2]
wherein R3 is as defined above, and Qi is [Qi-1], [Q-2], [Q1-3], [Q-4], or [Q-5] of the formula:
X X
X
Zt 0 1.
Y _ tR4 ~n N Z' B~ 0 R5 Ry IQ'-1 ] IQ-2] IQ'-3]
X X
Y ~ ~
- ,' _ O N- ' S
R
R7 Rg [Q-4] [Q-5]
wherein X, Y, Z1, Z2, n, R4, R5, R7, and R8 are as defined above; B1 is hydrogen, halogen, nitro, cyano, OR27, SR27, S020R27, NR11(R12), SO2NR11(R12), NR11-(COR13), NR11(S02R14)> N(S02R14)(S02R15), N(S02R14)(COR13), NHCOOR13, COOR27, CONR11(R12), CSNR11(R12), CR17=CR18COOR13, CR17=CR18CONR11-(R12), CH2CHWCOOR13, CH2CHWCONRII(R12), CR17=NOR33, CR17=NNR11-(R12), CR]7(Z2R34)2, OCO2R19, or OCOR19; R9 is C1-C6 alkyl, C1-C6 haloalkyl, cyano, carboxyl, hydroxy C1-C6 alkyl, C1-C6 alkoxy Ci-C6 alkyl, Ci-C6 alkoxy Ci-C6 alkoxy Ci-C6 alkyl, (C1-C6 alkyl)carbonyloxy C1-C6 alkyl, (C1-C6 haloalkyl)carbonyl-oxy C1-C6 alkyl, (C1-C6 alkoxy)carbonyl, or (C1-C6 alkyl)carbonyl; R27 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, benzyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, cyano C1-C6 alkyl, C2-C8 alkoxyalkyl, CZ C$
alkylthioalkyl, carboxy CI-C6 alkyl, (C1-C8 alkoxy)carbonyl C1-C6 alkyl, (C1-haloalkoxy)carbonyl CX6 alkyl, {(C1-C4 alkoxy) CI-C4 alkoxy}carbonyl C1-C6 alkyl, (C3-C8 cycloalkoxy)carbonyl C1-C6 alkyl, CHZCON(R")R'', CH2COON(R")R12, CH(Cl-C4 alkyl)CON(R")R12, CH(Ci-C4 alkyl)COON(R")Rt2, {(C1-C6 alkoxy)carbonyl Cj-C6 alkyl}oxycarbonyl C1-C6 alkyl, or hydroxy C1-C6 alkyl; and R", R12, R13, R14, R'', R", R18, R19, R33' R34' and Z2 are as defined above.
In the above definition of the present compounds, the respective substituents are exemplified as follows:
Examples of the Ci-C3 haloalkyl represented by R' include trifluoromethyl and chlorodifluoromethyl.
Examples of the CI-C3 alkyl represented by R2 and R3 include methyl, ethyl, and isopropyl.
Examples of the C I -C3 haloalkyl represented by R2 and R3 include trichloro-methyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, and pentafluoroethyl.
Examples of the Ci-C3 alkoxy CI -C3 alkyl represented by R2 and R3 include methoxymethyl.
Examples of the halogen represented by X, Y, and B include chlorine, fluorine, bromine, or iodine.
Examples of the C i-C6 alkyl represented by R IO include methyl, ethyl, isopropyl, propyl, isobutyl, butyl, t-butyl, amyl, isoamyl, and t-amyl.
Examples of the CI-C6 haloalkyl represented by RIO include 2-chloroethyl, 3-chloropropyl, and 2,2,2-trifluoroethyl.
Examples of the C3-C8 cycloalkyl represented by RI0 include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
Examples of the C3-C6 alkenyl represented by R10 include allyl, 1-methyl-2-propenyl, 3-butenyl, 2-butenyl, 3-methyl-2-butenyl, and 2-methyl-3-butenyl.
Examples of the C3-C6 haloalkenyl represented by R10 include 2-chloro-2-propenyl and 3,3-dichloro-2-propenyl.
Examples of the C3-C6 alkynyl represented by R 1O include propargyl, 1-methyl-2-propynyl, 2-butynyl, and 1,1-dirnethyl-2-propynyl.
Examples of the C3-C6 haloalkynyl represented by R10 include 4-bromo-2-butynyl.
Examples of the cyano C I -C6 alkyl represented by R10 include cyanomethyl.
Examples of the C2-C8 alkoxyalkyl represented by RIO include methoxy-methyl, methoxyethyl, ethoxymethyl, and ethoxyethyl.
Examples of the C2-C8 alkylthioalkyl represented by R10 include methylthio-methyl.
Examples of the carboxy C1-C6 alkyl represented by RlO include carboxy-methyl, 1-carboxyethyl, and 2-carboxyethyl.
= Examples of the (C1-C8 alkoxy)carbonyl C1-C6 alkyl represented by R10 include methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopro-poxycarbonylmethyl, butoxycarbonylmethyl, isobutoxycarbonylmethyl, t-butoxycar-bonylmethyl, amyloxycarbonylmethyl, isoamyloxycarbonylmethyl, t-amyloxycarbonyl-methyl, 1-methoxycarbonylethyl, I-ethoxycarbonylethyl, 1-propoxycarbonylethyl, 1-iso-propoxycarbonylethyl, 1-butoxycarbonylethyl, 1-isobutoxycarbonylethyl, 1-t-butoxycar-bonylethyl, I-amyloxycarbonylethyl, 1-isoamyloxycarbonylethyl, and 1-t-amyloxycar-bonylethyl.
Examples of the (C i-C6 haloalkoxy)carbonyl C 1-C6 alkyl represented by R 10 include 2-chloroethoxycarbonylmethyl.
Examples of the {(C 1-C4 alkoxy) C 1-C4 alkoxy } carbonyl C 1-C6 alkyl represented by RI0 include methoxymethoxycarbonylmethyl and 1-methoxymethoxy-carbonylethyl.
Examples of the (C3-C8 cycloalkoxy)carbonyl Ci-C6 alkyl represented by R 10 include cyclobutyloxycarbonylmethyl, cyclopentyloxycarbonyimethyl, cyclohexyl-oxycarbonylmethyl, 1-cyclobutyloxycarbonylethyl, 1-cyclopentyloxycarbonylethyl, and 1-cyclohexyloxycarbonylethyl.
Examples of the (C I-C6 alkyl)carbonyl C 1-C6 alkyl represented by R t 0 include methylcarbonylmethyl.
Examples of the (C I -C6 haloalkyl)carbonyl C I -C6 alkyl represented by R 10 include chloromethylcarbonylmethyl.
Examples of the {(C 1-C4 alkoxy) C 1-C4 alkyl } carbonyl C i-C6 alkyl represented by R10 include 2-methoxyethylcarbonylmethyl.
Examples of the (C3-C8 cycloalkyl)carbonyl CI-C6 alkyl represented by R10 include cyclopentylcarbonylmethyl.
Examples of the {(C 1-C6 alkoxy)carbonyl C 1-C6 alkyl } oxycarbonyl C 1-C6 alkyl represented by R10 include (ethoxycarbonyl)methoxycarbonylmethyl.
Examples of the C I -C3 haloalkyl represented by R2 and R3 include trichloro-methyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, and pentafluoroethyl.
Examples of the Ci-C3 alkoxy CI -C3 alkyl represented by R2 and R3 include methoxymethyl.
Examples of the halogen represented by X, Y, and B include chlorine, fluorine, bromine, or iodine.
Examples of the C i-C6 alkyl represented by R IO include methyl, ethyl, isopropyl, propyl, isobutyl, butyl, t-butyl, amyl, isoamyl, and t-amyl.
Examples of the CI-C6 haloalkyl represented by RIO include 2-chloroethyl, 3-chloropropyl, and 2,2,2-trifluoroethyl.
Examples of the C3-C8 cycloalkyl represented by RI0 include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
Examples of the C3-C6 alkenyl represented by R10 include allyl, 1-methyl-2-propenyl, 3-butenyl, 2-butenyl, 3-methyl-2-butenyl, and 2-methyl-3-butenyl.
Examples of the C3-C6 haloalkenyl represented by R10 include 2-chloro-2-propenyl and 3,3-dichloro-2-propenyl.
Examples of the C3-C6 alkynyl represented by R 1O include propargyl, 1-methyl-2-propynyl, 2-butynyl, and 1,1-dirnethyl-2-propynyl.
Examples of the C3-C6 haloalkynyl represented by R10 include 4-bromo-2-butynyl.
Examples of the cyano C I -C6 alkyl represented by R10 include cyanomethyl.
Examples of the C2-C8 alkoxyalkyl represented by RIO include methoxy-methyl, methoxyethyl, ethoxymethyl, and ethoxyethyl.
Examples of the C2-C8 alkylthioalkyl represented by R10 include methylthio-methyl.
Examples of the carboxy C1-C6 alkyl represented by RlO include carboxy-methyl, 1-carboxyethyl, and 2-carboxyethyl.
= Examples of the (C1-C8 alkoxy)carbonyl C1-C6 alkyl represented by R10 include methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopro-poxycarbonylmethyl, butoxycarbonylmethyl, isobutoxycarbonylmethyl, t-butoxycar-bonylmethyl, amyloxycarbonylmethyl, isoamyloxycarbonylmethyl, t-amyloxycarbonyl-methyl, 1-methoxycarbonylethyl, I-ethoxycarbonylethyl, 1-propoxycarbonylethyl, 1-iso-propoxycarbonylethyl, 1-butoxycarbonylethyl, 1-isobutoxycarbonylethyl, 1-t-butoxycar-bonylethyl, I-amyloxycarbonylethyl, 1-isoamyloxycarbonylethyl, and 1-t-amyloxycar-bonylethyl.
Examples of the (C i-C6 haloalkoxy)carbonyl C 1-C6 alkyl represented by R 10 include 2-chloroethoxycarbonylmethyl.
Examples of the {(C 1-C4 alkoxy) C 1-C4 alkoxy } carbonyl C 1-C6 alkyl represented by RI0 include methoxymethoxycarbonylmethyl and 1-methoxymethoxy-carbonylethyl.
Examples of the (C3-C8 cycloalkoxy)carbonyl Ci-C6 alkyl represented by R 10 include cyclobutyloxycarbonylmethyl, cyclopentyloxycarbonyimethyl, cyclohexyl-oxycarbonylmethyl, 1-cyclobutyloxycarbonylethyl, 1-cyclopentyloxycarbonylethyl, and 1-cyclohexyloxycarbonylethyl.
Examples of the (C I-C6 alkyl)carbonyl C 1-C6 alkyl represented by R t 0 include methylcarbonylmethyl.
Examples of the (C I -C6 haloalkyl)carbonyl C I -C6 alkyl represented by R 10 include chloromethylcarbonylmethyl.
Examples of the {(C 1-C4 alkoxy) C 1-C4 alkyl } carbonyl C i-C6 alkyl represented by R10 include 2-methoxyethylcarbonylmethyl.
Examples of the (C3-C8 cycloalkyl)carbonyl CI-C6 alkyl represented by R10 include cyclopentylcarbonylmethyl.
Examples of the {(C 1-C6 alkoxy)carbonyl C 1-C6 alkyl } oxycarbonyl C 1-C6 alkyl represented by R10 include (ethoxycarbonyl)methoxycarbonylmethyl.
Examples of the CI -C6 alkyl represented by R 11 and R 12 include methyl, ethyl, propyl, butyl, isopropyl, and isobutyl.
Examples of the CI-C6 haloalkyl represented by RI I and R12 include chloro-ethyl and bromoethyl.
Examples of the C3-C6 alkenyl represented by R i l and R 12 include allyl, 1-methyl-2-propenyl, and 3-butenyl.
Examples of the C3-C6 alkynyl represented by R11 and R12 include propargyl and I -methyl-2-propynyl.
Examples of the cyano C 1-C6 alkyl represented by R 11 and R 12 include cyanomethyl.
Examples of the C2-C8 alkoxyalkyl represented by R i l and R 12 include methoxymethyl and ethoxyethyl.
Examples of the C2-C8 alkylthioalkyl represented by R II and R 12 include methylthiomethyl and methylthioethyl.
Examples of the carboxy C i-C6 alkyl represented by RI I and R 12 include carboxymethyl and 1-carboxyethyl.
Examples of the (Cl-C6 alkoxy)carbonyl C1-C6 alkyl represented by R11 and R 12 include methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, butoxycarbonylmethyl, isobutoxycarbonylmethyl, t-butoxy-carbonylmethyl, amyloxycarbonyimethyl, isoamyloxycarbonylmethyl, t-amyloxycar-bonylmethyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-butoxycarbonylethyl, 1-isobutoxycarbonylethyl, 1-t-butoxycarbonylethyl, 1-amyloxycarbonylethyl, 1-isoamyloxycarbonylethyl, and I -t-amyl-oxycarbonylethyl.
Examples of the (C3-C8 cycloalkoxy)carbonyl CI-C6 alkyl represented by R i I and R12 include cyclopentyloxycarbonylmethyl.
Examples of the {(C I-C4 alkoxy) C 1-C4 alkoxy } carbonyl C 1-C6 alkyl represented by R i' and R1'' include rnethoxymethoxycarbonylmethyl and 1-methoxy-methoxycarbonylethyl.
Examples of the C i-C6 alkyl represented by R13 include methyl, ethyl, propyl, butyl, amyl, isopropyl, isobutyl, and isoamyl.
= Examples of the Ci-C6 haloalkyl represented by R13 include 2,2,2-trifluoro-ethyl.
Examples of the C3-C8 cycloalkyl represented by R13 include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
Examples of the C3-C6 alkenyl represented by R13 include allyl.
Examples of the C I-C6 alkyl represented by R 14 and R 15 include methyl, ethyl, propyl, butyl, and isopropyl.
Examples of the C I-C6 haloalkyl represented by R14 and R15 include trifluoromethyl, 2,2,2-trifluoroethyl, 2-chloroethyl, chloromethyl, and trichloromethyl.
Examples of the phenyl optionally substituted by methyl or nitro, which is represented by R14 and R 15, include phenyl, p-methylphenyl, 2-nitrophenyl, 3-nitro-phenyl, and 4-nitrophenyl.
Examples of the C 1-C6 alkyl represented by R16 include methyl, ethyl, propyl, butyl, amyl, isopropyl, isobutyl, t-butyl, isoamyl, and t-amyl.
Examples of the C i-C6 haloalkyl represented by R 16 include chloromethyl, dichloromethyl, bromomethyl, dibromomethyl, 1-chloroethyl, 1,1-dichloroethyl, 1-bromoethyl, and 1, 1 -dibromoethyl.
Examples of the C2-C6 alkenyl represented by R16 include vinyl, allyl, 1-propenyl, and I -methyl-2-propenyl.
Examples of the C2-C6 haloalkenyl represented by R16 include 3,3-dichloro-2-propenyl and 3,3-dibromo-2-propenyl.
Examples of the C2-C6 alkynyl represented by R16 include ethynyl and = 2-butynyl.
Examples of the C2-C6 haloalkynyl represented by R16 include 3-bromo-2-propynyl.
Examples of the C2-Cg alkoxyalkyl represented by R16 include methoxy-methyl, ethoxymethyl, and isopropoxymethyl.
Examples of the hydroxy Ci-C6 alkyl represented by R16 include hydroxy-methyl.
Examples of the C I -C6 alkyl represented by R 17 and R 18 include methyl.
Examples of the C 1-C6 alkyl represented by R 19 include methyl and ethyl.
Examples of the Ci-C6 alkyl represented by R33 include methyl and ethyl.
Examples of the C1-C6 haloalkyl represented by R33 include 2-chloroethyl.
Examples of the C3-C8 cycloalkyl represented by R33 include cyclopentyl.
Examples of the C3-C6 alkenyl represented by R33 include allyl.
Examples of the C3-C6 haloalkenyl represented by R33 include 2-chloro-2-propenyl.
Examples of the C3-C6 alkynyl represented by R33 include propargyl.
Examples of the C3-C6 haloalkynyl represented by R33 include 4-chloro-2-butynyl.
Examples of the cyano Ci-C6 alkyl represented by R33 include 2-cyanoethyl and cyanomethyl.
Examples of the (C I-C6 alkoxy)carbonyl C I-C6 alkyl represented by R33 include ethoxycarbonylmethyl.
Examples of the CI -C6 alkyl represented by R34 include methyl and ethyl.
Examples of the C1-C3 alkyl represented by R4 include methyl.
Examples of the CI -C6 alkyl represented by R5 include methyl, ethyl, propyl, butyl, amyl, isopropyl, isobutyl, and isoamyl.
Exarnples of the CI -C6 haloalkyl represented by R5 include 2-chloroethyl, 2-bromoethyl, 3-chlorobutyl, 3-bromobutyl, difluoromethyl, and bromodifluoromethyl.
Examples of the C3-C8 cycloalkylalkyl represented by R5 include cyclopentyl-methyl. Examples of the C3-C6 alkenyl represented by R5 include allyl, 1-methyl-2-ll propenyl, 3-butenyl, 2-butenyl, 3-methyl-2-butenyl, and 2-methyl-3-butenyl.
= Examples of the C3-C6 haloalkenyl represented by R5 include 2-chloro-2-propenyl and 3,3-dichloro-2-propenyl.
Examples of the C3-C6 alkynyl represented by R5 include propargyl, 1-methyl-2-propynyl, 2-butynyl, and 1, 1 -dimethyl-2-propynyl.
Examples of the C3-C6 haloalkynyl represented by R5 include 3-iodo-2-propynyl and 3-bromo-2-propynyl.
Examples of the cyano CI-C6 alkyl represented by R5 include cyanomethyl.
Examples of the C2-C8 alkoxyalkyl represented by R5 include methoxy-methyl, ethoxymethyl, and 1-methoxyethyl.
Examples of the C3-C8 alkoxyalkoxyalkyl represented by R5 include methoxyethoxymethyl.
Examples of the carboxy C1-C6 alkyl represented by R5 include carboxy-methyl, 1-carboxyethyl, and 2-carboxyethyl.
Examples of the (CI-C6 alkoxy)carbonyl C1-C6 alkyl represented by R5 include methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopro-poxycarbonyllnethyl, butoxycarbonylmethyl, isobutoxycarbonylmethyl, t-butoxycar-bonylmethyl, amyloxycarbonylmethyl, isoamyloxycarbonylmethyl, t-amyloxycarbonyl-methyl, I-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-propoxycarbonylethyl, I-iso-propoxycarbonylethyl, 1-butoxycarbonylethyl, 1-isobutoxycarbonylethyl, 1-t-butoxy-carbonylethyl, I-amyloxycarbonylethyl, I-isoamyloxycarbonylethyl, and 1-t-amyloxy-carbonylethyl.
Examples of the {( C 1-C4 alkoxy) C 1-C4 alkoxy } carbonyl C i-C6 alkyl represented by R5 include methoxymethoxycarbonylmethyl and 1-methoxymethoxy-carbonylethyl.
= Examples of the (C3-C8 cycloalkoxy)carbonyl CI-C6 alkyl represented by R5 include cyclobutyloxycarbonylmethyl, cyclopentyloxycarbonylmethyl, cyclohexyloxy-carbonylniethyl, 1-cyclobutyloxycarbonylethyl, 1-cyclopentyloxycarbonylethyl, and 1 -cyclohexyloxycarbonylethyl.
Examples of the C2-C8 alkylthioalkyl represented by R5 include methylthio-methyl.
Examples of the hydroxy Ci-C6 alkyl represented by R5 include hydroxy-methyl, hydroxyethyl, and hydroxypropyl.
Examples of the C I -C6 alkyl represented by R6 include methyl and ethyl.
Examples of the C1-C6 haloalkyl represented by R6 include bromomethyl, dibromomethyl, tribromomethyl, 1-bromoethyl, chloromethyl, dichloromethyl, and trichloromethyl.
Examples of the hydroxy CI-C6 a1kyI represented by R6 include hydroxy-methyl.
Examples of the CI-C6 alkoxy C 1-C6 alkyl represented by R6 include methoxymethyl, ethoxymethyl, propoxymethyl, and isopropoxymethyl.
Examples of the C I -C6 alkoxy C I -C6 alkoxy C I -C6 alkyl represented by R6 include methoxymethoxymethyl, methoxyethoxymethyl, and ethoxymethoxymethyl.
Examples of the (Cl-C6 alkyl)carbonyloxy C1-C6 alkyl represented by R6 include acetyloxymethyl, ethylcarbonyloxymethyl, and isopropylcarbonyloxymethyl.
Examples of the (C1-C6 haloalkyl)carbonyloxy C1-C6 alkyl represented by R6 include trifluoroacetyloxymethyl, chloroacetyloxymethyl, and trichloroacetyloxy-methyl.
Examples of the (C1-C6 alkoxy)carbonyl represented by R6 include methoxy-carbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, amyloxycarbonyl, isopro-poxycarbonyl, isobutoxycarbonyl, and isoamyloxycarbonyl.
Examples of the (C I -C6 alkyl)carbonyl represented by R6 include methyl-carbonyl, ethylcarbonyl, and isopropylcarbonyl.
Examples of the C1-C6 alkyl represented by R7 include methyl.
Examples of the C1-C6 alkyl represented by R8 include methyl and ethyl.
Examples of the C I -C6 haloalkyl represented by R8 include chloromethyl, bromomethyl, and fluoromethyl.
Examples of the C i-C6 hydroxyalkyl represented by R8 include hydroxy-methyl.
Examples of the C2-C8 alkoxyalkyl represented by R8 include methoxy-methyl, ethoxymethyl, isopropoxymethyl, butoxymethyl, and isobutoxymethyl.
Examples of the C3-C 1 p alkoxyalkoxyalkyl represented by R8 include methoxymethoxymethyl, methoxyethoxymethyl, and ethoxymethoxymethyl.
Examples of the (CI -C5 alkyl)carbonyloxy C1-C6 alkyl represented by R8 include acetyloxymethyl, ethylcarbonyloxymethyl, and isopropylcarbonyloxymethyl.
Examples of the (C I -C6 haloalkyl)carbonyloxy C i-C6 alkyl represented by R8 include 2-chloroethylcarbonyloxymethyl.
Examples of the carboxy Ci-C6 alkyl represented by R8 include carboxy-methyl.
Examples of the (C1-C8)alkoxycarbonyl represented by R8 include methoxy-carbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, amyloxycarbonyl, isopro-poxycarbonyl, isobutoxycarbonyl, and isoamyloxycarbonyl.
Examples of the (CI-C6 haloalkoxy)carbonyl represented by R8 include 2-chloroethoxycarbonyl, 2-bromoethoxycarbonyl, 3-chlorobutoxycarbonyl, 1-chloro-2-propoxycarbonyl, 1,3-dichloro-2-propoxycarbonyl, 2,2-dichloroethoxycarbonyl, 2,2,2-trifluoroethoxycarbonyl, 2,2,2-trichloroethoxycarbonyl, and 2,2,2-tribromoethoxy-carbonyl.
Examples of the (C3-Clp cycloalkoxy)carbonyl represented by R8 include cyclobutyloxycarbonyl, cyclopentyloxycarbonyl, and cyclohexyloxycarbonyl.
Examples of the (C3-Cg alkenyloxy)carbonyl represented by R8 include allyloxycarbonyl and 3-butenyloxycarbonyl.
Examples of the (C3-C8 alkynyloxy)carbonyl represented by R8 include propargyloxycarbonyl, 3-butynyloxycarbonyl, and 1-methyl-2-propynyloxycarbonyl.
Examples of the (CI-C6 alkyl)aminocarbonyl represented by R8 include methylaminocarbonyl, ethylaminocarbonyl, and propylaminocarbonyl.
Examples of the di(Cl-C6 alkyl)aminocarbonyl represented by R8 include dimethylaminocarbonyl, diethylaminocarbonyl, and diisopropylaminocarbonyl.
Examples of the (C1-C6 alkyl)aminocarbonyloxy C1-C6 alkyl represented by R8 include methylaminocarbonyloxymethyl, ethylaminocarbonyloxymethyl, and propyl-amin ocarbonyl oxymethyl .
Examples of the di(CI -C6 alkyl)aminocarbonyloxy C1-C6 alkyl represented by R8 include dimethylaminocarbonyloxyalkyl and diethylaminocarbonyloxyalkyl.
In the present compounds, preferred substituents from the viewpoint of their herbicidal activity are as follows:
R1 is preferably methyl substituted with one or more fluorine atoms, such as trifluoromethyl or chlorodifluoromethyl, or ethyl substituted with one or more fluorine atoms, such as pentafluoroethyl, and more preferably trifluoromethyl;
R2 is preferably CI -C3 alkyl such as methyl or ethyl, or hydrogen, and more preferably methyl or hydrogen;
R3 is preferably Ci-C3 alkyl such as methyl or ethyl, or hydrogen, and more preferably methyl or hydrogen; and Q is preferably [Q-l], [Q-2], [Q-3], or [Q-4].
Preferred examples of the present compounds from the viewpoint of their herbicidal activity are those which contain the above preferred substituents in combi-nation.
When Q is [Q-1], inore preferred compounds are those wherein X is hydrogen or fluorine and Y is chlorine. Among these compounds are more preferred ones wherein B is OR 10, S R10, N(R I I)R 12, NR 11 (S02R 14), or COOR IO.
Among these compounds are more preferred ones wherein R1a is C1-C6 alkyl, C3-C6 alkynyl, (C1-Cg alkoxy)carbonyl C I -C6 alkyl, or (C3-C8 cycloalkoxy)carbonyl C I -C6 alkyl; R
i I is hydrogen: R12 is (CI-C6 alkoxy)carbonyl Cl-C6 alkyl; and R14 is CI -C6 alkyl or Cl-C6 haloalkyl.
When Q is [Q-2], more preferred compounds are those wherein X is fluorine or hydrogen; Z1 is oxygen; R4 is hydrogen; and n is 1. Among these compounds are more preferred ones wherein R5 is C3-C6 alkynyl.
Typical examples of the preferred compounds are as follows:
7-Flu oro-6 -( 5-t ri fluoro methyl-3 -pyri dazin on -2-y l)-4 -prop arg yl -2H -1,4-benzoxazin-3-one;
7-Fluoro-6-(4-methyl-5 -trifluoromethyl-3-pyridazinon-2-yl )-4-propargyl-2H-1,4-benzoxazin-3-one;
6-(5-Trifl uoromethyl-3-pyridazinon-2-yl)-4-p ropargyl-2H- I,4-benzoxazin-3-one;
6-( 4-M ethy 1-5 -t rif luo rom et hyl -3-p y rid azi no n-2 -yl )-4-p rop argyl -2H -1,4-benzoxazin-3-one;
2-(4-Ch loro-2-fl uoro-5 -is opropoxyphen yl)-4-methyl-5-triflu oromethyl-pyridazin-3-one;
2-(4-Chloro-2-fluoro-5-methoxyphenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-one;
2-(4-Chl oro-2-fl uoro-5-ethoxyph enyl)-4-meth yl-5-trifluo romethylpyridazin-3-one;
2-(4-Ch loro-2-fluoro-5 -propargylo xyphenyl )-4-methyl-5-trifl uoro methyl-pyridazin-3-one;
Methyl 2-chloro-4-fluoro-5-(4-methyl-5-tri fluoromethyl-3-pyridazinon-2-yl)-phenoxyacetate;
Ethyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-phenoxyacetate;
Propyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-phenoxyacetate;
Isopropyl 2-chloro-4-fluoro-5-(4-methyl-.5-trifluoromethyl-3-pyridazinon-2-yl)phenoxyacetate;
Butyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-phenoxyacetate;
Pentyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-phenoxyacetate;
Cyclopentyl 2-chloro-4-fl uoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxyacetate;
Ethyl 2- { 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxy }propionate;
Methyl 2- { 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxy }propionate;
Ethyl 2-chloro-4-fl uoro-5-(4-methyl-5-trifl uoromethyl-3-pyridazinon-2-yl )-phenylthioacetate;
Methyl 2-chloro-4-fluoro-5-(4-methyl -5-trifluoromethyl -3 -pyridazinon-2-yl)-phenylthioacetate;
Ethyl 2- { 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenylthio }propionate;
Methyl 2- { 2-chloro-4-fluoro-5-(4-rnethyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenylthio } propionate;
Methyl 2-{ 2-chloro-4-fluoro-5-(5-trifluoromethyl-3-pyridazinon-2-yl)phe-noxy } propionate;
Ethyl 2- { 2-chloro-4-fluoro-5-(5-trifluoromethyl-3-pyridazinon-2-yl)phe-noxy }propionate;
Ethyl 2-chloro-4-fluoro-5-(5-trifl uoromethyl-3-pyridazinon-2-yl)phenylthio-acetate;
Methyl 2-chloro-4-fluoro-5-(5-trifluoromethyl-3-pyridazinon-2-yl)phenylthio-acetate;
Ethyl 2-{ 2-chloro-4-fluoro-5-(5-trifluoromethyl-3-pyridazinon-2-yl)phenyl-thio } propionate;
Methyl 2- { 2-chloro-4-fluoro-5-(5-trifluoromethyl-3-pyridazinon-2-yl)phenyl-thio } propionate;
Isopropyl 2- { 2-chl oro -4-fluoro-5 - (5-tri fl uoromethyl -3 -pyri dazinon-2-yl)-phenylthio }propionate;
Ethyl 2- { 2-chloro-4- flu oro- 5-(4- methyl-5 -trifl uoromethyI-3-pyridazinon-yl)phenylamino }propionate;
Ethyl 2- { 2-chloro-4-fluoro-5-(5-trifluoromethyl-3 -pyridazinon-2-yl)phenyl-amino } propionate;
N- { 2-c hloro-4-f lu oro-5 -(4-methyl -5-t rifluoromethyl -3-p yri dazi non -2-yl)-phenyl }methanesulfonamide;
N- { 2-c hloro-4-f lu oro-5 -( 4-methyl -5 -t rif luoromethyl -3-p yri dazi non -2-y 1)-phenyl }chloromethanesulfonamide;
N-{ 2-chloro-5-(4-methy1-5-trifluoromethyl-3-pyridazinon-2-yl)phenyl}-methanesulfonamide;
Methyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-benzoate;
Ethyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-benzoate;
Ethyl 2-chloro-5-(4-methyl-5-trifl uoromethyl-3-pyridazinon-2-yl)benzoate;
Isopropyl 2-chloro-_5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)ben-zoate; and 2-(4-Chloro-2-fluoro-5-propargyloxyphenyl)-6-methyl-5-trifluoromethylpyri-dazin-3-one.
Among these compounds, more preferred ones from the viewpoint of their herbicidal activity are as follows:
7-F luo ro-6-(5 -triflu oro met hyl-3 -p yrid azi non -2-y 1)-4-proparyg yl-2 H-1,4-benzoxazin-3-one;
7-Fluoro-6-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-4-propargyl-2H-1,4-benzoxazin-3-one;
6-(4-Methyl -5-trifluoromethyl -3-pyridazinon-2-y 1)-4-propargyl-2H -1,4-ben-zoxazin-3-one;
Ethyl 2- { 2-chloro-4-fluoro-5-(5-trifluoromethyl-3 -pyridazinon-2-yl) phe-noxy}propionate; and Ethyl 2- { 2-chloro-4-fl u oro-5-(5-trifl uoromethyl-3-pyridazinon-2-yl )phenyl-thio }propionate.
In addition, more preferred ones from the viewpoint of their selectivity between crop plants and undesired weeds are as follows:
2-(4-Chloro-2-fl uoro-5-propargyloxyphenyl)-4-methyl-5-trifluoromethylpyri-dazin-3-one;
Ethyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-phenoxyacetate;
N- { 2-chloro-4-fluoro-5-(4-methyl-5-tri fluoromethyl-3-pyridazinon-2-yl)phen-yl } methanesulfonamide; and Ethyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-benzoate.
The present compounds can be produced, for example, according to the production processes described below.
(Production Process 1) This is the production process in which among the present compounds, a compound of the fonnula:
Q1_1~ Ri N- [3]
wherein Ri, R2, R3, and Qt are as defined above, is produced by reacting a hydrazone derivative of the formula:
QI-NHN= C~ [4]
t E- R
=
wherein R1, R3, and Q1 are as defined above, with a compound of the formula:
R?
' 1 Ar3P=C-- COOR28 [5]
wherein R2 is as defined above; R28 is Ci-C6 alkyl such as methyl or ethyl;
and Ar is an optionally substituted phenyl such as phenyl.
The reaction is usually effected in a solvent. The reaction temperature is usually in the range of -20 to 150 C, preferably 0 to 100 C. The reaction time is usually in the range of a moment to 72 hours. The amounts of the reagents to be used in the reaction, although the proportion of I mole of compound [5] to 1 mole of compound [4] is ideal, can be freely changed depending upon the reaction conditions.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; aromatic hydro-carbons such as benzene, toluene, and xylene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran (THF), and ethylene glycol dimethyl ether;
nitro compounds such as nitromethane and nitrobenzene; acid amides such as formamide, N,N-dimethylformamide, and acetamide; tertiary amines such as pyridine, triethylamine, diisopropylethylamine, N,N-dimethylaniline, N,N-diethylaniline, and N-methylmor-pholine; sulfur cornpounds such as dimethylsulfoxide and sulforane; alcohols such as methanol, ethanol, ethylene glycol, and isopropanol; water; and mixtures thereof.
= After completion of the reaction, the reaction solvent is distilled out from the reaction mixture and the residue is subjected to chromatography, or the reaction mixture is subjected to ordinary post-treatinents such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as chromatography or recrystallization. Thus the desired compound of the present invention can be isolated.
The above reaction is effected through a compound of the formula:
Qi"'NHN=~
// R [6]
R2,~~r wherein R1, R2, R3, R28, and Q1 are as defined above.
This production process can also be conducted by isolating compound [6]
and effecting intramolecular cyclization of compound [6]. The cyclization can usually be effected in a solvent. The reaction temperature is usually in the range of -20 to 150 C, preferably 50 to 150 C. The reaction time is usually in the range of a moment to 72 hours.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; aromatic hydro-carbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloromethane, dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydro-furan, and ethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; esters such as ethyl formate, ethyl acetate, butyl acetate, and diethyl carbonate; nitro compounds such as nitromethane and nitrobenzene; nitriles such as acetonitrile and isobutyronitrile; acid amides such as formamide, N,N-dimethylformamide, and acetamide; tertiary amines such as pyridine, triethylamine, diisopropylethylamine, N,N-dimethylaniline, N,N-diethylaniline, and N-methylmorpholine; sulfur compounds such as dimethylsulfoxide and sulforane;
fatty acids such as formic acid, acetic acid, and propionic acid; alcohols such as methanol, ethanol, ethylene glycol, and isopropanol; water; and mixtures thereof.
As the reaction catalyst, acids such as sulfuric acid or bases such as sodium methylate can be used.
(Production Process 2) This is the production process according to the following scheme:
x O R'- x R'-F 6 Rj ---IN F ON ~ Rj ---~ O-)N
R; R3 [7] [gJ
X O R'-R'-'OOCO ~ ~ N Rt ~ R4 ~N-N \ R3 O~N R3 O H
[9] [10]
x o R'-~ ~ N R' R5! R3 [11]
wherein R5 1 is a substituent other than hydrogen, which is included in the definition of R5; R1, R2, R3, R4, and X are as defined above; R22 is CI-C6 alkyl; and D is chlorine, bromine, iodine, methanesulfonyloxy, trifluoromethanesulfonyloxy, or p-toluenesulfonyl-oxy.
Process for Producing Compound f8l from Compound f71 = Compound [8] can be produced by reacting compound [7] with a nitrating agent in a solvent.
Nitrating agent: nitric acid or the like Amount of nitratina agent: I to 10 moles per mole of compound [7]
Solvent: sulfuric acid Temperature: -10 C to room temperature Time: a moment to 24 hours Process for Producing Compound (9l from Compound181 Compound [9] can be produced by reacting compound [8] with a compound of the formula:
HO COOR22 [12]
wherein R4 and R22 are as defined above, in the presence of potassium fluoride in a solvent.
Aniount of compound [12]: 1 to 50 moles per mole of compound [8]
Amount of potassium fluoride: 1 to 50 moles per mole of compound [8]
Solvent: 1,4-dioxane or the like Temperature: room temperature to refluxing temperature under heating Time: a moment to 96 hours Process for Producinsz Compound (101 from Compound (91 Compound [10] can be produced by reducing compound [9] with iron powder or the like in the presence of an acid in a solvent.
Amount of iron powder: 3 moles to an excess per mole of compound [9]
Acid: acetic acid or the like Amount of acid: 1 to 10 moles Solvent: water, ethyl acetate, or the like Temperature: room temperature to refluxing temperature under heating .
Time: a moment to 24 hours Process for Producina Compound (1 11 from CornQound (101 Compound [ 1 1] can be produced by reacting compound [ 10] with a compound of the formula:
R51-D [13]
wherein R51 and D are as defined above.
The reaction is usually effected in the presence of a base in a solvent. The reaction temperature is usually in the range of -20 to 150 C, preferably 0 to 50 C. The reaction time is usually in the range of a moment to 48 hours. The amounts of the reagents to be used in the reaction are usually 1 to 3 moles of compound [ 13]
and usually 1 to 2 moles of the base, per mole of compound [10].
Examples of the base which can be used include inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate; and organic bases such as triethylamine, diisopropyl-ethylamine, pyridine, 4-dimethylaminopyridine, N,N-dimethylaniline, and N,N-diethyl-aniline.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; aromatic hydro-carbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloro-benzene and dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether; nitro compounds such as nitro-benzene; acid amides such as formamide, N,N-dimethylformamide, and acetamide;
tertiary amines such as pyridine, triethylamine, diisopropylethylamine, N,N-dimethyl-amine, N,N-diethylaniline, and N-methylmorpholine; and mixtures thereof.
After completion of the reaction, the reaction mixture is poured into water, if necessary, and subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatography or recrystallization. Thus the present compound [ 1 1] can be obtained.
The above compound [9] can also be produced according to the following scheme:
X O R' R4 X O R'-HO R' ---~ R'-'-OOCIJI- ~ Ri N
[141 [ 15 ]
X O R'- R4 X O R'-H ~~ N ~ Ri R''OOCO ~~ N ~ R' _ _ O,N R3 O,N R3 [16] [9l wherein R1, R2, R3, R4, R22 , and X are as defined above.
Process for ProducinQ Compound [ 151 from Compound f 141 Compound [15] can be produced by reacting compound [14] with a compound of the formula:
Br COOR '' [17]
wherein R4 and R'-2 are as defined above, in the presence of a base in a solvent.
Amount of compound [ 17]: 1 to 2 moles per mole of compound [ 14]
Base: sodium hydride, sodium carbonate, or the like Amount of base: I to 2 moles per mole of compound [ 14]
Solvent: 1,4-dioxane, N,N-dimethylformamide, or the like Teniperature: 0 to 100 C
Time: a moment to 24 hours Process for Producing Compound f9l from Compound [ 151 Compound [9] can be produced by reacting compound [ 15] with a nitrating agent in a solvent.
Nitrating agent: nitric acid or the like Amount of nitrating agent: 1 to 10 moles per mole of compound [15]
Solvent: sulfuric acid, acetic acid, or the like Temperature: -10 C to room temperature = Time: a moment to 24 hours Process for Producing Compound j161 from Comnound f 141 Compound [ 16] can be produced by reacting compound [ 14] with a nitrating agent in a solvent.
Nitrating agent: nitric acid or the like Amount of nitrating agent: 1 to 10 moles per mole of compound [ 14]
Solvent: sulfuric acid, acetic acid, or the like Temperature: -10 C to room temperature Time: a moment to 24 hours Process for Producing Compound (91 from Compound f 161 Compound [9] can be produced by reacting compound [16] with compound[17] in the presence of a base in a solvent.
Amount of compound [ 17]: 1 to 2 moles per mole of compound [ 16]
Base: sodium hydride, potassium carbonate, or the like Ainount of base: 1 to 2 moles per mole of compound [ 16]
Solvent: 1,4-dioxane, N,N-dimethylformamide, or the like Temperature: 0 to 100 C
Time: a moment to 24 hours (Production Process 3) This is the production process according to the following scheme:
X O R'- h O R'-Y / \ N \ R ' ---o- N R i 3-- Nr- - N-O,N R3 H,N R3 [18] [ 19]
X O R'- X O R'-S Ri R1 , H,N Rj O N R3 H =
[20] [21 ]
X O R'--~ N ~ Ri ~N N-[22~
wherein X, R1, R2, R3, R51, and D are as defined above.
Process for Producin!z Compound f 191 from Compound1181 Compound [19] can be produced by reducing compound [18] with iron powder or the like in the presence of an acid in a solvent.
Amount of iron powder: 3 moles to an excess per mole of compound [18]
Acid: acetic acid or the like Amount of acid: 1 to 10 moles per mole of compound [ 18]
Solvent: water, ethyl acetate, or the like Temperature: room temperature to refluxing temperature under heating Time: a moment to 24 hours Process for Producing Compound f211 from Compound [201 Compound [20] can be produced by reacting compound [ 19] with sodium thiocyanate, potassium thiocyanate, or the like in a solvent, and then reacting it with bromine or chlorine in a solvent.
Amount of sodium thiocyanate, potassium thiocyanate, or the like: I to moles per tnole of compound [ 19]
Amount of bromine or chlorine: I to 10 moles per mole of compound [19]
Solvent: aqueous hydrochloric acid, aqueous acetic acid, aqueous sulfuric acid, or the like Temperature: 0 to 50 C
Time: a moment to 150 hours Process for Producing Compound f211 from Compound f201 Compound [21 ] can be produced by 1) reactinj compound [20] with sodium nitrite, potassium nitrite, or the like in a solvent, and then 2) heatina it in an acidic solution.
<Reaction 1)>
Amount of sodium nitrite, potassium nitrite, or the like: I to 2 moles per mole of compound [20]
Solvent: aqueous hydrochloric acid or aqueous sulfuric acid Temperature: -10 to 10 C
Time: a moment to 5 hours <Reaction 2)>
Acidic solution: aqueous hydrochloric acid, aqueous sulfuric acid, or the like Temperature: 70 C to refluxing temperature under heating Time: a moment to 24 hours Process for Producina Compound f221 from Compound i211 Compound [22] can be produced by reacting compound [21 ] with compound [ 13] in the presence of a base in a solvent.
Amount of compound [13]: 1 to 3 moles per mole of compound [21]
Base: sodium hydride, potassium carbonate, or the like Amount of base: 1 to 2 moles per mole of compound [21 ]
Solvent: 1,4-dioxane, N,N-dimethylformamide, or the like Temperature: 0 to I 00 C
Time: a moment to 48 hours (Production Process 4) This is the production process accordina to the following scheme:
WO 97/07104 PCT/.TP96/02311 X O R'- X O R ' -O _ , N N R' H2N N R~ ------~- ~
- N- -H \ R; H \ R;
[23] [24]
X O R'-~ N \ R
jl N-N-N
R;
[25]
wherein X, R I, R2, R3, and R5 are as defined above.
Process for Producing Compound L241 from Com op und [23]
Compound [24] can be produced by reducing compound [23] with iron powder or the like in the presence of an acid in a solvent.
Amount of iron powder: 3 moles to an excess per mole of compound [23]
Acid: acetic acid or the like Amount of acid: i to 10 moles per mole of compound [23]
Solvent: water, ethyl acetate, or the like Temperature: room temperature to refluxing temperature under heating Time: a moment to 24 hours Process for Producina Compound [251 from Com op und [241 Compound [25] can be produced by 1) reacting compound [24] with a nitrite salt in a solvent to form a diazonium salt, and then 2) raising the temperature to cause the cyclization of the diazonium salt in a solvent.
<Reaction 1)>
Nitrite salt: sodium nitrite, potassium nitrite, or the like Amount of nitrite salt: 1 to 2 moles per mole of compound [24]
Solvent: aqueous hydrochloric acid, aqueous sulfuric acid, or the like Temperature: -10 to 10 C
Time: a moment to 5 hours <Reaction 2)>
= Solvent: aqueous hydrochloric acid, aqueous sulfuric acid, or the like Temperature: room temperature to 80 C
Time: a moment to 24 hours (Production Process 5) This is the production process according to the following scheme:
X 0 R'- X O R'-yl 6 N \ RI yi ON \ RI R; O,N R3 [26] [27]
X O R'- X O R'-yl N R1 -~~ yt N RI
N- N-H,N W HO R3 [28] [29]
X O R'-----i- y I 0 N' R t N
RlOI-O
[30]
wherein Y~ is a substituent other than nitro, which is included in the definition of Y;
RIOi is a substituent other than hydrogen, which is included in the definition of R lO; and X, R1, R2, and R3 are as defined above.
Process for Producing Compound f271 from compound f261 Compound [27] can be produced by adding nitric acid to compound [26] in a solvent (see Organic Synthesis Collective, Vol. 1, p. 372).
The reaction temperature is usually in the range of 0 to 100 C. The reaction time is usually in the range of a moment to 24 hours. The amounts of the reagents to be used in the reaction, although the proportion of 1 mole of nitric acid to I
mole of compound [26] is ideal, can be freely changed depending upon the reaction conditions.
Examples of the solvent which can be used include acidic solvents such as sulfuric acid.
Process for Producing Compound f281 from compound1271 Compound [28] can be produced by reducing compound [27] in a solvent (see Organic Synthesis Collective, Vol. 2, p. 471, and ibid., Vol. 5, p. 829).
For example, the production can be achieved by adding compound [27], which is neat or dissolved in a solvent such as ethyl acetate, to a mixture of acetic acid, iron powder, and water. The reaction temperature is usually in the range of 0 to 100 C.
The reaction time is usually in the range of a moment to 24 hours.
After completion of the reaction, the reaction mixture is filtered to collect the crystals, which may be precipitated by the addition of water, if necessary, or the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatography or recrystallization. Thus the desired product can be isolated.
Process for Producina Compound [291 from compound [281 Compound [29] can be produced by 1) reacting compound [28] with a nitrite salt in a solvent, and then 2) heating it in an acidic solvent.
<Reaction I )>
Nitrite salt: sodium nitrite, potassium nitrite, or the like Amount of nitrite salt: I to 2 moles per inole of compound [28]
Solvent: aqueous hydrochloric acid, aqueous sulfuric acid, or the like Temperature: -10 to 10 C
Time: ainoment to 5 hours W O 97/07104 PCT/dP96/02311 <Reaction 2)>
Acidic solvent: aqueous hydrochloric acid or aqueous sulfuric acid Temperature: 70 C to refluxing temperature under heating r.
Time: a moment to 24 hours.
Process for Producing Compound (301 from Compound [29]
Compound [30] can be produced by reacting compound [29] with a compound of the formula:
R101-D [31]
wherein R101 and D are as defined above, in the presence of a base in a solvent.
The reaction is usually effected in a solvent. The reaction temperature is usually in the range of -20 to 150 C, preferably 0 to 100 C. The reaction time is usually in the range of a moment to 72 hours. The amounts of the reagents to be used in the reaction, although the proportion of I mole of compound [31] and 1 mole of a base to I mole of compound [29] is ideal, can be freely changed depending upon the reaction conditions.
Examples of the base which can be used include organic bases and inorganic bases such as potassium carbonate, sodium hydroxide, and sodium hydride.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; aromatic hydro-carbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloromethane, dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydro-furan, and ethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; esters such as ethyl formate, ethyl acetate, butyl acetate, and diethyl carbonate; nitro compounds such as nitromethane and nitrobenzene: nitriles such as acetonitrile and isobutyronitrile; acid amides such as formamide, N,N-dimethylformamide, and acetamide; tertiary amines such as pyridine, triethylamine, diisopropylethylamine, N,N-dimethylaniline, N,N-diethylaniline, and N-methylmorpholine; sulfur compounds such as dimethylsulfoxide and sulforane;
and mixtures thereof.
After completion of the reaction, the reaction mixture is filtered to collect the crystals, which may be precipitated by the addition of water, if necessary, or the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatography or recrystallization. Thus the desired product can be isolated.
(Production Process 6) This is the production process according to the following scheme:
X O R'- X O R'-1.~ N "I R' 10 1,t N RI
N- N-H,N R3 H ; R3 [28] [32]
X O R'------a Y t N ~ R ' N
R'4 R;
[33]
wherein R23 and R24 are independently a substituent other than hydrogen, which is included in the definition of RI' and R 1 2; or COR 13, S02R 14, S02R 1 5, or COOR IO, wherein R10, R13, R 14, and R 15 are as defined above; X, Y 1, R1, R2, and R3 are as defined above.
Process for Producing compound (321 from Compound 1'281 Compound [32] can be produced by reacting compound [28] with a compound of the formula:
r R20-D [34]
wherein R20 is a substituent other than hydrogen, which is included in the definition of R i l or R 1V; or COR 13, S02R 14, SO2R 15, or COOR 10, wherein R 10, R 13, R
14, and R 15 are as defined above; and D is as defined above; or with a compound of the formula:
(R21)20 [35]
wherein R21 is COR13, S02R14, S02R15, or COOR10, wherein R1o, R13, R14, and are as defined above, usually in the presence of a base and usually in a solvent.
The reaction temperature is usually in the range of -20 to 200 C, preferably 0 to 180 C. The reaction time is usually in the range of a moment to 72 hours. The amounts of the reagents to be used in the reaction, although the proportion of 1 mole of compound [34] or [35] to 1 mole of compound [28] is ideal, can be freely changed depending upon the reaction conditions.
Examples of the base which can be used include organic bases such as pyridine and triethylamine, and inorganic bases.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; aromatic hydro-carbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloromethane, dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydro-furan, and ethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; esters such as ethyl formate, ethyl acetate, butyl acetate, and diethyl carbonate; nitro compounds such as nitromethane WO 97/07104 PCT/.TP96/02311 and nitrobenzene; nitriles such as acetonitrile and isobutyronitrile; acid amides such as formamide, N,N-dimethylformamide, and acetamide; tertiary amines such as pyridine, triethylamine, diisopropylethylamine, N,N-dimethylaniline, N,N-diethylaniline, and N-methylmorpholine; sulfur compounds such as dimethylsulfoxide and sulforane;
and mixtures thereof.
After completion of the reaction, the reaction mixture is filtered to collect the precipitated crystals, or the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subse-quent purification by a technique such as column chromatography or recrystallization.
Thus the desired product can be isolated.
Process for Producin= compound f33] from Compound [321 Compound [33] can be produced by reacting compound [32] with compound [34] or [35]. This production process is based on the process for producing compound [32] from compound [28).
(Production Process 7) This is the production process according to the followin; scheme:
X O R'- X O R=' Y6 N R t R t N ~T
Rs CIOiS
R-;
[36] [37]
X O R'- X O R'-Y ON \ Rt y Rt . ~ _ R' OO, S R i t R t'-NO, S
R3 R;
[38) [39l wherein X, Y, RI, R', R3, R 10, R1i, and R12 are as defined above.
WO 97/07104 PCT/,TP96/02311 Process for Produciniz compound [371 from compound f361 Compound [37] can be produced by reacting compound [36] with chloro-sulfonic acid without any solvent or in a solvent.
Amount of chlorosulfonic acid: 1 mole to an excess per mole of compound [36]
Solvent: sulfuric acid Temperature: 0 to 70 C
Time: a moment to 24 hours (see Org. Syn. Coll., Vol. 1, 8 (1941)) Process for Producing Compound f381 from Compound [37]
Compound [38] can be produced by reacting compound [37] with a compound of the formula:
R 1 O-OH [40]
wherein R10 is as defined above, in the presence of a base without any solvent or in a solvent.
Amount of compound [24]: 1 mole to an excess per mole of compound [37]
Base: organic bases such as triethylamine or inorganic bases such as potas-sium carbonate Amount of base: 1 to 2 moles per mole of compound [37]
Solvent: N,N-dimethylformamide, 1,4-dioxane, or the like Temperature: 0 to 100 C
Time: a moment to 24 hours Process for Producina Compound [391 from Compound 571 Compound [39] can be produced by reacting compound [37] with a compound of the formula:
R11Ri2NH [41]
wherein R I 1 and R12 are as defined above, in the presence or absence of a base without any solvent or in a solvent.
Amount of compound [41]: 1 mole to an excess per mole of compound [37]
Base: organic bases such as triethylamine or inorganic bases such as potas-sium carbonate Amount of base: 1 to 2 moles per mole of compound [37]
Solvent: 1,4-dioxane, N,N-dimethylformamide, or the like Temperature: 0 to 100 C
Time: a moment to 24 hours (Production Process 8) This is the production process according to the following scheme:
X O R'- X O R'-.I \ R i ---~
_ Y~~ N R t 47R3 N
0= C, \ OH R3 [42] [43]
X 0 R'-X O R'- y N Ri y ~ ~ N ~ R!
. R17~
_ N- R3 Ri7C R3 COOR'-'- jr R1s CONR"RI' R's [44] [45]
wherein X, Y, R 1, R2, R3, R1i, R 12, R 17, R 18, and R22 are as defined above.
Process for Producing Compound [431 from Compound [421 Compound [43] can be produced from compound [42] according to the method described in JP-A 5-294920/1993, pp. 15-16.
Process for Producing Compound f441 from Compound f431 Compound [44] can be produced by reacting compound [43] with a compound of the formula:
(C6H5)3P=CR 18COOR22 [45]
or (C2H50)2P(O)CHR 18COOR22 [46]
wherein R 18 and R22 are as defined above, in a solvent, and when compound [46] is used, in the presence of a base.
Amount of compound [45] or [46]: 1 to 2 moles per mole of compound [43]
Solvent: tetrahydrofuran, toluene, or the like Base: sodium hydride or the like Amount of base: 1 to 2 moles per mole of compound [43]
Temperature: 0 to 50 C
Time: a moment to 24 hours Process for Producing Compound f451 from Compound [441 Compound[45] can be produced by reacting compound [44] with compound [41].
(Production Process 9) This is the production process according to the following scheme:
X O R'- X O R'-' ~ ~ N R' --~ Y ~ Ri - N- - H,N R~ R3 CO,R 1;
w, [48] [49]
wherein W2 is chlorine or bromine; and X, Y, RI, R2, R3, and R13 are as defined above.
The reaction conditions are described, for example, in USP 5,208,212.
s The production can be achieved by converting compound [48] into a diazonium salt in a solution of hydrochloric acid, hydrobromic acid, or the like according to the ordinary method, and then reacting it with a compound of the formula:
CH2=CHCO2R13 [50]
wherein R 13 is as defined above, in the presence of a copper salt, such as copper (II) chloride or copper (II) bromide, in a solvent such as acetonitrile.
The reaction temperature is usually in the range of -20 to 150 C, preferably 0 to 60 C. The reaction time is usually in the range of a moment to 72 hours.
After completion of the reaction, the reaction mixture is filtered to collect the crystals, which may be precipitated by the addition of water, if necessary, or the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatography or recrystallization. Thus the desired product can be isolated.
(Production Process 10) This is the production process according to the following scheme:
X O R' X O R'-Yt N ~ Rt ~,t N ~ Rt .
N-' N-H,N R.; w3 R;
[28] [51]
X O R'-yi ~ ~ N Rt _ N-R ~;OOC
[52]
wherein W3 is brornine or iodine: and X, Yl, Rl, R2, R3, and R13 are as defined above.
------------Process for Producing Compound (511 from compound f281 Compound [51 ] can be produced by 1) making a diazonium salt from compound [28] in a solvent and then 2) reacting it with potassium iodide or copper ( I) bromide in a solvent.
<Reaction 1)>
Diazotizing agent: sodium nitrite, potassium nitrite, or the like.
Amount of diazotizing agent: 1 to 2 moles per mole of compound [28]
Solvent: aqueous hydrogen bromide, aqueous sulfuric acid, or the like.
Temperature: -10 to IO C
Time: a moment to 5 hours <Reaction 2)>
Amount of potassium iodide or copper ( I) bromide: 1 mole to an excess per mole of compound [28]
Solvent: aqueous hydrogen bromide, aqueous sulfuric acid, or the like Temperature: 0 to 80 C
Time: a moment to 24 hours (see Org. Syn. Coll., Vol. 2, 604 (1943), and ibid., Vol. 1, 136 (1941)) Process for Produciniz Compound (521 from Compound (5 11 Compound [52] can be produced by reacting compound [511 with a compound of the formula:
R 1-i-OH [53]
wherein R13 is as defined above, in the presence of a transition metal catalyst and a base in a solvent under an atmosphere of carbon monoxide.
Catalyst: PdC12(PPh3)2 or the like Amount of catalyst: a catalytic amount to 0.5 mole per mole of compound [511 Amount of compound [53]: 1 mole to an excess per mole of compound [51]
Base: organic bases such as diethylamine Amount of base: 1 to 2 moles per mole of compound [51]
Solvent: N,N-dimethylformamide or the like Pressure of carbon monoxide: 1 to 150 atm.
Temperature: 0 to 100 C
Time: a moment to 72 hours (see Bull. Chem. Soc. Jpn., 48 (7) 2075 (1975)) (Production Process 11) This is the production process according to the following scheme:
X O R'- X O R'-Y~~ N ~ Ri Y~~ N ~ Ri -' N- - N-o R:s HO Rs [54] [55]
wherein X, Y, R1, R2, R3, and R 19 are as defined above.
Compound [55] can be produced by hydrolyzing compound [54] in an acid solvent such as sulfuric acid, or in the presence of an acid such as boron tribromide in a solvent such as methylene chloride.
The reaction temperature is usually in the range of -20 to 150 C, preferably 0' to 100 C. The reaction time is usually in the range of a moment to 72 hours.
The amount of the acid to be used in the reaction, although the proportion of I mole of the acid to 1 mole of compound [54] is ideal, can be freely changed depending upon the reaction conditions.
After completion of the reaction, the reaction mixture is filtered to collect the crystals, which inay be precipitated by the addition of water, if necessary, or the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatob aphy or recrystallization. Thus the desired product can be isolated.
(Production Process 12) This is the production process according to the following scheme:
X O R'- X O R'-y RI _-T 1, N \ Rt % - N- - N-Z; O R3 Z' O R3 R'-sOR' 7 R,sZsR'-e [56] [57]
wherein X, Y, R1, R2, R3, Z2, and R17 are as defined above; Z3 is oxygen or sulfur;
R25 is hydrogen or Ci-C5 alkyl; and R26 is Cl-C6 alkyl, C3-C6 alkenyl, or C3-alkynyl.
Compound [57] can be produced by reacting compound [56] with a compound of the formula:
R26Z3H [58]
wherein R26 and Z3 are as defined above, in the presence or absence of a catalyst and usually in a solvent.
The amount of compound [58] to be used in the reaction, although the proportion of 1 mole of compound [58] to I mole of compound [56] is ideal, can be freely changed depending upon the reaction conditions.
Examples of the catalyst which can be used include p-toluenesulfonic acid.
Examples of the solvent which can be used include toluene, xylene or the like, or compound [56].
The reaction temperature is usually in the range of 0 to 200 C, preferably 50 to 150 C. The reaction time is usually in the range of a moment to 72 hours.
After completion of the reaction, the reaction mixture is filtered to collect the crystals, which may be precipitated by the addition of water, if necessary, or the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatography or recrystallization. Thus the desired product can be isolated.
(Production Process 13) This is the production process according to the following scheme:
X O R'- X O R'-.
y N 1~ R' --- y N I Ri %
- N- N-HO R3 Q /i R3 ~CI
[55] [59]
X O R'- X O R'-y I'_ N ~ Ri -y R' . N- N-[60] [61 ]
wherein R61 is a substituent other than methyl, which is included in the definition of R6;
and X, Y, RI, R2, and R3 are as defined above.
Process for Producing Compound f591 from Compound f551 Compound [59] can be produced by reacting compound [55] with 2,3-di-chloropropene in the presence of a base in a solvent.
Amount of 2,3-dichloropropene: I to 3 moles per mole compound [55]
Base: inorganic bases such as potassium carbonate Amount of base: 1 to 2 moles per mole of compound [55]
Solvent: N,N-dimethylformamide or the like Temperature: 0 to 70 C
Time: a moment to 24 hours Process for Producing Compound (601 from Compound 1591 Compound [60] can be produced by heating compound [59] in a solvent.
Solvent: N,N-dimethylformamide, N,N-dimethylaniline, N,N-diethylani-line, p-diisopropylbenzene, or the like Temperature: 70 to 200 C
Time: a moment to 24 hours Process for Producina Compound [61] from Compound [601 Compound [61) can be produced from compound [62] according to the method in which the methyl group in position 2 on the benzofuran ring is replaced with another substituent, as described in USP 5,308,829, columns 2-11.
(Production Process 14) This is the production process according to the following scheme:
X O R'- X O R'-~ Rt Rt --~-.
- N-[$5] [62]
X O R'- X O R'-N
R' Y N Rt N-Y S
R; O R3 [63] [64]
wherein X, Y, RI, R2, R3, and R7 are as defined above.
Process for Producina Compound (62] from compound [55]
Compound [62] can be produced by reacting compound [55] with a compound of the formula:
CH2=CR7CH2W2 [65]
wherein W2 and R7 are as defined above, in the presence of a base in a solvent.
Amount of compound [65]: 1 to 5 moles per mole of compound [55]
Base: inorganic bases such as potassium carbonate Amount of base: I to 2 moles per mole of compound [55]
Solvent: N,N-dimethylformamide, 1,4-dioxane, or the like Temperature: 0 to 70 C
Time: a moment to 24 hours Process for Producing Compound I631 from Compound r621 Compound [64] can be produced by heating compound [62] in a solvent.
Solvent: N,N-dimethylaniline, N,N-diethylaniline, p-diisopropylbenzene, or the like Temperature: 100 to 200 C
Time: a moment to 24 hours Process for Producing Compound [641 from Compound [631 Compound [64] can be produced by heating compound [63] in the presence of an acid in a solvent.
Acid: organic acids such as p-toluenesulfonic acid; and inorganic acids such as sulfuric acid Amount of acid: a catalytic amount to 1 mole per mole of compound [63]
Solvent: toluene, xylene, or the like Temperature: 100' to 250 C
Time: a moment to 24 hours (Production Process 15) This is the production process according to the following scheme:
X O R'- X O R'-Y N R1 y N ~ Rt -HO R; HO
R-~
O R
[63] [66]
X O R'- X O R'-y i N \ R t y ~~ N R i N- N-R3 O R;
R7 CH-2OH R7 Rg 1 [67] [68]
wherein R81 is a substituent other than methyl and hydroxymethyl, which is included in the definition of R8; and X, Y, R 1, R2, R3, and R7 are as defined above.
Process for Producing Compound f661 from Compound [631 Compound [66] can be produced by reacting compound [63] with a peracid in a solvent.
Peracid: m-chloroperbenzoic acid or peracetic acid Amount of peracid: I mole to an excess per mole of compound [63]
Solvent: halogenated hydrocarbons such as dichloromethane; and organic acids such as acetic acid Temperature: -20 C to room temperature Time: a moment to 24 hours Process for Producing Compound f671 from Compound (661 Compound [67] can be produced by reacting compound [66] in the presence of a base in a solvent.
Base: potassium carbonate or the like Ainount of base: I to 2 moles per mole of compound [66]
Solvent: methanol, ethanol, or the like Temperature: 0 to 50 C
Time: a moment to 5 hours Process for ProducinQ Compound [68] from Compound r671 Compound [68] can be produced from compound [67] according to the method in which the hydroxyalkyl group in position 2 on the dihydrobenzofuran ring is replaced with another substituent, as described in USP 5,411,935, columns 5-10.
(Production Process 16) This is the production process according to the following scheme:
X O R'- X O R'-~ N Rt y ~ ~ N \ Rt --a N- - N-0= C R3 0= Rs OH wl [42] [69]
X O R'-Y ~ N R' - N
O \
CH,R3' [70]
X O R'- X O R'- X O R'-Y N R I y ~ N Ri y N. \ R I
- N- N_ Z' ~,r R3 h, ; R34 R3 ;' 0 \ R33 CH,R3' Ril~ N \ CH,R;- R R;a / Z CH,R
~
R i-[71 ] [72] [73]
wherein Wl is halogen, preferably chlorine; R32 is hydrogen or CI -C5 alkyl;
and X, Y, Z2, R1, R2, R3, R11, R12, R33, and R34 are as defined above.
Process for ProducinQ Compound f691 from compound f421 Compound [69] can be produced by reacting compound [42] with a halogenating agent such as thionyl chloride in a solvent according to the ordinary method.
Process for Producing Compound f701 from Compound f691 Compound [70] can be produced by reacting compound [69] with a compound of the formula:
M(D(E)C ~ R32 [74]
wherein M is an alkali metal cation, preferably lithium cation or sodium cation; and R 19, R22, and R32 are as defined above, to give a compound of the formula:
X O R'-y 0- N Ri 0=C N R3 [75]
~ COOR19 R;'-COOR'-'- -wherein X, Y, R t, R 2, R3, R19, R22, and R32 are as defined above, and then hydro-lyzing and decarboxylating compound [75].
The first reaction is usually effected in a solvent. The reaction temperature is usually in the range of -20 to 50 C, preferably room temperature. The reaction time is usually in the range of a moment to 72 hours.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether; acid amides such as forinamide, N,N-dimethylformamide, and acetamide;
sulfur compounds such as dimethylsulfoxide and sulforane; and mixtures thereof.
The second reaction is effected in the presence of sulfuric acid, hydrobromic acid, or the like in a solvent such as a lower carboxylic acid, e.g., acetic acid, or without any solvent. The reaction temperature is usually in the range of 80 to 140 C, preferably 100 to 120 C. The reaction time is usually in the range of a moment to 72 hours.
Process for Producin(z Compound F711 from Compound f701 Compound [71] can be produced by reacting compound [70] with a compound of the formula:
H2N-O-R33 [76]
wherein R33 is as defined above.
The reaction is effected in a lower alcohol such as methanol, ethanol or isopropanol, or in a mixed solution of such a lower alcohol and water. The reaction temperature is in the range of 0 to 80 C. The reaction time is in the range of a moment to 72 hours.
Compound [76] can be used in the form of a free base or an acid addition salt such as a hydrochloride salt or a sulfate salt.
The above reaction can also be effected with the addition of a basic catalyst such as an organic base, e.g., pyridine; an alkali metal carbonate, e.g., sodium carbonate, potassium carbonate or the like; alkali metal hydrogencarbonate; or alkaline earth metal carbonate.
Compound [71 ] can also be produced by reacting a compound of the formula:
X R' Y N ~ Ri ' [77]
CH,R;'-wherein X, Y, R', R2, R3, and R32 are as defined above, with a compound of the formula:
R33-D [78]
wherein R33 and D are as defined above, in the presence of a base, usually in a solvent.
Examples of the base which can be used include alkali metal alcoholates and alkali metal hydrides such as sodium hydride.
The amounts of the reagents to be used in the reaction, although the propor-tion of about 1 mole of compound [78] and 1 to 2 moles of the base to 1 mole of compound [77] is ideal, can be freely changed depending upon the reaction conditions.
Examples of the solvent which can be used include ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether;
acid amides such as formamide, N,N-dimethylformamide, and acetamide; sulfur compounds such as dimethylsulfoxide and sulforane; alcohols such as methanol, ethanol, ethylene glycol, and isopropanol; and mixtures thereof.
The reaction temperature in the above reaction is in the range of -10 to 100 C, preferably 0 to 80 C. The reaction time is in the range of a moment to 72 hours.
Process for Producing Compound [72] from compound f701 Compound [72] can be produced by reacting compound [70] with a compound of the formula:
H2N N~R12 [79]
wherein R11 and R12 are as defined above.
The reaction is effected in a lower alcohol such as methanol, ethanol or isopropanol, or in a mixed solution of such a lower alcohol and water. The reaction temperature is in the range of 0 to 80 C. The reaction time is in the range of a moment to 72 hours.
Compound [79] can be used in the form of a free base or an acid addition salt such as a hydrochloride salt or a sulfate salt.
The above reaction can also be effected with the addition of a basic catalyst such as an organic base, e.g., pyridine; an alkali metal carbonate, e.g., sodium carbonate, potassium carbonate or the like; alkali metal hydrogencarbonate; or alkaline earth metal carbonate.
Process for Producina Compound L731 from Compound f701 Compound [73] can be produced by reacting compound [70] with a compound of the formula:
R34-Z2H [80]
wherein Z2 and R34 are as defined above, usually in the presence of a catalytic amount to an excess of an acid such as p-toluenesulfonic acid, hydrochloric acid or sulfuric acid, in an organic solvent such as benzene or chloroform.
The reaction temperature is in the range of -30 C to the boiling temperature of the reaction mixture. The reaction time is in the range of a moment to 72 hours.
(Production Process 17) This is the production process according to the following scheme:
H
Q1-NHN--C~ Ql-N ~ R1 II R l=~-O
[81] [82]
wherein Qi and R1 are as defined above.
Compound [82] can be produced by reacting compound [81] with a compound of the formula:
2' q 9 [83]
(RO)2PCH?COR ~ ~
wherein R 19 and R22 are as defined above, in a solvent.
The reaction temperature is usually in the range of 30 to 120 C, preferably 40 to 80 C. The reaction time is usually in the range of 5 to 72 hours. The amounts of the reagents to be used in the reaction, although the proportion of 1 mole of compound [83] to 1 mole of compound [81 ] is ideal, can be changed depending upon the reaction conditions.
Examples the solvent which can be used include tertiary amines such as triethylamine.
After completion of the reaction, the reaction solvent is distilled out from the reaction mixture and the residue is subjected to chromatography, or the reaction nuxture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatography or recrystallization. Thus the desired compound of the present invention can be isolated.
(Production Process 18) This is the production process according to the following scheme:
X X O R'-Y~~ NHN-C' --~ ji N Ri ~( i N-B4 0 R $4 R3 [99] [100]
X O R'--f Y ~ ~ N_ RI
_ N_.
[101]
wherein B3 is OR35, SR35, COOR35, COR16, or CR17=CR18COR16 (wherein R35 is (C 1-C6 alkyl)carbonyl C 1-C6 alkyl (C i-C6 haloalkyl)carbonyl C 1-C6 alkyl, {(C i-C4 alkoxy) C I -C4 alkyl } carbonyl C I -C6 alkyl, or (C3-C8 cycloalkyl)carbonyl C 1-C6 alkyl;
and R16, R17, and R18 are as defined above); B4 is a substituent derived from B3 by protecting its ketone or a[dehyde moiety with an alcohol; and X, Y, R 1, R2, and R3 are as defined above.
Process for ProducingCom o~[1001 from Compound 1991 Compound [100] can be produced in the same manner as described in Produc-tion Process 1, except that compound [99] is used in place of compound [4].
Process for Producing Compound f 101 ] from Compound f 1001 Compound [ 101 ] can be= produced by deprotecting the ketal or acetal moiety of compound [100] by the ordinary method.
Compound [99] can be produced in the same manner as described below in the production process for compound [4], except that the ketone or aldehyde moiety in the substituent B3 of a compound of the formula:
X
Y O NH2 [102]
wherein X, Y, and B3 are as defined above, is protected with an alcohol such as methanol to give a compound of the formula:
X
Y O NH2 [103]
wherein X, Y, and B4 are as defined above, and compound [103] is used in place of compound [91] as described below.
Compound [5], which is one of the starting compounds in the production of the present compounds by production process 1, can be obtained from commercial sources or can be produced, for example, according to the method described in Jikken Kagaku Kouza (Maruzen K.K.), 4th ed., Vol. 24, pp. 259-260.
Compound [4], which is the other starting compound used in production process 1, can be produced by reacting a compound of the formula:
Q R1CCV2R3 [841 wherein RI and R3 are as defined above; and V is iodine, bromine, or chlorine, with water in the presence of a base to give a compound of the formula:
1 I~I I~I 3 [85]
R -C-C-R' wherein R 1 and R3 are as defined above (hereinafter referred to as reaction 1), and then reacting compound [85] with a compound of the formula:
Q1-NHNH2 [86]
wherein Q i is as defined above (hereinafter referred to as reaction 2).
Compound [85] can also be reacted as its hydmte or acetal derivative in water or an alcohol.
Reaction 1 is usually effected in a solvent. The reaction temperature is usually in the range of 20' to 100 C. The reaction time is usually in the range of a moment to 24 hours. The amounts of the reagents to be used in the reaction, although the proportion of 2 moles of water and 2 moles of a base to 1 mole of compound [84] is ideal, can be changed, if necessary.
Examples of the base which can be used include organic bases and inorganic bases such as sodium acetate and potassium acetate.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; aromatic hydro-carbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloro-benzene and dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether; esters such as ethyl formate, ethyl acetate, butyl acetate, and diethyl carbonate; nitro compounds such as nitromethane and nitrobenzene; nitriles such as acetonitrile and isobutyronitrile; acid amides such as N,N-dimethylformamide; tertiary amines such as pyridine, triethylamine, diisopropyl-ethylamine, N,N-dimethylaniline, N,N-diethylaniline, and N-methylmorpholine;
sulfur compounds such as dimethylsulfoxide and sulforane; alcohols such as methanol, ethanol, ethylene glycol, and isopropanol; water; and mixtures thereof.
Reaction 2 is usually effected in a solvent. The reaction temperature is usually in the range of -20 to 200 C. The reaction time is usually in the range of a moment to 72 hours. The amounts of the reagents to be used in the reaction, although the proportion of 1 mole of compound [86] to 1 mole of compound [84] used in reaction 1 is ideal, can be freely changed depending upon the reaction conditions. If necessary, the hydrochloride salt or sulfate salt of compound [86] can also be used.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; aromatic hydro-carbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloromethane, dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydro-furan, and ethylene glycol dimethyl ether; esters such as ethyl formate, ethyl acetate, butyl acetate, and diethyl carbonate; nitro compounds such as nitromethane and nitro-benzene; nitriles such as acetonitrile and isobutyronitrile; acid amides such as form-amide, N,N-dimethylformamide, and acetamide; tertiary amines such as pyridine, triethylamine, diisopropylethylamine, N,N-dimethylaniline, N,N-diethylaniline, and N-methylmorpholine; sulfur compounds such as dimethylsulfoxide and sulforane;
fatty acids such as formic acid, acetic acid, and propionic acid; alcohols such as methanol, ethanol, ethylene glycol, and isopropanol; water; and mixtures thereof.
After completion of the reaction, the reaction mixture is filtered to collect the crystals, which may be precipitated by the addition of water, if necessary, or the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatography or recrystallization. Thus the desired product can be isolated.
Among the examples of compound [4], a compound of the formula:
X
H
Y2 ~ ~ NHI~C..~~
' - CF3 [87]
wherein X is as defined above; Y2 is halogen; and B2 is hydrogen, halogen, C1-alkoxy, or C1-C6 alkylthio, can also be produced according to the following scheme:
X
C- O R
Y2 NH2 ---~-- Y2 NHN--< CF3 O
[887 [89]
x 0 I I
C-OH
Y 2 / 'NHI~< -~- CF3 [871 [90]
wherein X, Y2, B2, and R22 are as defined above.
Process for Producing Compound f891 from Compound f881 Compound [89] can be produced by reacting compound [88] with a nitrite salt in hydrochloric acid or sulfuric acid to convert it into a diazonium salt, and then reacting the diazonium salt with a compound of the formula:
a ~ il CF3CCH2COR22 [104]
wherein R22 is as defined above, in the presence of a base such as sodium acetate or pyridine.
(see, e.g., Tetrahedron, Vol. 35, p. 2013.(1979)) Process for Produciniz Compound [90] from Compound f891 Compound [90] can be produced by hydrolyzing compound [89] usually in the presence of a base in a solvent.
The reaction temperature is in the range of 0 to 150 C, preferably 20 to I00 C. The reaction time is in the range of I to 24 hours, preferably 1 to 10 hours. The amounts of the reagents to be used in the reaction, although the proportion of 1 mole of a base to 1 mole of compound [89] is ideal, can be changed, if necessary.
Examples of the base which can be used include inorganic bases such as potassium hydroxide, lithium hydroxide, barium hydroxide, and sodium hydroxide.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; aromatic hydro-carbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloro-benzene and dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; nitro compounds such as nitromethane and nitrobenzene; acid amides such as N,N-dimethylformamide;
tertiary amines such as pyridine, triethylamine, diisopropylethylamine, N,N-dimethyl-aniline, N,N-diethylaniline, and N-methylmorpholine; sulfur compounds such as dimethylsulfoxide and sulforane; alcohols such as methanol, ethanol, ethylene glycol, and isopropanol; water; and mixtures thereof.
Process for Producing Compound f871 from Compound [90]
Compound [87] can be produced by heating compound [90] in a solvent.
The reaction temperature is in the range of 50 to 200 C, preferably 50 to 150 C. The reaction time is in the range of a moment to 72 hours.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; aromatic hydro-carbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloro-form, carbon tetrachloride, dichloromethane, dichloroethane, chlorobenzene, and wo 97/07104 PCT/JP96/02311 dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydro-furan, and ethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; esters such as ethyl formate, ethyl acetate, butyl acetate, and diethyl carbonate; nitro compounds such as nitromethane and nitrobenzene; nitriles such as acetonitrile and isobutyronitrile; acid amides such as formamide, N,N-dimethylformamide, and acetamide; tertiary amines such as pyridine, triethylamine, diisopropylethylamine, N,N-dimethylaniline, N,N-diethylaniline, and N-methylmorpholine; sulfur compounds such as dimethylsulfoxide and sulforane;
fatty acids such as formic acid, acetic acid, and propionic acid; alcohols such as methanol, ethanol, ethylene glycol, and isopropanol; water; and mixtures thereof.
The above reaction can also be effected with the use of a metal, e.g., copper, as a catalyst.
After completion of the reaction, the reaction mixture is filtered to collect the precipitated crystals, or the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatography or recrystalli-zation. Thus the desired compound can be isolated.
Compound [86] can also be produced by the following scheme:
Q i -NH2 NaNO2 Q 1 -N2+Cl- a) Na2SO3 [ 91 ] HC1 [92] b) SnC12 or c) H2 / catalyst Q!-NHNH2=HCl NaOH Qi-NHNH2 [93] [86]
wherein Q~ is as defined above.
(see Organic Synthesis Collective, Vol. 1, p. 442) Compound [91 ] is known in, or can be produced according to the method as described in, EP-61741-A; USP 4,670,046, USP 4,770,695, USP 4,709,049, USP
4,640,707, USP 4,720,297, USP 5,169,43 1 and JP-A 63-156787/1988.
Some examples of compound 191] can also be produced according to the following scheme:
X x Yi -0 0,. ,t, l NO2 R'1 R3 ' [941 C951 x i Y i NHIL
R
[96]
wherein R31 is COR 16 or COOR 10.
Process for Producina Compound [951 fToin Compound 1941 Compound [95] can be produced by reacting compound [94] with nitric acid in a solvent.
The reaction terriperature is usually in the range of 0 to 100 C. The reaction time is usually in the range of a moment to 24 hours, 'The amounts of the reagents to be used in the reaction, although the proportion of I rnole of nitric acid to 1 mole of compound [94] is ideal., can be freely changed depending upon the reaction conditions.
Examples of the solvent which can be used include acidic solvents such as inixtures of nitric acid and sulfuric acid.
(see Organic Synthesis ("ollective, Vol. 1, p. 372) Process for Producing Compound j961frorn Compound [95]
Cornpound [96] can be produced by reducing compound [95] in a mixture of acetic acid, iron powder, and water.
The reaction temperature is usually in the range of 0 to 100 C. The reaction time is usually in the range of a niornent to 24 hours.
After completion of the reaction, the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatography or recrystallization. Thus the desired compound can be isolated.
(see Organic Synthesis Collective, Vol. 2, p. 471, and ibid., Vol. 5, p. 829) The present compounds have excellent herbicidal activity, and some of them exhibit excellent selectivity between crop plants and unfavorable weeds. In particular, the present compounds have herbicidal activity against various unfavorable weeds as recited below, which may cause trouble in the foliar treatment and soil treatment on upland fields.
Polygonaceae:
wild buckwheat (Polygonum convolvulus), pale smartweed (Polygonum lapathifolium), Pennsylvania smartweed (Polygonum pensylvanicum), ladysthurnb (Poly-gonum persicaria), curly dock (Rumex crispus), broadleaf dock (Rumex obtusifolius), Japanese knotweed (Polygonum cuspidatum) Portulacaceae:
common purslane (Portulaca oleracea) Caryophyllaceae:
common chickweed (Stellaria media) Chenopodiaceae:
common lambsquarters (Chenopodium album), kochia (Kochia scoparia) Amaranthaceae:
redroot pigweed (Amaranthus retroflexus), smooth pigweed (Amaranthus hybridus) Crusiferae:
wild radish (Raphanus raphanistrum), wild mustard (Sinapis arvensis), shepherdspurse (Capsella bursa-pastoris) Leguminosae:
hemp sesbania (Sesbania exaltata), sicklepod (Cassia obtusifolia), Florida beggarweed (Desmodium tortuosum), white clover (Trifolium repens) Malvaceae: velvetleaf (Abutilon tlieophrasti), prickly sida (Sida spinosa) Violaceae:
field pansy (Viola arvensis), wild pansy (Viola tricolor) Rubiaceae:
catchweed bedstraw (cleavers) (Galium aparine) Convolvulaceae:
ivyleaf morningglory (Ipomoea hederacea), tall morningglory (Ipomoea purpurea), entireleaf morningglory (Ipomoea hederacea var. integriuscula), pitted morn-ingglory (Ipomoea lacunosa), field bindweed (Convolvulus arvensis) Labiatae:
red deadnettle (Lamium purpureum), henbit (Lamium amplexicaule) Solanaceae:
jimsonweed (Datura stramonium), black nightshade (Solanum nigrum) Scrophulariaceae:
birdseye speedwell (Veronica persica), ivyleaf speedwell (Veronica hederae-folia) Compositae:
common cocklebur (Xanthium pensylvanicum), common sunflower (Helian-thus annuus), scentless chamomile (Matricaria perforata or inodora), corn marigold (Chrysanthemum segetum), pineappleweed (Matricaria matricarioides), common ragweed (Ambrosia artemisiifolia), giant ragweed (Ambrosia trifida), horseweed (Erigeron canadensis), Japanese mugwort (Artemisia princeps), tall goldenrod (Solidago altissima) Boraginaceae:
field forget-me-not (Myosotis arvensis) Asclepiadaceae:
common milkweed (Asclepias syriaca) Euphorbiaceae:
sun spurge (Euphorbia helioscopia), spotted spurge (Euphorbia maculata) Gramineae:
barnyardgrass (Echinochloa crus-galli), green foxtail (Setccria viridis), giant foxtail (Setaria faberi), large crabgrass (Digitaria sanguinalis), goosegrass (Eleusine indica), annual bluegrass (Poa annua), blackgrass (Alopecurus myosuroides), wild oat (Avena fatua), johnsongrass (Sorghum halepense), quackgrass (Agropyron repens), downy brome (Bromus tectorum), bermudagrass (Cynodon dactylon), fall panicum (Panicum dichotomiforum), Texas panicum (Panicum texanum), shattercane (Sorghum vulgare) Commelinaceae:
common dayflower (Commelina communis) Equisetaceae:
field horsetail (Equisetum arvense) Cyperaceae:
rice flatsedge (Cyperus iria), purple nutsedge (Cyperus rotundus), yellow nutsedge (Cyperus esculentus) Furthermore, some of the present compounds have no problematic phyto-toxicity on main crops such as corn (Zea mays), wheat (Triticum aestivum), barley (Hordeum vulgare), rice (Oryza sativa), sorghum (Sorghum bicolor), soybean (Glycine max), cotton (Gossypium spp.), sugar beet (Beta vulgaris), peanut (Arachis hypogaea), sunflower (Helianthus annuus) and canola (Brassica napus); garden crops such as flowers and ornamental plants; and vegetable crops.
The present compounds can attain effective control of unfavorable weeds in the no-tillage cultivation of soybean (Glycine max), corn (Zea mays), and wheat (Triticum aestivum). Furthermore, some of them exhibit no problematic phytotoxicity on crop plants.
The present compounds have herbicidal activity against various unfavorable weeds as recited below under the flooding treatment on paddy fields.
Gramineae:
barnyardgrass (Echinochloa oryzicola) Scrophulariaceae:
common falsepimpernel (Lindernia procumbens) Lythraceae:
Rotala indica, Ammannia multifora Elatinaceae:
Elatine triandra Cyperaceae:
smallflower umbrellaplant (Cyperus difformis), hardstem bulrush (Scirpus juncoides), needle spikerush (Eleocharis acicularis), Cyperus serotinus, Eleocharis kuroguwai Pontederiaceae:
Monochoria vaginalis Alismataceae:
Sagittaria pygmaea, Sagittaria trifolia, Alisma canaliculatum Potamogetonaceae:
roundleaf pondweed (Potamogeton distinctus) Umbelliferae:
Oenanthejavanica Furthermore, some of the present compounds have no problematic phyto-toxicity on transplanted paddy rice.
The present compounds can attain effective control of various unfavorable weeds in orchards, grasslands, lawns, forests, waterways, canals, or other non-cultivated lands.
The present compounds also have herbicidal activity against various aquatic plants such as water hyacinth (Eichhornia crctssipes), which will grow in waterways, canals, or the like.
The present compounds have substantially the same characteristics as those of the herbicidal compounds described in the publication of International Patent Application, W095/34659. In the case where crop plants with tolerance imparted by introducing a herbicide tolerance gene described in the publication are cultivated, the present com-pounds can be used at greater doses than those used when ordinary crop plants without tolerance are cultivated, and it is, therefore, possible to attain effective control of other unfavorable plants.
When the present compounds are used as active ingredients of herbicides, they are usually mixed with solid or liquid carriers or diluents, surfactants, and other auxiliary agents to give formulations such as emulsifiable concentrates, wettable powders, flowables, granules, concentrated emulsions, and water-dispersible granules.
These formulations may contain any of the present compounds as an active ingredient at an amount of 0.001 % to 80% by weight, preferably 0.005% to 70%
by weight, based on the total weight of the formulation.
Examples of the solid carrier or diluent may include fine powders or granules of the following materials: mineral matters such as kaolin clay, attapulgite clay, bentonite, terra alba, pyrophyllite, talc, diatomaceous earth, and calcite;
organic substances such as walnut shell powder; water-soluble organic substances such as urea;
inorganic salts such as ammonium sulfate; and synthetic hydrated silicon oxide.
Examples of the liquid carrier or diluent may include aromatic hydrocarbons such as methylnaphthalene, phenylxylylethane, and alkylbenzenes (e.g., xylene);
alcohols such as isopropanol, ethylene glycol, and 2-ethoxyethanol; esters such as phthalic acid dialkyl esters; ketones such as acetone, cyclohexanone, and isophorone; mineral oils such as machine oil; vegetable oils such as soybean oil and cotton seed oil;
dimethylsulfoxide, N,N-dimethylformamide, acetonitrile, N-methylpyrrolidone, water, and the like.
Examples of the surfactant used for emulsification, dispersing, or spreading may include surfactants of the anionic type, such as alkylsulfates, alkylsulfonates, alkylarylsulfonates, dialkylsulfosuccinates, and phosphates of polyoxyethylene alkyl aryl ethers; and surfactants of the nonionic type, such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters.
Examples of the auxiliary agent used for formulation may include lignin-sulfonates, alginates, polyvinyl alcohol, gum arabic, carboxymethyl cellulose (CMC), and isopropyl acid phosphate (PAP).
The present compounds are usually formulated as described above and then used for the pre- or post-emergence soil, foliar, or flooding treatment of unfavorable weeds. The soil treatment may include soil surface treatment and soil incorporation. The foliar treatment may include application over the plants and directed application in which a chemical is applied only to the unfavorable weeds so as to keep off the crop plants.
The present compounds can be used, if necessary, in combination with other compounds having herbicidal activity. Examples of the compounds which can be used in combination with the present compounds may include various compounds described in Catalog 1995 Edition of Farm Chemicals Handbook (Meister Publishing Company);
AG
CHEM NEW COMPOUND REVIEW, VOL. 13, 1995 (AG CHEM INFORMATION
SERVICE); or JOSOUZAI KENKYU SOURAN (Hakuyu-sha). Typical examples of such compounds are as follows: atrazin, cyanazine, dimethametryn, metribuzin, pro-metryn, simazine, simetryn, chlorotoluron, diuron, dymuron, fluometuron, isoproturon, linuron, methabenzthiazuron, bromoxynil, ioxynil, ethalfluralin, pendimethalin, triflu-ralin, acifluorfen, acifluorfen-sodium, bifenox, chlomethoxynil, fomesafen, lactofen, oxa-diazon, oxyfluorfen, carfentrazone, flumiclorac-pentyl, flumioxazine, fluthiacet-methyl, sulfentrazone, thidiazimin, difenzoquat, diquat, paraquat, 2,4-D, 2,4-DB, DCPA, MCPA, MCPB, clomeprop, clopyralid, dicamba, dithiopyr, fluroxypyr, mecoprop, naploanilide, phenothiol, quinclorac, triclopyr, acetochlor, alachlor, butachlor, diethatyl-ethyl, metolachlor, pretilachlor, propachlor, bensulfuron-methyl, chlorsulfuron, chlori-_ 'WO 97/07104 PCT/JP96/02311 muron-ethyl, halosulfuron-methyl, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, sulfometuron-methyl, thifensulfuron-methyl, triasulfuron, tribe-nuron-methyl, azimsulfuron, cloransulam-methyl, cyclosulfamuron, flumeturam, flupyr-sulfuron, flazasulfuron, imazosulfuron, metosulam, prosulfuron, rimsulfuron, triflusul-furon-methyl, imazamethabenz-methyl, imazapyr, imazaquin, imazethapyr, imazameth, imazamox, bispyribac-sodium, pyriminobac-methyl, pyrithiobac-sodium, alloxydim-sodium, clethodim, sethoxydim, tralkoxydim, diclofop-methyl, fenoxaprop-ethyl, fenoxa-prop-p-ethyl, fluazifop-butyl, fluazifop-p-butyl, haloxyfop-methyl, quizalofop-p-ethyl, cyhalofop-butyl, clodinafop-propargyl, benzofenap, clomazone, diflufenican, norflura-zon, pyrazolate, pyrazoxyfen, isoxaflutole, sulcotrione, glufosinate-ammonium, glyphos-ate, bentazon, benthiocarb, bromobutide, butamifos, butylate, dimepiperate, dimethen-amid, DSMA, EPTC, esprocarb, isoxaben, mefenacet, molinate, MSMA, piperophos, pributycarb, propanil, pyridate, triallate, cafenstrol, flupoxam, and thiafluamide.
The following will describe typical examples of such a combination, where the present compounds are designated by their compound numbers shown in Tables to 5.
1. A mixture of one compound selected from the group consisting of compounds 1-495, 1-496, 1-499, 1-503 and 1-577, and one compound selected from the group consisting of atrazin, cyanazine, bromoxynil and bentazon at a weight ratio of 1: 1 to 100.
2. A mixture of one compound selected from the group consisting of compounds 1-495, 1-496, 1-499, 1-503 and 1-577, and one compound selected from the group consisting of clethodim, sethoxydim, dichlofop-methyl, quizalofop-p-ethyl, lacto-fen, acifluorfen, acifluorfen-sodium, fomesafen, flumiclorac-pentyl and dicamba at a weight ratio of I: 0.5 to 50.
3. A mixture of one compound selected from the group consisting of compounds 1-495, 1-496, 1-499, 1-503 and 1-577, and one compound selected from the group consisting of nicosulfuron, primisulfuron, prosulfuron, chlorimuran-ethyl, thifen-sulfuron, rimsulfuron, halosulfuron, oxasulfuron, isoxaflutole, imazethapyr and imaza-mox at a weight ratio of 1: 0.1 to 10.
4. A mixture of one compound selected from the group consisting of compounds 1-439, 1-482, 1-486, 1-496, 1-1076, 1-1123 and 1-1441, and one compound selected from the group consisting of isoproturon and chlorotoluron at a weight ratio of 1: 1 to 100.
5. A mixture of one compound selected from the group consisting of compounds 1-439, 1-482, 1-486, 1-496, 1-1076, 1-1123 and 1-1441, and one compound selected from the group consisting of mecoprop, fluroxypyr and ioxynil at a weight ratio of 1: 0.5 to 50.
6. A mixture of one compound selected from the group consisting of compounds 1-439, 1-482, 1-486, 1-496, 1-1076, 1-1123 and 1-1441, and one compound selected from the group consisting of diflufenican, metsulfuron-methyl, fenoxaprop-ethyl and clodinafop-propargyl at a weight ratio of 1: 0.1 to 10.
7. A mixture of one compound selected from the group consisting of compounds 1-1141, 1-1222 and 2-203, and one compound selected from the group consisting of glyphosate, glufosinate-ammonium and paraquat at a weight ratio of 1: 1 to 100.
Moreover, the present compounds may also be used in admixture with insecticides, acaricides, nematocides, fungicides, plant growth regulators, fertilizers, soil improver, and the like.
When the present compounds are used as active ingredients of herbicides, the application amount is usually in the range of 0.01 to 10,000 g, preferably 1 to 8000 g, per hectare, although it may vary depending upon the weather conditions, formulation type, application timing, application method, soil conditions, crop plants, unfavorable weeds, and the like. In the case of emulsifiable concentrates, wettable powders, flow-ables, concentrated emulsions, water-dispersible granules, or the like, the formulation is usually applied at a prescribed amount after dilution with water having a volume of about to 1000 liters per hectare, if necessary, with the addition of an adjuvant such as a spreading agent. In the case of granules or some types of flowables, the formulation is usually applied as such without any dilution.
ti Examples of the adjuvant used, if necessary, may include, in addition to the surfactants recited above, polyoxyethylene resin acids (esters), ligninsulfonates, abiet-ates, dinaphthylmethanedisulfonates, crop oil concentrates, and vegetable oils such as soybean oil, corn oil, cotton seed oil, and sunflower oil.
The present compounds can also be used as active ingredients of harvesting aids such as defoliants and desiccating agents for cotton, and desiccating agents for potato. In these cases, the present compounds are usually formulated in the same manner as the case where they are used as active ingredients of herbicides, and used alone or in combination with other harvesting aids for foliar treatment before the harvesting of crops.
The present invention will be further illustrated by the following production examples, reference examples, formulation examples, and test examples;
however, the present invention is not limited to these examples.
The following will describe production examples for the present compounds and the hydrazones of formula [2] as the intermediate compounds, where the present compounds are designated by their compound numbers shown in Tables 1 to 5.
Production Example 1(Production of Compound 2-631) To a mixed solution of 8.0 g (97.2 mmol) of sodium acetate and 50 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1,1-dibromo-3,3,3-trifluoro-acetone, and the reaction was allowed to proceed at 80 C for 30 minutes. Then, the reaction mixture was cooled to 0'C, to which 4.4 g (18.7 mmol) of 7-fluoro-6-hydra-zino-4-propargyl-2H-1,4-benzoxazin-3-one was added, and the reaction mixture was stirred at room temperature for 2 hours. The precipitated crystals were collected by filtra-tion, washed twice with 10 ml of water, and dried, which afforded 6.3 g (18.37 mmol) of 7-fluoro-6-trifluoroacetylmethylidenhydrazino-4-propargyl-2H-1,4-benzoxazin-3-one [another name: 3,3,3-trifluoro-2-oxopropanal 1-(7-fluoro-3-oxo-4-propargyl-2H-1,4-.~~ ---benzoxazin-6-ylhydrazone)], m.p. 190.6 C (decomp.).
To a mixed solution of 6.0 g (17.5 mmol) of the above compound and 50 ml of toluene was added 9.1 g (26.2 mmol) of carbethoxymethylenetriphenylphosphorane, and the mixture was heated under reflux for 1 hour. The toluene was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 1.3 g (3.5 mmol) of 7-fluoro-6-[5-trifluoromethyl-3-pyridazinon-2-yl]-4-propargyl-2H-1,4-benzoxazin-3-one (compound 2-631).
F F
O NHNH, ---~ ~ ~ NHN
~ CF3 ~--N ~_N - O
O O
F O
l N~~~///
/\f'-' N
O L.--Production Example 2 (Production of Compound 1-476) To a mixed solution of 5.3 g (53.5 mmol) of sodium acetate and about 100 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1,1-dibromo-3,3,3-tri-fluoroacetone, and the reaction was allowed to proceed at 70 C for 20 minutes.
Then, the reaction mixture was cooled to room temperature, to which a solution of 5.8 g (21.5 mmol) of 2-fluoro-4-chloro-5-isopropoxyphenylhydrazine dissolved in about 20 ml of diethyl ether was added, and the reaction mixture was stirred at room tempera-ture for 1 hour. The ether layer was separated and concentrated. Then, about 60 ml of THF was added to the residue, to which 8.3 g (23.0 mmol) of carbethoxyethylidene-triphenylphosphorane was added, and the mixture was heated under reflux for 2 hours.
The toluene was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 3.8 g (10.5 mmol) of 2-[2-fluoro-4-chloro-5-isopropoxyphenyl]-4-methyl-5-trifluoromethylpyridazin-3-one (compound 1-476).
F F
k C1 ~~ NHNH, ' Cl ~~ NHN
- =\ CFg t F O CH., CI o N \CF3 N-O
Production Example 3 (Production of Compound 1-391) First, 3.5 g (9.7 mmol) of 2-[2-fluoro-4-chloro-5-isopropoxyphenyl]-4-methyl-5-trifluoromethylpyridazin-3-one (compound 1-476) was dissolved in about ml of concentrated sulfuric acid under ice cooling, and the solution was warmed to room temperature. After 10 minutes, about 100 ml of water was added to the reaction mixture, and the precipitated crystals were collected by filtration, and washed twice with ml of water and once with 10 ml of hexane. These crystals were recrystallized from isopropanol, which afforded 3.2 g (9.0 mmol) of 2-[2-fluoro-4-chloro-5-hydroxy-phenyl] -4-methyl-5 -trifluoromethylpyridazin-3 -one (compound 1-391).
CI N CF3 Cl N ~ CF3 N
-J\
Production Example 4 (Production of Compound 1-486) First, 3.2 g (10 mmol) of compound 1-391 was dissolved in about 50 m1 of DMF, to which 2.0 g (13 mmol) of potassium carbonate was added at room temperature and 1.3 g(11 mmol) of propargyl bromide was then added, and the mixture was stirred at room temperature for 30 minutes, followed by the addition of 100 ml of water. The precipitated crystals were collected by filtration, washed with hexane, and recrystallized from isopropanol, which afforded 3.4 g (9 mmol) of compound 1-486.
F O CH; F O CH3 Cl CF3 01 Cl N, \ CFj N N _ HO O
Production Example 5 (Production of Compound 1-496) First, 3.2 g (10 mmol) of compound 1-391 was dissolved in about 50 ml of DMF, to which 0.44 g(11 mmol) of sodium hydride (60 wt.%, oil dispersion) was added, and the mixture was allowed to stand at room temperature for 30 minutes, followed by the addition of 1.8 g (11 mmol) of ethyl bromoacetate under ice cooling.
After stirring at room temperature for 1 hour, the reaction mixture was extracted with diethyl ether. The organic layer was washed with 10% aqueous HCI, aqueous sodium bicarbonate solution and then with saturated sodium chloride solution, and dried with anhydrous magnesium sulfate. The solvent was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 2.4 g (5.5 mmol) of compound 1-496.
Cl CF3 Cl O N ~\ CF3 O
HO
'- CO2 C-1 H5 Production Example 6 (Production of Compound 2-251) To a mixed solution of 5.3 g (53.5 mmol) of sodium acetate and about 50 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1, 1 -dibromo-3,3,3-trifluoro-acetone, and the reaction was allowed to proceed at 80 C for 1 hour. Then, the reaction mixture was cooled to 0 C, to which 4.4 g (18.7 mmol) of 7-fluoro-6-hydrazino-propargyl-2H-1,4-benzoxazin-3-one was added, and the reaction mixture was stirred at room temperature for 2 hours. The precipitated crystals were collected by filtration, washed twice with 10 ml of water and once with 10 ml of hexane, and then dissolved in 50 ml of toluene without drying. To this solution was added 8.8 g (24.3 mmol) of carbethoxyethylidenetriphenylphosphorane, and the mixture was heated under reflux for 1 hour, while conducting azeotropic dehydration. The toluene was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 3.5 g (9.01 mmol) of compound 2-25 1.
F F O CH, O ~~ NHNH, O N \ CF3 ~- ~-N
O O \.-Production Example 7 (Production of Compound 2-328) To a mixed solution of 5.3 g (53.5 mmol) of sodium acetate and about 50 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1, 1 -dibromo-3,3,3-trifluoro-acetone, and the reaction was allowed to proceed at 80 C for 1 hour. Then, the reaction mixture was cooled to 0 C, to which 4.8 g (18.7 mmol) of 6-fluoro-5-hydrazino-3-(sec-butyl)-1,3-benzothiazol-2-one was added, and the reaction mixture was stirred at room temperature for 2 hours. Then, 100 ml of ether was added to the reaction mixture, followed by stirring and phase separation, and the organic layer was concentrated. The residue was dissolved in 50 ml of THF, to which 8.8 g (24.3 mmol) of carbethoxyethyli-denetriphenylphosphorane was added, and the mixture was heated under reflux for 1 hour. The THF was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 3.7 g (9.6 mmol) of compound 2-328.
S NHNH2 Ni CF3 O~ O
Production Example 8 (Production of Compound 1-347) First, 50 ml of concentrated sulfuric acid was ice cooled, in which 7.0 g (22.8 mmol) of compound 1-34! was dissolved. Then, 1.51 g (24 mmol) of fuming nitric acid was added dropwise at 5 C or lower, followed by maturation at 0 to 5 C for 1 hour. The mixture was poured into 300 ml of ice-water and extracted three times with 50 ml of ether. The combined ether layer was washed with about 100 ml of water and neutralized with 100 ml of aqueous sodium bicarbonate solution, followed by phase separation. The organic layer was dried with magnesium sulfate and concentrated to half volume, and the residue was subjected to silica gel column chromatography, which afforded 6.1 g (17.4 mmol) of compound 1-347.
ci ~ ~ \ CF3 ci N CF3 - N-O,N
eroduction Examgle 9 (Production of Compound 1-353) First, 5.0 g of iron powder, 75 ml of acetic acid, and 10 ml of water were mixed, and the mixture was warmed to about 80 C, followed by maturation for about 15 minutes. Then, 6.0 g (17.1 mmol) of compound 1-347 was dissolved in 40 ml of ethyl acetate, which was added dropwise to the above mixture at 80 C or lower.
After maturation at about 80 C for 1 hour, the reaction mixture was allowed to stand for cooling to room temperature, and extracted twice with 100 ml of ethyl acetate.
The combined ethyl acetate layer was washed twice with 50 ml of water and neutralized with aqueous sodium bicarbonate solution, followed by phase separation. The organic layer was dried with magnesium sulfate, and the ethyl acetate was distilled out under reduced pressure. The residue was subjected to silica gel chromatography, which afforded 5.1 g (15.9 mmol) of compound 1-353.
CF; ci N ~\CF3 ci N-O,N H,N
Production Example 10 (Production of Compound 1-420) First, 500 mg (1.6 mmol) of compound 1-353 was mixed with 10 ml (77.3 mmol) of ethyl 2-bromopropionate, and the mixture was heated under reflux at about 160 C for about 12 hours. After allowing to stand for cooling, the reaction mixture was subjected to silica gel column chromatography, which afforded 60 mg (0.6 mmol) of compound 1-420.
CI 5~ N CF3 CI N CF3 NH2 HN
)-- CO-)CGH5 Production Example 11 (Production of Compound 1-1622) First, 6 ml (55.4 mmol) of ethyl acrylate, 0.5 g (4.8 mmol) of t-butyl nitrite, and 0.6 g (4.5 mmol) of copper (II) chloride were mixed together in 5 ml of acetonitrile, followed by ice cooling. Then, 1.0 g (3.1 mmol) of compound 1-353 dissolved in 5 ml of acetonitrile was added dropwise at 5 C or lower, followed by overnight maturation at room temperature. The reaction mixture was poured into ice-water and extracted twice with 100 ml of ethyl acetate. The combined ethyl acetate layer was washed with 50 ml of diluted hydrochloric acid and dried with magnesium sulfate. The solvent was distilled out under reduced pressure, and the residue was subjected to silica gel column chromato-graphy, which afforded 0.51 g (1.2 mmol) of compound 1-1622.
Cl ~ N CF3 Cl N CF3 -.r-H,N
- CO~C)HS
CI
Production Example 12 (Production of Compound 1-1221) To a mixed solution of 5.3 g (53.5 mmol) of sodium acetate and about 50 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1,1-dibromo-3,3,3-trifluoro-acetone, and the reaction was allowed to proceed at 80 C for 1 hour. Then, the reaction mixture was cooled to 0 C, to which 5.2 g (18.7 mmol) of methyl 2-(2-chloro-4-fluoro-5-hydrazinophenylthio)propionate was added, and the reaction mixture was stirred at room temperature for 2 hours. The precipitated crystals were collected by filtration, washed twice with 10 ml of water and once with 10 ml of hexane, and dried. The residue was dissolved in 50 ml of THF, to which 8.4 g (22.4 mmol) of carbethoxy-methylenetriphenylphosphorane was added, and the solution was stirred at room tempera-ture for 3 hours. The THF was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 3.8 g (9.0 mmol) of compound 1-1221.
F F
Cl ~ ~ NHNH, -- CI 1~ NHN-- ~- CF3 ~-- CO1CH3 ~- CO-)CHg F O
CI ~ ~ N CF3 Production Examnle 13 (Production of Compound 2-821) To a mixed solution of 8.0 g (97.2 mmol) of sodium acetate and about 50 ml of water was added under ice cooling 6.9 g (24.3 mmol) of 3,3 -dibromo- 1, 1, 1 -trifluoro-butanone, and the reaction was allowed to proceed at 80 C for 30 minutes.
Then, the reaction mixture was cooled to 0 C, to which 4.4 g (18.7 mmol) of 7-fluoro-6-hydra-zino-4-propargyl-2H-1,4-benzoxazin-3-one was added, and the reaction mixture was stirred at room temperature for 2 hours. The precipitated crystals were collected by filtration, washed twice with 10 ml of water, and dried, which afforded 6.1 g (17.0 mmol) of 1,1,1-trifluoro-2,3-butandione 3-(7-fluoro-3-oxo-4-propargyl-2H-1,4-benzoxazin-6-ylhydrazone).
To a mixed solution of 6.1 g (17.0 mmol) of the above compound and 50 ml of THF was added 7.1 g (20.4 mmol) of carbethoxymethylenetriphenylphosphorane, and the mixture was heated under reflux for 1 hour. The THF was distilled out under W O 97/07104 PC'r/JP96/02311 reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 0.61 g(1.6 mmol) of 7-fluoro-6-(6-methyl-5-trifluoromethyl-3-pyrida-zinon-2-yl)-4-propargyl-2H-1,4-benzoxazin-3-one (compound 2-821).
O F
CH; CH, ~~ O NHN
CF3~
Br Br CF3 N O
F O
---r O 0 N \ CF3 N-O
Reference Example 1 This is a production example for 3,3-dibromo-1,1,1-trifluoro-2-butanone used in Production Example 13.
First, 34.0 g of sodium acetate was dissolved in 270 ml of acetic acid, to which 25 g (0.20 mol) of 1, 1, 1 -trifluoro-2-butanone was added, and while keeping the temperature at 15 to 20'C, 66.3 g (0.42 mol) of bromine was added dropwise over 45 minutes. The reaction mixture was stirred for 5 hours, while keeping the temperature at 15 to 20'C, and then allowed to stand at room temperature for 68 hours.
The super-natant was taken and washed with 600 ml of concentrated sulfuric acid. Further washing with 307 ml of concentrated sulfuric acid and distillation under normal pressure gave 28 g (0.10 mol) of 3,3-dibromo- 1, 1, 1 -trifluoro-2-butanone.
Y""CH3 CF3-=-- CF3~ CH3 Br Br Production Exam lp e 14 (Production of Compound 1-1346) To a mixed solution of 5.3 g (53.5 mmol) of sodium acetate and about 50 ml of water was added under ice cooling 6.9 g (24.3 mmol) of 3,3-dibromo- 1, 1, 1 -trifluoro-2-butanone, and the reaction was allowed to proceed at 80 C for 1 hour. Then, the reaction mixture was cooled to 0 C, to which 3.3 g(18.7 mmol) of 2-chloro-4-fluoro-5-hydrazinophenol was added, and the reaction mixture was stirred at room temperature for 2 hours. The precipitated crystals were collected by filtration, washed twice with 10 ml of water and once with 10 ml of hexane, dried, and then dissolved in 50 n-d of THF. To this solution was added 8.8 g(24.3 mmol) of carbethoxymethylenetriphenylphos-phorane, and the mixture was stirred at room temperature for 3 hours. The THF
was distilled out under reduced pressure, and the residue was subjected to silica gel chromato-graphy, which afforded 0.51 g (1.6 mmol) of compound 1-1346.
F F
ci 0 NHNH2 --~ CI ~ 5 NHN=~_ CF3 HO HO O
F O
--= CI 0 N CF3 Production Hxamnle 15 (Production of Compound 1-1441) First, 3.2 g (10 mmol) of compound 1-1346 was dissolved in about 50 ml of DMF, to which 2.0 g (13 mmol) of potassium carbonate was added at room temperature and 1.3 g(11 mmol) of propargyl bromide was then added, and the mixture was stirred at room temperature for 30 minutes, followed by the addition of 100 ml of water. The precipitated crystals were collected by filtration, washed with hexane, and recrystallized from isopropanol, which afforded 3.2 g (8.5 mmol) of compound 1-1441.
F O F
Cl N X CF3 CF3 Production Example 16 (Production of Compound 1-499) This example followed the procedures of Production Example 5, except that 1.8 g(1.1 mmol) of n-pentyl chloroacetate was used in place of ethyl bromoacetate.
After the addition of this compound, the reaction mixture was stirred at 40 C
for 3 hours and then extracted with diethyl ether. The organic layer was washed with 10%
HCI, aqueous sodium bicarbonate solution and saturated sodium chloride solution, and dried with anhydrous magnesium sulfate. The solvent was distilled out under reduced pressure, and the residue was subjected to silica gel chromatography, which afforded 3.8 g (8.0 mmol) of compound 1-499.
Cl 0 N, \ CF3 IV ~ CF3 N
HO O
~,-COOnC5H1 I
Production Example 17 (Production of Compound 2-203) To a mixed solution of 5.3 g (53.5 mmol) of sodium acetate and about 50 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1,1-dibromo-3,3,3-trifluoro-acetone, and the reaction was allowed to proceed at 80 C for 1 hour. Then, the reaction mixture was cooled to 0 C, to which 4.0 g (18.7 mmol) of 6-hydrazino-4-propargyl-2H-1,4-benzoxazin-3-one was added, and the reaction mixture was stirred at room tempera-ture for 2 hours. The precipitated crystals were collected by filtration, washed twice with ml of water and once with 10 ml of hexane, and then dissolved in 50 ml of THF
without drying. To this solution was added 8.8 g (24.3 mmol) of carbethoxyethylidene-triphenylphosphorane, and the mixture was heated under reflux for 3 hours. The THF
was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 3.3 g (8.8 mmol) of compound 2-203.
O J~I\~ NHNH, ~-N
N O
O
Production Exam lp e 18 (Production of Compound 1-1222) To a mixed solution of 5.3 g (53.5 mmol) of sodium acetate and about 50 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1,l-dibromo-3,3,3-trifluoro-acetone, and the reaction was allowed to proceed at 80 C for 1 hour. Then, the reaction mixture was cooled to 0 C, to which 5.5 g (18.7 nunol) of ethyl 2-(2-chloro-4-fluoro-5-hydrazinophenylthio)propionate was added, and the reaction mixture was stirred at room temperature for 2 hours. The precipitated crystals were collected by filtration, washed twice with 10 ml of water and once with 10 ml of hexane, dried, and then dissolved in 50 ml of THF. To this solution was added 8.4 g (22.4 mmol) of carbethoxymethylene-triphenylphosphorane, and the mixture was stirred at room temperature for 3 hours. The THF was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 4.3 g (9.9 mmol) of cornpound 1-1222.
F F
CI NHNH, IP C1 NHN-_ CF3 O
S>- CO1C2H5 CO,C2HS
F O
--- Cl ~ ~ N \CF3 -~-- CO,C?HS
Production Example 19 (Production of Compound 1-476) To a mixed solution of 5.3 g (53.5 mmol) of sodium acetate and about 100 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1, 1 -dibromo-3,3,3-trifluoroacetone, and the reaction was allowed to proceed at 70 C for 20 minutes. Then, the reaction mixture was cooled to room temperature, to which a solution of 5.8 g (21.5 mmol) of 2-fluoro-4-chloro-5-isopropoxyphenylhydrazine dissolved in about 20 ml of diethyl ether was added, and the reaction mixture was stirred at room tempera-ture for I hour. The ether layer was separated, washed once with 10 ml of saturated sodium chloride solution, and dried with magnesium sulfate. The diethyl ether was distilled out, which afforded 6.5 g (20.0 mmol) of 3,3,3-trifluoro-2-oxo-propanal l-(4-chloro-2-fl uoro-5 -is opropoxyphenylhydrazone) .
1H-NMR (250 MHz, CDC13, TMS S(ppm)) 1.39 (6H, d, J = 6.0 Hz), 4.38-4.52 (1 H, m), 7.15 (IH, d, J = 10.5 Hz), 7.22 (1 H, d, J = 7.3 Hz), 7.43 (1 H, q, J = 1.7 Hz), 9.18 (1 H, br).
This compound was dissolved in 50 ml of THF. To this solution was added 8.3 g (23.0 mmol) of carbethoxyethylidenetriphenylphosphorane, and the mixture was heated under reflux for 2 hours. The THF was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 3.8 g (10.5 mmol) of 2-[2-fluoro-4-chloro-5-isopropoxyphenyl]-4-methyl-5-trifluoromethyl-pyridazin-3-one (compound 1-476).
F F
Cl O NHNH, ~ CI o NHN=\
, CF3 O O O
---= CI 0 N \ CF3 N
O
Production Example 20 (Production of Compound 1-642) To a mixed aqueous solution of 5.3 g (53.5 mmol) of sodium acetate and about 100 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1,1-dibromo-3,3,3-trifluoroacetone, and the reaction was allowed to proceed at 70 C for 20 minutes.
WO 97/07104 PCT/dP96/02311 Then, the reaction mixture was cooled to room temperature. Separately, 5.8 g (21.5 mmol) of crude ethyl 2-chloro-4-fluoro-5-hydrazinobenzoate hydrochloride was dissolved in 30 ml of water, to which 100 mI of diethyl ether was added, and while cooling, the mixture was neutralized by the addition of saturated sodium hydrogen-carbonate solution, followed by washing with saturated sodium chloride solution, which afforded a solution of ethyl 2-chloro-4-fluoro-5-hydrazinobenzoate in diethyl ether. This solution was added to the above reaction mixture, followed by vigorous stirring at room temperature for 2 hours. The ether layer was separated, washed once with 10 ml of saturated sodium chloride solution, and dried with magnesium sulfate. The diethyl ether was distilled out. The residue was dissolved in 50 ml of THF, to which 8.3 g (23.0 mmol) of carbethoxyethylidenetriphenylphosphorane was added, and the mixture was heated under reflux for 2 hours. The THF was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 3.8 g (10.0 mmol) of compound 1-642.
F F
CI NHNHi = HCI = Cl NHN-- - )-- CF3 CO,CGHS CO2)C,)H5 0 ----~ Cl ~ ~ CF3 - N
Reference Example 2 This is a production example for ethyl 2-chloro-4-fluoro-5-hydrazinoberizoate hydrochloride used in Production Example 20.
First, 50 g (0.29 mol) of 2-chloro-4-fluorobenzoic acid was dissolved in 150 ml of hydrochloric acid at room temperature, to which a mixed acid of 28 ml (0.31 mol) of fuming nitric acid and 56 ml of concentrated sulfuric acid was added dropwise at 35 to 45 C. Then, the solution was stirred at 40 C for 1 hour and poured into 250 ml of ice-water. The precipitated crystals were collected by filtration and recrystallized from a mixed solution of hexane and ethyl acetate, which afforded 55 g (0.25 mol) of 2-chloro-4-fluoro-5-nitrobenzoic acid. Then, 55 g (0.25 mol) of 2-chloro-4-fluoro-5-nitrobenzoic acid was dissolved in 50 ml of ethyl acetate, to which 33 g (0.28 mol) of thionyl chloride was added, and the mixture was heated under reflux for 3 hours and then allowed to stand for cooling to room temperature. Then, 20 ml of ethanol and 30 g of triethylamine were added under ice cooling, and the mixture was stirred at room temperature for 2 hours. The solvent was distilled out, and the residue was purified by silica gel chromatography, which afforded 57 g (0.23 mol) of ethyl 2-chloro-4-fluoro-5-nitrobenzoate.
F F
Cl C] NO, CO.)H CO-)H
F
CI 0 NO, Then, 60 g of iron powder and 500 ml of 10% acetic acid wvere mixed, and the mixture was heated to 40 C. Separately, 50 g (0.20 mol) of ethyl 2-chloro-4-fluoro-5-nitrobenzoate was dissolved in a mixed solution of 20 ml of acetic acid and 20 ml of ethyl acetate, and added dropwise to the above iron powder-acetic acid mixed solution.
Then, the reaction mixture was stirred at 50 C for 1 hour and filtered through CeliteT"''.
The filtrate was extracted with 100 ml of ethyl acetate. The ethyl acetate layer was washed with aqueous sodium bicarbonate solution and saturated sodium chloride solution, and dried with magnesium sulfate. The solvent was distilled out, and the residue was purified by silica gel chromatography, which afforded to 40 g(0.18 mol) of ethyl 5-amino-2-chloro-4-fluorobenzoate.
Then, 19 g (87.4 mmol) of ethyl 5-amino-2-chloro-4-fluorobenzoate was dissolved in 120 ml of hydrochloric acid, followed by cooling to 0 C, to which a solution of 6.3 g (91.7 mmol) of sodium nitrite dissolved in 10 ml of water was added dropwise at 10 C or lower. The mixture was stirred at 0 C for 30 minutes and then cooled to -30 C, into which a solution of 58 g (0.31 mol) of anhydrous tin (II) chloride dissolved in 40 ml of hydrochloric acid was poured, followed by further stirring at 0 C
for 3 hours.
The precipitated crystals were collected by filtration and then dried, which afforded 13.6 g (50.7 mmol) of crude ethyl 2-chloro-4-fluoro-5-hydrazinobenzoate hydrochloride.
Production Exam,.ple 21 (Production of Compound 1-1789) First, 5.0 g (15.5 mmol) of compound 1-391 was dissolved in about 50 ml of DMF, to which 2.8 g (20.2 mmol) of potassium carbonate was added at room temperature and then 1.5 g (17.1 mmol) of 3-bromo-2-methyl-l-propene was added, and the mixture was stirred at room temperature for 30 minutes, followed by the addition of 100 n-d of water. The precipitated crystals were collected by filtration, washed with hexane, and recrystallized from isopropanol, which afforded 4.4 g (13.2 mmol) of compound 1-1789.
CI ~N~ ~ ~ CF3 aw- CI ON~CF3 - HO O~ ~/
~-~CH3 Production Exam lp e 22 (Production of Compound 4-451) First, 4.0 g (12.0 mmol) of compound 1-1789 was dissolved in 20 ml of N,N-dimethylaniline, and the solution was heated at 180 C for 3 hours. After cooling to room temperature, 100 ml of ethyl acetate was added, and the mixture was washed with 1 N aqueous hydrochloric acid and saturated sodium chloride solution, and dried with =
magnesium sulfate. The solvent was distilled out, and the precipitated crystals were recrystallized from isopropanol, which afforded 3.4 g (10.2 mmol) of 2-[4-chloro-6-fluo ro-3-hydroxy-2 -(2-methyl-2-p ropenyl)]-4-me thyl-5-trifluo romethylpyridazin-3 -one, m.p. 133.2 C.
The product was dissolved in 30 ml of xylene, to which a catalytic amount of p-toluenesulfonic acid was added, and the mixture was heated under reflux for 1 hour.
After cooling to room temperature, 100 ml of ethyl acetate was added, and the mixture was washed with aqueous sodiuln bicarbonate solution and sodium chloride solution, and dried with magnesium sulfate. The solvent was distilled out, and the residue was purified by silica gel column chromatography, which afforded 3.0 g(9.0 mmol) of compound 4-45 1.
Cl ~~ N CF3 r Cl ~~ N ~ CF3 - - -O- ~i HO
~(\CH3 CH3 IN Cl ~ ~ N \ CF3 N
O
Production Example 23 (Production of Compound 1-483) First, 5.0 g (15.5 mmol) of compound 1-391 was dissolved in about 20 ml of DMF, to which 2.4 g (17.1 mmol) of potassium carbonate was added at room temperature. The solution was heated to about 40'C, to which 1.7 g (17.1 mmol) of 2,3-dichloropropene was added, and after 1 hour, the mixture was allowed to stand for cooling and poured into ice-water. The precipitated crystals were collected by filtration, washed with hexane, and recrystallized from isopropanol, which afforded 5.2 g (13.1 mmol) of compound 1-483.
O\ CH; F O CH3 C1 CF3 -~' CI ON ~\CF3 N-l N
HO Q /~
~'(\Cl Production Exam in e 24 (Production of Compound 3-139) First, 3.0 g (7.6 mmol) of compound 1-436 was dissolved in 10 ml of N,N-dimethylaniline, and the solution was heated under reflux for 3 hours. After cooling to room temperature, 50 ml of ethyl acetate was added, and the mixture was washed with I N aqueous hydrochloric acid and saturated sodium chloride solution, and dried with magnesium sulfate. The solvent was distilled out, and the precipitated crystals were recrystallized from isopropanol, which afforded 2.2 g (5.6 mmol) of 2-[4-chloro-6-fluoro-3-hydroxy-2-(2-chloro-2-propenyl)] -4-methyl-5-trifl uoromethylpyridazin-3-one.
IH-NMR (300 MHz, CDC13, TMS S(ppm)) 2.41 (3H, q, J= 1.9 Hz), 3.56 (1 H, d, J = 16.3 Hz), 3.72 (1 H, d, J = 16.3 Hz), 4.91 (1 H, q, J= 1.4 Hz), 5.12 (1 H, d, J = 1.5 Hz), 5.72 (1 H, s), 7.25 (1 H, d, J= 8.7 Hz), 8.00 (IH, s) The product was dissolved in 10 ml of trifluoromethanesulfonic acid cooled by ice, and the solution was stirred under ice cooling. After 30 minutes, the solution was poured into ice-water, and the precipitated crystals were collected by filtration and subjected to silica gel column chromatography, which afforded 1.9 g (5.4 mmol) of compound 3-139.
CI ON CF3 CI ~~ N CF3 N
O /~ HO
~C1 CI
--- CI ~ ~ CF3 -O /
Production Example 25 (Production of Compound 1-1744) This example followed the procedures of Production Example 20, except that 6.1 g (21.5 mmol) of ethyl 2,4-dichloro-5-hydrazinobenzoate hydrochloride was used in place of ethyl 2-chloro-4-fluoro-5-hydrazinobenzoate hydrochloride, which afforded 4.8 g (12.2 mmol) of compound 1-1744.
wo 97/07104 PCT/JP96/02311 Cl Cl 0 CH3 CI J~ NHNH, = HCl CI N ~ CF~
_ N _.
CO,Et CO,Et The ethyl 2,4-dichloro-5-hydrazinobenzoate hydrochloride used above was produced from 2,4-dichlorobenzoic acid by the same process as shown in Reference Example 2.
Production Example 26 (Production of Compound 1-1279) To a mixed aqueous solution of 5.3 g (53.5 mmol) of sodium acetate and about 100 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1,1-dibromo-3,3,3-trifluoroacetone, and the reaction was allowed to proceed at 70 C for 20 niinutes.
Then, the reaction mixture was cooled to room temperature. Separately, 5.8 g (21.5 mmol) of ethyl 2-chloro-4-fluoro-5-hydrazinobenzoate hydrochloride was dissolved in 30 ml of water, to which 100 ml of diethyl ether was added, and while cooling, the mixture was neutralized by the addition of saturated sodium hydrogen-carbonate solution, followed by washing with saturated sodium chloride solution, which afforded a solution of ethyl 2-chloro-4-fluoro-5-hydrazinobenzoate in diethyl ether. This solution was added to the above reaction mixture, followed by vigorous stirring at room temperature for 2 hours. The ether layer was separated, washed once with 10 ml of saturated sodium chloride solution, and dried with magnesium sulfate. The diethyl ether was distilled out, and a small amount of hexane was added to give 4.3 g (12.6 mmol) of ethyl 2-chloro-4-fluoro-5-(2-oxo-3,3,3-trifluoropentylidenehydrazino)benzoate.
This product was dissolved in 50 ml of THF, to which 5.0 g (14.4 mmol) of carbethoxy-methylenetriphenylphosphorane was added, and the mixture was heated under reflux for 2 hours. The THF was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 3.6 g (9.7 mmol) of compound 1-1279.
F F
CI ~~ NHNH, HCI --- CI J::~ NHN-'"- - ~CF~
CO,C,Hs CO,C~HS O
F O
--~-- CI N ~}- CF;
N-/
CO,C,H5 Production Exa=le 27 (Production of Compound 1-1780) First, 50 g (0.61 mol) of sodium acetate and 41 g(0.14 mol) of 1,1-dibromo-3,3,3-trifluoroacetone were mixed with 500 ml of water, and the mixture was stirred at 80 C for 30 minutes and then cooled to 0 C. Then, 45 g (0.14 mol) of 4-bromo-2-fluoro-5-isopropoxyphenylhydrazine hydrochloride was added at 10 C or lower, and the mixture was stirred at 10 C or lower for 3 hours. The precipitated crystals were collected by filtration and dried, which afforded 35 g (94.3 mmol) of 3,3,3-trifluoro-2-oxopro-panal 1-(4-bromo-2-fluoro-5-isopropoxyphenylhydrazone).
Then, 16 g (46.0 mmol) of carbethoxymethylenetriphenylphosphorane and 16 g (43.1 mmol) of 3,3,3-trifluoro-2-oxopropanal 1-(4-bromo-2-fluoro-5-isopropyloxy-phenylhydrazone) were stirred in 100 ml of THF at room temperature for 4 hours. After completion of the reaction, the reaction mixture was concentrated, and the residue was subjected to silica gel chromatography, which afforded 9.4 g (23.8 mmol) of compound 1-1780.
F F
Br NHNH, = HCl -- Br NHN
= CF3 T O -7"' O O
F O
--r Br N CF3 - N-Reference Example 3 ~ This is a production example for 4-bromo-2-fluoro-5-isopropoxyphenylhydra-zine hydrochloride used in Production Example 27.
First, 93 g (0.49 mol) of 2-bromo-4-fluorophenol was suspended in 200 ml of water, into which 55 g (0.59 mol) of methyl chloroformate and a solution of 21.5 g (0.51 mol) of sodium hydroxide in 60 ml of water were poured together at 10 C
or lower, and the mixture was stirred at the same temperature for 2 hours. The precipitated crystals were collected by filtration, washed with water, and dried in a vacuum oven, which afforded 111.6 g (0.45 mol) of methyl 2-bromo-4-fluorophenoxyformate.
Then, 1 10 g (0.44 mol) of methyl 2-bromo-4-fluorophenoxyformate was dissolved in 250 ml of sulfuric acid, to which a mixed acid of 30 g of fuming nitric acid and 30 ml of sulfuric acid was added dropwise at 5 C or lower, and the mixture was stirred for 2 hours. The reaction mixture was poured onto ice, and the precipitated crystals were collected by filtration, washed with water, and dried, which afforded 126 g (0.43 mol) of inethyl2-bromo-4-fluoro-5-nitrophenoxyformate.
Then, 125 g (0.43 mol) of methyl 2-bromo-4-fluoro-5-nitrophenoxyformate was suspended in 200 ml of water, to which 19 g (0.47 mol) of sodium hydroxide was added, and the mixture was stirred at 50 to 60 C for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and washed with chloro-form. The aqueous layer was acidified with aqueous hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was dried and concentrated, which afforded 104 g (0.43 mol) of 2-bromo-4-fluoro-5-nitrophenol.
F F
Br ~ ~ -----~ Br O ---~
= HO O
F F
Br o NO2 -- Br o NO2 O HO
/~-- OCH;
Then, 100 g (0.42 mol) of 2-bromo-4-fluoro-5-nitrophenol was dissolved in 400 ml of dimethylformamide, to which 70 g (0.50 mol) of potassium carbonate was added and after warming to 50 C, 94 g (0.55 mol) of isopropyl iodide was added dropwise, and the mixture was stirred at 45 to 50 C for 1 hour. After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. The ethyl acetate layer was washed with water and then with diluted hydrochloric acid, dried, and concentrated. The residue was subjected to column chromatography, which afforded 99.8 g (0.36 mol) of 2-bromo-4-fluoro-5-nitrophenyl isopropyl ether.
Then, 60 g (0.22 mol) of 2-bromo-4-fluoro-5-nitrophenyl isopropyl ether was dissolved in 300 ml of ethyl acetate, to which 1.0 g of 10% palladium-carbon was added, and the hydrogenation was effected under an atmosphere of hydrogen.
After completion of the reaction, the palladium-carbon was removed by filtration, and the filtrate was concentrated, which afforded 52 g (0.21 mol) of 4-bromo-2-fluoro-5-iso-propoxyaniline.
. Then, 108 g (0.57 mol) of tin (II) chloride was dissolved in 100 ml of concentrated hydrochloric acid, followed by cooling to -30'C, to which a diazonium solution prepared from 47 g(0.19 mol) of 4-bromo-2-fluoro-5-isopropoxyaniline, 13.5 g (0.20 mol) of sodium nitrite, and 120 ml of hydrochloric acid was added dropwise at 0 C
or lower, and the mixture was stirred at room temperature for 2 hours. The precipitated crystals were collected by filtration and dried in a vacuum oven to give 45 g(0.14 mol) of the crude product, 4-bromo-2-fluoro-5-isopropoxyphenylhydrazine hydrochloride.
F F
Br NO2 ) -- Br o NH, 77-- O '7-- O
F
Y -~- Br O NHNH,' HCl '7- O
Production Example 28 (Production of Compound 1-1783) First, 19 g (52.4 mmol) of carbethoxyethylidenetriphenylphosphorane and 19 g (63.2 mmol) of 3,3,3-trifluoro-2-oxopropanal 1-(4-bromo-2-fluoro-5-isopropyloxy-phenylhydrazone) were heated under reflux in 100 ml of THF for 5 hours. After completion of the reaction, the reaction mixture was concentrated, and the residue was subjected to silica gel chromatography, which afforded 9.1 g (22.2 n~unol) of compound 1-1783.
O
Br ~~ NH CF3 --~ Br ~~ N ~ CF3 N--7 O '7- O
Producti n Example 29 (Production of Compound 1-1748) This example followed the procedures of Production Example 27, except that 41 g (0.41 mol) of 2,4-dichloro-5-isopropoxyphenylhydrazine hydrochloride was used in place of 4-bromo-2-fluoro-5-isopropoxyphenylhydrazine hydrochloride, which afforded 31.3 g (91.3 mmol) of 3,3,3-trifluoro-2-oxopropanal 1-(2,4-dichloro-5-isopro-poxyphenylhydrazone). Then, this compound and 40 g (0.11 mol) of carbethoxy-ethylidenetriphenylphosphorane were heated under reflux in 100 ml of THF for 5 hours.
After completion of the reaction, the reaction mixture was concentrated, and the residue was subjected to silica gel column chromatography, which afforded 21 g (54.8 mmol) of compound 1-1748.
ci ci Cl NHNH, = HCl CI NHN-: - ~- CF3 /'--O -7--0 0 cl 0 cH;
-- Cl ~ ~ N \ CF.~ "
"_" -?-O
J
The 2,4-dichloro-5-isopropoxyphenylhydrazine hydrochloride used above was produced from 2,4-dichlorophenol by the same process as shown in Reference Example 3.
Production Example 30 (Production of Compound 1-1029) First, 9 g (22.8 mmol) of 2-(4-bromo-2-fluoro-5-isopropyloxyphenyl)-5-trifluoromethylpyridazin-3-one was added to 50 ml of sulfuric acid, and the mixture was stirred for 1 hour. After completion of the reaction, the reaction mixture was poured onto ice and extracted with ethyl acetate. The ethyl acetate layer was dried and concentrated, and the residue was subjected to column chromatography (eluent, hexane : ethyl acetate =
5: 1), which afforded 5.9 g (16.7 mmol) of compound 1-1029.
F O F O
\ CF3 ~ Br ~~ N CF3 Br O N N - N~~~-JJJ
-?,- O HO
Production Exam lp e 31 (Production of Compound 1-392) First, 9 g (22.0 mmol) of 2-(4-bromo-2-fluoro-5-isopropyloxyphenyl)-4-methyl-5-trifluoromethylpyridazin-3-one was added to 50 ml of sulfuric acid, and the mixture was stirred for 1 hour. After completion of the reaction, the reaction mixture was poured onto ice and extracted with ethyl acetate. The ethyl acetate layer was dried and concentrated, and the residue was subjected to column chromatography (eluent, hexane :
ethyl acetate = 5: 1), which afforded 4.2 g (11.5 mmol) of compound 1-392.
\CF3 Br O NN \CF3 ---~ Br O N, HO
'WO 97/07104 PCT/JP96/02311 Production Example 32 (Production of Compound 1-1274) First, 7.4 g (90.2 mmol) of sodium acetate and 8.0 g (28.2 mmol) of 1,1-di-bromo-3,3,3-trifluoroacetone were mixed with 70 ml of water, and the mixture was .
stirred at 80 C for 30 minutes and then cooled, to which 7.0 g of ethyl 2-chloro-5-hydrazinocinnamate was added at 10 C or lower, and the mixture was stirred for 3 hours.
The precipitated crystals were collected by filtration and dried, which afforded 9.6 g (27.5 mmol) of ethyl 2-chloro-5-(3,3,3-trifluoro-2-oxopropylidenehydrazino)cinnamate.
1H-NMR (250 MHz, CDC13, TMS S(ppm)) 1.36 (3H, t, J = 6.9 Hz), 4.30 (2H, q, J = 6.9 Hz), 6.4-6.6 (1 H, m), 7.2-7.5 (3H, m), 7.65 (1 H, d, J = 2.5 Hz), 8.0-8.1 (1H, m) Then, 1.0 g (2.9 mmol) of carbethoxymethylenetriphenylphosphorane and 1.0 g (2.9 mmol) of ethyl 2-chloro-5-(3,3,3-trifluoro-2-oxopropylidenehydrazino)-cinnamate were stirred in 10 ml of THF at room temperature for 1 hour. After comple-tion of the reaction, the reaction mixture was concentrated, and the residue was subjected to column chromatography (eluent, hexane : ethyl acetate = 5: 1), which afforded 0.43 g (11.5 mmol) of compound 1-1274.
Cl ~ ~ NHNH2 Cl NHN-- ~- CF3 O
CO,Et CO,Et O
-- Cl CF3 N-CO,Et Reference Example 4 The ethyl 2-chloro-5-hydrazinocinnamate used in Production Example 32 was produced by the following process.
First, 60 g of tin (II) chloride was dissolved in 60 ml of concentrated hydro-chloric acid, and the mixture was cooled to -30 C, to which a diazonium solution prepared from 19 g of ethyl 5-amino-2-chlorocinnamate and 6.3 g of sodium nitrite was added dropwise at 0 C or lower. The reaction mixture was stirred at room temperature for I hour, and the precipitated crystals were collected by filtration. These crystals were -added to ice-water, neutralized with 2N aqueous sodium hydroxide, and extracted with chloroform. The chloroform layer was dried and concentrated, which afforded 7.0 g of ethyl 2-chloro-5-hydrazinocinnamate.
Cl ~ NH, - Cl NHNH, CO,Et CO,Et Production Example 33 (Production of Compound 1-637) First, 1.1 g (2.9 mmol) of carbethoxyethylidenetriphenylphosphorane and 1.0 g (2.9 mmol) of ethyl 2-chloro-5-(3,3,3-trifluoro-2-oxopropylidenehydrazino)-cinnamate were heated under reflux in 10 ml of THF for 3 hours. After completion of the reaction, the reaction mixture was concentrated, and the residue was subjected to column chromatography (eluent, hexane : ethyl acetate = 5: 1), which afforded 0.66 g (1.7 mmol) of compound 1-637.
Cl NHN=~ CF3 C1 N CF3 N-JJJ
CO,Et CO.)Et Production Exam 1~ e 34 (Production of Compound 1-367) First, 0.5 g (1.6 mmol) of compound 1-353 was dissolved in 1.5 ml of pyridine, to which 0.2 g (1.7 mmol) of methanesulfonyl chloride was added dropwise, followed by stirring for 2 hours. The reaction mixture was poured into ice-water and extracted with ethyl acetate. The ethyl acetate layer was washed with diluted hydrochloric acid, dried, and concentrated. The residue was subjected to column chromatography (eluent, hexane : ethyl acetate = 3: 1), which afforded 0.42 g(1.1 mmol) of compound 1-367.
F O CH , F 0 CH3 CI CF, ~~ N ~ CF3 N- - N'-H, N HN,, SO,CH 3 Production ExampI e 35 (Production of Compound 1-369) This example followed the procedures of F'roduction Example 34, except that 0.23 g(1.6 mmol) of chloromethylsialfonyl chloride was used in place of methane-sulfonyl chloride, which afforded 0.38 g (091 mmol) of cornpound 1-369.
F 0 C'H F 0 C113 , CI CF3 C! N% CF4 N- N-H1N HN\
SO,CHzCI
Production Examnle 36 (Production of Compound 1-391) First, 32.3 g of 5-aminCy-2-chloro-4-fluoropherrolwas tnixed with 150 ml of concentrated hydrochloric acid, and the mixture was stirred at 50 C for 30 minutes, to which a solution of 15 g of sodiurn nitrite dissolved in 40 rnl of water was added drop-wise at 0 C over 10 minutes. After stirring at 0 C for 1 hour, the mixture was cooled to -50 C. Then, a solution of 132 g of tiri (11) chloride dissolveci in 132 g oi'concentrated sulfuric acid was rapidly added dropwise at --50 C., and the mixture was gradually warmed to room ternperature and stirred for 1 hour. The solids formed were collected by filtration and dried at 80 C under reduced pressure to give 75 g of the crude 2-fluoro-4-chloro-5-hydroxyphenylhydrazine hydrochloride crystals.
I H-NMR (DMS(3-d(,, TMS Fi (ppm)) 3-5 (2H, br), 6.73 (1 H, d), 7.22 (1 H, d), 8.20 (1 H, s), 9-11 (2H, br) Then, 49.2 g of sodium acetate and 40.5 g of 1,1-dibromo-3,3,3-trifluoro-acetone were dissolved in 400 ml of water, and the solution was heated at 80 to 90 C for 40 minutes. The solution was cooled to O C, to which 75 g of the crude 2-fluoro-4-chloro-5-hydroxyphenylhydrazine hydrochloride crystals obtained above was added, and the mixture was stirred at room temperature for 70 minutes. The precipitated crystals were collected by filtration and dried under reduced pressure, which afforded 35.4 g of 3,3,3-trifluoro-2-oxopropanal 1-(4-chloro-2-fluoro-5-hydroxyphenylhydrazone).
1H-NMR (300 MHz, CDC13, TMS S(ppm)) 5.49 (1H, s), 7.15 (1H, d, J
10.5Hz),7.25(1H,d,J=7.4Hz),7.38(1H,q,J=1.8Hz),8.75(1H,s) Then, 12.9 g of 3,3,3-trifluoro-2-oxopropanal 1-(4-chloro-2-fluoro-5-hydroxyphenylhydrazone) and 22.3 g of carbethoxyethylidenetriphenylphosphorane were dissolved in 110 ml of tetrahydrofuran, and the solution was heated under reflux for 3 hours. The solvent was distilled out under reduced pressure, and the residue was subjected to silica gel chromatography, which afforded 8.8 g of 2-(2-fluoro-4-chloro-5-hydroxyphenyl) -4-methyl-5-tri fluoromethylpyridazin-3-One (compound 1-391).
F F
Cl O NH, ci 0 NHNH, = HCI
HO HO
F O
~ CF3 ~ CF3 Cl NHN- - N-HO
HO
The 5-amino-2-chloro-4-fluorophenol used above can be produced by the method described in the publication of European Patent Application, EP-61741-A.
Production Example 37 (Production of Compound 1-332) First, 2 g of 3,3,3-trifluoro-2-oxo-l-propanal 1-(4-chlorophenylhydrazone) and 2 g of ethyl diethylphosphonoacetate were mixed with 20 ml of triethylamine, and the reaction was allowed to proceed at 50 C for 24 hours. The solvent was distilled out under reduced pressure, and the residue was subjected to column chromatography, which afforded 1.16 g of 2-(4-chlorophenyl)-5-tri fluoromethylpyridazin-3-one (compound 1-332).
Reference Example 5 _ The 3,3,3-trifluoro-2-oxopropanal 1-(4-chloro-2-fluoro-5-isopropoxyphenyl-hydrazone) produced in Production Example 19 can also be produced by the following process.
F F
ci NN=~ O CF3 CI 0 NH O CF3 ~ O C02Et O N~
~ C02H
5 First, 20.1 g of ethyl 4,4,4-trifluoroacetoacetate and 25 g of sodium acetate were dissolved in 150 ml of water, to which a diazonium solution in hydrochloric acid prepared from 20.3 g of 4-chloro-2-fluoro-5-isopropoxyaniline, 20 ml of concentrated hydrochloric acid, 20 ml of water, and 7.35 g of sodium nitrate was added dropwise at 10 C or lower. After stirring at room temperature for 1 hour, the precipitated crystals 10 were collected by filtration, washed with water, and dried, which afforded 34 g of the desired product as orange crystals (yield, 85%).
F F
ci ~ ~ NH2 N F;
N~/
7O -7-O CO2Et Then, 15.9 g of the ester obtained above and 1.7 g of lithium hydroxide monohydrate were added to 30 ml of 1,4-dioxane and 3 ml of water, and the mixture was heated.under reflux for 6 hours. The reaction mixture was poured into ice-water, 15 neutralized with diluted hydrochloric acid, and extracted witli ethyl acetate. The ethyl acetate layer was dried and concentrated, and the precipated crystals were washed with hexane, which afforded 11.3 g of the desired product as yellow crystals (yield, 76.3%).
F F
Cl NH O CF3 - ci ~~ NH j O N~ O ~
CO2H ~
Then, 7.4 g of the carboxylic acid obtained above was dissolved in 42 n-d of N,N-dimethylformamide, and the reaction solution was heated to 100 C and kept at the same temperature for 30 minutes. Thereafter, the reaction solution was cooled to room temperature, poured into water, and extracted with ethyl acetate. The ethyl acetate layer was washed with diluted hydrochloric acid, dried with magnesium sulfate, and concen-trated, which afforded 5.9 g of the desired product as orange crystals (yield, 90%).
iH-NMR (250 MHz, CDC13, TMS S(ppm)) 1.39 (6H, d, J = 6.0 Hz), 4.38-4.52 (1 H, m), 7.15 (1 H, d, J = 10.5 Hz), 7.22 (1 H, d, J = 7.3 Hz), 7.43 (1 H, q, J= 1.7 Hz), 9.18 (1 H, br) Reference Example 6 In the same manner as described in Reference Example 2, 3,3,3-trifluoro-2-oxopropanal 4-chlorophenylhydrazone was produced.
Cl NH CF3 Cl ~~ H
N=~ N~
CO2Et CO2H
First, 5.0 g of the ester as the starting material and 0.67 g of lithium hydroxide monohydrate were added to a mixed solution of 30 ml of 1,4-dioxane and 2 ml of water, and the mixture was heated under reflux for 1.5 hours. The reaction mixture was poured into ice-water, neutralized with diluted hydrochloric acid, and extracted with ethyl acetate. The ethyl acetate layer was dried with magnesium sulfate and concentrated, and the precipitated crystals were washed with a mixed solvent of hexane and diethyl ether (hexane : diethyl ether = 2 1), which afforded 3.3 g of the desired compound as yellow crystals (yield, 73%).
~ ~ Cl NN~CF3 Cl ~~ NH O 3 ~ CF3 N
Process 1) A solution prepared by dissolving 3.3 g of the carboxylic acid obtained by the above reaction in 10 ml of dimethylsulfoxide was heated to 100 C and kept at the same temperature for 10 minutes, followed by cooling to room temperature.
Thereafter, the reaction mixture was subjected to silica gel chromatography (eluent, hexane : ethyl acetate = 7: 1), which afforded 2.55 g of the desired product (yield, 91%).
Process 2) A reaction mixture prepared by adding 5.0 g of the carboxylic acid obtained by the above reaction, 0.5 ml of quinoline, and 0.1 g of copper powder to 40 ml of toluene was heated to 100 C and kept at the same temperature for 20 minutes.
After completion of the reaction, the reaction mixture was cooled to room temperature and subjected to silica gel chromatography (eluent, hexane : ethyl acetate = 8 :
1), which afforded 3.6 g of the desired product (yield, 86%).
Some of the present compounds are shown with their compound numbers in Tables 1 to 5, where the symbol "n" refers to normal-; "i", iso-; "s", secondary-; and "C", cyclo-.
Compounds of the formula:
X O R'-Y ~ ~ N Rt - N-Compound X Y R 3 R' R Z B
No.
1- 2 H C1 H CFZ Cl H H
1- 3 H Br H CF2 Cl H H
1- 5 H C1 H CFz C1 CH3 H
1- 6 H Br H CFa C1 CH3 H
1- 7 F F H CFZ Cl H H
1- 9 F Br H CF2 C1 H H
1 -10 F F H CF2 Cl CH3 H
1 -11 F C1 H CF2 Cl CH3 H
1 -12 F Br H CF2 Cl CH3 H
1- 13 H F H CF2 Cl CH3 NOz TABLE 1 (contn'd) Compound x y R 3 R' R 2 B
No.
1 -14 H C1 H CF2 Cl CH3 N01 1 -15 H Br H CF2 Cl CH3 N02 1 -16 F F H CF2 Cl CHa NOz 1 -18 F Br H CF2 Cl CH3 NO2 1- 19 H F H CF2 Cl CH3 NH2 1 -20 H C1 H CF2 Cl CH3 NH2 1 -21 H Br H CF2 Cl CH3 NH2 1 -22 F F H CF2 Cl CH3 NH2 1 -23 F C1 H CF2 Cl CH3 NH2 1 -24 F Br H CF2 Cl CHa NH2 1 -26 H C1 H CF2 Cl CH3 OH
1 -27 H Br H CF2 Cl CH3 OH
1 -28 F F H CF2 Cl CH3 OH
1 -29 F Cl H CF2 Cl CH3 OH
1 -30 F Br H CF2 Cl CH3 OH
1 -31 H C1 H CF2 Cl CH3 NHCH3 1 -32 H Cl H CF2 Cl CH3 NHC2 H a 1-33 H C1 H CF2 Cl CH3 NHCH2 CH= CH2 1 -34 H C1 H CF2 Cl CH3 NHCH2 C= CH
1 -35 H C1 H CF2 Cl CH3 NHCH(CH 3 )C = CH
1 -36 H C1 H CF2 Cl CH3 NHSO2 CHI
TABLE 1 (contn'd) ~
Compound X Y R3 R' R z B
No.
1- 37 H Cl H CF2 Cl GH3 NHSO2 C z H s 1 -38 H C1 H CF2 Cl CH3 NHSO2 CHZ Cl 1 -39 H C1 H CF2 Cl CH3 NHSOz CF3 1 -40 H C1 H CF2 Cl CHa N(CH3 )S0 2 CH3 1- 41 H C1 H CF2 C1 CH3 N(CH2 C CH)SO 2 CH3 1 -42 H C1 H CF2 Cl CH3 NHCOOCH 3 1 -43 H C1 H CF2 Cl CH3 NHCOOC2 H s 1 -44 H C1 H CF2 Cl CH3 NHCOO " C s H 7 1 -45 H C1 H CF2 Cl CH3 NHCOO ' C, H, 1- 46 H C1 H CF2 Cl CH3 NHCO0 C 4 H 9 1 -47 H C1 H CF2 Cl CH3 NHCOO " C s H
1 -48 H Cl H CF2 Cl CH3 NHCH2 COOCH a 1 -49 H Cl H CF2 Cl CH3 NHCH2 COOC2 H s 1 -50 H Ci H CF2 Cl CH3 NHCH2 COO C, H, 1 - 51 H Cl H CF2 Cl CH3 NHCH2 C00 " C, H g 1 -52 H Cl H CF2 Cl CH3 NHCH2 COO " C s H õ
1 -53 H Cl H CF2 Cl CHs NHCH2 COO ' C 3 H 7 1 -54 H Cl H CF2 Cl CH3 NHCH2 COO ' C s H q 1- 55 H Cl H CF2 Cl CH3 NHCH2 COO ' C 6 H õ
1 -56 H Cl H CF2 Cl CH3 NHCH(CH 3)COOCH 3 =
1 -57 H C1 H CF2 Cl CH3 NHCH(CH3 )COOC 2 H s 1 -58 H C1 H CF2 Cl CHa NHCH(CH3 )COO " C3 H, 1 -59 H C1 H CF2 Cl CH3 NHCH(CH3 )COO C, H9 TABLE 1 (contn'd) Compound X y R3 R' R Z B
No.
1 -60 H Cl H CF2 Cl CH3 NHCH(CH3 )C00 Cs Hõ
1 -61 H C1 h CF2 Cl CH3 NHCH(CH3 )C00 ' C3 H 7 1 -62 H C1 H CF2 Cl CH3 NHCH(CH3 )C00 ' C5 H g 1 -63 H C1 H CF2 Cl CHa NHCH(CH 3 )C00 ' C6 H11 1 -64 F Cl H CF2 Cl CH3 NHCHa 1 -65 F C1 H CF2 Cl CH3 NHC 2 H s 1 -66 F C1 H CF2 Cl CH3 NHCH2 CH=CH2 1 -67 F Cl H CF2 Cl CH3 NHCH2 C CH
1 -68 F Ci H CF2 Cl CH3 NHCH(CH a)C = CH
1- 69 F Cl H CF2 Cl CH3 NHSO2 CH3 1- 70 F C1 H CF2 Cl CH3 NHSOa C 2 H s 1 -71 F Ci H CF2 Cl CH3 NHSOZ CH2 Cl 1 -72 F C1 H CF2 Cl CH3 NHSO2 CF3 1 -73 F Cl H CF2 Cl CH3 N(CH3 )SO 2 CH3.
1 -74 F C1 H CF2 Cl CH3 N(CH2 C= CH)S0 2 CH3 1 -75 F Cl H CF2 Cl CH3 NHCOOCH 3 1 -76 F Cl H CF2 Cl CH3 NHCOOC2 H s 1 -77 F Ci H CF2 Cl CH3 NHCO0 " C, H 7 1 -78 F C1 H CF2 Cl CH3 NHCOO ' C 3 H T
1 -79 F Cl H CF2 Cl CH3 NHCO0 " C 4 H a 1- 80 F Ci H CF2 Cl CH3 NHCOO " C s H,1 1 -81 F C1 H CF2 Cl CH3 NHCH2 COOCH 3 1- 82 F C1 H CF2 C1 CH3 NHCH2 COOCz H s TABLE 1 (contn'd) compound X y R3 R' R 2 B
No.
1 -83 F C1 H CF2 Cl CH3 NHCH2 C00 " C 3 H 7 1- 84 F C1 H CF2 Cl CH3 NHCH2 C00 " C 4 H g 1 -85 F C1 H CF2 Cl CH3 NHCH2 C00 " C 5 H õ
1 -86 F C1 H CF2 Cl CH3 NHCH2 COO ' C 3 H 7 1- 87 F Cl . H CF2 C1 CH3 NHCH2 C00 ' C s H fl 1 -88 F Cl H CF2 Cl CH3 NH2 CH2 COO ' C 6 H õ
1 -89 F C1 H CF2 Cl CH3 NHCH(CH3 )COOCH 3 1 -90 F C1 H CF2 Cl CH3 NHCH(CH3 )COOC 2 H 5 1- 91 F C1 H CF2 Cl CH3 NHCH(CH3 )COO " C3 H 7 1 -92 F C1 H CF2 Cl CH3 NHCH(CH3 )COO " C4 H s 1 -93 F Ci H CF2 Cl CH3 NHCH(CH3 )COO " C; Hõ
1 -94 F C1 H CF2 Cl CH3 NHCH(CH3 )COO ' C3 H 7 1 -95 F C1 H CF2 Cl CH3 NHCH(CH3 )COO c C; H y 1- 96 F C1 H CF2 Cl CH3 NHCH(CH3 )COO C C6 Hõ
1 -97 H Cl H CF2 Cl CH3 OCH3 1 -98 H C1 H CF2 Cl CH3 OC 2 H 6 1 -99 H C1 H CF2 Cl CH3 0' C 3 H 7 1 -100 H Cl H CF2 Cl CH3 0" C 3 H 7 1 -101 H C1 H CF2 Cl CH3 OCH2 CH2 Cl 1 -102 H C1 H CF2 Cl CH3 OCF2 CF2 H
1-103 H C1 H CF2 Cl CH3 0' C 5= H 9 1 -104 H C1 H CF2 C1 CH3 0' C 6 H
TABLE 1 (contn'd) s Compound x Y R 3 R' R Z B
No.
1 -105 H C1 H CF2 Cl CHs OCHz CH=CHz 1- 106 H C1 R CF2 Cl CH3 OCH2 CCI = CH2 1 -107 H C1 H CF2 Cl CH3 OCH2 CCl = CHC1 1 -108 H ci H CF2 Cl CH3 OCH(CH s)CH =CH2 1 -109 H C1 H CF2 Cl CH3 OCH2 C= CH
1 -110 H C1 H CF2 Cl CH3 OCH(CH 3)C = CH
1 -111 H CI H CF2 Cl CH3 OCH2 C CBr 1 -112 H Cl H CF2 Cl CH3 OCH2 C= CC1 1- 113 H C1 H CF2 Cl CH3 OCHz C CCH 2 Cl 1 -114 H ci H CF2 Cl CH3 OCH2 CN
1- 115 H ci H CF2 Cl CH3 OCH2 OCH 3 1- 116 H ci H CF2 CI CH3 OCH2 0C2 H 5 1 -117 H ci H CF2 Cl CH3 OCH2 SCH , 1 -118 H ci H CF2 Cl CH3 OCH2 COOCH 3 1 -119 H ci H CF2 Cl CHa OCH2 COOC2 H s 1 -120 H C1 H CF2 Cl CH3 OCH2 C00 C 3 H7 1- 121 H Cl H CF2 Cl CH3 OCH2 C00 C, H 9 1 -122 H Cl H CF2 Cl CH3 OCH2 C00 " C.5 Hõ
1- 123 H C1 H CF2 Cl CH3 OCH2 COO ' C a H 7 1 -124 H C1 H CF2 Cl CH3 OCH2 COO ' C 5 H 9 1 -125 H C1 H CF2 Cl CH3 OCH2 COO ' C 6 H õ
1 -126 H C1 H CF2 Cl CH3 OCH(CH 3)COOCH 3 1 -127 H Cl H CF2 Cl CH3 OCH(CH 3)COOC 2 H s TABLE 1 (contn'd) Compound X y R 3 R' R 2 B
No.
1 -128 H C1 H CF2 Cl CH3 OCH(CH 3 )C00 " C3 H 7 1- 129 H C1 H CFz Cl CH3 OCH(CH 3 )C00 " C4 H 9 1 -130 H C1 H CF2 Cl CH3 OCH(CH 3)C00 " C5 Hõ
1- 131 H C1 H CF2 Cl CH3 OCH(CH 3 )C00 ' C3 H, 1 -132 H Cl H CF2 C1 CH3 OCH(CH 3)C00 c CS H 9 1- 133 H C1 H CF2 Cl CH3 OCH(CH 3)C00 ' C6 Hõ
1 -134 H C1 H CF2 Cl CH3 OCH2 CON(CH3 ) 2 1 -135 H C1 H CF2 Cl CH3 OCH2 CON(C 2 H s) 2 1 -136 H C1 H CF2 C1 CH3 OCH2 CON(CH3 ) C 2 H s 1 -137 H C1 H CF2 Cl CH3 OCH(CH a)CON(CH 3 2 1 -138 H C1 H CF2 C1 CH3 OCH(CH3 )CON(C 2 H;)2 1 -139 H C1 H CF2 Cl CH3 OCH(CHs )CON(CH 3)Ca H s 1 -140 H C1 H CF2 Cl CH3 OCH 2 COON(CH 3 ) 2 1 -141 H C1 H CF2 Cl CH3 OCH 2 COON(C 2 H 5- )Z
1 -142 H C1 H CF2 Cl CH3 OCH(CH3 )COON(CH3 ) 2 1 -143 H C1 H CF2 C1 CH3 OCH(CH3 )COON(C 2 H 5) 2 1 -144 F Cl H CF2 Cl CH3 OCH3 1 -145 F C1 H CF2 Cl CH3 OC 2 H 5 1- 146 F C1 H CF2 Cl CH3 0' C 3 H, 1 -147 F C1 H CF2 Cl CH3 0" C 3 H, 1 -148 F C1 H CF2 C1 CH3 OCH2 CH2 Cl 1 -149 F C1 H CF2 Cl CH3 OCF2 CF2 H
1- 150 F C1 H CFz C1 CH3 0' C 6 H 9 WO 97/07104 PCT/.BP96/02311 TABLE 1 (contn'd) Compound X Y R 3 R' R 2 B
No.
1- 151 F C1 H CF2 Cl CHs 0' C 6 H õ
1-152 F Cl H CF2 Cl CH3 OCH2, CHZ =CH2 1 -153 F C1 H CF2 Cl CHa OCHa CC1 =CH2 1 -154 F C1 H CF2 Cl CH3 OCH2 CC1 = CHCI
1 -155 F Ci H CF2 Cl CH3 OCH(CH 3)CH =CH2 1 -156 F Cl H CF2 Cl CH3 0CH2 C= CH
1 -157 F C1 H CF2 Cl CHa OCH(CH 3)C = CH
1 -158 F Cl H CF2 Cl CH3 OCH2 C CBr 1 -159 F Cl H CF2 Cl CH3 OCH2 C CC1 1 -160 F C1 11 CF2 C1 CH3 OCH2 C= CCH 2 Cl 1 -161 F C1 H CF2 Cl CH3 OCH2 CN
1 -162 F C1 H CF2 Cl CH3 OCH2 OCH 3 1 -163 F C1 H CF2 Cl CH3 OCH2 OC2 H s 1 -164 F C1 H CF2 Cl CH3 OCH2 SCH a 1 -165 F C1 H CF2 Cl CH3 OCH2 COOCH 3 1- 166 F C1 H CF2 C1CHa OCH2 COOC2 H s 1 - 168 F Cl H CFz Cl CH3 OCH2 C00 C, H fl 1- 169 F C1 H CF2 Cl CH3 OCH 2 C00 n C s H õ
1- 170 F Cl H CF2 Cl CH3 OCH2 COO ' C, H, 1- 171 F C1 H CF2 Cl CH3 OCH2 C00 ' C 5 H o 1- 172 F C1 H CF2 Cl CH3 OCH2 COO ' C e H õ
1- 173 F C1 H CF2 Cl CH3 OCH(CH 3)COOCH 3 WO 97/07104 PCT/.iP96/02311 TABLE 1 (contn'd) ~
Compound x Y R3 R' R Z B
No.
1 -174 F C1 H CF2 Cl CH3 OCH(CH a)COOC 2 H s 1 -175 F C1 H CF2 C1 CH3 OCH(CH 3 )C00 " C 3 H T
1 -176 F C1 H CF2 C1 CH3 OCH(CH 3 )C00 C, H y 1- 177 F C1 H CF2 Cl CH3 OCH(CH 3)C00 " C; H,1- 178 F C1 H CF2 Cl CH3 OCH(CH 3 )C00 ' C3 H;
1 -179 F C1 H CF2 Cl CH3 OCH(CH a)C00 ' Cs H 9 1- 180 F C1 H CF2 C1 CH3 OCH(CH 3)C00 c C6 Hõ
1 -181 F Cl H CF2 Cl CH3 OCH2 CON(CH3 ) 2 1- 182 F C1 H CF2 Cl CH3 OCH2 CON(C 2 H 5) 2 1 -183 F Cl H CF2 Cl CH3 OCH2 CON(CH3 ) C 2 H s 1 -184 F C1 H CF2 Cl CH3 OCH(CH 3)CON(CH 3) 2 1- 185 F Cl H CF2 Cl CH3 OCH(CH3 )CON(C z. H 5)2 1- 186 F C1 H CF2 Cl CH3 OCH(CH3 )CON(CH 3)C2 H 5 1 -187 F Cl H CF2 Cl CH3 OCH 2 COON(CH 3) 2 1- 188 F CI H CF2 Cl CH3 OCH 2 COON(C 2 H 5)2 1 -189 F Cl H CF2 Cl CH3 OCH(CH3 )COON(CH3 ) 2 1- 190 F C1 H CF2 Cl CH3 OCH(CH3 )COON(C 2 H$) 2 1 -191 H F H CF2 Cl CH3 SH
1 -192 H C1 H CF2 Cl CH3 SH
1 -193 H Br H CF2 Cl CH3 SH
1- 194 F F H CF2 Cl CH3 SH
1 -195 F C1 H CF2 Cl CH3 SH
1 -196 F Br H CF2 Cl CH3 SH
TABLE 1 (contn'd) Compound X y R3 R' R Z B
No.
1 -197 H C1 H CF2 Cl CH3 SCH 3 1 -198 H C1 li CF2 'C1 CHa SCz H s 1 -199 H Cl H CF2 Cl CH3 S' C, H, 1 -200 H Cl H CF2 Cl CH3 SCH2 CHZ Cl 1 - 201 H Ci H CF2 C 1 CH3 S' C; H 9 1 -202 H Cl H CF2 Cl CH3 S.' C 6 H õ
1 -203 H Ci H CF2 Cl CH3 SCH2 CH=CHz 1 -204 H Cl H CF2 Cl CH3 SCH2 CCl = CH2 1 -205 H C1 H CF2 C1 CH3 SCH2 CCl =CHCI
1 -206 H Cl H CF2 C1 CH3 SCH(CH 3)CH =CH2 1 -207 H C1 H CF2 C1 CH3 SCH2 C= CH
1 -208 H Cl H CF2 C1 CH3 SCH(CH a)C = CH
1 -209 H C1 H CF2 C1 CH3 SCHz COOCH a 1 -210 H Cl H CF2 C1 CHs SCH2 COOCZ H s 1 - 211 H C1 H CFZ C1 CH3 SCHZ C00 " C, H, 1 -212 H C1 H CF2 Cl CH3 SCH2 COO " C 4 H a 1 -213 H Cl H CF2 Cl CH3 SCH2 COO " C 3 H õ
1- 214 H Cl H CF2 C1 CHa SCH2 COO ' C a H 7 1- 215 H C1 H CF2 C1 CH3 SCHZ C00 ' C 5 H 9 = 1 -216 H C1 H CF2 C1 CH3 SCH2 COO ' C 6 H õ
1 -217 H Cl H CF2 Cl CH3 SCH(CH 3)COOCH 3 1 -218 H C1 H CF2 Cl CH3 SCH(CH a)COOC 2 H 5 TABLE 1 (contn'd) ~
Compound X y R 3 R' R 2 B
No.
1- 219 H C1 H CF2 Cl CH3 SCH(CH 3 )C00 C3 H, 1 -220 H Ci H CF2 Cl 'CH3 SCH(CH 3 )C00 " C4 H 9 1 -221 H C1 H CF2 Cl CH3 SCH(CH 3 )C00 " Cs Hõ
1 -222 H C1 H CF2 Cl CH3 SCH(CH 3)C00 C3 H, 1 -223 H C1 H CF2 Cl CH3 SCH(CH 3)C00 Cs H s 1 -224 H C1 H CF2 Cl CH3 SCH(CH 3 )C00 ' C6 H
1 -225 H C1 H CF2 Cl CH3 SCH2 CON(CH3 ) 2 1 -226 H C1 H CF2 Cl CH3 SCH2 CON(C 2'H 5) 2 1 -227 H C 1 H CF2 C 1 CH 3 SCH2CON ( tetramethylene ) 1 -228 H C 1 H CF2 C 1 CH3 SCHZCON ( pentamethylene ) 1 -229 H C1 H CF2 Cl CH3 SCH2CON
(ethyleneoxyethylene) 1- 230 H Ci H CF2 Cl CH3 SCH(CH3 )CON(CH 3) 2 1 -231 H Ci H CF2 Cl CH3 SCH(CH3 )CON(C2 H;) 2 1 -232 H C1 H CF2 Cl CHa SCH(CH3)CON
(tetramethylene) 1 -233 H Ci H CF2 Cl CH3 SCH(CH3)CON
(pentamethylene) 1 -234 F C1 H CF2 Cl CH3 SCH 3 1 -235 F C1 H CF2 C1 CH3 SC2 H s 1- 236 F C1 H CF2 Cl CH3 S' C, H
1 -237 F C1 H CF2 Cl CH3 SCH2 CH2 Cl 1- 238 F C1 H CFs CI CH3 S' C s H 9 TABLE 1 (contn'd) Compound X Y R3 R' R Z B
No.
1 -239 F C1 H CF2 CI CH3 S' C 6 H
1 -240 F Cl H CF2 Cl CH3 SCH2 CH-CH2 1 -241 F C1 H CF2 Cl CH3 SCH2 CC1 =CH2 1 -242 F C1 H CFz Cl CH3 SCH2 CCI = CHCI
1 -243 F C1 H CF2 Cl CH3 SCH(CH 3)CH = CHI
1 -245 F C1 H CF2' C1 CH3 SCH(CH )C=CH
1 -247 F Cl H CF2 Cl CH3 SCH2 COOC2 H a 1 - 248 F C1 H CFZ CI CH3 SCHZ C00 " C 3 H, 1 -249 F C1 H CF2 C1 CH3 SCH2 COO " C, H 9 1 -250 F Cl H CF2 C1 CH3 SCH2 COO " C 5 H õ
1 -251 F Cl H CF2 Cl CH3 SCH2 COO ' C a H 7 1 -252 F C1 H CF2 C1 CH3 SCH2 COO ' C 5 H 9 1 -253 F C1 H CF2 Cl CH3 SCH2 COO c C 6 H õ
1 -254 F Ci H CF2 CI CH3 SCH(CH a)COOCH , 1 -255 F C1 H CF2 Cl CH3 SCH(CH ,. )COOC 2 H 5 1 -256 F Cl H CF2 Cl CHa SCH(CH 3)C00 " C3 H 7 1 -257 F Cl H CF2 C1 CH3 SCH(CH 3)C00 " C4 H g 1 -258 F Cl H CF2 C1 CH3 SCH(CH 3)C00 " C5 Hõ
1 -259 F Cl H CF2 Cl CH3 SCH(CH 3)C00 ' C3 H, 1 -260 F C1 H CF2 C1 CH3 SCH(CH 3)C00 ' C5 H fl 1 -261 F Cl H CF2 Cl CH3 SCH(CH 3 )C00 ' C6 Hõ
TABLE I (contn'd) Compound x y R 3 R' R Z B
No.
1 -262 F- Cl H CF2 Cl CH3 SCH2 CON(CH3 ) 2 1 -263 F C1 H CF2 Cl -CH3 SCH2 CON(C 2 H s) 2 1 -264 F C 1 H CF2 C 1 CH3 SCH2CON ( tetramethylene ) 1 -265 F C l H CF2 C l CH a SCH2CON ( pentamethylene ) 1= 266 F C1 H CF2 Cl CH3 SCH2CON
(ethyleneoxyethylene) 1 -267 F C1 H CF2 Cl CHa SCH(CHa )CON(CH a) 2 1 -268 F C1 H CF2 Cl CH3 SCH(CH3 )CON(C2 H 5) 2 1 -269 F Ci H CF2 Cl CH3 SCH(CH3)COrr (tetramethylene) 1 -270 F C1 H CF2 Cl CH3 SCH(CH3)CON
(pentamethylene) 1 -271 H F H CF2 Cl CH3 SO2 Cl 1 -272 H C1 H CF2 Cl CH3 SO2 Cl 1 -273 H Br H CF2 Cl CH3 SOz Cl 1 -274 F F H CF2 Cl CHa SO2 Cl 1 -275 F C1 H CF2 Cl CH3 SOZ Ci 1 -276 F Br H CF2 Cl CH3 SOz Cl 1 -277 H C1 H CF2 Cl CH3 SOz OCH s 1- 278 H C1 H CF2 Cl CH3 SO2 OC2 H s 1 - 279 H C1 H CF2 C1 CH3 S02 0' C a H7 1 -280 H C1 H CF2 Cl CHa SO2 OCH 2 CH = CHz TABLE 1 lcontn'dl Compound X Y R3 R' R z B
No.
1 -282 F C1 H CF2 Cl CH3 SOz 0C2 H s 1- 283 F C1 H CF2 Cl CH3 SO2 0' C 3 H7 1 -284 F C1 H CF2 Cl CH3 S02 OCH 2 CH = CH2 1 -285 H Cl H CF2 Cl CH3 S02 N(CH3 ) 2 1 -286 H C1 H CF2 Cl CH3 SOz N(Ca H 5)2 1 -287 F C1 H CF2 Cl CH3 SO2 N (CH 3) 2 1 -288 F C1 H CF2 Cl CH3 SO2 N(Ca H 5) 2 1 -289 H C1 H CF2 Cl CH3 COOH
1 -290 H Cl H CF2 Cl CH3 COOCH 3 1 -291 H C1 H CF2 Cl CH3 COOC 2 H 5 1 -292 H Cl H CF2 Cl CH3 C00" C a H
1 -293 H C1 H CF2 Cl CH3 C00" C, H v 1 -294 H Cl H CF2 Cl CH3 CO0 C 5 H,, 1- 295 H C1 H CF2 Cl CH3 C00' C 3 H 7 1 -296 H C1 H CF2 Cl CH3 COOCHZ CH2 C1 1 -297 H C1 H CF2 C1 CH3 COOCH2 CH2 Br 1 -298 H C1 H CF2 C1 CH3 CON(CH a) 2 1 -299 H Cl H CF2 C1 CH3 CONHCH a 1- 300 H C1 H CF2 C1 CH3 CON(C2 H s) 2 1 -301 H Cl H CF2 C1 CH3 CONHC2 H 5 1 -302 H C1 H CF2 Cl CH3 COCH s 1 -304 H C1 H CF2 C1 CH3 COCH2 Cl TABLE 1 (contn'd) Compound X Y R 3 R' R 2 B
No.
1 -305 H Cl H CF2 Cl CH3 CHO
1 -306 H C1 H CF2 Cl CH3 CH = CHCOOCH 3 1 -307 H C1 H CF2 Cl CH3 CH = CHCOOCZ H 5 1 -308 H C1 H CF2 Cl CH3 CH2 CH2 COOCH 3 1- 309 H C1 H CF2 Cl CH3 CH2 CH2 COOC2 H s 1 -310 F C1 H CF2 Cl CH3 COOH
1 -311 F Cl H CF2 Cl CH3 COOCH a 1 -312 F C1 H CF2 Cl CH3 COOC 2 H s 1 -313 F C1 H CF2 Cl CH3 C00 C 3 H 7 1- 314 F C1 H CF2 Cl CH3 C00" C 4 H q 1- 315 F C1 H CF2 Cl CH3 CO0 C 5 H õ
1- 316 F C1 H CF2 Cl CH3 COO' C 3 H
1 -317 F Cl H CF2 Cl CH3 COOCH2 CH2 Cl 1 -318 F C1 H CF2 Cl CH3 COOCH2 CHz Br 1 -319 F CI H CF2 Cl CH3 CON(CH a) 2 1 -320 F C1 H CF2 Cl CH3 CONHCH 3 1- 321 F C1 H CF2 Cl CH3 CON(C2 H 5)2 1 -322 F Cl H CF2 Cl CHa CONHC2 H s 1 -323 F C1 H CF2 Cl CH3 COCH 3 1 -324 F Cl. H CF2 Cl CHa COC2 H s 1 -325 F C1 H CF2 Cl CH3 COCH2 Cl 1 -326 F C1 H CF2 Cl CH3 CHO
TABLE 1 (contn'd) ti Compound x y R3 R' R 2 B
No.
1 -327 F C1 H CF2 Cl CH3 CH = CHCOOCH 3 1 -328 F C1 H CF2 Cl CH3 CH = CHCOOC2 H;
1 -329 F G1 H CF2 Cl CH3 CH2 CH2 COOCH 3 1 -330 F C1 H CF2 Cl CH3 CH2 CHz COOC2 H 5 1- 333 H Br H CF3 H H
1 -336 H Br H CF3 CH3 H
1- 339 F Br H CF3 H H
1 -342 F Br H CF3 CH3 H
1 -344 H C1 H CF3 CH3 NOz 1 -345 H Br H CF3 CH3 NO2 : 1 -346 F F H CF3 CH3 NO2 1 -347 F C1 H CF3 CH3 NOz 1 -348 F Br H CF3 CH3 N02 TABLE 1 (contn'd) fi NomPound X Y R 3 R' R 2 B x 1 -351 H Br H CF3 CH3 NH2 1 -353 F Cl H CF3 CH3 NH2 1 -354 H Cl H CF3 CH3 NHCH(CH3 )COOCH 3 1 -355 H C1 H CF3 CH3 NHCH(CH3 )COOC 2 H;
1- 356 H C1 H CF3 CH3 NHCH(CH3 )C00 C3 H 7 1 -357 H C1 H CF3 CH3 NHCH(CH3 )C00 " C4 H 9 1 -358 H C1 H CF3 CH3 NHCH(CH3 )C00 " C5 Hõ
1 -359 H C1 H CF3 CH3 NHCH(CH3 )C00 ' C, H7 1- 360 H C1 H CF3 CH3 NHCH(CH3 )COO ' CS H fl 1 -361 H C1 H CF3 CH3 NHCH(CH3 )COO ' C6 Hõ
1 -363 F C1 H CF3 CH3 NHC 2 H;
1 -364 F CI H CF3 CH3 NHCH2 CH = CHZ
1 -365 F Cl H CF3 CH3 NHCH2 C CH
1 -366 F C1 H CF3 CH3 NHCH(CH 3)C=CH
1 -367 F C1 H CF3 CH3 NHSOz CH3 1- 368 F C1 H CF3 CH3 NHSOa C 2 H e 1 -369 F Cl H CF3 CH3 NHSO2 CH2 Cl 1 -371 F Cl H CF3 CH3 N(CH3 )S0 2 CH3 1 -372 F C1 H CF3 CH3 N(CH2 C= CH)SO 2 TABLE 1 (contn'd) Compound X y R 3 R' R Z B
No.
1 -373 F C1 H CF3 CHa NHCOOCH
1 -374 F C1 H CF3 CH3 NHCOOC2 H s 1 -375 F C1 H CF3 CH3 NHCOO " C 3 H 7 1 -376 F C1 H CF3 CH3 NHCOO ' C 3 H 7 1 -378 F C1 H CF3 CH3 NHCO0 " C 5 H
1 -380 F C1 H CF3 CH3 NHCH2 COOC2 H s 1 -381 F C1 H CF3 CH3 NHCH2 COO " C 3 H 7 1 -382 F CI H CF3 CH3 NHCH2 COO " C, H s 1 -383 F Cl H CF3 CH3 NHCH2 COO C 5 H õ
1 -384 F Cl H CF3 CHa NHCH2 COO ' C a H, 1 -385 F C1 H CF3 CH3 NHCH2 COO ' C 5 H 9 1 -386 F Br H CF3 CH3 NH2 1 -387 H F H CF3 CHa OH
1 -389 H Br H CF3 CH3 OH
1 -392 F Br H CF3 CH3 OH
1-393 H Cl H CF3 CH3 NHCH3 1 -395 H C1 H CF3 CH3 NHCH2 CH = CHz TABLE 1 (contn'd) Compound X Y R 3 R' R 2 B
No.
1 -396 H C1 H CF3 CH3 NHCH2 C= CH
1 -397 H C1 H CF3 CH3 NHCH(CH 3)C CH
1 -399 H Ci H CF3 CH3 NHSO2 C 2 H s 1 -401 H C1 H CF3 CH3 NHSOz CF3 1 -402 H C1 H CF3 CH3 N(CH3 )SO 2 CH3 1 -403 H Ci H CF3 CH3 N(CH2 C=CH)SO 2 CH3 1 -405 H C1 H CFa CH3 NHCOOC2 H s 1 -406 H C1 H CF3 CH3 NHCOO C s H 7 1 -407 H C1 H CF3 CH3 NHCOO C 3 H, 1 -408 H C1 H CF3 CH3 NHCO0 " C 4 H s 1 -409 H C1 H CF3 CH3 NHCOO " C s H
1 -412 H C1 H CF3 CH3 NHCH2 C00 " C, H T
1 -413 H C1 H CF3 CH3 NHCH2 C00 " C 4 H q 1 -414 H C1 H CF3 CH3 NHCH2 C00 " C s H õ
1 -415 H C1 H CF3 CH3 NHCH2 COO ' C 3 H 7 1 -416 H C1 H CF3 CH3 NHCH2 COO ' C s H a 1 -417 H C1 H CF3 CH3 NHCH2 COO ' C H
1 -418 F C1 H CF3 CH3 NH CH2 COO ' C 6 H
WO 97/07104 ]PCT/JP96/02311 TABLE 1 (contn'd) Compound X Y R3 R' R Z B
No.
1 -419 F C1 H CF3 CH3 NHCH(CH 3)COOCH 3 1 -420 F Cl H CF3 -CH3 NHCH(CH3 )COOC 2 H 5 1- 421 F C1 H CF3 CH3 NHCH(CH3 )C00 " C3 H, 1 -422 F C1 H CF3 CH3 NHCH(CH3 )C00 " C, H 9 1 -423 F C1 H CF3 CH3 NHCH(CH3 )COO C; Hõ
1 -424 F C1 H CF3 CHa NHCH(CH3 )C00 C 3 H 7 1 -425 F C1 H CF3 CHs NHCH(CH3 )COO C 5 H 9 1 -426 F Cl H CF3 CH3 NHCH(CH3 ) COO' ' CI Hõ
1 -428 H C1 H CF3 CHa OC 2 H s 1 -429 H Cl H CF3 CH3 0' C a H 7 1 -430 H Cl H CF3 CH3 0" C 3 H 7 1 -431 H Cl H CF3 CH3 OCH2 CH2 C1 1 -432 H Cl H CF3 CHa OCF2 CF2 H
1 -433 H Cl H CF3 CH3 0' C 5 H 9 1 -434 H C1 H CF3 CH3 0' C 6 H õ
1 -435 H Cl H CF3 CH3 OCH2 CH = CH2 1 -436 H C1 H CF3 CH3 OCH2 CC1 =CH2 1 -437 H C1 H CF3 CHa OCH2 CCI = CHCI
1 -438 H C1 H CF3 CH3 OCH(CH 3)CH = CHZ
1 -440 H C1 H CF3 CH3 OCH(CH 3)C=CH
TABLE 1 (contn'd) e Compound x I, R 3 R' R 2 B
No.
1 -441 H C1 H CF3 CH3 OCH2 C= CBr 1 -442 H CI H CF3 --CH3 OCH2 C=CC1 1 -443 H Cl H CF3 CH3 OCH2 C= CCH 2 Cl 1 -445 H Cl H CF3 CH3 OCH2 OCH , 1 -446 H C1 H CF3 CH3 OCH2 OC2 H s 1 -447 H Cl H CF3 CH3 OCH2 SCH 3 1 -448 H Cl H CFa CH3 OCH2 COOCH 3 1 -449 H C1 H CF3 CH3 OCH2 COOC2 H s 1 -450 H C1 H CF3 CH3 OCH2 C00 " C, H, 1 -451 H C1 H CF3 CH3 OCH2 C00 " C 4 H 9 1 -452 H Ci H CF3 CH3 OCH2 C00 " C; H õ
1 -453 H C1 H CF3 CH3 OCH2 COO ' C a H 7 1 -454 H C1 H CF3 CH3 OCH2 COO ' C s H fl 1 -455 H C1 H CF3 CH3 OCH2 COO ' C 6 H õ
1 -456 H C1 H CF3 CH3 OCH(CH 3)COOCH 3 1 -457 H Cl H CF3 CH3 OCH(CH 3)COOC 2 H s 1 -458 H C1 H CF3 CH3 OCH(CH 3)C00 C3 H7 1 -459 H C1 H CF3 CH3 OCH(CH 3 )C00 " C4 H 9 1 -460 H Cl H CF3 CH3 OCH(CH 3 )C00 " C5 Hõ
1 -461 H C1 H CF3 CH3 OCH(CH 3)C00 ' C3 H, 1 -462 H C1 H CF3 CH3 OCH(CH 3)C00 ' C5 H g 1 -463 H Cl H CF3 CH3 OCH(CH 3 )COO ' CR Hõ
TABLE 1 (contn'dl Compound X Y R 3 R1 R 2 B
No.
1 -464 H Cl H CF3 CH3 OCH 2 CON(CHa ) 2 1 -465 H Ci H CF3 CH3 OCH2 CON(C 2 H 5) 2 1 -466 H C1 H CF3 CH3 OCH2 CON(CH3 ) C 2 H;
1 -467 H C1 H CF3 CH3 OCH(CH 3)CON(CH ,) 2 1 -468 H C1 H CF3 CH3 OCH(CHs )CON(C 2 H;)=.
1 -469 H C1 H CF3 CH3 OCH(CH3. )CON(CH 3)C2 H;
1 -470 H C1 H CF3 CH3 OCH 2 COON(CH a) 2 1 -471 H Cl H CF3 CH3 OCH 2 COON(C 2 H 5)2 1 -472 H Cl H CF3 CHa OCH(CH3 )COON(CH3 ) z 1 -473 H Cl H CFa CH3 OCH(CH3 )COON(C 2 H s) 2 1 -476 F Cl H CF3 CH3 0' C 3 H 7 1 -477 F C1 H CF3 CH3 0 C, H 7 1 -478 F C1 H CF3 CH3 OCH2 CH2 Cl 1 -480 F C1 H CF3 CH3 0' C s H g 1 -481 F Cl H CF3 CH3 OC C 6 H õ
1 -482 F C l H CF3 CH3 OCH2 CH = CH 2 I -483 F Cl H CF3 CH3 OCH2 CCI = CHZ
1 -484 F C1 H CF3 CH3 OCH2 CC1 =CHCI
1 -485 F Cl H CF3 CH3 OCH(CH 3)CH = CH2 1 -486 F Cl H CF3 CH3 OCH2 C CH
TABLE 1 (contn'd) :
Compound X Y R3 R' R 2 B
No.
1 -487 F Ci H CF3 CH3 OCH(CH 3)C=CH
1 -488 F C1 H CF3 CH3 OCHZ C CBr 1 -489 F C1 H CF3 CH3 OCH2 C= CCl 1 -490 F C1 H CF3 CH3 OCH2 C= CCH 2 Cl 1 -491 F C1 H CF3 CH3 OCHz CN
1 -492 F Ci H CF3 CH3 OCH2 OCH 3 1 -493 F C1 H CF3 CH3 OCHZ 0C2 H;
1 -494 F Cl H CF3 CH3 OCH2 SCH 3 1 -496 F Cl H CF3 CH3 OCHz COOC2 H s 1 -498 F Cl H CF3 CH3 OCH2 C00 " C 4 H 9 1 -499 F C1 H CF3 CH3 OCH2 COO " C 5 H õ
1 -501 F C1 H CF3 CH3 OCHz COO C s H 9 1 -502 F C1 H CF3 CH3 OCHZ COO ' C 6 H õ
1 -503 F C1 H CF3 CH3 OCH(CH 3)COOCH 3 1 -504 F Cl H CF3 CH3 OCH(CH 3)COOC 2 H s 1 -505 F C1 H CF3 CH3 OCH(CH 3)C00 " C3 H 7 1 -506 F C1 H CF3 CH3 OCH(CH 3)C00 " C4 H9 1 -507 F Cl H CF3 CH3 OCH(CH 3)C00 " C5 H
1 -508 F Cl H CF3 CH3 OCH(CH 3-)C00 ' C3 H 7 1 -509 F C1 H CF3 CH3 OCH(CH 3 )C00 ' CS H 9 TABLE 1 (contn'd) Compound X Y R 3 R' R 2 B
No.
1 -510 F C1 H CF3 CH3 OCH(CH 3 )C00 ' C6 H
1 -511 F Ci H CF3 CH3 OCH2 CON(CH3 ) 2 1- 512 F C1 H CF3 CHa OCH2 CON(C 2 H s) 2 1- 513 F C1 H CF3 CH3 OCH2 CON(CH3 ) C 2 H;
1 -514 F Cl H CF3 CH3 OCH(CH 3)CON(CH 3) 2 1 -515 F C1 H CF3 CH3 OCH(CH3 )CON(C 2 H 5 )2 1- 516 F C1 H CF3 CH3 OCH(CH3 )CON(CH 3)C2 H;
1 -517 F C1 H CF3 CH3 OCH 2 COON(CH ,)2 1- 518 F C1 H CF3 CHa OCH 2 COON(C 2 H s)a 1 -519 F C1 H CF3 CHa OCH(CH3 )COON(CH3 ) 2 1 -520 F C1 H CF3 CHa OCH(CH3 )COON(C 2 H;) 2 1 -523 H Br H CF3 CH3 SH
1 -526 F Br H CF3 CH3 SH
1- 529 H C1 H CF3 CHI S' C s H 7 1 -530 H C1 H CF3 CH3 SCHZ CH2 Cl 1- 531 H C1 H CF3 CH3 Sc C s H s 1 -532 H C1 H CF3 CHa Sc C 6 H õ
TABLE 1 (contn'd) s Compound X Y R3 R' R 2 B
No.
1 -533 H C1 H CF3 CHa SCH2 CH = CHa 1 -534 H Cl H CF3 CHa SCH2 CC1 = CH2 1 -535 H Ci H CF3 CH3 SCH2 CCl = CHC1 1 -536 H Ci H CF3 CH3 SCH(CH a)CH = CH2 1 -537 H C1 H CF3 CH3 SCH2 C= CH
1 -538 H Cl H CF3 CH3 SCH(CH ,)C=CH
1 -539 H C1 H CF3 CH3 SCH2 COOCH , 1 -540 H C1 H CFa CH3 SCH2 COOC2 H s 1- 541 H C1 H CF3 CHa SCH2 C00 " C a H, 1 -542 H C1 H CF3 CH3 SCH2 C00 " C 4 H g 1 -543 H C1 H CF3 CH 3 SCH2 C00 C s H õ
1 -544 H C1 H CF3 CH3 SCH2 COO C a H7 1 -545 H C1 H CF3 CH3 SCH2 COO ' C s H s 1 -546 H Cl H CF3 CH3 SCH2 COO ' C 6 H õ
1 -547 H Cl H CF3 CH3 SCH(CH a)COOCH , 1 -548 H C1 H CF3 CHa SCH(CH 3)COOC 2 H s 1 -549 H C1 H CF3 CH3 SCH(CH 3 )C00 " C3 H, 1 -550 H Cl H CF3 CH3 SCH(CH 3 )C00 " C, H 9 1- 551 H Cl H CF3 CHa SCH(CH 3 )C00 " Cs Hii 1 -552 H C1 H CF3 CH3 SCH(CH 3 )C00 ' C3 H T
1 -553 H Cl H CF3 CH3 SCH(CH 3 )C00 ' C5 H 9 1 -554 H C1 H CF3 CH3 SCH(CH a)C00 ' C6 Hi i TABLE 1 (contn'd) Compound X Y R3 R' R a B
No.
1 -555 H C1 H CF3 CH3 SCH2 CON(CH3 ) 2 1 -556 H C1 H CF3 CH3 SCH2 CON(C 2 H;) 2 1- 557 H C 1 H CF3 CH3 SCHaCON ( tetramethylene ) 1 -558 H C 1 H CF3 CH 3 SCHaCON ( pentamethylene ) 1 -559 H Cl H CF3 CH3 SCH2CON
(ethyleneoxyethylene) 1 -560 H Cl H CF3 CH3 SCH(CH3 )CON(CH 3 1- 561 H C1 H CF3 CH3 SCH(CH3 )CON(C2 H;) z 1 -562 H C1 H CF3 CH3 SCH(CH3)CON
(tetramethylene) 1 -563 H C1 H CFs CH3 SCH(CH3)CON
(pentamethylene) 1 -565 F Cl H CF3 CH3 SC2 H 5 1 -566 F C1 H CF3 CHa S' C a H 7 1 -567 F C1 H CF3 CH3 SCH2 CH2 Cl 1 -568 F C1 H CF3 CH3 Sc C 5 H 9 1 -569 F C1 H CF3 CH3 S' C 6 H õ
1 -570 F Cl H CF3 CH3 SCH2 CH = CH2 1 -571 F C1 H CF3 CH3 SCH2 CCI =CH2 1 -572 F C1, H CF3 CH3 SCH2 CC1 =CHCI
1 -573 F Cl H CF3 CH3 SCH(CH 3)CH =CH2 1 -574 F C1 H CF3 CH3 SCH2 C= CH
TABLE 1 (contn'd) +
Compound x y R 3 R' R Z B
No.
1 -575 F C1, H CF3 CH3 SCH(CH 3)C=CH
1 -578 F Cl H CF3 CH3 SCH2 C00 C 3 H, 1 -579 F C1 H CF3 CH3 SCH2 COO " C 4 H 9 1 -581 F Cl. H CF3 CH3 SCH2 COO ' C 3 H 7 1 -582 F C1 H CF3 CH3 SCH2 COO ' Cs H
1 -583 F C1 H CF3 CH3 SCH2 COO ' C 6 H
1 -584 F C1 H CF3 CH3 SCH(CH 3)COOCH 3 1 -585 F Cl H CF3 CH3 SCH(CH 3)COOC 2 H 5 1 -586 F C1 H CF3 CH3 SCH(CH 3)C00 " C3 H~
1 -587 F C1 H CF3 CH3 SCH(CH 3)C00 C4 H
1- 588 F C1 H CF3 CH3 SCH(CH 3)C00 " CS H
1 -589 F C1 H CF3 CH3 SCH(CH 3)C00 ' C3 H 7 1 -590 F C1 H CF3 CH3 SCH(CH 3)C00 ' C5 H 9 1 -591 F Cl H CF3 CH3 SCH(CH 3 )C00 ' C6 Hõ
1--592 F Cl H CF3 CH3 SCH2 CON(CH3 ) 2 1- 593 F Cl H CF3 CH3 SCH2 CON(C 2 H e)2 1 -594 F C 1 H CF3 CH3 SCH2CON ( tetramethylene ) 1 -595 F C 1 H CF3 CH3 SCH2CON ( pentamethylene ) 1 -596 F C i H CF3 CH3 SCH2CON
(ethyleneoxyethylene) TABLE 1 (contn'd) Compound X Y R 3 R' R2 B
No.
1 -597 F C1 H CF3 CHa SCH(CH3 )CON(CH a) 2 1 -598 F C1 H CF3 CH3 SCH(CH3 )CON(C2 H;) 2 1 -599 F C1 H CF3 CH3 SCH(CH3)CON
(tetramethylene) 1 -600 F C1 H CF3 CH3 SCH(CH3)CON
(pentamethylene) 1 -601 H F H CF3 CH3 SOZ Ci 1 -602 H C1 H CF3 CH3 SOZ Cl 1 -603 H Br H CF3 CH3 SO2 Cl 1 -605 F C1 H CF3 CH3 SOz C1 1 -606 F Br H CF3 CH3 SO2 Cl 1 -609 H C1 H CF3 CH3 SO2 0' C 3 H T
1 -610 H C1 H CF3 CH3 SOz OCH 2 CH=CH2 1 -611 F C1 H CF3 CH3 SOz OCH s 1 -613 F C1 H CF3 CH3 SOz 0' C 3 H z 1 -614 F C1 H CF3 CH3 S02 OCH' 2 CH = CH2 1 -615 H C1 H CF3 CH3 SO2 N(CH3 ) 2 1 -616 H C1 H CF3 CHa SO2 N(Cz H b) 2 1- 617 F C1 H CF3 CH3 802 N(CH 3 ) 2 TABLE 1 (contn'd) r Compound X Y R3 R' R Z B
No.
1- 618 F C1 H CFa CHa SOz N(Cz H s) 2 1 -622 H C1 H CF3 CH3 C00" C 3 H
1 -623 H C1 H CF3 CH3 C00" C4 H 9 1 -624 H C1 H CF3 CH3 CO0 C s H õ
1- 625 H C1 H CF3 CHa COW C 3 H 7 1 -627 H C1 H CF3 CH3 COOCHZ CH2 Br 1 -628 H C1 H CF3 CH3 CON(CH a) 2 1 -630 H C1 H CF3 CH3 CON(C2 H 5) 2 1 -633 H C1 H CF3 CH3 COC2 H s 1 -634 H C1 H CF3 CH3 COCH2 Cl 1 -636 H C1 H CF3 CHa CH = CHCOOCH 3 1 -637 H C 1 H CF3 CH3 CH = CHCOOC z H s =
1 -638 H C1 H CF3 CH3 CHa CHz COOCH s TABLE 1 (contn'd) Compound x y R' R' R 2 B
No.
1 -641 F C1 H CF3 CH3 COOCH , 1 -643 F C1 H CF3 CH3 C00 C 3 H, 1 -644 F Cl H CF3 CH3 C00" C 4 H 9 1 -645 F C1 H CF3 CH3 CO0 C s H,i 1 -646 F Cl H CF3 CH3 .C00' C 3 H, 1 -648 F Cl H CF3 CH3 COOCH2 Cff Z Br 1 -649 F C1 H CF3 CH3 CON(CH a) 2 1 -651 F Cl H CF3 CH3 CON(C2 H 5) 2 1 -652 F C1 H CF3 CH3 CONHC2 H;
1 -654 F Ci H CF3 CH3 COC2 H 5 1 -655 F Ci H CF3 CH3 COCH2 Cl 1 -657 F C1 H CF3 CH3 CH = CHCOOCH 3 1 -658 F C1 H CF3 CH3 CH= CHCOOC2 H s 1 -660 F Cl H CF2 Cl CH3 CH2 CHz COOC2 H
1 -662 H F H CF2 Cl H N02 WO 97/07104 PCT/dP96/02311 TABLE 1 (contn'd) Compound x Y R 3 R' R Z B
No.
1 -663 H C1 H CF2 Cl H NO2 1 -664 H Br H CF2 Cl H NO2 1 -665 F F H CF2 Cl H NOZ
1 -666 F C1 H CF2 Cl H NOz 1 -667 F Br H CF2 C1 H NOz 1 -668 H F H CF2 Cl H NH2 1 -669 H C1 H CF2 Cl H NH2 1 -670 H Br H CF2 Cl H NH2 1 -671 F F H CF2 Cl H NH2 1 -672 F Cl H CF2 Cl H NH2 1 -673 F Br H CF2 Cl H NHZ
1 -674 H F H CF2 Cl H OH
1 -675 H C1 H CF2 Cl H OH
1 -676 H Br H CF2 Cl H OH
1 -677 F F H CF2 Cl H OH
1 -678 F Cl H CF2 Cl H OH
1 -679 F Br H CF2 C1 H OH
1 -680 H C1 H CF2 Cl H NHCH3 1 -681 H C1 H CF2 Cl H NHC2 H s 1 -682 H C1 H CF2 Cl H NHCH2 CH=CH2 1 -683 H C1 H CF2 Cl H NHCH2 C= CH
1 -684 H Cl H CF2 C1 H NHCH(CH 3)C=CH
1 -685 H C1 H CF2 Cl H NHSO2 CH3 TABLE 1 (contn'd) }
Compound x y R 3 R' R 2 B
No.
1 -686 H C1 H CF2 Cl H NHSOz C 2 H s 1 -687 H Cl H CF2 Cl H NHSOZ CH2 Cl 1 -688 H Ci H CF2 Cl H NHSO2 CF3 1 -689 H Ci H CF2 Cl H N(CH3 )SO 2 CH3 1 -690 H C1 H CF2 Cl H N(CH2 C= CH)SO 2 CH3 1 -691 H C1 H CF2 Cl H NHCOOCH 3 1 -692 H C1 H CF2 Cl H NHCOOC2 H s 1 -693 H Cl H CF2 Cl H NHCOO " C 3 H 7 1 -694 H C1 H CF2 Cl H NHCOO ' C 3 H, 1 -695 H C1 H CF2 Cl H NHCOO " C 4 H 9 1 -696 H C1 H CF2 Cl H NHCOO " C s H õ
1 -697 H C1 H CF2 Cl H NHCH2 COOCH 3 1 -698 H Cl H CF2 Cl H NHCH2 COOC2 H s 1- 699 H Cl H CF2 Cl H NHCH2 C00 " C 3 H 7 1 -700 H C1 H CF2 Cl H NHCH2 C00 " C 4 H 9 1 -701 H C1 H CF2 Cl H NHCH2 C00 " C s H
1 -702 H Ci H CF2 Cl H NHCH2 COO ' Ca H;
1 -703 H C1 H CF2 Cl H NHCH2 COO ' C s H s 1 -704 H C1 H CF2 Cl H NHCH2 COO ' C 6 H õ
1 -705 H C1 H CF2 Cl H NHCH(CH 3)COOCH , 1 -706 H Cl H CF2 C1 H NHCH(CH3 )COOC 2 H 6 1 -707 H C1 H CF2 Cl H NHCH(CH3 )COO " C3 H 7 1 -708 H Cl H CF2 Cl H NHCH(CH3 )COO " C4 H 9 TABLE 1 (contn'd) Compound x y R 3 R' R 2 B
No.
1 -709 H ci H CF2 Cl H NHCH(CH3 )C00 " C. Hõ
1- 710 H ci H CF2 Cl H NHCH(CH3 )C00 ' C3 H T
1 -711 H C1 H CF2 Cl H NHCH(CH3 )C00 ' C. H s 1 -712 H C1 H CF2 Cl H NHCH(CH3 )C00 ' C. H
1 -713 F Cl H CF2 Cl H NHCH3 1 -714 F C1 H CF2 C1 H NHC 2 H s 1 -715 F Cl H CF2 Cl H NHCH2 CH=CH2 1 -716 F ci H CF2 Cl H NHCH2 C CH
1 -717 F C1 H CF2 Cl H NHCH(CH 3)C=CH
1 -718 F C1 H CF2 Cl H NHSO2 CHa 1- 719 F Cl H CF2 Cl H NHSO2 C 2 H;
1 -720 F ci H CF2 Cl H NHSOz CH2 Cl 1 -721 F C1 H CF2 Cl H NHSO2 CF3 1 -722 F C1 H CF2 Cl H N(CH3 )S0 2 CH3 1- 723 F C1 H CF2 Cl H N(CH2 C CH)SO 2 CH3 1 -724 F C1 H CF2 Cl H NHCOOCH 3 1 -725 F C1 H CF2 Cl H NHCOOC2 H s 1 -726 F C1 H CF2 Cl H NHCOO " C 3 H, 1 -727 F C1 H CF2 Cl H NHCOO ' C a H 7 1 -728 F C1 H CF2 Cl H NHCO0 " C, H 9 1 -729 F Cl H CF2 Cl H NHCOO " C 5 H õ
1 -730 F Cl H CF2 Cl H NHCH2 COOCH 3 1 -731 F C1 H CF2 Cl H NHCH2 COOC2 H 5 TABLE 1 (contn'd) Compound X Ir R 3 R' R Z B
No.
1 -732 F Ci H CF2 Cl H NHCH2 C00 " C 3 H 7 1 -733 F C1 H CF2 Cl H NHCH2 C00 " C, H 9 1 -734 F Cl H CF2 Cl H NHCH2 C00 " C 5 H
1 -735 F Cl H CF2 Cl H NHCH2 COO ' C 3 H
1 -736 F C1 H CF2 Cl H NHCH2 COO ' C; H
1- 737 F Cl H CF2 Cl H NH2 CH2 COO ' C 6 H
1 -738 F C1 H CF2 Cl H NHCH(CH3 )COOCH 3 1 -739 F C1 H CF2 Cl H NHCH(CH3 )COOC 2 H 5 1- 740 F C1 H CF2 C1 H NHCH(CH3 )COO C 3 H 7 1 -741 F C1 H CF2 Cl H NHCH(CH3 )C00 " C 4 H 9 1 -742 F C1 H CF2 C1 H NHCH(CH3 )COO " C; Hõ
1 -743 F Cl H CF2 C1 H NHCH(CH3 )COO ' C3 H 7 1 -744 F Cl H CF2 C1 H NHCH(CH3 )COO ' CS H 9 1 -745 F Cl H C F2 Cl H NHCH (CH3 )COO c Cs Hõ
1 -747 H C1 H CF2 Cl H OC 2 H 5 1- 748 H C1 H CF2 C1 H 0' C a H 7 1- 749 H C1 H CFZ C1 H 0" C 3 H 7 1 -750 H C1 H CF2 Cl H OCH2 CH2 Cl 1 -751 H Cl H CF2 Cl H OCF2 CF2 H
1- 752 H C1 H CFz C1 H 0' C 5 H fl 1 -753 H C1 H CF2 Cl H 0' C 6 Hõ
1 -754 H C1 H CF2 Cl H OCH2 CH=CH2 TABLE 1 (contn'd) Compound X y R3 R' R z B
No.
1 -755 H Ci H CF2 Cl H OCH2 CCI =CH2 1 -756 H Ci H CF2 Cl H OCH2 CCl =CHCI
1 -757 H C1 H CF2 Cl H OCH(CH 3)CH =CH2 1 -758 H C1 H CF2 Cl H OCH2 C= CH
1 -759 H C1 H CF2 Cl H OCH(CH 3)C CH
1 -760 H Cl H CF2 Cl H OCH2 C CBr 1 -761 H C1 H CF2 C1 H OCH2 C= CC1 1 -762 H Ci H CF2 C1 H OCH2 C CCH 2 Cl 1 -763 H C1 H CF2 Cl H OCH2 CN
1 -764 H C1 H CF2 Cl H OCH2 OCH 3 1 -765 H C1 H CF2 Cl H OCH2 0C2 H s 1 -766 H C1 H CF2 Cl H OCH2 SCH '3 1 -767 H Cl H CF2 Cl H OCH2 COOCH 3 1 -768 H C1 H CF2 Cl H OCH2 COOC2 H a 1 -769 H Cl H CF2 C1 H OCH 2 C00 " C 3 H 7 1- 770 H C1 H CFz C1 H OCHa C00 " C 4 H 9 1- 771 H C1 H CF2 Cl H OCH 2 C00 " C 5 H I , 1 -772 H Cl H CF2 C1 H OCH2 COO ' C, H, 1- 773 H C1 H CF2 C1 H OCH2 C00 ' C 5 H 9 1- 774 H C1 H CFz C1 H OCHZ C00 ' C 6 H I I
1 -775 H C1 H CF2 Cl H OCH(CH 3)COOCH
1 -776 H Cl H CF2 Cl H OCH(CH 3 )COOC 2 H a WO 97/07104 PCT/.TP96/02311 TABLE 1 (contn'd) Compound x Y R 3 R' R Z B
= No.
1 -777 H CI H CF2 Cl H OCH(CH 3)C00 " C3 H 1 1 -778 H CI H CF2 Cl H OCH(CH 3)CQO C4 H9 1 -779 H C1 H CF2 Cl H OCH(CH 3 )C00 " C5 Hõ
1 -780 H Cl H CF2 Cl H OCH(CH 3 )C00 ' C3 H T
1- 781 H C1 H CF2 Cl H OCH(CH 3)COQ ' CS H s 1 -782 H C1 H CF2 Cl H OCH(CH 3)C00 ' C6 H
1 -783 H C1 H CF2 Cl H OCH2 CON(CH3 ) 2 1 -784 H C1 H CF2 Cl H OCH2 CON(C 2-H ;) 2 1 -785 H Cl H CF2 Cl H OCH2 CON(CH3 ) C 2 H s 1 -786 H C1 H CF2 Cl H OCH(CH 3)CON(CH ,) 2 1- 787 H C1 H CF2 Cl H OCH(CH3 )CON(C 2 H 5)2 1 -788 H C1 H CF2 Cl H OCH(CH3 )CON(CH 3)C2 H5 1 -789 H C1 H CF2 Cl H OCH 2 CQQN(CH 3 ) 2 1- 790 H CI H CF2 Cl H OCH 2 COON(C 2 H 5)z 1 -791 H C1 H CF2 Cl H QCH(CHa )COON(CH3 ) 2 1 -792 H C1 H CF2 Cl H OCH(CH3 )COON(C 2 H 5) 2 1 -793 F CI H CF2 Cl H OCH3 1- 794 F C1 H CFz C1 H QC 2 H s 1- 795 F C1 H CF2 Cl H 0' C a H 7 1 -796 F C1 H CF2 Cl H Q" C a H 7 1 -797 F C1 H CF2 Cl H OCH2 CH2 Cl 1- 799 F C1 H CFz C1 H Q' C 5 H 9 '134 TABLE 1 (contn'd) Compound X Y R 3 R' R2 B
No.
1 -800 F C1 H CF2 Cl H 0' C 6 H õ
1 -801 F C1 H CF2 Cl H OCH2 CH =CH2 1 -802 F C1 H CF2 Cl H OCH2 CC1 =CH2 1 -803 F C1 H CF2 Cl H OCH2 CC1 = CHCI
1 -804 F C1 H CF2 Cl H OCH(CH a)CH = CHz 1 -805 F C1 H CF2 Cl H OCH2 C CH
1 -806 F C1 H CF2 Cl H OCH(CH a)C=CH
1 -807 F C1 H CF2 Cl H OCH2 C CBr 1 -808 F Ci H CF2 C1 H OCH2 C= CC1 1 -809 F C1 H CF2 C1 H OCH2 C= CCH 2 Cl 1 -810 F Cl H CF2 C1 H OCH2 CN
1 -812 F Cl H CF2 C1 H OCH 2 0C2 H s 1 -813 F C1 H CFz' Cl H 0CH2 SCH a 1 -814 F C1 H CF2 Cl H OCH 2 COOCH , 1 -815 F Cl H CF2 Cl H 0CH2 COOC 2 H 5 1- 816 F Cl H CF2 C1 H OCH 2 COO C 3 H 7 1 - 817 F C1 H CF2 Cl H OCH2 C00 C, H 9 1 -818 F C1 H CF2 C1 H OCH2 COO " C 5 H õ
1 -819 F C1 H CFz C1 H OCH 2 COO ' C s H, 1 - 820 F C l H CFZ Cl H OCHZ C00 ' C 5 H g 1 - 821 F C1 H CFZ C1 H OCH2 C00 ' C 6 H
1 -822 F C1 H CF2 Cl H OCH(CH 3)COOCH 3 TABLE 1 (contn'd) Compound X Y R 3 R' R 2 B
No.
1 -823 F Ci H CF2 Cl H OCH(CH 3)COOC 2 H s 1 -824 F Ci H CF2 Cl H OCH(CH 3 )C00 " C3 H 7 1 -825 F C1 H CF2 Cl H OCH(CH 3)C00 " C, H 9 1 -826 F Cl H CF2 Cl H OCH(CH 3)C00 " C; Hõ
1 -827 F C1 H CF2 Cl H OCH(CH 3 )C00 ' C3 H, 1 -828 F C1 H CF2 C1 H OCH(CH 3)C00 ' Cs H 9 1 -829 F Cl H CF2 Cl H OCH(CH 3)C00 ' Cs Hõ
1 -830 F C1 H CF2 Cl H OCH2 CON(CH3 ) 2 1- 831 F C1 H CF2 Cl H OCH2 CON(C 2 H 5) 2 1 -832 F C1 H CF2 Cl H OCH2 CON(CH3 ) C 2 H s 1 -833 F C1 H CF2 Cl H OCH(CH 3)CON(CH ,) 2 1- 834 F C1 H CF2 Cl H OCH(CH3 )CON(C 2 H 5)2 1 -835 F Ci H CF2 Cl H OCH(CH3 )CON(CH 3)C2 H 5 1 -836 F C1 H CF2 Cl H OCH 2 COON(CH a) 2 1 -837 F C1 H CF2 Cl H OCH 2 COON(C 2 H 5)2 1 -838 F Ci H CF2 Cl H OCH(CH3 )COON(CH3 ) 2 1- 839 F C1 H CF2 C1 H OCH(CH3 )COON(C 2 H s) 2 1 -840 H F H CF2 Cl H SH
1 -841 H C1 H CF2 Cl H SH
1 -842 H Br H CF2 Cl H SH
1 -843 F F H CF2 Cl H SH
1 -844 F C1 H CF2 Cl H SH
1 -845 F Br H CF2 Cl H SH
WO 97/07104 PCT/.TP96/02311 TABLE 1 (contn'd) Compound X Y R 3 R' R Z B =
No.
1 -846 H Cl H CFz Cl H SCH a 1 -847 H C1 H CF2 Cl H SC2 H 5 1 -848 H Cl H CF2 Cl H S' C a H T
1 -849 H C1 H CF2 Cl H SCH2 CH2 Cl 1 -850 H C1 H CF2 Cl H SC C 5 H
1 -851 H C1 H CF2 Cl H S' C 6 H
1 -852 H C1 H CF2 Cl H SCH2 CH=CH2 1 -853 H C1 H CF2 Cl H SCH2 CC1 = CH2 1 -854 H Ci H CF2 Cl H SCH2 CC1 = CHC1 1 -855 H C1 H CF2 Cl H SCH(CH 3)CH =CH2 1 -856 H C1 H CF2 Cl H SCH2 C= CH
1 -857 H Cl H CF2 Cl H SCH(CH 3)C=CH
1 -858 H C1 H CF2 Cl H SCH2 COOCH 3 1 -859 H C1 H CF2 Cl H SCH2 COOC2 H s 1 - 860 H C1 H CFZ Cl H SCHz C00 " C, H 7 1- 861 H Cl H CF2 Cl H SCH2 COO " C 4 H 9 1- 862 H C1 H CF2 Cl H SCHZ COO C 5 H
1 -863 H C1 H CF2 Cl H SCH2 COO ' C s H 7 1 -864 H Cl H CF2 C1 H SCH2 COO c C s H s 1 -865 H C1 H CF2 C1 H SCH2 COO ' C 6 H õ
1 -866 H Cl H CF2 Cl H SCH(CH 3)COOCH s 1 -867 H C1 H CF2 C1 H SCH(CH 3)COOC 2 H s 1 -868 H C1 H CF2 Cl H SCH(CH 3 )C00 " C3 H, TABLE R (contn'd) Compound X Y R 3 R' R Z B
No.
1 -869 H C1 H CF2 Cl H SCH(CH 3 )C00 C4 H o 1 -870 H C1 H CF2 Cl H SCH(CH 3)C00 " C; Hõ
1- 871 H C1 H CF2 Cl H SCH(CH 3)C00 ' C3 H z 1 -872 H Cl H CF2 Cl H SCH(CH 3)C00 C C; H 9 1- 873 H Cl H CF2 Cl H SCH(CH 3 )C00 ' C6 Hõ
1 -874 H C1 H CF2 Cl H SCH2 CON(CH3 ) 2 1- 875 H Cl H CF2 Cl H SCH2 CON(C 2 H;)2 1 -876 H C 1 H CF2 C 1 H SCH2CON ( tetramethylene ) 1 -877 H C 1 H CF2 C l H SCH2CON ( pentamethylene ) (ethyleneoxyethylene) 1 -879 H C1 H CF2 C1 H SCH(CH3 )CON(CH 3 2 1- 880 H C1 H CF2 C1 H SCH(CH3 )CON(C2 H Z
1- 881 H C1 H CF2 Cl H SCH(CH3)CON
(tetramethylene) 1 -882 H C1 H CF2 Cl H SCH(CH3)CON
(pentamethylene) 1 -884 F Cl H CF2 C1 H SC2 H s { 1 -885 F Cl H CF2 Cl H S' C a H 7 1 -886 F Cl H CF2 Cl H SCH2 CH2 Cl TABLE 1 (contn'd) ~
Compound x y R3 R' R 2 B
No.
1- 887 F C1 H CFz C1 H S' C s H s 1- 888 F C1 H CFz C1 H S' C e H õ
1 -889 F C1 H CF2 Cl H SCHZ CH=CH2 1 -890 F C1 H CF2 Cl H SCH2 CCI = CH2 1 -891 F Cl H CF2 Cl H SCH2 CCl =CHC1 1 -892 F C1 H CF2 Cl H SCH(CH 3)CH = CH2 1 -893 F C1 H CF2 Cl H SCH2 C= CH
1 -894 F C1 H CF2 Cl H SCH(CH 3)C=CH
1 -895 F C1 H CF2 Cl H SCH2 COOCH 3 1 -896 F Cl H CF2 Cl H SCH2 COOC2 H 5 1 -897 F C1 H CF2 Cl H SCH2 COO " C 3 H 7 1 - 898 F C1 H CFz C1 H SCH2 C00 C, H 9 1 - 899 F C1 H CF2 Cl H SCH2 C00 " C; H õ
1 -900 F Cl H CF2 Cl H SCH2 COO ' C a H 7 1- 901 F Cl H CF2 Cl H SCH2 C00 ' C 5 H 9 1 -902 F C1 H CF2 Cl H SCH2 COO ' C s H õ
1 -903 F C1 H CF2 Cl H SCH(CH 3)COOCH 3 1 -904 F Cl H CF2 Cl H SCH(CH 3)COOC 2 H s 1 -905 F Cl H CF2 Cl H SCH(CH 3)C00 C3 H, 1- 906 F Cl H CF2 Cl H SCH(CH 3)C00 C4 H q 1 -907 F Ci H CF2 Cl H SCH(CH 3)C00 " C5 Hõ
1 -908 F C1 H CF2 Cl H SCH(CH 3 )C00 C3 H 7 1 -909 F C1 H CF2 Cl H SCH(CH 3)C00 ' C6 H 9 TABLE 1 (contn'd) Compound X I, R 3 R' R Z
No. B
1- 910 F C1 H CF2 Cl H SCH(CH 3 )C00 ' C6 Hõ
1 -911 F Ci H CF2 Cl H SCHz CON(CH3 ) 2 1 -912 F Cl H CF2 Cl H SCH2 CON(C 2 H 5) 2 1 -913 F C1 H CF2 Cl H SCH2CON (tetramethylene) 1 -914 F C 1 H CF2 C 1 H SCHZCON ( pentamethylene ) 1 -915 F Cl H CF2 C1 H SCH2CON
(ethyleneoxyethylene) 1 -916 F C1 H CF2 C1 H SCH(CH3 )CON(CH ,) 2 1 -917 F Cl =H CF2 Cl H SCH(CH3 )CON(C2 H 5) 2 1 -918 F C1 H CF2 Cl H SCH(CH3)CON
(tetramethylene) 1 -919 F Cl H CF2 C1 H SCH(CH3)CON
(pentamethylene) 1 -920 H F H CF2 Cl H SOZ Cl 1 -921 H C1 H CF2 Cl H SO2 Cl 1 -922 H Br H CF2 Cl H S02 Cl 1 -923 F F H CF2 C1 H SOZ Cl 1 -924 F Cl H CF2 Cl H SOZ Cl 1 -925 F Br H CF2 Cl H SOZ Cl 1 -926 H C1 H CF2 Cl H SO2 OCH 3 1 -927 H C1 H CF2 Cl H SO2 0C2 H 5 1 - 928 H C1 H CFz Cl H S02 0' C 3 H, 1 -929 H Cl H CF2 Cl H S02 OCH 2 CH=CH2 TABLE X (contn'd) Compound x y R 3 R' R 2 B
No.
1 -930 F C1 H CF2 Cl H SO2 OCH 3 1 -931 F Cl H CF2 Cl H S02 0C2 H;
1 - 932 F C1 H CFa C1 H S02 0' C 3 H r 1 -933 F ci H CF2 Cl H S02 OCH 2 CH=CH2 1 -934 H ci H CF2 Cl H SOZ N(CH3 ) 2 1 -935 H C1 H CF2 Cl H SOz N(CZ H 5) 2 1 -936 F ci H CF2 Cl H SOZ N (CH ,) 2 1 - 937 F C1 H CF2 C1 H SOz N(Cz H s) z 1 -938 H C1 H CF2 Cl H COOH
1 -939 H ci H CF2 Cl H COOCH
1 -940 H C1 H CF2 Cl H COOC 2 H 5 1- 941 H C1 H CF2 Cl H C00" C3 H 7 1 - 942 H C1 H CFZ C 1 H C00" C 4 H 9 1 -943 H C1 H CF2 C1 H C00" C s H 11 1 -944 H Cl H CF2 Cl H COO' C 3 H, 1 -945 H C1 H CF2 C1 H COOCH2 CH2 Cl 1 -946 H ci H CF2 C1 H COOCH2 CHZ Br 1 -947 H C1 H CF2 Cl H CON(CH 3) 2 1 -948 H Cl H CF2 Cl H CONHCH 3 1- 949 H Cl H CF2 Cl H CON(C2 H 2 1 -950 H Cl H CF2 Cl H CONHC2 H s 1 -951 H ci H CF2 Cl H COCH 3 1 -952 H C1 H CF2 C1 H COCz H s TABLE 1 (contn'd) :
Compound X Y R3 R' R 2 B
No.
1 -953 H C1 H CF2 Cl H COCH2 C1 1 -954 H C1 H CF2 Cl H CHO
1 -955 H C1 H CF2 Cl H CH=CHCOOCH 3 1 -956 H C l H CF2 C 1 H CH = CHCOOC 2 H;
1 -957 H C1 H CF2 Cl H CH2 CH2 COOCH 3 1 -958 H C1 H CF2 C1 H CH2 CH2 COOC2 H;
1 -959 F C1 H CF2 Cl H COOH
1 -960 F Cl H CF2 Cl H COOCH 3 1 -961 F Cl H CF2 Cl H COOC 2 H s 1- 962 F C1 H CF2 Cl H C00" C 3 H 7 1 -963 F CI H CF2 Cl H C00" C 4 H 9 1 - 964 F C1 H CF2 C1 H C00" C s Hõ
1- 965 F C1 H CF2 Cl H COO' C3 H 7 1 -966 F C1 H CF2 Cl H COOCH2 CH2 Cl 1 -967 F C1 H CF2 Cl H COOCH2 CH2 Br 1 -968 F C1 H CF2 Cl H CON(CH 3 ) 2 1 -969 F C1 H CF2 Cl H CONHCH 3 1- 970 F C1 H CF2 Cl H CON(C2 H s) 2 1 -971 F C1 H CF2 Cl H CONHC2 H s 1 -972 F C1 H CF2 Cl H COCH , 1 -973 F C1 H CF2 Cl H COC2 H s 1 -974 F Cl H CF2 Cl H COCH2 Cl 1 -975 F C1 H CF2 Cl H CHO
TABLE 1 (contn'd) Compound X Y R3 R' R Z
No. B
1 -976 F C1 H CF2 Cl H CH=CHCOOCH 3 1 -977 F C1 H CF2 Cl H CH= CHCOOC2 H s 1 -978 F Ci H CF2 Cl H CH2 CH2 COOCH , 1 -979 F C1 H CF2 Cl H CH2 CH2 COOC2 H 5 1 -982 H Br H CF3 H NO2 1 -984 F C1 H CF3 H NOz 1 -985 F Br H CF3 H NO2 1- 988 H Br H CF3 H NH2 1 -991 H C1 H CF3 H NHCH(CH3 )COOCH , 1 -992 H Ci H CF3 H NHCH(CH3 )COOC 2 H 5 1 -993 H C1 H CF3 H NHCH(CH3 )COO " C 3 H 7 1 -994 H C1 H CF3 H NHCH(CH3 )COO " C4 H 9 1 -995 H C1 H CF3 H NHCH(CH3 )COO CS Hõ
1- 996 H C1 H CF3 H NHCH(CH3 )COO ' C3 H, 1 -997 H C1 H CF3 H NHCH(CH3 )COO ' CS H 9 TABLE 1 (contn'd) Compound x Ir R 3 R' R 2 B
No.
1 -998 H Ci H CF3 H NHCH(CH3 )C00 ' C. H
1- 1000 F C1 H CF3 H NHC 2 H;
1 -1001 F C1 H CF3 H NHCH2 CH = CHz 1 -1002 F Ci H CF3 H NHCH2 C= CH
1 -1003 F C 1 H CF3 H NHCH(CH 3) C= CH
1 -1005 F C1 H CF3 H NHSO2 C z H;
1 -1006 F C1 H CF3 H NHSOz CH2 Cl 1 -1007 F C1 H CF3 H NHSOz CF3 1- 1008 F C1 H CF3 H N(CH3 )SO 2 CH3 1 -1009 F C1 H CF3 H N(CH2 C CH)SO 2 CH3 1 -1011 F C1 H CF3 H NHCOOC2 H s 1 - 1012 F C1 H CF3 H NHC00 " C, H 7 1- 1013 F C1 H CF3 H NHCOO ' C 3 H, 1 -1014 F C1 H CF3 H NHCOO " C H 9 1 -1015 F C1 H CF3 H NHCOO " C H õ
COOC2 H;
1 -1018 F C1 H CF3 H NHCH2 COO " C 3 H 7 1- 1019 F C1 H CFa H NHCHz C00 " C 4 H c 1 -1020 F C1 H CF3 H NHCH2 COO " C 5 H 11 TABLE 1 (contn'd) t Compound x y R3 R' R Z B
No.
1 -1021 F C1 H CF3 H NHCH2 COO ' C, H;
1 -1022 F C1 H CF3 H NHCH2 COO ' C s H g 1 -1023 F Br H CF3 H NH2 1 -1026 H Br H CF3 H OH
1 -1029 F Br H CF3 H OH
1 -1032 H Ci H CF3 H NHCHZ CH = CHz 1 -1034 H C1 H CF3 H NHCH(CH 3)C=CH
1 -1036 H C1 H CF3 H NHSOz C 2 H s 1 -1037 H C1 H CF3 H NHSOz CH2 Cl 1 -1039 H C1 H CF3 H N(CH3 )SO 2 CH3 1 -1040 H C1 H CF3 H N(CH2 C= CH)SO 2 CH3 1 -1041 H C1 H CF3 H NHCOOCH a 1 -1043 H C1 H CF3 H NHCOO C 3 H, TABLE 1 (contn'd) Compound x Y R 3 R ' R Z B
No.
1 -1044 H C1 H CF3 H NHCOO ' C, H 7 1 -1045 H C1 H CF3 H NHCOO " C 4 H 9 1 -1046 H C1 H CF3 H NHCOO " C s H
1 -1048 H C1 H CF3 H NHCH2 COOC2 H s 1- 1049 H C1 H CF3 H NHCH2 COO " C y H
1- 1050 H C1 H CF3 H NHCH2 COO " C 4 H
1 -1051 H C1 H CF3 H NHCH 2 C00-" C s H
1 -1052 H C1 H CF3 H NHCH2 COO C 3 H, 1 -1053 H C1 H CF3 H NHCH2 COO ' C s H 9 1 -1054 H C1 H CF3 H NHCH2 COO C C 6 H õ
1- 1055 F C1 H CF3 H NH CH2 COO c C 6 H õ
1 -1056 F C1 H CF3 H NHCH(CH 3 )COOCH 3 1 -1057 F Ci H CF3 H NHCH(CH3 )COOC 2 H.5 1 -1058 F C1 H CF3 H NHCH(CH3 )C00 "* C3 H, 1 -1059 F C1 H CF3 H NHCH(CH3 )COO " C. H fl 1 -1060 F C1 H CF3 H NHCH(CH3 )COO " C. H
1- 1061 F C1 H CF3 H NHCH(CH3 )COO ' C3 H, 1 -1062 F C1 H CF3 H NHCH(CH3 )C00 C Cs H 9 1 -1063 F C1 H CF3 H NHCH(CH3 )C00 ' C6 H
1 -1065 H C1 H CF3 H OC 2 H s 1 -1066 H C1 H CF3 H 0' C, H, TABLE 1 (contn'd) Compound x Y R 3 R' R Z B
No.
1- 1067 H C1 H CF3 H 0" C 3 H 7 1- 1068 H C1 H CF3 H OCH2 CH2 Cl 1 -1069 H Cl H CF3 H OCF2 CF2 H
1 -1070 H Cl H CF3 H 0' C s H 9 1 -1071 H ci H CF3 H 0' C 6 H õ
1-1072 H C1 H CF3 H OCH2 CH=CH2 1 -1073 H C1 H CF3 H OCH2 CC1 =CH2 1- 1074 H Cl H CF3 H OCH2 CC1 = CHC1 1 -1075 H ci H CF3 H OCH(CH 3)CH =CH2 1 -1076 H ci H CF3 H OCH2 C CH
1 -1077 H ci H CF3 H OCH(CH 3)C= CH
1 -1078 H ci H CF3 H OCH2 C CBr 1 -1079 H Cl H CF3 H OCH2 C= CCl 1 -1080 H C1 H CF3 H OCH2 C CCH 2 Cl 1- 1082 H Cl H CF3 H OCH2 OCH 3 1- 1083 H Cl H CF3 H OCH2 0Ca H s 1 -1084 H C1 H CF3 H OCH 2 SCH a 1 -1085 H ci H CF3 H OCH2 COOCH a 1- 1086 H C1 H CF3 H OCH2 COOC2 H s 1 -1087 H C1 H CF3 H OCH2 COO " C, H 7 1 -1088 H C1 H CF3 H OCH2 COO " C, H9 1 -1089 H C1 H CF3 H OCH2 COO " C 5 H
TABLE 1 (contn'dl Compound X Y R 3 R' R 2 B
No.
1 -1090 H Cl H CF3 H OCH2 COO ' C 3 H 7 1 -1091 H Ci H CF3 H OCH2 C00 ' C; H
1 -1093 H Ci H CF3 H OCH(CH 3 )COOCH 3 1 -1094 H C1 H CF3 -H OCH(CH 3)COOC 2 H 5 1- 1095 H C1 H CF3 H OCH(CH 3)C00 " C3 H 7 1 -1096 H C1 H CF3 H OCH(CH 3)C00 " C4 H 9 1 -1097 H C1 H CF3 H OCH(CH 3)C00 C5 Hõ
1 -1098 H C1 H CF3 H OCH(CH 3)C00 ' Ca H, 1 -1099 H C1 H CF3 H OCH(CH 3)C00 ' C; H 9 1 -1100 H CI H CF3 H OCH(CH 3)C00 ' C6 Hõ
1 -1101 H C1 H CF3 H OCH2 CON(CH3 ) 2 1 -1102 H C1 H CF3 H OCH2 CON(C 2 H;) 2 1- 1103 H C1 H CF3 H OCH2 CON(CH3') C 2 H5 1 -1104 H Cl H CF3 H OCH(CH 3)CON(CH ,) 2 1 -1105 H C1 H CF3 H OCH(CH3 )CON(C 2 H 5)2 1- 1106 H C1 H CF3 H OCH(CH3 )CON(CH s)Cz H s 1 -1107 H C1 H CF3 H OCH 2 COON(CH 3 ) 2 1 -1108 H C1 H CF3 H OCH 2 COON(C 2 H s)z 1 -1109 H C1 H CF3 H OCH(CH3 )COON(CH3 ) 2 1 -1110 H C1 H CF3 H OCH(CH3 )COON(C 2 H 5) 2 TABLE 1 (contn'd) ~
Compound X Y R 3 R' R 2 B
No.
1 -1112 F C1 H CF3 H OC 2 H s 1 -1113 F C1 H CF3 H 0' C 3 H, 1 -1114 F C1 H CF3 H 0" C 3 H, 1- 1117 F C1 H CF3 H 0' C s H 9 1- 1118 F C1 H CF3 H 0' C 6 H õ
1 -1119 F C1 H CF3 H OCH2 CH =CH2 1 -1120 F C1 H CF3 H OCH2 CCI =CH2 1- 1121 F C1 H CF3 H OCH2 CCI = CHC1 1 -1122 F Ci H CF3 H OCH(CH 3 )CH =CH2 1 -1124 F C1 H CF3 H OCH(CH s)C CH
1 -1125 F C1 H CF3 H OCH2 C CBr 1 -1126 F Cl H CF3 H OCH2 C= CC1 1 -1127 F C1 H CF3 H OCH2 C CCH 2 Cl 1 -1130 F C1 H CF3 H OCH2 0C2 H s 1 -1133 F C1 H CF3 H OCH2 COOC2 H a 1 - 1134 F C1 H CF3 H OCHz C00 " C 3 H, TABLE 1 (contn'd) Compound x y R 3 R' R2 B
No.
1 -1135 F C1 H CF3 H OCH2 C00 " C 4 H s 1 -1136 F Cl H CF3 H OCH2 C00 " C 5 H,1 1 -1137 F C1 H CF3 H OCH2 COO C 3 H z 1 -1138 F C1 H CF3 H OCHz COO ' C S H a 1 -1139 F C1 H CF3 H OCH2 COO ' C 6 H õ
1 -1140 F C1 H CF3 H OCH(CH 3)COOCH a 1 -1141 F C1 H CF3 H OCH(CH 3)COOC 2 H s 1 -1142 F CI H CF3 H OCH(CH 3)C00 " C3 H 7 1- 1143 F C1 H CF3 H OCH(CH 3)C00 " C4 H 9 1- 1144 F C1 H CF3 H OCH(CH 3 )C00 " C5 Hõ.
1- 1145 F C1 H CF3 H OCH(CH 3 )C00 ' C3 H, 1 -1146 F Cl H CF3 H OCH(CH 3 )C00 ' CS H o 1- 1147 F C1 H CF3 H OCH(CH 3)C00 ' C6 H,-1 -1148 F C1 H CF3 H OCH2 CON(CH3 ) 2 1 -1149 F C1 H CF3 H OCH2 CON(C 2 H s) 2 1 -1150 F C1 H CF3 H OCH2 CON(CH3 ) C 2 H s 1- 1151 F C1 H CF3 H OCH(CH 3)CON(CH 3 ) 2 1 -1152 F C1 H CF3 H OCH(CH3 )CON(C 2 H 6)2 1 -1153 F C1 H CF3 H OCH(CH3 )CON(CH 3)C2 H;
1 -1154 F C1 H CF3 H OCH 2 COON(CH ,) 2 1 -1155 F C1 H CF3 H OCH 2 COON(C 2 H s)Z
1 -1156 F C1 H CF3 H OCH(CH3 )COON(CH3 ) Q
1- 1157 F C1 H CF3 H OCH(CH3 )COON(C 2 H 5 ) 2 TABLE 1 (contn'd) Compound X Y R 3 R' R Z B
No.
1 -1160 H Br H CF3 H SH
1 -1163 F Br H CF3 H SH
1 -1165 H C1 H CF3 H SC2 H s 1 -1166 H CI H CF3 H S' C, H T
1 -1167 H C1 H CF3 H SCHZ CH2 Cl 1 -1168 H C1 H CF3 H Sc C s H fl 1- 1169 H C1 H CF3 H SC C 6 H õ
1 -1170 H Ci H CF3 H SCH2 CH=CH2 1 -1171 H C1 H CF3 H SCH2 CCI =CH2 1 -1172 H C1 H CF3 H SCH 2 CCI=CHC1 1 -1173 H C1 H CF3 H SCH(CH 9)CH = CH2 1 -1175 H C1 H CF3 H SCH(CH 3)C=CH
1 -1176 H C1 H CF3 H SCH2 COOCH , 1 -1177 H Cl H CF3 H SCH2 COOC2 H 5 :
1 -1178 H C1 H CF3 H SCH2 C00 " C 3 H, 1 -1179 H C1 H CF3 H SCH2 C00 " C< H 9 ~
1- 1180 H C1 H CF3 H SCH2 COO " C 5 H 11 TABLE 1 (contn'd) Compound x y R a R' R 2 B
No.
1 -1181 H Ci H CF3 H SCH2 COO ' C a H T
1- 1182 H C1 H CF3 H SCH2 COO ' C s H 9 1 -1183 H C1 H CF3 H SCHZ COO ' C 6 H õ
1- 1184 H C1 H CF3 H SCH(CH a)COOCH a 1 -1185 H C1 H CF3 H SCH(CH 3)COOC 2 H;
1- 1186 H C1 H CF3 H SCH(CH 3 )C00 Ca H T
1 -1187 H C1 H CF3 H SCH(CH 3 )C00 " C4 H 9 1- 1188 H C1 H CF3 H SCH(CH 3)C00 " CS Hõ
1 -1189 H C1 H CF3 H SCH(CH 3 )C00 ' C 3 H7 1- 1190 H C1 H CF3 H SCH(CH 3 )C00 ' C 5 H 9 1- 1191 H C1 H CF3 H SCH(CH 3 )C00 ' C6 Hõ
1 -1192 H C1 H CF3 H SCH2 CON(CH3 ) 2 1- 1193 H C1 H CF3 H SCHZ CON(C 2 H 5) 2 1 -1194 H C 1 H CF3 H SCHZCON ( tetramethylene ) 1 -1195 H C 1 H CF3 H SCH2CON ( pentamethylene ) 1 -1196 H Ci H CF3 H SCH2CON
(ethyleneoxyethylene) 1 -1197 H C1 H CF3 H SCH(CH3 )CON(CH a) 2 1- 1198 H C1 H CF3 H SCH(CH3 )CON(C2 H s) 2 1 -1199 H Ci H CF3 H SCH(CH3)CON
(tetramethylene) 1 -1200 H C i H CF3 H SCH ( CH3 ) CON
(pentamethylene) TABLE 1 (contn'd) Compound x Y R 3 R' R z B
No.
1 -1202 F ci H CF3 H SC2 H s 1 -1203 F C1 H CF3 H S' C 3 H T
1 -1204 F C1 H CF3 H SCH2 CH2 Cl 1 -1205 F C1 H CF3 H S' C s H
1 -1206 F C1 H CF3 H S' C 6 H õ
1 -1207 F C1 H CF3 H SCH2 CH=CH2 1 -1208 F C1 H CF3 H SCH2 CC1 = CH2 1 -1209 F ci H CF3 H SCH2 CCI =CHCI
1 -1210 F C1 H CF3 H SCH(CH 3 )CH =CH2 1 -1211 F C1 H CF3 H SCH2 C= CH
1 -1212 F CI H CF3 H SCH(CH 3)C=CH
1 -1213 F ci H CF3 H SCH2 COOCH 3 1 -1214 F C1 H CF3 H SCH2 COOCa H 5 1- 1216 F ci H CF3 H SCH2 C00 " C, H 9 1- 1217 F C1 H CF3 H SCH2 C00 C s H,i 1 -1219 F C1 H CF3 H SCH2 COO C s H o 1 -1220 F C1 H CF3 H SCH2 COO ' C 6 H11 =
1- 1221 F C1 H CF3 H SCH(CH a)COOCH a 1 -1222 F C1 H CF3 H SCH(CH 3)COOC 2 H 6 TABLE 1 fcontn'dl Compound X y R3 R' R Z B
No.
1- 1223 F C1 H CF3 H SCH(CH 3 )C00 " C. H, 1 -1224 F CI H CF3 H SCH(CH 3)C00 " C4 H 9 1 -1225 F C1 H CF3 H SCH(CH 3)C00 C5 Hõ
1 -1226 F C1 H CF3 H SCH(CH 3)C00 ' C3 H 7 1 -1227 F Cl H CF3 H SCH(CH 3)C00 c C5 H
1- 1228 F Cl H CF3 H SCH(CH 3)C00 ' C6 H
1 -1229 F C1 H CF3 H SCH2 CON(CH3 ) 2 1- 1230 F C1 H CF3 H SCH2 CON(C 2-H s) 2 1 -1231 F C 1 H CF3 H SCHZCON ( tetramethylene ) 1 -1232 F C 1 H CF3 H SCH2CON ( pentamethylene ) (ethyleneoxyethylene) 1 -1234 F C1 H CF3 H SCH(CH3 )CON(CH a) 2 1 -1235 F Ci H CF3 H SCH(CH3 )CON(C2 H 5) 2 1 -1236 F C i H CF3 H SCH ( CH3 ) CON
(tetramethylene) 1 -1237 F C l H CF3 H SCH ( CH3 ) CON
(pentamethylene) 1 -1238 H F H CF3 H SOZ Cl 1 -1239 H Cl H CF3 H SO2 Cl 1 -1240 H Br H CF3 H SOZ C1 1 -1241 F F H CF3 H SOz Cl 1 -1242 F CI H CF3 H SOZ Cl TABLE 1 (contn'd) Compound X Y R 3 R' R 2 B
No.
1 -1243 F Br H CF3 H SO2 Cl 1- 1246 H C1 H CF3 H SOz 0' C 3 H T
1 -1247 H Ci H CF3 H SO2 OCH 2 CH=CH2 1 -1248 F C1 H CF3 H SOz OCH , 1 -1249 F C1 H CF3 H SOz 0C2 H s 1-1250 F C1 H CF3 H S02 0' C 3 H 7 1 -1251 F C1 H CF3 H SO2 OCH 2 CH=CH2 1 -1252 H C1 H CF3 H SOZ N(CH3 ) 2 1- 1253 H C1 H CF3 H S02 N (C2 H s) 2 1- 1254 F Cl H CF3 H SO2 N (CH ,) 2 1 -1255 F Ci H CF3 H SOz N (C2 H 5)2 1 -1256 H Cl H CF3 H COOH
1- 1257 H C1 H CF3 H COOCH a 1 -1258 H C1 H CF3 H CoOC 2 H 5 1- 1259 H C1 H CF3 H Coo C, H, 1 -1260 H Cl H CF3 H Coo" C, H
1 -1261 H C1 H CF3 H CoO C.5 H
1 -1262 H C1 H CF3 H C00' C a H 7 1 -1263 H Cl H CF3 H COOCH2 CH2 C1 1 -1264 H Ci H CF3 H COOCHZ CH2 Br 1- 1265 H C1 H CF3 H- CON(CH 3 ) 2 TABLE 1 (contn'd) compound X y R3 R' R Z B
No.
1 -1267 H C1 H CF3 H CON(C2 H 5) 2 1 -1270 H C1 H CF3 H COC2 H s 1 -1271 H C1 H CF3 H COCH2 Cl 1 -1273 H C1 H CF3 H CH = CHCOOCH 3 1 -1274 H C 1 H CF3 H CH = CHCOOC 2 H s 1 -1276 H CI H CFa H CH2 CH2 COOC2 H 5 1 -1278 F C1 H CF3 H COOCH , 1 -1279 F C1 H CF3 H COOC2 H s 1 -1280 F C1 H CF3 H C00" C, H 7 1 -1281 F C1 H CF3 H C00 C, H s 1- 1282 F C1 H CF3 H C00" C s H õ
1 -1283 F C1 H CF3 H C00' C s H 7 1 -1284 F C1 H CF3 H COOCHz CH2 Cl 1 -1285 F C1 H CF3 H COOCHZ CH2 Br 1 -1286 F CI H CF3 H CON(CH 3 ) 2 1 -1288 F Cl H CF3 H CON(C2 H 5 ) 2 TABLE 1 (contn'd) Compound x Y R3 R' R 2 B
No.
1 -1289 F Ci H CF3 H CONHC2 H;
1 -1292 F C1 H CF3 H COCH2 Cl 1 -1294 F C1 H CF3 H CH = CHCOOCH
1 -1295 F C1 H CF3 H CH= CHCOOC2 H s 1 -1296 F C1 H CF3 H CH2 CH2 C60CH , 1 -1297 F C1 H CF3 H CH2 CH2 COOC2 H;
1 -1298 H F CH3 CF3 H NOz 1- 1300 H Br CH3 CF3 H NOz 1- 1302 F C1 CH3 CF3 H NOz 1 -1303 F Br CH3 CF3 H N02 1- 1306 H Br CH3 CF3 H NH2 1 -1308 F C1 CH3 CF3 H NH2 1 -1309 H C1 CH3 CF3 H NHCH(CH3 )COOCH 3 1 -1310 H C1 CH3 CF3 H NHCH(CH3 )COOC 2 H 5 1- 1311 H C1 CH3 CF3 H NHCH(CH3 )COO " C3 H, TABLE 1 (contn'd) Compound X Y R3 R' R Z B
= No.
1- 1312 H C1 CH3 CF3 H NHCH(CH3 )COO C, H 9 1- 1313 H C1 CHs CF3 H NHCH(CH3 )COO " C5 Hõ
1- 1314 H C1 CH3 CF3 H NHCH(CH3 )COO C3 H 7 1- 1315 H C1 CH3 CF3 H NHCH(CH3 )COO ' Cs H 9 1- 1316 H Cl CH3 CF3 H NHCH(CH3 )COO ' C6 Hõ
1 -1318 F C1 CH3 CF3 H NHC 2 H s 1 -1319 F C1 CH3 CF3 H NHCH2 CH=Cff2 1 -1321 F C1 CH3 CF3 H NHCH(CH 3)C = CH
1 -1323 F C1 CH3 CF3 H NHSOa C 2 H s 1 -1324 F CI CH3 CF3 H NHSOz CH2 C1 1 -1326 F C1 CH3 CF3 H N(CH3 )SO 2 CH3 1 -1327 F C1 CH3 CF3 H N(CH 2 C = CH)SO 2 CH3 1 -1329 F C1 CH3 CF3 H NHCOOC2 H s 1 -1331 F C1 CH3 CF3 H NHCOO ' C 3 H 7 1 -1332 F C1 CH3 CF3 H NH COO C 4 H e 1 -1333 F C1 CH3 CF3 H NHCOO C 5 H õ
TABLE 1 (contn'd) Compound x Y R 3 R' R Z B
No.
1 -1334 F C1 CH3 CF3 H NHCH2 COOCH , 1 -1335 F C1 CH3 CF3 H NHCH2 COOC2 H s 1 -1336 F C1 CH3 CF3 H NHCH2 COO C 3 H, 1 -1337 F C1 CH3 CF3 H NHCH2 COO " C, H
1= 1338 F C1 CH3 CF3 H NHCH2 COO C s H1- 1339 F C1 CH3 CFa H NHCH2 COO ' C a 1- 1340 F C1 CH3 CF3 H NHCH2 COO ' C; H
1 -1341 F Br CH3 CF3 H NH2 1 -1344 H Br CH3 CF3 H OH
1 -1347 F Br CH3 CF3 H OH
1- 1349 H C1 CH3 CF3 H NHC 2 H s 1 -1350 H C1 CH3 CF3 H NHCH2 CH = CHz 1 -1351 H C1 CH3 CF3 H NHCH 2 C= CH
1 -1352 H C1 CH3 CF3 H NHCH(CH ,)C = CH
1 -1353 H C1 CH3 CF3 H NHSOZ CH3 =
1- 1354 H C1 CH3 CF3 H NHSOZ C 2 H s 1- 1355 H C1 CH3 CF3 H NHSOz CH2 Cl 1- 1356 H Ci CH3 CF3 H NHSOZ CF3 TABLE 1 (contn'd) compound X Y R 3 R' R 2 B
No.
1 -1357 H C1 CHa CF3 H N(CH3 )SO 2 CHa 1 -1358 H C1 CH3 CF3 H N(CH2 C= CH)SO 2 CHa 1 -1360 H C1 CH3 CF3 H NHCOOC2 H s 1 -1361 H C1 CH3 CF3 H NHCOO " C 3 H, 1 -1362 H C1 CH3 CF3 H NHCOO ' C 3 H, 1- 1363 H Ci CH3 CF3 H NHCOO C, H 9 1 -1364 H C1 CH3 CF3 H NHCOO " C 5 H,t 1 -1365 H C1 CH3 CF3 H NHCH2 COOCH , 1 -1366 H C1 CH3 CF3 H NHCH2 COOC2 H;
1 -1367 H C1 CH3 CF3 H NHCH2 C00 " C, H, 1 -1368 H C1 CH3 CF3 H NHCH2 C00 " C, H 9 1 -1369 H C1 CH3 CF3 H NHCH2 C00 " C; HI1- 1370 H C1 CH3 CF3 H NHCHz COO ' C 3 H T
1 -1371 H C1 CH3 CF3 H NHCH2 COO ' C s H o 1- 1372 H C1 CH3 CF3 H NHCH2 COO ' C 6 H õ
1- 1373 F Cl CH3 CF3 H NH CHz COO ' C 6 H õ
1 -1374 F C1 CH3 CF3 H NHCH(CH 3 )COOCH , 1 -1375 F C1 CH3 CF3 H NHCH(CH3 )COOC 2 H s 1 -1376 F C1 CHa CF3 H NHCH(CH3 )COO " C3 H 7 1 -1377 F C1 CH3 CF3 H NHCH(CH3 )COO " C, H 9 = 1- 1378 F CI CH3 CF3 H NHCH(CH3 )COO " CS H,i 1- 1379 F Cl CH3 CF3 H NHCH(CH3 )COO ' C3 H, TABLE 1 (contn'd) Compound X y R 3 R' R 2 B =
No.
1 -1380 F C1 CH3 CF3 H NHCH(CH3 )C00 C CS H 9 1- 1381 F C1 CH3 CF3 H NHCH(CH3 )C00 ' C6 Hõ
1 -1383 H C1 CH3 CF3 H OC 2 H s 1- 1384 H C1 CH3 CF3 H 0' C s H 7 1 -1385 H C1 CH3 CF3 H 0" C 3 H T
1 -1386 H C1 CH3 CF3 H OCH2 CH2 Cl 1- 1388 H C1 CH3 CF3 H 0' C s H s 1 -1389 H C1 CH3 CF3 H 0' C 6 H õ
1 -1390 H Ci CH3 CF3 H OCH2 CH = CHZ
1 -1391 H C1 CHa CF3 H OCH2 CC1 =CH2 1 -1392 H C1 CH3 CF3 H OCH2 CC1 = CHC1 1 -1393 H C1 CH3 CF3 H OCH(CH 3)CH = CH2 1 -1395 H Ci CH3 CF3 H OCH(CH 3)C=CH
1 -1396 H C1 CH3 CF3 H OCH2 C CBr 1 -1398 H C1 CH3 CF3 H OCH2 C= CCH 2 Cl 1- 1399 H C1 CH3 CF3 H OCH2 CN =
1 -1402 H Ci CH3 CF3 H OCHZ SCH 3 TABLE I (contn'd) Compound x Y R3 R' R 2 B
No.
1- 1404 H C1 CH3 CF3 H OCH2 COOC2 H s 1 -1405 H C1 CH3 CF3 H OCH2 C00 " C 3 H, 1 -1406 H C1 CH3 CF3 H OCHZ C00 " C, H 9 1 -1407 H C1 CH3 CF3 H OCHZ C00 " C s H õ
1- 1408 H C1 CH3 CF3 H OCH2 COO ' C 3 H1- 1409 H C1 CH3 CF3 H OCH2 COO ' C s H
1 -1410 H C1 CH3 CF3 H OCH2 COO ' C 6 H õ
1 -1411 H C1 CH3 CF3 H OCH(CH s)COOCH 3 1 -1412 H C1 CH3 CF3 H OCH(CH 3)COOC 2 H s 1 -1413 H C1 CH3 CF3 H OCH(CH 3)C00 " C. H z 1 -1414 H CI CH3 CF3 H OCH(CH 3)C00 " C4 H fl 1- 1415 H C1 CH3 CF3 H OCH(CH 3)C00 " Cs Hõ
1- 1416 H C1 CH3 CF3 H OCH(CH 3)C00 C3 H 7 1- 1417 H C1 CH3 CF3 H OCH(CH 3)C00 C5 H 9 1 -1418 H Ci CH3 CF3 H OCH(CH 3)C00 ' C6 Hõ
1- 1419 H C1 CH3 CF3 H OCH2 CON(CH3 ) 2 1- 1420 H C1 CH3 CF3 H OCH2 CON(C 2 H s) 2 1- 1421 H Ci CH3 CF3 H OCHz CON(CH3 ) C 2 H s 1 -1422 H C1 CH3 CF3 H 0CH(CH s)CON(CH 3) 2 1 -1423 H C1 CH3 CF3 H OCH(CH3 )CON(C 2 H s )2 1 -1424 H C1 CH3 CF3 H OCH(CH3 )CON(CH 3)C2 H s 1 -1425 H C1 CH3 CF3 H OCH 2 COON(CH 3) 2 TABLE 1 (contn'd) Compound X Y R 3 R' R 2 B
No.
1 -1426 H C1 CH3 CF3 H OCH 2 COON(C 2 H 5)2 1 -1427 H C1 CH3 CF3 H OCH(CH3 )COON(CH3 ) 2 1 -1428 H C1 CH3 CF3 H OCH(CH3 )COON(C 2 H;) Z
1 -1430 F C1 CH3 CF3 H OC 2 H a 1- 1431 F C1 CH3 CF3 H 0' C a H 7 1- 1432 F C1 CH3 CF3 H 0 C, H, 1- 1433 F C1 CH3 CF3 H OCH2 CH2 Cl 1- 1435 F C1 CH3 CF3 H 0' C 5 H s 1- 1436 F Cl CH3 CF3 H 0' C 6 H.,, 1- 1437 F Cl CH3 CF3 H OCH2 CH =CH2 1 -1438 F C1 CH3 CF3 H OCH2 CC1 =CH2 1 -1439 F Ci CH3 CF3 H OCH2 CCl =CHCI
1 -1440 F Cl CH3 CF3 H OCH(CH 3)CH =CH2 1- 1441 F C1 CH3 CF3 H OCH2 C= CH
1 -1442 F Cl CH3 CF3 H OCH(CH 3)C=CH
1- 1443 F Cl CH3 CF3 H OCH2 C CBr 1 -1444 F C1 CH3 CF3 H OCH2 C= CC1 1 -1445 F C1 CH3 CF3 H OCH2 C= CCH 2 Cl 1 -1446 F Cl CH3 CF3 H OCH2 CN
TABLE 1 (contn'd) Compound X Y R 3 R' R2 B
No.
1 -1448 F C1 CH3 CF3 H OCH2 0C2 H s 1 -1451 F C1 CH3 CF3 H OCHz COOC2 H s 1 -1452 F C1 CH3 CF3 H OCHZ C00 C 3 H, 1 -1453 F C1 CH3 CF3 H OCH2 C00 C, H 9 1- 1454 F C1 CH3 CF3 H OCH2 C00 C 5 H õ
1 -1455 F C1 CH3 CF3 H OCH2 COO ' C 3 H, 1- 1456 F C1 CH3 CF3 H OCH2 COO ' C 5 H 9 1- 1457 F C1 CH3 CF3 H OCHz COO ' C 6 H õ
1 -1458 F C1 CH3 CF3 H OCH(CH 3)COOCH 3 1 -1459 F C1 CH3 CF3 H OCH(CH 3)COOC 2 H 5 1 -1460 F C1 CH3 CF3 H OCH(CH 3)C00 " C3 H T
1 -1461 F C1 CH3 - CF3 H' OCH(CH 3)C00 " C, H s 1- 1462 F C1 CH3 CF3 H OCH(CH 3)C00 C5 Hõ
1- 1463 F C1 CH3 CF3 H OCH(CH 3)C00 ' C3 H, 1 -1464 F C1 CH3 CF3 H OCH(CH 3)C00 ' CS H 9 1- 1465 F C1 CH3 CF3 H OCH(CH 3)C00 C6 Hõ
1 -1466 F C1 CH3 CF3 H OCH2 CON(CH3 ) 2 1- 1467 F C1 CH3 CF3 H OCH2 CON(C 2 H s) 2 1- 1468 F C1 CH3 CF3 H OCH2 CON(CH3 ) C 2 H 5 1 -1469 F C1 CH3 CF3 H OCH(CH 3)CON(CH 3) 2 1 -1470 F C1 CH3 CF3 H OCH(CH3 )CON(C 2 H;)2 TABLE 1 (contn'd) Compound X Y R 3 R' R Z B
No.
1 -1471 F ci CH3 CF3 H OCH(CH3 )CON(CH 3 )C2 H s 1 -1472 F C1 CH3 CF3 H OCH 2 COON(CH 3) 2 1 -1473 F C1 CH3 CF3 H OCH 2 COON(C 2 H;)2 1 -1474 F Cl CH3 CF3 H OCH(CH3 )COON(CH3 ) 2 1 -1475 F Cl CH3 CF3 H OCH(CH3 )COON(C 2 H 5) 2 1 -1477 H Cl CH3 CF3 H SH
1- 1478 H Br CHa CF3 H SH
1 -1481 F Br CH3 CF3 H SH
1 -1482 H ci CH3 CF3 H SCH 3 1 -1483 H C1 CH3 CF3 H SC2 H s 1 -1484 H C1 CHa CF3 H S' C 3 H7 1 -1485 H ci CH3 CF3 H SCH2 CH2 Cl 1 -1486 H C1 CH3 CF3 H Sc C s H s 1- 1487 H C1 CHs CF3 H S' C 6 H õ
1 -1488 H ci CHa CF3 H SCH2 CH = CH2 1 -1489 H Cl CH3 CF3 H SCH2 CC1 = CHZ
1 -1490 H ci CH3 CF3 H SCH2 CCl = CHC1 1 -1491 H C1 CH3 CF3 H SCH(CH 3 )CH = CH2 1 -1492 H C1 CH3 CF3 H SCH2 C= CH
1 -1493 H C1 CH3 CF3 H SCH(CH 3 )C=CH
TABLE 1 (contn'dl ~
; Compound x Y R 3 R' R 2 B
No.
1 -1495 H C1 CH3 CF3 H SCH2 COOC2 H;
1 -1496 H C1 CH3 CF3 H SCH2 C00 " C 3 H 7 1- 1497 H C1 CH3 CF3 H SCHZ C00 " C, H
1 -1498 H C1 CH3 CF3 H SCH2 C00 " C 5 H
1 -1499 H CI CH3 CF, H SCH2 COO ' C 3 H
1 -1500 H C1 CH3 CF3 H SCH2 COO ' C 5 H
1- 1501 H C1 CH3 CF3 H SCH2 C00 ' C 6 H
1 -1502 H C1 CH3 CF3 H SCH(CH 3 )COOCH 3 1- 1503 H C1 CH3 CF3 H SCH(CH 3 )COOC 2 H 5 1 -1504 H C1 CH3 CF3 H SCH(CH 3 )C00 " C3 H
1 -1505 H C1 CH3 CF3 H SCH(CH 3)C00 " C, H
1 -1506 H C1 CH3 CF3 H SCH(CH 3)C00 " CS H
1- 1507 H C1 CH3 CF3 H SCH(CH 3)C00 ' C3 H, 1 -1508 H C1 CH3 CF3 H SCH(CH 3)C00 ' CS H 9 1 -1509 H C1 CH3 CF3 H SCH(CH 3 )C00 ' Cs Hõ
1 -1510 H Ci CH3 CF3 H SCH2 CON(CH3 ) 2 1- 1511 H C1 CH3 CF3 H SCH2 CON(C 2 H 5) 2 1 -1512 H C 1 CH 3 CF3 H SCH2CON ( tetramethylene ) 1 -1513 H C I CH 3 CF3 H SCHZCON ( pentamethylene ) (ethyleneoxyethylene) 1 -1515 H C1 CH3 CF3 H SCH(CH3 )CON(CH 3) 2 TABLE 1 (contn'd) Compound x Y R 3 R' R 2 B
No.
1- 1516 H C1 CH3 CF3 H SCH(CH3 )CON(C2 H s) 2 1 -1517 H C1 CH3 CF3 H SCH(CH3)CON
(tetramethylene) 1 -1518 H C1 CH3 CF3 H SCH(CH3)CON
(pentamethylene) 1 -1520 F C1 CH3 CF3 H SC2 H s 1 -1521 F C1 CH3 CF3 H S' C 3 H 7 1 -1522 F C1 CH3 CF3 H SCH2 CH2 Cl 1- 1523 F C1 CH3 CF3 H Sc C s H 9 1- 1524 F Ci CH3 CF3 H S' C 6 H õ
1 -1525 F C1 CH3 CF3 H SCH2 CH = CH2 1 -1526 F C1 CH3 CF3 H SCH2 CCI =CH2 1 -1527 F Ci CH3 CF3 H SCH2 CCI =CHCI
1 -1528 F C1 CH3 CF3 H SCH(CH 3)CH = CH2 1 -1530 F C1 CH3 CF3 H SCH(CH 3)C=CH
1 -1532 F C1 CH3 CF3 H SCH2 COOC2 H s 1 -1533 F C1 CH3 CF3 H SCH2 COO " C a H 7 1 -1534 F C1 CH3 CF3 H SCH2 COO " C, H o 1- 1535 F C1 CH3 CF3 H SCH2 COO " C 6 H,t 1 -1536 F Cl CHa CF3 H SCH2 COO ' C 3 H 7 TABLE 1 (contn'd) Compound x y R 3 R' R z B
No.
1 -1537 F C1 CH3 CF3 H SCHZ COO C C; H
1 -1538 F C1 CH3 CF3 H SCH2 COO ' C 6 H
1 -1539 F C1 CH3 CF3 H SCH(CH 3)COOCH 3 1- 1540 F C1 CH3 CF3 H SCH(CH 3)COOC 2 H 5 1-1541 F C1 CH3 CF3 H SCH(CH 3)C00 " C3 H;
1 -1542 F C1 CH3 CF3 H SCH(CH 3)C00 " C4 H y 1- 1543 F C1 CH3 CF3 H SCH(CH 3)C00 " CS Hõ
1 -1544 F C1 CH3 CF3 H SCH(CH 3)C00 ' C3 H, 1 -1545 F C1 CH3 CF3 H SCH(CH 3)C00 ' C5 H s 1- 1546 F C1 CH3 CF3 H SCH(CH 3)C00 ' C6 Hõ
1 -1547 F C1 CH3 CF3 H SCH2 CON(CH3 ) 2 1 -1548 F C1 CH3 CF3 H SCH2 CON(C 2 H;)2 1 -1549 F C 1 CH3 CF3 H SCH2CON ( tetramethylene ) 1 -1550 F C 1 CH 3 CF 3 H SCH2CON ( pentamethylene ) (ethyleneoxyethylene) 1 -1552 F C1 CH3 CF3 H SCH(CH3 )CON(CH a) 2 1- 1553 F C1 CH3 CF3 H SCH(CH3 )CON(C2 H 5) 2 1 -1554 F C 1 CH3 CF3 H SCH ( CH3 ) CON
(tetramethylene) 1 -1555 F C 1 CH3 CF3 H SCH ( CH, ) CON
(pentamethylene) TABLE 1 (contn'd) Compound X Y R 3 R' R Z B
No.
1 -1557 H Ci CH3 CF3 H SOZ Cl 1 -1558 H Br CH3 CF3 H S02 Cl 1 -1559 F F CH3 CF3 H SO2 Cl 1 -1560 F Cl CH3 CF3 H SO2 C1 1 -1561 F Br CH3 CF3 H SO2 Cl 1 -1562 H C1 CH3 CF3 H SOz OCH 3 1 -1563 H C1 CH3 CF3 H SOz 0C2 H s 1- 1564 H C1 CH3 CF3 H SO2 0' C 3 H, 1 -1565 H C1 CH3 CF3 H SO2 OCH 2 CH = CH2 1 -1566 F C1 CH3 CF3 H SOz OCH 3 1 -1567 F Cl CH3 CF3 H S02 0C2 H s 1- 1568 F C1 CH3 CF3 H SOZ 0' C, H, 1 -1569 F C1 CH3 CF3 H S0Z OCH 2 CH = CH2 1 -1570 H Ci CH3 CF3 H SOZ N(CH3 ) 2 1- 1571 H C1 CH3 CF3 H SO2 N (C2 H 5) 2 1- 1572 F C1 CH3 CF3 -H SOz N (CH 3) 2 1- 1573 F C1 CH3 CF3 H S0Z N (C2 H 5) 2 1 -1575 H C1 CH3 CF3 H COOCH 3 =
1 -1576 H C1 CHa CF3 H COOC 2 H 5 1 -1577 H C1 CH3 CF3 H C00" C 3 H 7 1- 1578 H C1 CH3 CF3 H C00" C, H 9 TABLE 1 (contn'd) .
Compound x Y R3 R' R2 B
No.
1- 1579 H C1 CH3 CF3 H C00" C s H
1 -1580 H C1 CH3 CF3 H C00' C a H;
1 -1581 H C1 CH3 CF3 H COOCH2 CH2 Cl 1 -1582 H C1 CH3 CF3 H COOCH2 CHz Br 1- 1583 H Cl CH3 CF3 H CON(CH 3) 2 1 -1584 H Ci CH3 CF3 H CONHCH 3 1 -1585 H C1 CH3 CF3 H CON(C2 H s) 2 1- 1586 H C1 CH3 CF3 H CONHC2 H s 1 -1588 H C1 CH3 CF3 H COC2 H s 1 -1589 H C1 CH3 CF3 H COCHz Cl 1 -1591 H C1 CH3 CF3 H CH = CHCOOCH 3 1 -1592 H C1 CH3 CF3 H CH=CHCOOC2 H s 1 -1593 H C1 CH3 CF3 H CH2 CHz COOCH 3 1 -1594 H Cl CH3 CF3 H CH2 CHZ COOC2 H s 1 -1597 F C1 CH3 CF3 H COOC2 H s 1- 1598 F C1 CH3 CF3 H C00" C 3 H 1 1 -1599 F C1 CH3 CF3 H C00" C 4 H 9 = 1 -1600 F Cl CH3 CF3 H C00" C s H,,.
1 -1601 F C1 CH3 CF3 H COO' C, H, TABLE 1 (contn'd) Compound x Y R 3 R' R Z B
No.
1 -1602 F C1 CH3 CF3 H COOCH2 CH2 Cl 1 -1603 F Cl CH3 CF3 H COOCH2 CH2 Br 1 -1604 F Cl CH3 CF3 H CON(CH ,) 2 1 -1606 F C1 CH3 CF3 H CON(C2 H s) 2 1 -1607 F C1 CH3 CF3 H CONHC2 H s 1 -1608 F CI CH3 CF3 H COCH , 1 -1610 F CI CH3 CF3 H COCH2 Cl 1 -1612 F C1 CH3 CF3 H CH = CHCOOCH 3 1-1613 F C1 CH3 CF3 H CH=CHCOOC2 H s 1 -1614 F Ci CH3 CF3 H CH2 CH2 COOCH a 1 -1615 F C1 CH3 CF3 H CH2 CH2 COOC2 H s 1 -1618 H Br CH3 CF3 H H
1 -1620 F Cl CH3 CF3 H H
1 -1621 F Br CH3 CF3 H H
1- 1622 F C1 H CF3 CH3 CH2 CHC1CO2 C 2 H s 1- 1623 F Cl H CF3 H CH2 CHC1CO2 C 2 H b TABLE I (contn'd) compound x Y R 3 R' R Z B
= No.
1 -1628 F C1 CH3 CF3 H OCH2 COz H
1 -1629 F C1 H CF3 H OCH (CH3 ) CO2 H
1 -1630 F C1 H CF3 CH3 OCH(CH3 ) CO2 H
1 -1631 F C1 CH3 CF3 H OCH(CH3 ) COZ H
1 -1634 H C1 CH3 CF3 H OCH2 COz H
1 -1635 H C1 H CF3 H OCH(CH3 ) C02 H
1 -1636 H C1 H CF3 CH3 OCH(CH3 ) CO2 H
1- 1637 H C1 CH3 CF3 H OCH(CH3 ) COz H
1- 1639 F Ci H CF3 CH3 SCH2 CO2 H
1 -1640 F C1 CH3 CF3 H SCH2 COz H
1 -1641 F C1 H CF3 H SCH(CH3 ) CO2 H
1 -1642 F C1 H CF3 CH3 SCH(CH3 ) COz H
1 -1643 F C1 CH3 CF3 H SCH(CH3 ) CO2 H
1 -1644 H C1 H CF3 H SCHZ COz H
1 -1645 H C1 H CF3 CH3 SCH2 COz H
1- 1646 H C1 CH3 CF3 H SCH2 COz H
1 -1647 H C1 H CF3 H SCH(CH3 ) CO2 H
TABLE 1 (contn'd) Compound X Y R3 R' R 2 B
No.
1 -1648 H C1 H CF3 CH3 SCH(CH3 ) CO2 H
1 -1649 H C1 CH3 CF3 H SCH(CH3 ) CO2 H
1 -1650 F C1 H CF3 CH3 OCH (C2 H 5 )C0 2 CH3 1- 1652 C1 C1 H CF3 H OCH2C02C2Hs 1 -1653 C1 C1 H CF3 H OCH2CO2 ' C3H7 1 -1656 C1 C1 H CF3 CH3 OCH2CO2 ' C3H7 1 -1659 C1 C1 CH3 CF3 H OCH2CO2 ' C3H7 1 -1660 C1 C1 H CF3 H OCH2C = CH
1-1661 C1 Cl H CF3 H OCH(CH 3)C =CH
1- 1662 C1 C1 H CF3 H OCH(CH 3)C02C2H5 1 -1663 C1 C1 H CF3 CH3 OCH2C = CH
1 -1664 C1 C1 H CF3 CH3 OCH(CH 3)C = CH
1 -1665 C1 C1 H CF3 CH3 OCH(CH 3)C02CZHs 1 -1667 C1 C1 CH3 CF3 H OCH(CH 3)C CH
1 -1668 CI C1 CH3 CF3 H OCH(CH 3)C02C2H5 1 -1669 F Br H CF3 H OCH2CO2CH3 TABLE 1 (contn'd) Compound. x Y R 3 R' R a B
No.
1 -1670 F Br H CF3 H OCH2COzCaHs 1- 1671 F Br H CF3 H OCH2C02 C3H7 1- 1672 F Br H CFa CH3 OCH2CO2CH3 1 -1673 F Br H CFa CH3 OCH2C02C2Hs 1 -1674 F Br H CF3 CH3 OCH2CO2 C3H7 1 -1675 F Br CH3 CF3 H OCH2CO2CH3 1 -1676 F Br CH3 'CF3 H OCH2CO2CzHs 1 -1677 F Br CH3 CF3 H OCH2CO2 C3H7 1 -1678 F Br H CF3 H OCH Z C= Cff 1- 1679 F Br H CF3 H OCH(CH 3)C = CH
1 -1680 F Br H CF3 H OCH(CH 3)C0aC2Hs 1 -1681 F Br H CF3 CH3 OCH2C = CH
1 -1682 F Br H CF3 CH3 OCH(CH 3)C = CH
1- 1683 F Br H CF3 CH3 OCH(CH 3)C02CZHs 1 -1684 F Br CH3 CF3 H OCH2C CH
1 -1685 F Br CH3 CF3 H OCH(CH 3)C = CH
1- 1686 F Br CH3 CF3 H OCH(CH 3)COzC2Hs WO 97/07104 PC'E'/JP96/02311 TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No. 1-1687 C1 Cl H CF3 H H
1-1688 C1 Cl H CF3 H OH
1-1689 Cl Cl H CF3 H NO2 1-1690 C1 Cl H CF3 H NH2 1-1691 Cl C1 H CF3 H NHSO2CH3 1-1693 C1 Cl H CF3 H NHCH2CO2CH3 1-1695 C1 Cl H CF3 H NHCH2CO21C3H7 1-1696 C1 Cl H CF3 H NHCH(CH3)CO2CH3 1-1697 C1 Cl H CF3 H NHCH(CH3)CO2C2H5 1-1698 C1 C1 H CF3 H NHCH(CH3)C021C3H7 1-1699 Cl Cl H CF3 H COZH
1-1700 Ci Cl H CF3 H CO2CH3 1-1701 C1 Cl H CF3 H C02C2H5 1-1702 CI C1 H CF3 H C02nC3H7 1-1703 C1 C1 H CF3 H C02nC4H9 1-1704 Cl C1 H CF3 H C02nC5H11 1-1705 Cl Cl H CF3 H C021C3H7 1-1706 Cl C1 H CF3 H CO2CH2CH2C1 1-1707 Cl C1 H CF3 H CO2CH2CH2Br 1-1708 Cl Cl H CF3 H CON(CH3)2 1-1709 Cl Cl H CF3 H CONHCH3 1-1710 C1 Cl H CF3 H CON(C2H5)2 1-1711 Cl Cl H CF3 H CONHC2H5 1-1712 Cl C1 H CF3 H COCH3 1-1713 Cl C1 H CF3 H COC2H5 1-1715 Cl Cl H CF3 H CHO
1-1716 Cl Cl H CF3 H CH=CHCO2CH3 1-1717 Cl Ci H CF3 H 01C3H7 1-1719 Cl C1 H CF3 CH3 OH
TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No.
1-1720 C1 Ci H CF3 CH3 NO2 1-1723 Cl C1 H CF3 CH3 NHSO2CH2C1 1-1725 C1 Cl H CF3 CH3 NHCH2CO2C2H5 1-1727 C1 C1 H CF3 CH3 NHCH(CH3)CO2CH3 1-1728 C1 C1 H CF3 CH3 NHCH(CH3)C02CZH5 1-1729 Cl Cl H CF3 CH3 NHCH(CH3)CO21C3H7 1-1733 Cl Cl H CF3 CH3 C02nC3H7 1-1734 Cl Cl H CF3 CH3 C02nC4H9 1-1735 Cl C1 H CF3 CH3 C0211C5H11 1-1736 Cl Cl H CF3 CH3 C02''C3H7 1-1738 Cl C1 H CF3 CH3 CO2CH2CH2Br 1-1739 Cl C1 H CF3 CH3 CON(CH3)2 1-1741 C1 Cl H CF3 CH3 CON(C2H5)2 1-1742 Cl Cl H CF3 CH3 CONHC2H5 1-1743 Ci C1 H CF3 CH3 COCH3 1-1744 Cl Cl H CF3 CH3 COC2H5 1-1745 Cl C1 H CF3 CH3 COCH2C1 1-1747 Cl C1 H CF3 CH3 CH=CHCO2CH3 1-1748 Cl Cl H CF3 CH3 OlC3H7 1-1749 C1 Cl CH3 CF3 H H
1-1750 C1 Cl CH3 CF3 H OH
1-1751 Cl Cl CH3 CF3 H NO2 1-1752 C1 Cl CH3 CF3 H NH2 TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No.
1-1753 Cl C1 CH3 CF3 H NHSO2CH3 1-1754 Cl C1 CH3 CF3 H NHSO2CH2C1 1-1755 Ci Cl CH3 CF3 H NHCH2CO2CH3 1-1756 C1 Cl CH3 CF3 H NHCH2CO2C2H5 1-1757 Cl C1 CH3 CF3 H NHCH2CO21C3H7 1-1758 Cl C1 CH3 CF3 H NHCH(CH3)C02CH3 1-1759 Cl C1 CH3 CF3 H NHCH(CH3)C02C2H5 1-1760 Cl Cl CH3 CF3 H NHCH(CH3)CO21C3H7 1-1761 Ci C1 CH3 CF3 H CO2H
1-1762 Cl Cl CH3 CF3 H CO2CH3 1-1763 Cl Cl CH3 CF3 H C02C2H5 1-1764 Cl Cl CH3 CF3 H C02nC3H7 1-1765 Cl Cl CH3 CF3 H C02nC4Hg 1-1766 C1 C1 CH3 CF3 H C021'C5H11 1-1767 Cl Cl CH3 CF3 H C021C3H7 1-1769 C1 Cl CH3 CF3 H CO2CH2CH2Br 1-1770 C1 Cl CH3 CF3 H CON(CH3)2 1-1771 C1 Cl CH3 CF3 H CONHCH3 1-1772 Cl C1 CH3 CF3 H CON(C2H5)2 1-1773 Cl C1 CH3 CF3 H CONHC2H5 1-1774 Cl C1 CH3 CF3 H COCH3 1-1775 Cl C1 CH3 CF3 H COC2H5 1-1776 C1 Cl CH3 CF3 H COCH2C1 1-1778 C1 C1 CH3 CF3 H CH=CHCO2CH3 1-1779 Cl Cl CH3 CF3 H O''C3H7 1-1780 F Br H CF3 H 0 lC3H7 1-1781 F Br H CF3 H N(SO2CH3)2 1-1782 F Br H CF3 H NHSO2CH3 1-1783 F Br H CF3 CH3 0 1C3H7 TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No.
1-1784 F Br H CF3 CH3 N(SOZCH3)2 1-1785 F Br H CF3 CH3 NHSO2CH3 1-1786 F Br CH3 CF3 H Oi C3H7 1-1787 F Br CH3 CF3 H N(SOZCH3)Z
1-1788 F Br CH3 CF3 H NHSO2CH3 1-1789 F C1 H CF3 CH3 OCH2C(CH3)=CH2 1-1791 F C1 H CF3 CH3 OCH2CO2C$H17 1-1793 F C1 H CF3 CH3 C(CH3)=NOH
1-1794 F C1 H CF3 CH3 C(CH3)=NOCH3 1-1795 F C1 H CF3 CH3 C(CH3)=NOC2H5 1-1796 F C1 H CF3 CH3 C(CH3)=NO''C3H7 1-1797 F C1 H CF3 CH3 C(C2H5)=NOH
1-1798 F C1 H CF3 CH3 C(C2H5)=NOCH3 1-1799 F C1 H CF3 CH3 C(C2H5)=NOC2H5 1-1800 F C1 H CF3 CH3 C(C2H5)=NO1C3H7 1-1801 F C1 H CF3 CH3 C(CH3)=NNH2 1-1802 F C1 H CF3 CH3 C(CH3)=NNHCH3 1-1803 F C1 H CF3 CH3 C(CH3)=NN(CH3)2 1-1804 F C1 H CF3 CH3 C(CH3)=NNHC2H5 1-1805 F C1 H CF3 CH3 C(CH3)=NN(C2H5)2 1-1806 F C1 H CF3 CH3 C(CZHS)=NNH2 1-1807 F C1 H CF3 CH3 C(C2H5)=NNHCH3 1-1808 F C1 H CF3 CH3 C(C2H5)=NN(CH3)2 1-1809 F C1 H CF3 CH3 C(C2H5)=NNHC2H5 1-1810 F C1 H CF3 CH3 C(C2H5)=NN(C2H5)2 1-1811 F C1 H CF3 CH3 C(CH3)(OCH3)2 1-1812 F C1 H CF3 CH3 C(CHg)(OC2H5)2 1-1813 F C1 H CF3 CH3 C(CH3)(Ci C3H7)2 1-1814 F C1 H CF3 CH3 I~
O
TABLE 1 (contn'd) Compound X Y R3 R1 R2 B =
No.
O
1-1815 F C1 H CF3 CH3 iO~
C'O
~ ~o~
1-1817 F Cl H CF3 CH3 1-1818 F Cl H CF3 H OCH2C(CH3)=CH2 1-1819 F Cl H CF3 H OCH2CO2C7H15 1-1821 F Cl H CF3 H COOCH2C6H5 1-1822 F C1 H CF3 H C(CH3)=NOH
1-1823 F C1 H CF3 H C(CH3)=NOCH3 1-1824 F C1 H~ CF3 H C(CH3)=NOC2H5 1-1825 F Cl H CF3 H C(CH3)=NOlC3H7 1-1826 F C1 H CF3 H C(C2H5)=NOH
1-1827 F C1 H CF3 H C(C2H5)=NOCH3 1-1828 F C1 H CF3 H C(C2H5)=NOC2H5 1-1829 F C1 H CF3 H C(C2H5)=NOlC3H7 1-1830 F C1 H CF3 H C(CH3)=NNH2 1-1831 F Cl H CF3 H C(CH3)=NNHCH3 1-1832 F Cl H CF3 H C(CH3)=NN(CH3)2 1-1833 F C1 H CF3 H C(CH3)=NNHC2H5 1-1834 F Cl H CF3 H C(CH3)=NN(C2H5)2 1-1835 F C1 H CF3 H C(C2H5)=NNH2 1-1836 F C1 H CF3 H C(C2H5)=NNHCH3 1-1837 F C1 H CF3 H C(C2H5)=NN(CH3)2 1-1838 F C1 H CF3 H C(C2H5)=NNHC2H5 1-1839 F C1 H CF3 H C(C2H5)=NN(C2H5)2 1-1840 F C1 H CF3 H C(CH3)(OCH3)2 TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No.
1-1841 F C1 H CF3 H C(CH3)(OC2H5)2 1-1842 F C1 H CF3 H C(CH3)(C1C3H7)2 C'O~
~ ~~~
C~1O
o~
~ ~o~
1-1847 F C1 CH3 CF3 H OCH2C(CH3)=CH2 1-1851 F C1 CH3 CF3 H C(CH3)=NOH
1-1852 F C1 CH3 CF3 H C(CH3)=NOCH3 1-1853 F C1 CH3 CF3 H C(CH3)=NOC2H5 1-1854 F C1 CH3 CF3 H C(CH3)=NOlC3H7 1-1855 F C1 CH3 CF3 H C(C2H5)=NOH
1-1856 F C1 CH3 CF3 H C(C2H5)=NOCH3 1-1857 F C1 CH3 CF3 H C(C2H5)=NOC2H5 1-1858 F C1 CH3 CF3 H C(C2H5)=NO1C3H7 1-1859 F C1 CH3 CF3 H C(CH3)=NNH2 1-1860 F C1 CH3 CF3 H C(CH3)=NNHCH3 1-1861 F C1 CH3 CF3 H C(CH3)=NN(CH3)2 TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No.
1-1862 F C1 CH3 CF3 H C(CH3)=NNHC2H5 1-1863 F Cl CH3 CF3 H C(CH3)=NN(C2H5)2 1-1864 F C1 CH3 CF3 H C(C2H5)=NNH2 1-1865 F Cl CH3 CF3 H C(C2H5)=NNHCH3 1-1866 F C1 CH3 CF3 H C(C2H5)=NN(CH3)2 1-1867 F Cl CH3 CF3 H C(C2H5)=NNHC2H5 1-1868 F Cl CH3 CF3 H C(C2H5)=NN(C2H5)2 1-1869 F Cl CH3 CF3 H C(CH3)(OCH3)2 1-1870 F C1 CH3 CF3 H C(CH3)(OC2H5)2 1-1871 F C1 CH3 CF3 H C(CH3)(C1C3H7)2 C'O
1-1872 F C1 CH3 CF3 H I~O
~ ~~~
C,-O
CZHS
~~o~
1-1875 F Cl CHg CF3 H
1-1876 H C1 H CF3 CH3 OCH2C(CH3)=CH2 1-1879 H Cl H CF3 CHg COOCH2C6H5 1-1880 H C1 H CF3 CH3 C(CH3)=NOH
1-1881 H Cl H CF3 CH3 C(CH3)=NOCH3 1-1882 H C1 H CF3 CH3 C(CH3)=NOC2H5 1-1883 H C1 H CF3 CHg C(CH3)=NOlC3H7 ti TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No.
1-1884 H Cl H CF3 CH3 C(C2H5)=NOH
1-1885 H Cl H CF3 CH3 C(C2H5)=NOCH3 1-1886 H C1 H CF3 CH3 C(C2H5)=NOC2H5 1-1887 H Cl H CF3 CH3 C(C2H5)=NO1C3H7 1-1888 H Cl H CF3 CH3 C(CH3)=NNH2 1-1889 H Cl H CF3 CH3 C(CH3)=NNHCH3 1-1890 H Cl H CF3 CH3 C(CH3)=NN(CH3)2 1-1891 H Cl H CF3 CH3 C(CH3)=NNHC2H5 1-1892 H C1 H CF3 CH3 C(CH3)=NN(C2H5)2 1-1893 H Cl H CF3 CH3 C(C2H5)=NNH2 1-1894 H C1 H CF3 CH3 C(C2H5)=NNHCH3 1-1895 H Cl H CF3 CH3 C(CZHS)=NN(CH3)2 1-1896 H Cl H CF3 CH3 C(C2H5)=NNHC2H5 1-1897 H Cl H CF3 CH3 C(C2H5)=NN(C2H5)2 1-1898 H C1 H CF3 CH3 C(CH3)(OCH3)2 1-1899 H C1 H CF3 CH3 C(CH3)(OC2H5)Z
1-1900 H C1 H CF3 CH3 C(CH3)(C1C3H7)2 C'O
~
1-1901 H Cl H CF3 CH3 I -O
1-1902 H Cl H CF3 CH3 ~~~~
C'o~
1-1903 H C1 H CF3 CH3 (-O
~ ~o) 1-1904 H Cl H CF3 CH3 1-1905 H Cl H CF3 H OCH2C(CH3)=CH2 WO 97/07104 PCT/.IP96/02311 TABLE 1 (contn'd) Compound X Y R3 Rl R2 B No.
1-1907 H Cl H CF3 H OCH2C02C8H17 1-1909 H C1 H CF3 H C(CH3)=NOH
1-1910 H C1 H CF3 H C(CH3)=NOCH3 1-1911 H C1 H CF3 H C(CH3)=NOC2H5 1-1912 H C1 H CF3 H C(CHg)=NOlC3H7 1-1913 H Cl H CF3 H C(C2H5)=NOH
1-1914 H C1 H CF3 H C(C2H5)=NOCH3 1-1915 H Cl H CF3 H C(CZH5)=NOCZH5 1-1916 H C1 H CF3 H C(C2H5)=NOlC3H7 1-1917 H C1 H CF3 H C(CH3)=NNH2 1-1918 H C1 H CF3 H C(CH3)=NNHCH3 1-1919 H Cl H CF3 H C(CH3)=NN(CH3)2 1-1920 H Cl H CF3 H C(CH3)=NNHC2H5 1-1921 H C1 H CF3 H C(CH3)=NN(C2H5)2 1-1922 H Cl H CF3 H C(C2H5)=NNH2 1-1923 H Cl H CF3 H C(C2H5)=NNHCH3 1-1924 H C1 H CF3 H C(C2H5)=NN(CH3)2 1-1925 H C1 H CF3 H C(C2H5)=NNHC2H5 1-1926 H Cl H CF3 H C(C2H5)=NN(C2H5)2 1-1927 H Cl H CF3 H C(CH3)(OCH3)2 1-1928 H C1 H CF3 H C(CH3)(OC2H5)2 1-1929 H C1 H CF3 H C(CHg)(CC3H7)2 'O~
1-1930 H Cl H CF3 H i CH3 ~O
1-1931 H C1 H CF3 H i'O~
~O =
I "1 O
TABLE 1 (contn'd) Compound X y R3 Ri R2 g No.
~~o~
1-1934 H C1 CH3 CF3 H OCH2C(CH3)=CH2 1-1938 H C1 CH3 CF3 H C(CH3)=NOH
1-1939 H C1 CH3 CF3 H C(CH3)=NOCH3 1-1940 H C1 CH3 CF3 H C(CH3)=NOC2H5 1-1941 H C1 CHg CF3 H C(CH3)=N0'C3H7 1-1942 H C1 CH3 CF3 H C(C2H5)=NOH
1-1943 H C1 CH3 CF3 H C(CZH5)=NOCH3 1-1944 H C1 CH3 CF3 H C(C2H5)=NOC2H5 1-1945 H C1 CH3 CF3 H C(C2H5)=N01C3H7 1-1946 H C1 CH3 CF3 H C(CH3)=NNH2 1-1947 -H C1 CH3 CF3 H C(CH3)=NNHCH3 1-1948 H C1 CH3 CF3 H C(CH3)=NN(CH3)2 1-1949 H C1 CH3 CF3 H C(CH3)=NNHC2H5 1-1950 H C1 CH3 CF3 H C(CH3)=NN(C2H5)2 1-1951 H C1 CH3 CF3 H C(C2H5)=NNH2 1-1952 H C1 CH3 CF3 H C(C2H5)=NNHCH3 1-1953 H Cl CH3 CF3 H C(C2H5)=NN(CHg)2 1-1954 H C1 CHg CF3 H C(C2H5)=NNHC2H5 1-1955 H C1 CH3 CF3 H C(C2H5)=NN(C2H5)Z
1-1956 H C1 CH3 CF3 H C(CH3)(OCH3)2 1-1957 H C1 CH3 CF3 H C(CHg)(OC2H5)2 1-1958 H C1 CH3 CF3 H C(CH3)(C1C3H7)2 1-1959 H C1 CH3 CF3 H C~C]
Io c,o) 1-1960 H C1 CH3 CF3 H I'0 TABLE 1 (contn'd) Compound X Y R3 Rl R2 B
No.
1-1961 H Cl CH3 CF3 H C0 C'O) 1-1962 H C1 CH3 CF3 H 1\0 1-1963 Cl C1 H CF3 CH3 OCH2C(CH3)=CH2 1-1964 Cl C1 H CF3 CH3 OCH2C02C7H15 1-1966 C1 Cl H CF3 CH3 COOCH2C6H5 1-1967 Cl Cl H CF3 CH3 C(CH3)=NOH
1-1968 C1 Cl H CF3 CH3 C(CH3)=NOCH3 1-1969 Cl C1 H CF3 CH3 C(CHg)=NOC2H5 1-1970 Cl Cl H CF3 CH3 C(CH3)=NO'-C3H7 1-1971 Cl Ci H CF3 CH3 C(C2H5)=NOH
1-1972 C1 Cl H CF3 CH3 C(C2H5)=NOCH3 1-1973 Cl Cl H CF3 CH3 C(C2H5)=NOC2H5 1-1974 C1 Ci H CF3 CH3 C(C2H5)=NO1C3H7 1-1975 C1 Cl H CF3 CH3 C(CH3)=NNH2 1-1976 Cl C1 H CF3 CH3 C(CH3)=NNHCH3 1-1977 C1 Cl H CF3 CH3 C(CH3)=NN(CH3)2 1-1978 C1 C1 H CF3 CH3 C(CH3)=NNHC2H5 1-1979 C1 Cl H CF3 CH3 C(CH3)=NN(C2H5)2 1-1980 Cl C1 H CF3 CH3 C(C2H5)=NNH2 1-1981 C1 C1 H CF3 CH3 C(C2H5)=NNHCH3 1-1982 Cl C1 H CF3 CH3 C(C2H5)=NN(CH3)2 1-1983 C1 Cl H CF3 CH3 C(C2H5)=NNHC2H5 1-1984 C1 Cl H CF3 CH3 C(C2H5)=NN(C2H5)2 1-1985 C1 Cl H CF3 CH3 C(CH3)(OCH3)2 1-1986 C1 Cl H CF3 CH3 C(CH3)(OC2H5)2 1-1987 C1 C1 H CF3 CH3 C(CH3)(C1C3H7)2 '0 1-1988 C1 Cl H CF3 CH3 ~~p~
WO 97/07104 PCT/.dP96/02311 TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No.
I-O
1-1989 C1 C1 H CF3 CH3 I'C~
C'C
1-1990 C1 Cl H CF3 CH3 I",Q
~~o~
1-1992 C1 C1 H CF3 H OCH2C(CH3)=CH2 1-1995 Ci C1 H CF3 H COOCH2C6H5 1-1996 C1 C1 H CF3 H C(CH3)=NOH
1-1997 C1 C1 H CF3 H C(CH3)=NOCH3 1-1998 C1 C1 H CF3 H C(CH3)=NOC2H5 1-1999 C1 C1 H CF3 H C(CH3)=NO1C3H7 1-2000 C1 C1 H CF3 H C(C2H5)=NOH
1-2001 C1 C1 H CF3 H C(C2H5)=NOCH3 1-2002 C1 C1 H CF3 H C(C2H5)=NOC2H5 1-2003 C1 C1 H CF3 H C(C2H5)=NO'-C3H7 1-2004 C1 C1 H CF3 H C(CH3)=NNH2 1-2005 C1 C1 H CF3 H C(CH3)=NNHCH3 1-2006 C1 C1 H CF3 H C(CH3)=NN(CH3)2 1-2007 C1 C1 H CF3 H C(CH3)=NNHC2H5 1-2008 C1 C1 H CF3 H C(CH3)=NN(C2H5)2 1-2009 C1 C1 H CF3 H C(C2H5)=NNH2 1-2010 C1 C1 H CF3 H C(C2H5)=NNHCH3 1-2011 C1 C1 H CF3 H C(C2H5)=NN(CH3)2 1-2012 C1 C1 H CF3 H C(C2H5)=NNHC2H5 1-2013 C1 C1 H CF3 H C(C2H5)=NN(C2H5)2 1-2014 Cl C1 H CF3 H C(CH3)(OCH3)2 TABLE 1 (contn'd) Compound X Y R3 Ri R2 B
No. 1-2015 C1 C1 H CF3 H C(CH3)(OC2H5)Z
1-2016 C1 C1 H CF3 H C(CHg)(CCgH7)2 C'O~
1-2017 C1 C1 H CF3 H I '-, 0 ~ ~o~
C.1O
~
1-2019 C1 Ci H CF3 H 10 ~ ~o~
1-2021 C1 C1 CH3 CF3 H OCH2C(CH3)=CH2 1-2023 C1 Ci CH3 CF3 H OCH2C02C8H17 1-2025 C1 C1 CH3 CF3 H C(CH3)=NOH
1-2026 C1 C1 CH3 CF3 H C(CH3)=NOCH3 1-2027 C1 C1 CH3 CF3 H C(CH3)=NOC2H5 1-2028 C1 C1 CH3 CF3 H C(CH3)=NOlC3H7 1-2029 C1 C1 CH3 CF3 H C(C2H5)=NOH
1-2030 C1 C1 CH3 CF3 H C(C2H5)=NOCH3 1-2031 C1 C1 CH3 CF3 H C(CZH5)=NOC2H5 1-2032 C1 C1 CH3 CF3 H C(C2H5)=NO1C3H7 1-2033 C1 C1 CH3 CF3 H C(CH3)=NNH2 1-2034 C1 C1 CH3 CF3 H C(CH3)=NNHCH3 TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No.
1-2035 C1 C1 CH3 CF3 H C(CH3)=NN(CH3)2 1-2036 C1 C1 CH3 CF3 H C(CHg)=NNHC2H5 1-2037 C1 C1 CH3 CF3 H C(CH3)=NN(C2H5)2 1-2038 C1 C1 CH3 CF3 H C(C2H5)=NNH2 1-2039 C1 C1 CH3 CF3 H C(C2H5)=NNHCH3 1-2040 Ci C1 CH3 CF3 H C(C2H5)=NN(CH3)2 1-2041 C1 C1 CH3 CF3 H C(C2H5)=NNHC2H5 1-2042 C1 C1 CH3 CF3 H C(C2H5)=NN(C2H5)2 1-2043 C1 C1 CHg CF3 H C(CH3)(OCH3)2 1-2044 C1 C1 CH3 CF3 H C(CH3)(OC2H5)2 1-2045 C1 C1 CH3 CF3 H C(CH3)(C''C3H7)2 C'0 ~ ~o ~
Clo]
1-2048 C1 C1 CH3 CF3 H ~~O , ~ ~o~
1-2052 F C1 H CF3 CH3 OCH2COOCH2COOi C3H7 1-2053 F C1 H CF3 CH3 OCH2COOCH(CH3)COOCH3 1-2054 F C1 H CF3 CH3 OCH2COOCH(CH3)COOC2H5 1-2055 F C1 H CF3 CH3 OCH2COOCH(CH3)COO1C3H7 =
TABLE 1 (contn'd) Compound X Y R3 R1 R2 B =
No.
1-2056 F Cl H CF3 CH3 OCH(CH3)COOCH2COOCH3 1-2057 F Cl H CF3 CH3 OCH(CH3)COOCH2COOC2H5 1-2058 F Cl H CF3 CH3 OCH(CH3)COOCH2COOlC3H7 1-2059 F Cl H CF3 CH3 OCH(CH3)COOCH(CH3)COOCH3 1-2060 F Cl H CF3 CH3 OCH(CH3)COOCH(CH3)COOC2H5 1-2061 F Cl H CF3 CH3 OCH(CHg)COOCH(CH3)COO1C3H7 1-2062 F Cl H CF3 H OCH2COOCH2COOCH3 1-2063 F Cl H CF3 H OCH2COOCH2COOC2H5 1-2064 F Cl H CF3 H OCH2COOCH2COOlC3H7 1-2065 F Cl H CF3 H OCH2COOCH(CH3)COOCH3 1-2066 F Cl H CF3 H OCH2COOCH(CH3)COOC2H5 1-2067 F Cl H CF3 H OCH2COOCH(CH3)COOlC3H7 1-2068 F Cl H CF3 H OCH(CH3)COOCH2COOCH3 1-2069 F Cl H CF3 H OCH(CH3)COOCH2COOC2H5 1-2070 F Cl H CF3 H OCH(CH3)COOCH2COO1C3H7 1-2071 F Cl H CF3 H OCH(CH3)COOCH(CH3)COOCH3 1-2072 F Cl H CF3 H OCH(CH3)COOCH(CH3)COOC2H5 1-2073 F Cl H CF3 H OCH(CH3)COOCH(CH3)COOlC3H7 1-2074 F Cl CH3 CF3 H OCH2COOCH2COOCH3 1-2075 F Cl CH3 CF3 H OCH2COOCH2COOC2H5 1-2076 F C1 CH3 CF3 H OCH2COOCH2COOlC3H7 1-2077 F Cl CH3 CF3 H OCH2COOCH(CH3)COOCH3 1-2078 F Cl CH3 CF3 H OCH2COOCH(CH3)COOC2H5 1-2079 F Cl CH3 CF3 H OCH2COOCH(CH3)CO01C3H7 1-2080 F Cl CH3 CF3 H OCH(CH3)COOCH2COOCH3 1-2081 F Cl CH3 CF3 H OCH(CH3)COOCH2COOC2H5 1-2082 F Cl CH3 CF3 H OCH(CH3)COOCH2COO1C3H7 1-2083 F Cl CH3 CF3 H OCH(CH3)COOCH(CH3)COOCH3 1-2084 F Cl CH3 CF3 H
OCH(CH3)COOCH(CH3)COOC2H5 1-2085 F Cl CH3 CF3 H OCH(CH3)COOCH(CH3)COO'C3H7 TABLE I (contn'd) Compound X Y R3 R1 R2 g No.
1-2088 H C1 H CF3 CH3 OCH2COOCH2COOlC3H7 1-2089 H C1 H CF3 CH3 OCH2COOCH(CH3)COOCH3 1-2090 H C1 H CF3 CH3 OCH2COOCH(CH3)COOC2H5 1-2091 H C1 H CF3 CH3 OCH2COOCH(CH3)COO1C3H7 1-2092 H C1 H CF3 CH3 OCH(CH3)COOCH2COOCH3 1-2093 H C1 H CF3 CH3 OCH(CH3)COOCH2COOC2H5 1-2094 H C1 H CF3 CH3 OCH(CH3)COOCH2COOlC3H7 1-2095 H C1 H CF3 CH3 OCH(CH3)COOCH(CH3)COOCH3 1-2096 H C1 H CF3 CH3 OCH(CH3)COOCH(CH3)COOC2H5 1-2097 H C1 H CF3 CH3 OCH(CH3)COOCH(CH3)COOlC3H7 1-2100 H C1 H CF3 H OCH2COOCH2COOlC3H7 1-2101 H C1 H CF3 H OCH2COOCH(CH3)COOCH3 1-2102 H C1 H CF3 H OCH2COOCH(CH3)COOC2H5 1-2103 H C1 H CF3 H OCH2COOCH(CH3)COOlC3H7 1-2104 H C1 H CF3 H OCH(CH3)COOCH2COOCH3 1-2105 H C1 H CF3 H OCH(CH3)COOCH2COOC2H5 1-2106 H C1 H CF3 H OCH(CH3)COOCH2COO1C3H7 1-2107 H C1 H CF3 H OCH(CH3)COOCH(CH3)COOCH3 1-2108 H C1 H CF3 H OCH(CH3)COOCH(CH3)COOC2H5 1-2109 H C1 H CF3 H OCH(CH3)COOCH(CH3)COOlC3H7 1-2112 H C1 CH3 CF3 H OCH2COOCH2COOlC3H7 1-2113 H C1 CH3 CF3 H OCHZCOOCH(CH3)COOCH3 1-2114 H Ci CH3 CF3 H OCH2COOCH(CH3)COOC2H5 1-2115 H C1 CH3 CF3 H OCH2COOCH(CH3)COOlC3H7 TABLE 1 (contn'dl Compound X Y R3 R1 R2 B
No.
1-2116 H C1 CH3 CF3 H OCH(CH3)COOCH2COOCH3 1-2117 H C1 CH3 CF3 H OCH(CH3)COOCH2COOC2H5 1-2118 H C1 CH3 CF3 H OCH(CH3)COOCH2COO'-C3H7 1-2119 H C1 CH3 CF3 H OCH(CH3)COOCH(CH3)COOCH3 1-2120 H C1 CH3 CF3 H OCH(CH3)COOCH(CH3)COOC2H5 1-2121 H C1 CH3 CF3 H OCH(CH3)COOCH(CH3)COOlC3H7 1-2124 C1 C1 H CF3 CH3 OCH2COOCH2COOlC3H7 1-2125 C1 C1 H CF3 CH3 OCH2COOCH(CH3)COOCH3 1-2126 Ci C1 H CF3 CH3 OCH2COOCH(CH3)COOC2H5 1-2127 C1 C1 H CF3 CH3 OCH2COOCH(CHg)COO1C3H7 1-2128 C1 C1 H CF3 CH3 OCH(CH3)COOCH2COOCH3 1-2129 C1 C1 H CF3 CH3 OCH(CH3)COOCH2COOC2H5 1-2130 C1 C1 H CF3 CH3 OCH(CH3)COOCH2COOlC3H7 1-2131 C1 C1 H CF3 CH3 OCH(CH3)COOCH(CH3)COOCH3 1-2132 C1 C1 H CF3 CH3 OCH(CH3)COOCH(CH3)COOC2H5 1-2133 C1 C1 H CF3 CH3 OCH(CH3)COOCH(CH3)COO1C3H7 1-2136 C1 C1 H CF3 H OCH2COOCH2COOiC3H7 1-2137 C1 C1 H CF3 H OCH2COOCH(CH3)COOCH3 1-2138 Cl C1 H CF3 H OCH2COOCH(CH3)COOC2H5 1-2139 C1 Cl H CF3 H OCH2COOCH(CH3)COOlC3H7 1-2140 Ci C1 H CF3 H OCH(CH3)COOCH2COOCH3 1-2141 C1 C1 H CF3 H OCH(CH3)COOCH2COOC2H5 1-2142 C1 C1 H CF3 H OCH(CH3)COOCH2COOlC3H7 1-2143 C1 C1 H CF3 H OCH(CH3)COOCH(CH3)COOCH3 1-2144 C1 C1 H CF3 H OCH(CH3)COOCH(CH3)COOC2H5 1-2145 C1 C1 H CF3 H OCH(CH3)COOCH(CH3)CO01C3H7 TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No.
1-2148 C1 Ci CH3 CF3 H OCH2COOCH2COO1C3H7 1-2149 C1 C1 CH3 CF3 H OCH2COOCH(CH3)COOCH3 1-2150 C1 C1 CH3 CF3 H OCH2COOCH(CH3)COOC2H5 1-2151 C1 C1 CH3 CF3 H OCH2COOCH(CH3)COOlC3H7 1-2152 C1 C1 CH3 CF3 H OCH(CH3)COOCH2COOCH3 1-2153 C1 C1 CH3 CF3 H OCH(CH3)COOCH2COOC2H5 1-2154 C1 C1 CH3 CF3 H OCH(CH3)COOCH2COOlC3H7 1-2155 C1 C1 CH3 CF3 H OCH(CH3)COOCH(CH3)COOCH3 1-2156 C1 Cl CH3 CF3 H OCH(CH3)COOCH(CH3)COOC2H5 1-2157 Cl Cl CH3 CF3 H OCH(CH3)COOCH(CH3)COO1C3H7 Compounds of the formula:
X R'-Zi ~ ~ N R' (R4 - - N-' nN 3 O Rs R
Compound X Z' n R 3 R' R Z R' R 5 No.
2 - 1 H 0 1 H CF2 Cl CH3 H H
2 - 2 H 0 1 H CF2 C1 CHa H CH3 2 - 3 H' 0 1 H CF2 C1 CH3 H C 2 H 5 2 - 4 H 0 1 H CFZ C1 CH3 H "C 3 H, 2- 5 H 0 1 H CFz C1 CH3 H 'C a H 7 2- 6 H 0 1 H CF2 C1 CH3 H 'C , H 9 2-7 H 0 1 H CFZ C1 CH3 H C , H fl 2 - 9 H 0 1 H CF2.C1 CH3 H CH2 CHZ Br 2-10 H 0 1 H CF2 C1 CH3 H CH2 CH=CH2 2- 11 H 0 1 H CF2 Cl CH3 H CH(CH a)CH = CH2 2- 12 H 0 1 H CF2 Cl CHa H CH2 CC1 = CH2 2-13 H 0 1 H CF2 Cl CH3 H CH2 C=CH
2-14 H 0 1 H CF2 Cl CH3 H CH(CH a)C=CH.
TABLE 2 (contn'd) Compound X Z' n R3 R' R2 R' No. R5 2.- 15 H 0 1 H CF2 Cl CH3 H CH2 CN
2 -16 H 0 1 H-- CF2 Cl CH3 H CH2 OCH 3 2 -17 H 0 1 H CF2 Cl CH3 H CH2 0C2 H;
2 -18 H 0 1 H CF2 Cl CH3 H CH2 COOH
2 -19 H 0 1 H CF2 Cl CH3 H CH2 COOCH 3 2 -20 H 0 1 H CF2 Cl CH3 H CH2 COOCz H s 2 -21 H 0 1 H CF2 Cl CH3 H CH2 C00 " C 3 H
2 -22 H 0 1 H CF2 Cl CH3 H CH2 COO " C, H
2- 23 H 0 1 H CF2 Cl CH3 H CH2 C00 " C S H õ
2- 24 H 0 1 H CFa C1 CH3 H CHz C00 ' C 3 H, 2- 25 H 0 1 H CF2 Cl CH3 H CHz C00 ' C s H 9 2- 26 H 0 1 H CFz Cl CH3 H CHa C00 ' C 6 H õ
2 -27 H 0 1 H CF2 Cl CH3 H CH(CH 3)COOH
2 -28 H 0 1 H CF2 Cl CH3 H CH(CH 3)COOCH 3 2 -29 H 0 1 H CF2 Cl CH3 H CH(CH 3)COOC 2 H 5 2 -30 H 0 1 H CF2 Cl CH3 H CH(CH3 )CO0 C 3 H;
2 -31 H 0 1 H CF2 Cl CH3 H CH(CH3 )C00 C 4 H
2 -32 H 0 1 H CF2 Cl CH3 H CH(CH3 )C00" C s H
2 -33 H 0 1 H CF2 Cl CH3 H CH(CH3 )COO' C a H
2 -34 H 0 1 H CF2 Cl CH3 H CH(CHA COO'CjH9 2 -35 H 0 1 H CF2 Cl CH3 H CH(CH3 )C00' C 6 H
2 -36 H 0 1 H CF2 Cl CH3 CH3 H
2 -37 H 0 1 H CF2 Cl CH3 CH3 CH3 TABLE 2 (contn'd) Compound. X Z' n R' R' R 2 R' R 5 No.
2 -38 H 0 1 H CF2 Cl CH3 CH3 C2 H s 2- 39 H 0 1 H CF2 Cl CH3 CH3 "C 3 H 7 2- 40 H 0 1 H CF2 Cl CH3 GH3 'C 3 H T
2- 41 H 0 1 H CF2 Cl CH3 CH3 'C , H 9 2 -42 H 0 1 H CF2 Cl CH3 CH3 C 4 H9 2 -43 H 0 1 H CF2 Cl CH3 CH3 CH2 CH=CH2 2 -44 H 0 1 H CF2 Cl CH3 CH3 CH(CH 3 )CH = CHZ
2 -45 H 0 1 H CF2 Cl CH3 CH3 CH2 C= CH
2-46 H 0 1 H CF2 Cl CH3 CH3 CH(CH 3)C= CH
2 -47 H 0 1 H CF2 Cl CH3 CH3 CH2 OCH a 2- 48 H 0 1 H CF2 Cl CH3 CH3 CH2 0C2 H s 2 -49 F 0 1 H CF2 Cl CH3 H H
2 -50 F 0 1 H CF2 Cl CH3 H CH3 2- 51 F 0 1 H CF2 Cl CH3 H C2 H s 2- 52 F 0 1 H CF2 Cl CH3 H nC 3 H 7 2- 53 F 0 1 H CF2 Cl CH3 H 'C a H 7 2 -54 F 0 1 H CF2 Cl CH3 H 'C 4 H o 2- 55 F 0 1 H CF2 Cl CH3 H C 4 H Q
2- 56 F 0 1 H CF2 Cl CH3 H CH2 CH2 Cl 2- 57 F 0 1 H CF2 Cl CH3 H CH2 CHz Br 2 -58 F 0 1 H CF2 Cl CH3 H CH2 CH= CH2 2 -59 F 0 1 H CF2 Cl CH3 H CH(CH 3)CH =CH2 2- 60 F 0 1 H CF2 Cl CH3 H CH2 CC1 = CH2 TABLE 2 (contn'd) compound X Z' 11 R a R' R2 R' R 5 = No.
2 -61 F 0 1 H CF2 Cl CH3 H CH2 C=CH
2 -62 F 0 1 H CF2 Cl -CH3 H CH(CH a)C=CH
2 -63 F 0 1 H CF2 C1 CH3 H CHz CN
2- 65 F 0 1 H CF2 C1 CH3 H CH2 0C2 H s 2 -66 F 0 1 H CF2 CI CH3 H CHz COOH
2 -67 F 0 1 H CF2 Cl CH3 H CHZ COOCH 3 2 -68 F 0 1 H CF2 C1 CH3 H 'CH2 COOC2 -H s 2- 69 F 0 1 H CFZ CI CH3 H CH2 C00 C a H 7 2- 70 F 0 1 H CF2 C1 CH3 H CH2 COO " C, H o 2- 71 F 0 1 H CF2 C1 CH3 H CH2 C00 " C 5 H
2- 72 F 0 1 H CF2 Cl CHa H CH2 C00 ' C a H 7 2- 73 F 0 1 H CF2 CI CHa H CH2 C00 ' C s H s 2- 74 F 0 1 H CF2 CI CH3 H CH2 C00 ' C 6 H õ
2 -75 F 0 1 H CF2 C1 CH3 H CH(CH 3 )COOH
2 -76 F 0 1 H CF2 Cl CH3 H CH(CH 3)COOCH
2 -77 F 0 1 H CF2 C1 CH3 H CH(CH 3)COOC 2 H 5 2- 78 F 0 1 H CF2 C1 CH3 H CH(CH3 )C00" C 3 H T
2 -79 F 0 1 H CF2 CI CH3 H CH(CH3 )C00" C 4 H g 2 -80 F 0 1 H CF2 Cl CH3 H CH(CH3 )CO0 C; H õ
2 -81 F 0 1 H CF2 C1 CH3 H CH(CH3 )COO' C 3 H 7 2 -82 F 0 1 H CF2 CI CH3 H CH(CH3 )C00' C 6 H n 2- 83 F 0 1 H CF2 C1 CH3 H CH(CH3 )C00' C 6 H õ
TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R4 R5 No.
2 -84 F 0 1 H CF2 Cl CH3 CH3 H
2 -85 F 0 1 H CF2 C1 CHa CH3 CH3 2 -86 F 0 1 H CF2 Cl CH3 CH3 C2 H s 2- 87 F 0 1 H CF2 C1 CH3 CH3 "C , H 7 2- 88 F 0 1 H CFz C1 CH3 CH3 'C 3 H 7 2 -89 F 0 1 H CF2 C1 CH3 CH3 'C 4 H s 2- 90 F 0 1 H CF2 Cl CHa CH3 "C 4 H 9 2 -91 F 0 1 H CF2 C1 CH3 CH3 CH2 CH=CH2 2- 92 F 0 1 H CF2 C1 CH3 CH3 CH(CH 3)CH = CHz 2-94 F 0 1 H CF2 C1 CH3 CH3 CH(CH 3)C CH
2- 95 F 0 1 H CF2 C1 CH3 CH3 CH2 OCH , 2 -96 F 0 1 H CF2 C1 CH3 CHs CH2 0C2 H s 2- 97 H S 0 H CF2 Cl CH3 - H
2 -98 H S 0 H CFZ Cl CH3 - CH3 2- 100 H S 0 H CF2 Cl CH3 - "C 3 H, 2- 101 H S 0 H CF2 Cl CH3 - "C , H 9 2- 102 H S 0 H CF2 Cl CHa - 'C a H7 2-103 H S 0 H CF2 C1 CH3 - 'C , H g 2- 105 H S 0 H CF2 C1 CH3 - CHZ CHZ Br WO 97/07104 PCT/.FP96/02311 TABLE 2 (contn'd) Compound X Z' n R 3 R' R Z R' R 5 No.
2-106 H S 0 H CF2 Cl CH3 - CH2 CH=CH2 2 -107 H S 0 H CF2 Cl -CH3 - CH(CH 3)CH = CHZ
2- 108 H S 0 H CF2 CI CH3 - CHz CCI = CH2 2- 109 H S 0 H CF2 Cl CH3 - CH2 C= CH
2 -110 H S 0 H CF2 C1 CH3 - CH(CH 3)C= CH
2- 111 H S 0 H CF2 C1 CH3 - CHz CN
2- 112 H S 0 H CF2 Cl CH3 - CHz OCH 3 2- 113 H S 0 H CF2 Cl CH3 - CHZ OCZ H s 2 -115 H S 0 H CF2 C1 CH3 - CHz COOCH 3 2 - 117 H S 0 H CF2 C1 CH3 - CHZ C00 " C 3 H, 2- 118 H S 0 H CF2 Cl CH3 - CH2 COO ' C, H 9 2- 119 H S 0 H CF2 C1 CH3 - CHZ COO C; H
2- 120 H S 0 H CF2 Cl CH3 - CHz COO ' C, H
2- 121 H S 0 H CF2 Cl CH3 - CHz C00 ' C s H s 2 -122 H S 0 H CF2 Cl CH3 - CHZ COO C C 6 H,i 2- 123 'H S 0 H CF2 Cl CH3 - CH(CH 3)COOH
2- 124 H S 0 H CF2 Cl CH3 - CH(CH 3)COOCH , = 2 -125 H S 0 H CF2 Cl CH3 - CH(CH 3)COOC 2 H s 2- 126 H S 0 H CF2 C1 CH3 - CH(CH3 )C00" C 3 H, 2- 127 H S 0 H CF2 Cl CH3 - CH(CH3 )C00" C 4 H 9 2 -128 H S 0 H CF2 Cl CH3 - CH(CH3 )C00" C 5 H 11 TABLE 2 fcontn'dl Compound X Z' n R3 R' R 2 R' RS
No.
2 -129 H S 0 H CF2 Cl CH3 - CH(CH3 )C00' C 3 H T
2- 130 H S 0 H CFZ C1 CH3 - CH(CH3 )C00' C 5 H 9 2- 131 H S 0 H CF2 C1 CH3 - CH(CH3 )C00' C s H õ
2 -132 F S 0 H CF2 Cl CH3 - H
2- 133 F S 0 H CF2 Cl CH3 - CH3 2- 134 F S 0 H CF2 Cl CH3 - C2 H 5 2- 135 F S 0 H CF2 Cl CH3 - nC 3 H7 2- 136 F S 0 H CF2 Cl CH3 - C 4 H 9 2- 137 F S 0 H CFa C1 CH3 - 'C 3 H T
2- 138 F S 0 H CF2 Cl CH3 - 'C 4 H s 2- 139 F S 0 H CF2 Cl CH3 - CH2 CH2 Cl 2 -140 F S 0 H CF2 Cl CH3 - CH2 CH2 Br 2 -141 F S 0 H CF2 Cl CH3 - CH2 CH=CH2 2 -142 F S 0 H CF2 C 1 Cli 3 - CH(CH 3) )CH = CH 2 2- 143 F S 0 H CF2 Cl CH3 - CH2 CCI =CH2 2- 144 F S 0 H CF2 Cl CH3 - CH2 C= CH
2-145 F S 0 H CF2 Cl CH3 - CH(CH 3)C=CH
2 -146 F S 0 H CF2 Cl CH3 - CH2 CN
2- 147 F S 0 H CF2 Cl CH3 - CH2 OCH 3 2- 148 F S 0 H CF2 Cl CH3 - CH2 OCz H 3 2- 150 F S 0 H CFa Cl CH3 - CH2 COOCH 3 2- 151 F S 0 H CF2 Cl CH3 - CH2 COOC2 H 5 TABLE 2 (contn'd) K
Compound X Z' n R 3 R' R2 R' R5 No.
2- 152 F S 0 H CF2 Cl CH3 - CH2 C00 " C a H7 2- 153 F S 0 H CF2 Cl CH3 -- CH2 C00 " C 4 H g 2- 154 F S 0 H CF2 Cl CH3 - CH2 C00 C s H õ
2- 155 F S 0 H CF2 Cl CH3 - CH2 COO C, H, 2- 156 F S 0. H CF2 Cl CH3 - CH2 COO ' C s H 9 2- 157 F S 0 H CF2 C1 CH3 - CH2 COO C C 6 H õ
2 -158 F S 0 H CF2 Cl CH3 - CH(CH 3)COOH
2- 159 F S 0 H CF2 Cl CH3 - CH(CH 3)COOCH 3 2- 160 F S 0 H CF2 Cl CH3 - CH(CH a)COOC 2 H 5 2- 161 F S 0 H CF2 Cl CH3 - CH(CH3 )C00" C, H 7 2- 162 F S 0 H CF2 Cl CH3 - CH(CH3 )C00" C 4 H 9 2 -163 F S 0 H CF2 Cl CH3 - CH(CH3 )C00 C 5 H,1 2- 164 F S 0 H CF2 Cl CH3 - CH(CH3 )C00' C, H 7 2- 165 F S 0 H CF2 Cl CH3 - CH(CH3 )C00' C; H g 2- 166 F S 0 H CF2 Cl CH3 - CH(CH3 )COOc C 6 H
2 -167 H 0 0 H CF2 Cl CH3 - H
2- 168 H 0 0 H CF2 Cl CH3 - CH3 2- 169 H 0 0 H CF2 Cl CH3 - C2 H s 2- 170 H 0 0 H CF2 Cl CH3 - "C 3 H 7 2- 171 H 0 0 H CF2 Cl CH3 - C , H s 2 -172 H 0 0 H CF2 Cl CH3 - 'C s H 7 2 -173 H 0 0 H CF2 Cl CH3 - 'C , H, 2-174 H 0 0 H CF2 Cl CH3 - CHa CH=CHz WO 97/07104 PC'T/JP96/02311 TABLE 2 (contn'd) Compound X Z' n R' R' R 2 R' R 5 No.
2 -175 H 0 0 H CF2 Cl CH3 - CH(CH 3)CH =CH2 2 -176 H 0 0 H CF2 Cl CH3 - 'CHa C=CH
2 -177 H 0 0 H CF2 Cl CH3 - CH(CH 3)C CH
2 -178 H 0 0 H CF2 Cl CH3 - CH2 OCH 3 2 -179 H 0 0 H CFz Cl CH3 - CHz 'OCz H s 2 -180 F 0 0 H CF2 Cl CH3 - H
2 -181 F 0 0 H CF2 Cl CH3 - CH3 2- 183 F 0 0 H CF2 Cl CH3 - "C a H7 2 -184 F 0 0 H CF2 Cl CH3 - "C 4 H g 2 -185 F 0 0 H CF2 Cl CH3 - CH2 CH=CH2 2 -186 F 0 0 H CF2 Cl CH3 - CH(CH 3)CH =CH2 2- 187 F 0 0 H CF2 Cl CH3 - CH 2 C= CH
2 -188 F 0 0 H CF2 C1 CH3 - CH(CH 3)C=CH
2 -189 F 0 0 H CF2 Cl CH3 - CH2 OCH 3 2 -190 F 0 0 H CF2 Cl CH3 - CHz OCa H s 2- 194 H 0 1 H CF3 CH3 H "C 3 H, 2 -195 H 0 1 H CF3 CH3 H 'C 3 H 7 2- 196 H 0 1 H CF3 CH3 H 'C 4 H 2 2- 197 H 0 1 H CF3 CH3 H "C 4 H 9 WO 97/07104 PCTJ,6P96102311 TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R4 R 5 No.
2- 198 H 0 1 H CF3 CH3 H CH2 CH2 Cl 2- 199 H 0 1 H CF3 -CH3 H CH2 CHa Br 2 -200 H 0 1 H CF3 CH3 H CHZ CH=CH2 2 -201 H 0 1 H CF3 CH3 H CH(CH 3)CH = CH2 2 -202 H 0 1 H CF3 CH3 H CH2 CC1 =CH2 2 -203 H 0 1 H CF3 CH3 H CH2 C=CH
2 -204 H 0 1 H CF3 CH3 H CH(CH 3)C=CH
2 -205 H 0 1 H CF3 CH3 H CHz CN
2 -206 H 0 1 H CF3 CH3 H CHz OCH 3 2 -209 H 0 1 H CF3 CHa H CH2 COOCH 3 2 -211 H 0 1 H CF3 CH3 H CH2 C00 " C 3 H 7 2 -212 H 0 1 H CF3 CH3 H CH2 COO " C, H 9 2- 213 H 0 1 H CF3 CH3 H CHZ COO " C 5 H õ
2- 214 H 0 1 H CF3 CH3 H CH2 C00 ' C 3 H 7 2- 215 H 0 1 H CF3 CH3 H CH2 C00 ' C s H Q
2 -216 H 0 1 H CF3 CH3 H CHz COO ' C 6 H õ
2 -217 H 0 1 H CF3 CH3 H CH(CH 3 )COOH
2 -218 H 0 1 H CF3 CH3 H CH(CH 3)COOCH 3 2 -219 H 0 1 H CF3 CH3 H CH(CH 3)COOC 2 H 5 WO 97/07104 PC'1'/JP96/02311 TABLE 2 (contn'd) Compound X Z' n R' R' R Z R' R 5 No.
2 -220 H 0 1 H CF3 CH3 H CH(CH3 )C00" C 3 H, 2- 221 H 0 1 H CF3 CH3 H CH(CH3 )C00" C, H 9 2 -222 H 0 1 H CF3 CH3 H CH(CH3 )C00" C; H õ
2 -223 H 0 1 H CF3 CH3 H CH(CH3 )C00' C 3 H7 2 -224 H 0 1 H CF3 CH3 H CH(CH3 )COOC C s H 9 2 -225 H 0 1 H CF3 CH3 H CH(CH3 )C00' C s H õ
2- 229 H 0 1 H CF3 CH3 CH3 "C 3 H, 2 -230 H 0 1 H CF3 CH3 CH3 'C 3 H 7 2 -231 H 0 1 H CF3 CH3 CH3 'C 4 H 9 2- 232 H 0 1 H CF3 CH3 CH3 "C < H 9 2 -233 H 0 1 H CF3 CH3 CH3 CH2 CH = CH2 2 -234 H 0 1 H CF3 CH3 CH3 CH(CH 3)CH = CHZ
2 -235 H 0 1 H CF3 CH3 CH3 CH2 C= CH
2 -236 H 0 1 H CF3 CH3 CH3 CH(CH 3)C=CH
2 -238 H 0 1 H CF3 CH3 CH3 CH2 0C2 H s 2 -241 F 0 1 H CF3 CH3 H C2 H 5 2- 242 F 0 1 H CF3 CH3' H "C 3 H, TABLE 2 (contn'd) Compound X Z' n R3 R' R Z R' R s No.
2 -243 F 0 1 H CFa CHa H 'C 3 H 7 2- 244 F 0 1 H CF3 CH3 H 'C 4 H g 2- 245 F 0 1 H CF3 CH3 H "C 4 H 9 2 -246 F 0 1 H CF3 CH3 H CHZ CH2 Cl 2 -247 F 0 1 H CF3 CH3 H CH2 CHz Br 2 -248 F 0 1 H CF3 CH3 H CH2 CH=CHa 2 -249 F 0 1 H CF3 CH3 H CH(CH 3)CH = CH2 2 -250 F 0 1 H CF3 CH3 H CHz CCl = CH2 2 -251 F 0 1 H CF3 CH3 H CH2 C=CH
2 -252 F 0 1 H CF3 CH3 H CH(CH 3)C=CH
2 -258 F 0 1 H CF3 CH3 H CHz COOC2 H s 2 -259 F 0 1 H CF3 CH3 H CH2 C00 " C 3 H7 2 -260 F 0 1 H CF3 CH3 H CH2 C00 " C 4 H o 2 -261 F 0 1 H CF3 CH3 H CH2 C00 " C s H õ
2 -262 F 0 1 H CF3 CH3 H CH2 COO ' C a H 7 2 -263 F 0 1 H CF3 CH3 H CH2 COO C C 6 H s 2 -264 F 0 1 H CF3 CH3 H CH2 COO ' C 6 H õ
2 -265 F 0 1 H CF3 CH3 H CH(CH 3)COOH
TABLE 2 (contn'd) Compound. X Z' n R 3 R' R 2 R' R s No.
2 -266 F 0 1 H CFa CH3 H CH(CH 3)COOCH 3 2 -267 F 0 1 H CF3 CH3 H CH(CH 3)COOC 2 H;
2 -268 F 0 1 H CF3 CH3 H CH(CH3 )C00" C 3 H 7 2 -269 F 0 1 H CF3 CH3 H CH(CH3 )C00" C, H s 2 -270 F 0 1 H CF3 CH3 H CH(CH3 )C00" C s H 11 2- 271 F 0 1 H CF3 CH3 H CH(CH3 )C00' C 3 H 7 2 -272 F 0 1 H CF3 CH3 H CH(CH3 )C00' C; H 9 2 -273 F 0 1 H CF3 CH3 H CH(CH3 )C00' C 6 Hii 2 -275 F 0 1 H CFa CH3 CH3 CH3 2- 277 F 0 1 H CF3 CH3 CH3 "C 3 H 7 2 -278 F 0 1 H CF3 CH3 CH3 'C 3 H, 2- 279 F 0 1 H CF3 CH3 CH3 'C , H2 2- 280 F 0 1 H CF3 CH3 CH3 "C , H o 2 -281 F 0 1 H CF3 CH3 CH3 CHZ CH = CH2 2 -282 F 0 1 H CF3 CH3 CH3 CH(CH 3)CH = CHz 2 -283 F 0 1 H CF3 CH3 CH3 CHz C= CH
2 -284 F 0 1 H CF3 CH3 CH3 CH(CII 3)C=CH
2 -286 F 0 1 H CF3 CH3 CH3 CHz 0C2 H s TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R4 R 5 No.
2 -290 H S 0 H CF3 CH3 - "C 3 H 7 2- 291 H S 0 H CF3 CH3 - "C , H 9 2 -292 H S 0 H CF3 CH3 - C 3 H, 2 -293 H S 0 H CF3 CH3 - 'C 4 H 9 2 -295 H S 0 H CF3 CH3 - CH2 CH2 Br 2 -296 H S 0 H CF3 CH3 - CHz CH=CH2 2 -297 H S 0 H CF3 CH3 - CH(CH 3)CH =CH2 2 -298 H S 0.H CF3 CH3 - CH2 CC1 =CH2 2 -299 H S 0 H CF3 CH 3 - CH 2 C= CH
2 -300 H S 0 H CF3 CH3 - CH(CH 3)C=CH
2 -303 H S 0 H CF3 CH3 - CH2 0C2 H s 2 -306 H S 0 H CF3 CH3 - CH2 COOC2 H;
2 -307 H S 0 H CF3 CH3 - CHZ C00 " C 3 H 7 2 -308 H S 0 H CF3 CH3 - CH2 C00 " C, H
2 -309 H S 0 H CF3 CH3 - CH2 C00 " C 5 H
2 -311 H S 0 H CF3 CH3 - CH2 COO ' C b H
TABJLE 2 (contn'd) ;
Compound X Z' n R 3 R' R~ R' R S
No.
2 -312 H S 0 H CF3 CH3 - CH2 COO c C s H õ
2 -313 H S 0 H CF3 CH, - -CH(CH 3 )COOH
2 -314 H S 0 H CF3 CH3 - CH(CH a)COOCH a 2 -315 H S 0 H CF3 CH3 - CH(CH3 )COOC 2 H s 2- 316 H S 0 H CF3 CH3 - CH(CH3 )C00" C a H 7 2- 317 H S 0 H CF3 CH3 - CH(CH3 )C00" C 4 H 9 2 -318 H S 0 H CF3 CH3 - CH(CH3 )C00" C s H õ
2- 319 H S 0 H CF3 CH3 - CH(CH3 )C00' C 3 H 7 2 -320 H S 0 H CF3 CH3 - CH(CH3 )C00' C 5 H 9 2 -321 H S 0 H CF3 CH3 - CH(CH3 )C00' C 6 H
2- 326 F S 0 H CF3 CH3 - C , H fl 2 -327 F S 0 H CF3 CH3 - 'C 3 H, 2- 328 F S 0 H CF3 CH3 - SC 4 H s 2 -330 F S 0 H CF3 CH3 - CH2 CH2 Br 2 -331 F S 0 H CF3 CH3 - CH2 CH=CH2 2 -332 F S 0 H CF3 CH3 - CH(CH 3)CH =CH2 2 -333 F S 0 H CF3 CH3 - CH2 CC1 = CH2 TABLE 2 (contn'd) Compound X Z' n R3 R' R 2 R' R 5 No.
2 -334 F S 0 H CF3 CH3 - CH2 C=CH
2 -335 F S 0 H CF3 CH3 - CH(CH 3)C=CH
2 -338 F S 0 H CF3 CH3 - CH2 0C2 H s 2 -340 F S 0 H CF3 CH3 - CH2 COOCH , 2 -342 F S 0 H CF3 CH3 - CH2 C00 " C, H 7 2 -343 F S 0 H CF3 CH3 - CH2 C00 " C 4 H 9 2 -344 F S 0 H CF3 CH3 - CH2 C00 " C S H õ
2- 345 F S 0 H CF3 CH3 - CH2 COO ' C, H, 2 -346 F S 0 H CF3 CH3 - CH2 COO ' C s H 9 2 -347 F S 0 H CF3 CH3 - CH2 COO ' C 6 H
2 -348 F S 0 H CF3 CH3 - CH(CH 3)COOH
2 -349 F S 0 H CF3 CH3 - CH(CH 3)COOCH 3 2 -350 F S 0 H CF3 CH3 - CH(CH3 )COOC 2 H;
2 -351 F S 0 H CF3 CH3 - CH(CH3 )C00" C 3 H, 2 -352 F S 0 H CF3 CH3 - CH(CH3 )C00" C 4 H g 2 -353 F S 0 H CF3 CH3 - CH(CH3 )CQO" C s H õ
2 -354 F S 0 H CF3 CH3 - CH(CH3 )C00' C, H, 2 -355 F S 0 H CF3 CH3 - CH(CH3 )COQ' C s H fl 2- 356 F S 0 H CF3 CH3 - CH(CH3 )C00' C 6 H i TABLE 2 (contn'd) compound X Z' n R 3 R' R 2 R' R 5 No.
2 -360 H 0 0 H CF3 CH3 - "C 3 H 7 2 -361 H 0 0 H CF3 CH3 - C , H s 2 -363 H 0 0 H CF3 CH3 - C , H s 2 -364 H 0 0 H CF3 CH3 - CH2 CH=CHa 2 -365 H 0 0 H CF3 CH3 - CH(CH 3)CH = CHz 2 -366 H 0 0 H CF3 CH3 - CHz C=CH
2 -367 H 0 0 H CF3 CH3 - CH(CH 3)C=CH
2- 373 F 0 0 H CF3 CH3 - "C 3 H 7 2- 374 F 0 0 H CF3 CH3 - "C , H 9 2 -375 F 0 0 H CF3 CH3 - CH2 CH=CH2 2 -376 F 0 0 H CF3 CH3 - CH(CH 3)CH = CH2 2 -377 F 0 0 H CF3 CH 3 - CH2 C= CH
2 -378 F 0 0 H CF3 CH3 - CH(CH a)C=CH
2 -379 F 0 0 H CF3 CH3 - CHz OCH s TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R4 R g No.
2 -381 H 0 1 H CF2 Cl H H H
2 -382 H 0 1 H CF2 Cl H H CH3 2- 383 H 0 1 H CF2 Cl H H CZ H s 2 - 384 H 0 1 H CF2 C l H H C 3 H, 2-385 H 0 1 H CF2C1 H H 'C3H, 2-386 H 0 1 I1 CF2 Cl H H C , H
2 -387 H 0 1 H CF2 Cl H H "C , H 9 2- 388 H 0 1 H CF2 Cl H H CH2 CH2 Cl 2 -389 H 0 1 H CF2 Cl H H CH2 CH2 Br 2 -390 H 0 1 H CF2 Cl H H CH2 CH=CH2 2- 391 H 0 1 H CF2 Cl H H CH(CH 3)CH =CH2 2- 392 H 0 1 H CF2 Cl H H CH2 CC1 =CH2 2 -393 H 0 1 H CF2 Cl H H CH2 C=CH
2 -394 H 0 1 H CF2 Cl H H CH(CH 3)C=CH
2 -395 H 0 1 H CF2 Cl H H CH2 CN
2 -396 H 0 1 H CF2 Cl H H CH2 OCH , 2- 397 H 0 1 H CF2 Cl H H CH2 0C2 H s 2 -398 H 0 1 H CF2 Cl H H CHZ COOH
2 -399 H 0 1 H CF2 Cl H H CHz COOCH 3 2 -400 H 0 1 H CF2 Cl H H CH2 COOC2 H 5 2 - 401 H 0 1 H CF2 C1 H H CHz C00 " C a H, 2 - 402 H 0 1 H CF2 C1 H H CH2 C00 " C4 H 9 TABLE 2 (contn'd) compound X Z' n R3 R' R 2 R' RS
No.
2 -403 H 0 1 H CF2 Cl H H CH2 C00 " C 5 H õ
2 - 404 H 0 1 H CFz C1 H H CH2 C00 ' C 3 H, 2- 405 H 0 1 H CFz C1 H H CHz C00 ' C s H s 2 -406 H 0 1 H CFz Cl H H CH2 COO c C 6 H
2 -407 H 0 1 H CF2 C 1 H H CH(CH 3) )COOH
2 -408 H 0 1 H CF2 Cl H H CH(CH 3 )COOCH
2 -409 H 0 1 H CF2 Cl H H CH(CH 3)COOC 2 H;
2- 410 H 0 1 H CF2 Cl H H CH(CH3 )C00" C3 H 7 2- 411 H 0 1 H CF2 Cl H H CH(CH3 )C00" C 4 H 9 2 -412 H 0 1 H CF2 Cl H H CH(CH3 )C00" C 5 H õ
2- 413 H 0 1 H CF2 Cl H H CH(CH3 )C00' C a H 7 2 - 414 H 0 1 H CF2 C l H H CH ( CH3 ) Coo'C5SHg 2 -415 H 0 1 H CF2 Cl H H CH(CH3 )COOC C 6 H õ
2 -416 H 0 1 H CF2 Cl H CH3 H
2 -417 H 0 1 H CF2 Cl H CH3 CH3 2- 418 H 0 1 H CF2 Cl H CH3 C2 H s 2- 419 H 0 1 H CF2 Cl H CH3 "C 3 H 7 2- 420 H 0 1 H CF2 Cl H CH3 'C a H 7 2 -421 H 0 1 H CF2 Cl H CH3 'C 4 H o 2- 422 H 0 1 H CF2 Cl H CH3 "C 4 H o 2 -423 H 0 1 H CF2 Cl H CH3 CH2 CH=CH2 2 -424 H 0 1 H CF2 Cl H CH3 CH(CH a)CH =CH2 2 -425 H 0 1 H CF2 Cl H CH3 CH2 C= CH
TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R' R 5 No.
2 -426 H 0 1 H CF2 Cl H CH3 CH(CH 3)C=CH
2 -427 H 0 1 H CF2 Cl H CH3 CH2 OCH , 2 -428 H 0 1 H CFZ Cl H CH3 CH2 OC2 H 5 2 -429 F 0 1 H CF2 Cl H H H
2 -430 F 0 1 H CF2 Cl H H CH3 2- 431 F 0 1 H CF2 Cl H H C2 H s 2- 432 F 0 1 H CF2 Ci H H "C 3 H, 2 - 433 F 0 1 H CF2 Cl H H 'C 3 H, 2- 434 F 0 1 H CF2 Cl H H 'C , H 9 2 -435 F 0 1 H CF2 Cl H H "C , H 9 2 -436 F 0 1 H CF2 Cl H H CHZ CH2 C1 2- 437 F 0 1 H CF2 Cl H H CH2 CH2 Br 2 -438 F 0 1 H CF2 Cl H H CH2 CH=CH2 2 -439 F 0 1 H CF2 Cl H H CH(CH 3)CH =CH2 2- 440 F 0 1 H CF2 Cl H H CH2 CCl =CH2 2 -441 F 0 1 H CF2 Cl H H CH2 CCH
2 -442 F 0 1 H CF2 Cl H H CH(CH )C=CH
2 -443 F 0 1 H CF2 Cl H H CH2 CN
2 -444 F 0 1 H CF2 Cl H H CH2 OCH 3 2 -445 F 0 1 H CF2 Cl H H CH2 OCZ H 5 2 -446 F 0 1 H CF2 Cl H H CH2 COOH
2 -447 F 0 1 H CF2 Cl H H CH2 COOCH 3 TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R' R 5 No.
2 -448 F 0 1 H CF2 Cl H H CH2 COOC2 H s 2-449 F 0 1 H CF2 Cl - H H CH2 C00 " C 3 H;
2 - 450 F O 1 H CFZ C1 H H CH2 C00 C, H 9 2 -451 F 0 1 H CF2 Cl H H CH2 C00 " C s H õ
2-452 F 0 1 H CF2 C l H H CHZ C00 ' C 3 H, 2- 453 F 0 1 H CFa Cl H H CH2 C00 ' C s H 9 2 -454 F 0 1 H CF2 Cl H H CH2 COO C C 6 H õ
2 -455 F 0 1 H CF2 Cl H H CH(CH a)COOH
2 -456 F 0 1 H CF2 Cl H H CH(CH 3 )COOCH , 2 -457 F 0 1 H CF2 Cl H H CH(CH 3)COOC 2 H s 2 -458 F 0 1 H CF2 Cl H H CH(CH3 )C00 C 3 H, 2 -459 F 0 1 H CF2 Cl H H CH(CH3 )C00" C, H o 2 -460 F 0 1 H CF2 Cl H H CH(CH3 )C00" C 5 H õ
2- 461 F 0 1 H CF2 Cl H H CH(CH3 )C00' C 3 H, 2 -462 F 0 1 H CF2 Cl H H CH(CH3 )COOc C 5 H 9 2 -463 F 0 1 H CF2 Cl H H CH(CH3 )C00' C 6 H õ
2 -464 F 0 1 H CF2 Cl H CH3 H
2 -465 F 0 1 H CF2 Cl H CH3 CH3 2- 466 F 0 1 H CF2 Cl H CH3 C2 H s 2-467 F 0 1 H CF2 Cl H CH3 C 3 H 7 2 -468 F 0 1 H CF2 C1 H CH3 'C , H, 2-469 F 0 1 H CF2 Cl H CH3 'C 4 H 9 2- 470 F 0 1 H CF2 Cl H CH3 C 4 H 9 TABLE 2 (contn'd) Compound X Z' n R' R' R 2 No. R' R
2 -471 F 0 1 H CF2 Cl H CH3 CH2 CH=CH2 2- 472 F 0 1 H CF2 Cl H CH3 CH(CH 3)CH = CH2 2- 473 F 0 1 H CF2 Cl H CH3 CH2 C= CH
2 -474 F 0 1 H CF2 Cl H CHa CH(CH s)C=CH
2 -475 F 0 1 H CF2 Cl H CH3 CH2 OCH 3 2- 476 F 0 1 H CFZ Cl H CH3 CH2 0C2 H 5 2 -477 H S 0 H CF2 Cl H - H
2 -478 H S 0 H CF2 Cl H - CH3 2- 479 H S 0 H CF2 Cl H - C 2 H s 2- 480 H S 0 H CFZ Cl H - "C 3 H 7 2 -481 H S 0 H CF2 Cl H - "C , H 9 2 -482 H S 0 H CF2 Cl H - 'C s H 7 2-483 H S 0 I-I CF2 Cl H - 'C 4 H
2- 484 H S 0 H CF2 Cl H - CH2 CH2 Cl 2 -485 H S 0 H CF2 Cl H - CH2 CH2 Br 2 -486 H S 0 H CF2 Cl H - CH2 CH=CH2 2 -487 H S 0 H CF2 Cl H - CH(CH 3)CH =CH2 2- 488 H S 0 H CF2 C1 H - CH2 CC1 = CH2 2-489 H S 0 H CF2 Cl H - CH2 C=CH
2 -490 H S 0 H CF2 Cl H - CH(CH 3)C=CH
2 -492 H S 0 H CF2 Cl H - CH2 OCH 3 2 -493 H S 0 H CF2 Cl H - CH2 0C2 H 5 TABLE 2 (contn'd) compound X Z' n R 3 R' R 2 R' R 5 No.
2 -494 H S 0 H CF2 Cl H - CH2 COOH
2 -495 H S 0 H CF2 Cl H - CH2 COOCH , 2 -496 H S 0 H CF2 Cl H - CH2 COOC2 H s 2 - 497 H S 0 H CFZ C1 H - CHz C00 " C, H, 2 - 498 H S 0 H CF2 C l H - CHZ C00 " C, H 9 2- 499 H S 0 H CF2 C1 H - CH2 C00 " C 5 H õ
2 -500 H S 0 H CF2 C1 H - CH2 COO ' C 3 H7 2 -501 H S 0 H CF2 C1 H - CH2 COO C C s H 9 2- 502 H S 0 H CF2 C1 H - CH2 C00 ' C 6 H õ
2 -503 H S 0 H CF2 C1 H - CH(CH ,)COOH
2 -504 H S 0 H CF2 C1 H - CH(CH 3 )COOCH 3 2 -505 H S 0 H CF2 C1 H - CH(CH 3)COOC 2 H 5 2 -506 H S 0 H CF2 Cl H - CH(CH3 )C00" C a H, 2 -507 H S 0 H CF2 C1 H - CH(CH3 )C00" C, H s 2 -508 H S 0 H CF2 C1 H - CH(CH3 )C00" C 5 H õ
2- 509 H S 0 H CF2 C1 H - CH(CH3 )C00' C 3 H, 2- 510 H S 0 H CF2 Cl H - CH(CH3 )C00' C; H 9 2 -511 H S 0 H CF2 Cl H - CH(CH3 )C00' C 6 H õ
2 -512 F S 0 H CF2 Cl H - H
2 -513 F S 0 H CF2 Cl H - CH3 2 -514 F S 0 H CF2 Cl H - C2 H 5 2- 515 F S 0 H CFZ Cl H - C , H, 2- 516 F S 0 H CF2 Cl H - "C , H 9 TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R' R S
No.
2 - 517 F S 0 H CF2 C1 H - C 3 H, 2 -518 F S 0 H CF2 Cl H - 'C-, H 9 2- 519 F S 0 H CF2 Cl H - CH2 CH2 Cl 2- 520 F S 0 H CF2 Cl H - CHz CH2 Br 2 -521 F S 0 H CF2 Cl H - CH2 CH=CH2 2 -522 F S 0 H CF2 Cl H - CH(CH 3 )CH = CH2 2- 523 F S 0 H CF2 Cl H - CH2 CCl = CH2 2 -524 F S 0 H CF2 C l H - CH 2 C CH
2-525 F S 0 H CF2 Cl H - CH(CH a)C=CH
2 -526 F S 0 H CF2 Cl H - CH2 CN
2 -527 F S 0 H CF2 Cl H - CH2 OCH
2- 528 F S 0 H CF2 Cl H - CH2 0C2 H s 2 -529 F S 0 H CF2 Cl H - CH2 COOH
2 -530 F S 0 H CF2 Cl H - CH2 COOCH 3 2 -531 F S 0 H CF2 Cl H - CH2 COOC2 H 5 2 -532 F S 0 H CF2 Cl H - CH2 COO C 3 H, 2 -533 F S 0 H CF2 Cl H - CH2 COO C H
2- 534 F S 0 H CF2 Cl H - CH2 COO " C H
2 -535 F S 0 H CF2 Cl H - CH2 COO ' C a H
2 -536 F S 0 H CF2 Cl H - CHz COO ' C s H 9 2 -537 F S 0 H CF2 Cl H - CH2 COO ' C 6 H
2 -538 F S 0 H CF2 Cl H - CH(CH 3 )COOH
2 -539 F S 0 H CF2 Cl H - CH(CH 3 )COOCH 3 TABLE 2 (contn'd) Compound X Z' n R' R' R 2 R' R 5 No.
2 -540 F S 0 H CF2 Cl H - CH(CH 3)COOC 2 H;
2 -541 F S 0 H CF2 Cl H - CH(CH3 )C00" C 3 H 7 2 -542 F S 0 H CF2 Cl H - CH(CH3 )C00" C, H s 2 -543 F S 0 H CF2 Cl H - CH(CH3 )C00" C; H i, 2 -544 F S 0 H CF2 Cl H - CH(CH3 )C00' C a H 7 2 -545 F S 0 H CF2 Cl H - CH(CH3 )C00' C s H 9 2 -546 F S 0 H CF2 Cl H - CH(CH3 )C00' C 6 H õ
2 -547 H 0 0 H CF2 Cl H - H
2 -548 H 0 0 H CF2 Cl H - CH3 2- 549 H 0 0 H CF2 Cl H - C 2 H s 2 -550 H 0 0 H CF2 Cl H - "C 3 H, 2- 551 H 0 0 H CF2 Cl H - "C 4 H s 2 - 552 H 0 0 H CF2 Cl H - 'C , H, 2 -553 H 0 0 H CF2 Cl H - 'C 4 H fl 2 -554 H 0 0 H CF2 Cl H - CH2 CH=CHZ
2 -555 H 0 0 H CF2 Cl H - CH(CH 3)CH =CH2 2 -556 H 0 0 H CF2 Cl H - CH2 C=CH
2-557 H 0 0 H CF2 Cl H - CH(CH 3)C=CH
2 -558 H 0 0 H CF2 Cl H - CH2 OCH a 2- 559 H 0 0 H CF2 C1 H - CH2 0C2 H s 2- 560 F 0 0 H CF2 Cl H - H
TABLE 2 (contn'd) Compound X Z' n R 3 R' R Z R' R 5 No.
2- 562 F 0 0 H CF2 Cl H - C2 H s 2-563 F 0 0 H CF2 C1 -H - "C 3 H, 2- 564 F 0 0 H CFZ Cl H - "C , H 9 2 -565 F 0 0 H CF2 Cl H - CH2 CH=CH2 2 -566 F 0 0 H CF2 Cl H - CH(CH 3)CH = CH2 2 -567 F 0 0 H CF2 Cl H - CH2 C=CH
2 -568 F 0 0 H CF2 Cl H - CH(CH 3)C CH
2 -569 F 0 0 H CF2 Cl H - CH2 OCH , 2-570 F 0 0 H CF2 Cl H - CH2 0C2 H 5 2 -573 H 0 1 H CF3 H H C2 H s 2 -574 H 0 1 H CF3 H H "C a H
2- 575 H 0 1 H CF3 H H 'C 3 H, 2- 576 H 0 1 H CF3 H H 'C H 9 2-577 H 0 1 H CF3 H H "C t H 9 2 -578 H 0 1 H CF3 H H CH2 CH2 Cl 2 -579 H 0 1 H CF3 H H CH2 CH2 Br 2 -580 H 0 1 H CF3 H H CH2 CH=CH2 2- 581 H 0 1 H CF3 H H CH(CH 3)CH =CH2 2- 582 H 0 1 H CF3 H H CH2 CC1 = CHz 2 -583 H 0 1 H CF3 H H CH2 C= CH
2 -584 H 0 1 H CF 3 H H CH (CH 3) C= CH
TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R' R' No.
2 -587 H 0 1 H CF3 H H CH2 0C2 H s 2 -589 H 0 1 H CF3 H H CH2 COOCH , 2 -590 H 0 1 H CF3 H H CH2 COOC2 H;
2 -591 H 0 1 H CF3 H H CH2 C00 " C, H, 2 -592 H 0 1 H CF3 H H CH2 C00 " C 4 H s 2- 593 H 0 1 H CF3 H H CH2 COO C 5 H õ
2 -594 H 0 1 H CF3 H H CH2 COO ' C 3 H7 2 -595 H 0 1 H CF3 H H CH2 COO ' C s H 9 2 -596 H 0 1 H CF3 H H CH2 COO c C 6 H õ
2 -597 H 0 1 H CF3 H H CH(CH a)COOH
2 -598 H 0 1 H CF3 H H CH(CH a)COOCH 3 2 -599 H 0 1 H CF3 H H CH(CH 3)COOC 2 H s 2 -600 H 0 1 H CF3 H H CH(CH3 )COO' C 3 H 7 2- 601 H 0 1 H CF3 H H CH(CH3 )C00" C, H 9 2 -602 H 0 1 H CF3 H H CH(CH3 )C00" C 5 H õ
2 -603 H 0 1 H CF3 H H CH(CH3 )C00' C s H 7 2 -604 H 0 1 H CF3 H H CH(CH3 )COOC C s H 9 2 -605 H 0 1 H CF3 H H CH(CH3 )C00' C 6 H õ
TABLE 2 (contn'd) Compound X Z' n R' R' R 2 R~ R 5 No.
2 -608 H 0 1 H CF3 H CH3 C2 H s 2 -609 H 0 1 H CF3 H CH3 "C 3 H, 2 -610 H 0 1 H CF3 H CH3 'C 3 H, 2 -611 H 0 1 H CF3 H CH3 'C , H s 2- 612 H 0 1 H CF3 H CH3 nC , H q 2 -613 H 0 1 H CF3 H CH3 CH2 CH=CH2 2 -614 H 0 1 H CF3 H CH3 CH(CH s)CH = CHz 2 -616 H 0 1 H CF3 H CH3 CH(CH s)C=CH
2 -621 F 0 1 H CF3 H H C2 H s 2 -622 F 0 1 H CF3 H H "C 3 H, 2- 623 F 0 1 H CF3 H H 'C 3 H, 2 -624 F 0 1 H CF3 H H 'C , H 9 2 -625 F 0 1 H CF3 H H "C , H 9 2 -626 F 0 1 H CF3 H H CH2 CHZ Cl 2- 627 F 0 1 H CF3 H H CHz CH2 Br 2 -628 F 0 1 H CF3 H H CH2 CH=CH2 2 -629 F 0 1 H CF3 H H CH(CH 3)CH = CH2 2 -630 F 0 1 H CF3 H H CHZ CC1 = CH2 TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R' R s No.
2 -631 F 0 1 H CF3 H H CH Z C= CH
2 -632 F 0 1 H CF3 -H H CH(CH 3)C=CH
2 -635 F 0 1 H CF3 H H CH2 0CZ H s 2 -636 F 0 1 H CF3 H H CHz COOH
2 -637 F 0 1 H CF3 H H CHa COOCH 3 2 -638 F 0 1 H CF3 H H CHz COOC2 H s 2 -639 F 0 1 H CF3 H H CHz C00 " C, H, 2- 640 F 0 1 H CF3 H H CH2 C00 " C, H s 2- 641 F 0 1 H CF3 H H CHZ C00 " C s H õ
2 -642 F 0 1 H CF3 H H CH2 COO ' C, H, 2- 643 F 0 1 H CF3 H H CHz C00 ' C 5 H a 2 -644 F 0 1 H CF3 H H CH2 COO C C s H õ
2 -645 F 0 1 H CF3 H H CH(CH s)COOH
2 -646 F 0 1 H CF3 H H CH(CH 3)COOCH 3 2 -647 F 0 1 H CF3 H H CH(CH 3)COOC 2 H 5 2 -648 F 0 1 H CF3 H H CH(CH3 )C00" C 3 H, 2- 648 F 0 1 H CF3 H H CH(CH3 )C00" C, H o 2 -650 F 0 1 H CF3 H H CH(CH3 )C00" C s H t, 2 -651 F 0 1 H CF3 H H CH(CH3 )C00' C 3 H, 2 -652 F 0 1 H CF3 H H CH(CH3 )COOc C 5 H o 2 -653 F 0 1 H CF3 H H CH(CH3 )C00' C 6 H õ
TABLE 2 (contn'd) ~ Compound X Z' n R3 R' R2 R4 Rs No.
2 -656 F 0 1 H CF3 H CH3 C2 H;
2 -657 F 0 1 H CF3 H CH3 C a H7 2 -658 F 0 1 H CF3 H CH3 'C 3 H 7 2 -659 F 0 1 H CF3 H CH3 'C , H 9 2 -660 F 0 1 H CF3 H CH3 "C , H g 2 -661 F 0 1 H CF3 H CH3 CH2 CH=CH2 2 -662 F 0 1 H CF3 H CH3 CH(CH 3)CH =CH2 2 -664 F 0 1 H CF3 H CH3 CH(CH 3)C=CH
2 -665 F 0 1 H CF3 H CH3 CHz OCH , 2 -666 F 0 1 H CF3 H CH3 CH2 QCZ H;
2 -670 H S 0 H CF3 H - "C 3 H T
2- 671 H S 0 H CF3 H - "C 4 H 9 2 -672 H S 0 H CF3 H - C , H 7 2 -673 H S 0 H CF3 H - 'C , H
2 -674 H S 0 H CF3 H - CH2 CH2 Cl 2 -675 H S 0 H CF3 H - CH2 CH2 Br TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 No. R' R 5 2 -676 H S 0 H CF3 H - CH2 CH=CH2 2 -677 H S 0 H CF3 H - CH(CH 3)CH = CH2 2 -678 H S 0 H CF3 H - CHZ CCl = CH2 2 -679 H S 0 H CF3 H - CH 2 C= CH
2 -680 H S 0 H__CF3 H - CH(CH 3)C CH
2 -683 H S 0 H CF3 H - CH2 0C2 H;
2 -686 H S 0 H CF3 H - CH2 COOC2 H s 2 -687 H S 0 H CF3 H - CH2 C00 " C a H 7 2 -688 H S 0 H CF3 H - CHa COO " C 4 H 9 2 -689 H S 0 H CF3 H - CHZ C00 " C 5 H õ
2 -690 H S 0 H CF3 H - CH2 COO ' C 3 H7 2 -691 H S 0 H CF3 H - CHz COO ' C s H 9 2 -692 H S 0 H CF3 H - CHZ COO ' C 6 H õ
2 -693 H S 0 H CF3 H - CH(CH ,)COOH
2 -694 H S 0 H CF3 H - CH(CH 3 )COOCH , 2 -695 H S 0 H CF3 H - CH(CH3 )COOC 2 H 5 2 -696 H S 0 H CF3 H - CH(CH3 )C00" C 3 H 7 2 -697 H S 0 H CF3 H - CH(CH3 )C00" C, H 9 2 -698 H S 0 H CF3 H - CH(CH3 )C00" C 5 H õ
TABLE 2 (contn'd) :
Compound X
No. Z' n R 3 R' R Z R R
2 -699 H S 0 H CF3 H - CH(CH3 )C00' C 3 H 7 2 -700 H S 0 H CF3 H - CH(CH3 )C00' C; H 9 2 -701 H S 0 H CF3 H - CH(CH3 )C00' C 6 H õ
2 -704 F S 0 H CF3 H - C2 H s 2 - 705 F S 0 H CF3 H - C 3 H, 2- 706 F S 0 H CF3 H - C , H a 2 - 707 F S 0 H CF3 H - 'C 3 H, 2 -709 F S 0 H CF3 H - CH2 CH2 Cl 2 -710 F S 0 H CF3 H - CH2 CHZ Br 2 -711 F S 0 H CF3 H - CH2 CH=CH2 2 -712 F S 0 H CF3 H - CH(CH 3)CH = CH2 2 -713 F S 0 H CF3 H - CH2 CCI = CH2 2 -714 F S 0 H CF3 H - CH2 C=CH
2 -715 F S 0 H CF3 H - CH(CH 3)C=CH
= 2 -718 F S 0 H CF3 H - CH2 0C2 H s 2 -721 F S 0 H CF3 H - CHz COOC2 H s TABLE 2 (contn'd) Compound X Z' n R 3 R' R Z R' R 5 No.
2 - 722 F S 0 H CF3 H - CHZ C00 " C, H, 2- 723 F S 0 H CF3 H - CH2 C00 " C 4 H 9 2 -724 F S 0 H CF3 H - CH2 COO " C 5 H õ
2 -725 F S 0 H CF3 H - CH2 COO ' C, H 7 2- 726 F S 0 H CF3 H - CH2 C00 ' C s H 9 2 -727 F S 0 H CF3 H - CH2 COO C C 6 H õ
2 -728 F S 0 H CF3 H - CH(CH 3)COOH
2 -729 F S 0 H CF3 H - CH(CH 3)COOCH 3 2 -730 F S 0 H CF3 H - CH(CH3 )COOC 2 H 5 2- 731 F S 0 H CF3 H - CH(CH3 )C00" C 3 H7 2 -732 F S 0 H CF3 H - CH(CH3 )C00" C 4 H 9 2 -733 F S 0 H CF3 H - CH(CH3 )C00" C 5 H,i 2 -734 F S 0 H CF3 H - CH(CH3 )COO' C 3 H, 2 -735 F S 0 H CF3 H - CH(CH3 )COOc C a H 9 2 -736 F S 0 H CF3 H - CH(CH3 )C00' C 6 H õ
2 -739 H 0 0 H CF3 H - C2 H s 2- 740 H 0 0 H CF3 H - "C 3 H 7 2- 741 H 0 0 H CF3 H - "C , H 9 2 -742 H 0 0 H CF3 H - ' C 3 H, 2- 743 H 0 0 H CF3 H - 'C 4 H9 2 -744 H 0 0 H CF3 H - CH2 CH=CH2 TABLE 2 (contn'd) Compound X Z' n R' R' R z R' R s No.
2 -745 H 0 0 H CF3 H - CH(CH 3)CH =CH2 2 -746 H 0 0 H CF3 H - CH 2 C= CH
2 -747 H 0 0 H CF3 H - CH(CH 3)C=CH
2 -749 H 0 0 H CF3 H - CH2 0C2 H;
2 -753 F 0 0 H CF3 H - "C , H7 2 -754 F 0 0 H CF3 H - "C 4 H fl 2 -755 F 0 0 H CF3 H - CH2 CH=CH2 2 -756 F 0 0 H CF3 H - CH(CH 3)CH = CH2 2 -757 F 0 0 H CF3 H - CH2 C= CH
2 -758 F 0 0 H CF3 H - CH(CH 3)C=CH
2 -760 F 0 0 H CF3 H - CHz 0C2 H;
2 -763 H 0 1 CH3 CF3 H H C2 H s 2-764 H 0 1 CH3 CF3 H H "C a H 7 2 -765 H 0 1 CH3 CF3 H H 'C a H 7 2- 766 H 0 1 CHa CFa H H 'C 4 H s 2- 767 H 0 1 CH3 CF3 H H "C 4 H 9 TABLE 2 (contn'd) compound X Z' n R 3 R' R 2 R' R' No. 2 -768 H 0 1 CH3 CF3 H H CH2 CH2 Cl 2 -769 H O 1 CH3 CF3 H H CH2 CH2 Br 2 -770 H 0 1 CH3 CF3 H H CH2 CH = CH 2 2 -771 H 0 1 CH3 CF3 H H CH(CH 3)CH = CHZ
2 -772 H 0 1 CH3 CF3 H H CH2 CC1 =CH2 2 -773 H 0 1 CH3 CF3 H H CH2 C=CH
2 -774 H 0 1 CH3 CF3 H H CH(CH 3)C=CH
2 -777 H 0 1 CHa CF3 H H CH2 0C2 H s 2 -779 H 0 1 CH3 CF3 H H CH2 COOCH , 2 -780 H 0 1 CH3 CF3 H H CHz COOC2 H;
2- 781 H O 1 CH3 CF3 H H CH2 C00 " C 3 H 7 2 -782 H 0 1 CH3 CF3 H H CHZ C00 " C 4 H o 2 -783 H 0 1 CH3 CF3 H H CH2 C00 " C 5 H õ
2 -784 H 0 1 CHs CF3 H H CH2 COO ' C a H 7 2 -785 H 0 1 CHa CF3 H H CH2 COO ' C b H 9 2 -787 H 0 1 CH3 CF3 H H CH(CH 3)COOH
2 -788 H 0 1 CH3 CF3 H H CH(CH 3)COOCH 3 2 -789 H 0 1 CH3 CF3 H H CH(CH 3 )COOC 2 H s TABLE 2 (contn'd) Compound X Z' n R 3 R' R2 R' R 5 No.
2 -790 H 0 1 CH3 CF3 H H CH(CH3 )C00" C, H7 2 - 791 H 0 1 CH3 CF3 H H CH(CH3 )C00" C , H 9 2 -792 H 0 1 CH3 CF3 H H CH(CH3 )C00" C; H õ
2 -793 H 0 1 CH3 CF3 H H CH(CH3 )C00' C 3 H 7 2 -794 H 0 1 CH3 CF3 H H CH(CH, )C00' C 5 H g 2 -795 H 0 1 CH3 CF3 H H CH(CH3 )C00' C 6 H õ
2 -796 H 0 1 CHa CF3 H CH3 H
2 -797 H 0 1 CH3 CF3 H CHa CH3 2 -798 H 0 1 CH3 CF3 H CH3 C2 H s 2 -799 H 0 1 CH3 CF3 H CH3 C 3 H, 2 -800 H 0 1 CH3 CF3 H CH3 'C 3 H, 2- 801 H 0 1 CH3 CF3 H CH3 'C , H 9 2 -802 H 0 1 CH3 CF3 H CHa "C , H 9 2 -803 H 0 1 CH3 CF3 H CH3 CHZ CH = CH2 2 -804 H 0 1 CH3 CF3 H CH3 CH(CH a)CH = CH2 2 -805 H 0 1 CH3 CF3 H CH3 CH2 C= CH
2 -806 H 0 1 CH3 CF3 H CH3 CH(CH 3 )C=CH
2 -811 F 0 1 CH3 CF3 H H C2 H s 2-812 F 0 1 CH3 CF3 H H "C 3 H, TABLE 2 (contn'd) Compound X Z' n R' R' R 2 R' R5 No.
2- 813 F 0 1 CH3 CF3 H H 'C , H 7 2-814 F 0 1 CH3 CF3 H H 'C , H a 2- 815 F 0 1 CH3 CF3 H H "C , H 9 2 -816 F 0 1 CH3 CF3 H H CH2 CH2 Cl 2 -817 F 0 1 CH3 CF3 H H CH2 CH2 Br 2 -818 F 0 1 CH3 CF3 H H CH2 CH=CH2 2- 819 F 0 1 CH3 CF3 H H CH(CH 3)CH = CH2 2 -820 F 0 1 CH3 CF3 H H CH2 CCl =CH2 2 -821 F 0 1 CH3 CF3 H H CH2 C=CH
2 -822 F 0 1 CH3 CF3 H H CH(CH 3)C=CH
2 -824 F 0 1 CH3 CFa H H CHz OCH 3 2 -827 F 0 1 CH3 CF3 H H CHZ COOCH , 2- 828 F 0 1 CH3 CF3 H H CHz COOCz H s 2 -829 F 0 1 CH3 CF3 H H CH2 C00 " C, H 7 2 -830 F 0 1 CH3 CF3 H H CHZ COO " C4 H 9 2 -831 F 0 1 CH3 CF3 H H CH2 COO " C 5 H õ
2 -832 F 0 1 CH3 CF3 H H CHZ COO ' C, H r 2 -833 F 0 1 CH3 CF3 H H CH2 COO C C s H y 2 -835 F 0 1 CHa CF3 H H CH(CH 3)COOH
TABLE 2 (contn'd) F Compound X Z' n R3 R' R 2 R4 R 5 No.
2 -836 F 0 1 CH3 CF3 H H CH(CH 3 )COOCH
2 -837 F 0 1 CH3 CF3 H- H CH(CH 3)COOC 2 H;
2 -838 F 0 1 CH3 CF3 H H CH(CH3 )C00" C a H T
2 -839 F 0 1 CH3 CF3 H H CH(CH3 )C00" C4 H 9 2 -840 F 0 1 CH3 CF3 H H CH(CH3 )C00" C 5 H õ
2 -841 F 0 1 CH3 CF3 H H CH(CH, )C00' C, H
2 -842 F 0 1 CH3 CF3 H H CH(CH3 )C00' C 5 H
2 -843 F 0 1 CH3 CF3 H H CH(CH3 )COOc C o H 1, 2 -846 F 0 1 CH3 CF3 H CH3 C 2 H s 2- 847 F 0 1 CH3 CF3 H CH3 "C a H, 2- 848 F 0 1 CH3 CF3 H CHa 'C a H i 2 -849 F 0 1 CH3 CF3 H CH3 'C , H 9 2 -850 F 0 1 CH3 CF3 H CH3 "C 4 H 9 2 -851 F 0 1 CH3 CF3 H CH3 CH2 CH = CHz 2 -852 F 0 1 CH3 CF3 H CH3 CH(CH 3)CH = CH2 2 -853 F 0 1 CH3 CF3 H CHa CH2 C CH
2 -854 F 0 1 CH3 CF3 H CH3 CH(CH ,)C=CH
TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R' R 5 ~
No.
2- 860 H S 0 CH3 CF3 H -, "C 3 H, 2- 861 H S 0 CH3 CF3 H - "C 4 H 9 2 -862 H S 0 CH3 CF3 H 'C s H z 2 -863 H S 0 CH3 CF3 H 'C 4 H Q
2 -864 H S 0 CH3 CF3 H - CH2 CH2 Cl 2 -865 H S 0 CH3 CF3 H - CHZ CHZ Br 2 -866 H S 0 CH3 CF3 H - CH2 CH= CH2 2 -867 H S 0 CH3 CF3 H - CH(CH ,)CH = CHz 2 -868 H S 0 CH3 CF3 H - CH2 Ccl = CHz 2 -870 H S 0 CH3 CF3 H - CH(CH 3)C=CH
2 -873 H S 0 CH3 CF3 H - CH2 OC2 H s 2 -876 H S 0 CH3 CF3 H - CHz COOC2 H 5 2 -877 H S 0 CH3 CF3 H - CH2 C00 " C 3 H 7 2 -878 H S 0 CH3 CF3 H - CHz C00 " C 4 H 9 2 -879 H S 0 CH3 CF3 H - CH2 COO " C b H,i 2 -880 H S 0 CH3 CF3 H - CHz COO ' C3 H 7 WO 97/07104 PCT/Jl'96/02311 TABLE 2 (contn'd) Compound X Z' n R 3 R' R Z R' R s No.
2 -882 H S 0 CH3 CF3 H - CH2 COO C C 6 H õ
2- 883 H S 0 CH3 CF3 H - CH(CH 3)COOH
2 -884 H S 0 CH3 CF3 H - CH(CH 3)COOCH 3 2 -885 H S 0 CH3 CF3 H - CH(CH3 )COOC 2 H 5 2 -886 H S 0 CH3 CF3 H - CH(CH3 )C00" C 3 H 7 2 -887 H S 0 CH3 CF3 H - CH(CH3 )C00" C 4 H 9 2 -888 H S 0 CH3 CF3 H - CH(CH3 )CO0 C 5 H õ
2 -889 H S 0 CH3 CF3 H - CH(CH3 )COO' C 3 H 7 2 -890 H S 0 CH3 CF3 H - CH(CH3 )COOc C s H 9 2 -891 H S 0 CH3 CF3 H - CH(CH3 )COOc C 6 H õ
2- 895 F S 0 CH3 CF3 H - "C 3 H 7 2 -897 F S 0 CH3 CF3 H - 'C 3 H z 2 -899 F S 0 CH3 CF3 H - CH2 CH2 Cl 2 -900 F S 0 CH3 CF3 H - CH2 CH2 Br 2 -901 F S 0 CH3 CF3 H - CH2 CH= CH2 2 -902 F S 0 CH3 CF3 H - CH(CH 3)CH = CH2 Y =
2 -903 F S 0 CH3 CF3 H - CHZ CCl = CH2 TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R' R s No.
2-904 F S 0 CH3 CF3 H - CH2 C=CH
2 -905 F S 0 CH3 CF3 H - CH(CH 3)C=CH
2 -906 F S 0 CH3 CF3 H - CH 2. CN
2 -908 F S 0 CH3 CF3 H - CH2 0C2 H s 2 -911 F S 0 CH3 CF3 H - CHz COOC2 H;
2- 912 F S 0 CH3 CF3 H - CH2 C00 " C, H 7 2 -913 F S 0 CH3 CF3 H - CH2 C00 " C, H q 2 -914 F S 0 CH3 CF3 H - CH2 COO C s Hi, 2 -915 F S 0 CH3 CF3 H - CH2 COO ' C 3 H7 2- 916 F S 0 CH3 CF3 H - CH2 COO ' C s H 9 2 -917 F S 0 CH3 CF3 H - CH2 COO C C 6 H,1 2 -918 F S 0 CH3 CF3 H - CH(CH 3)COOH
2 -919 F S 0 CH3 CF3 H - CH(CH 3)COOCH 3 2- 920 F S 0 CH3 CF3 H - CH(CH3 )COOC 2 H s 2 -921 F S 0 CH3 CF3 H - CH(CH3 )C00" C, H 7 2 -922 F S 0 CH3 CF3 H - CH(CH3 )C00" C, H 9 2 -923 F S 0 CH3 CF3 H - CH(CH3 )C00" C s H õ
2 -924 F S 0 CH3 CF3 H - CH(CH3 )COO' C 3 H T
2 -925 F S 0 CH3 CF3 H - CH(CH3 )C00' C s H o 2 -926 F S 0 CH3 CF3 H - CH(CH3 )C00' C 6 H õ
TABLE 2 (contn'd) y Compound X Z' n R' R' R 2 R' R 5 No.
2 -929 H 0 0 CH3 CF3 H - C2 H s 2 -930 H 0 0 CH3 CF3 H - "C 3 H, 2 -932 H 0 0 CH3 CF3 H - 'C a H 1 2 -933 H 0 0 CH3 CF3 H - 'C , H a 2 -934 H 0 0 CH3 CF3 H - CH2 CH=CH2 2 -935 H 0 0 CH3 CF3 H - CH(CH 3)CH = CH2 2 -936 H 0 0 CHa CF3 H - CH2 C=CH
2 -937 H 0 0 CH3 CF3 H - CH(CH 3)C=CH
2 -938 H 0 0 CHa CF3 H - CHZ OCH a 2- 939 H 0 0 CH3 CF3 H - CH2 0C2 H;
2 -942 F 0 0 CH3 CF3 H - Cz H 5 2 -945 F 0 0 CH3 CF3 H - CH2 CH=CH2 2 -946 F 0 0 CH3 CF3 H - CH(CH 3)CH =CH2 2 -948 F 0 0 CH 3 CF 3 H - CH(CH 3 ) C= CH
TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R' R 5 No.
2 -950 F 0 0 CH3 CF3 H - CH2 0CZ H;
WO 97f07104 PCT'/JP96/023I I
Compounds of the formula:
X O R'-Y I N Rt N-Compound X y Z2 R3 R' R 2 I~ 6 No.
3 - 1 H F 0 H CF2 Cl H CH3 3 - 2 H Cl 0 H CF2 Cl H CH3 3 - 3 H Br 0 H CF2 C1 H CH3 3 - 4 F F 0 H CF2 Cl H CH3 3 - 5 F C1 0 H CF2 Cl H CH3 3- 6 F Br 0 H CFZ C1 H CH3 3 - 7 H F 0 H CF2 Cl CHa CH3 3 - 8 H C1 0 H CF2 Cl CHa CH3 3 - 9 H Br 0 H CF2 Cl CH3 CH3 3 -10 F F 0 H CF2 Cl CH3 CH3 3- 11 F C1 0 H CF2 Cl CH3 CH3 3 -12 F Br 0 H CF2 Cl CH3 CH3 3- 13 H F 0 H CF2 Cl H C2 H
3- 14 H C1 0 H CF2 Cl H C2 H s TABLE 3 (contn'd) Compound x Y Z 2 R3 R' R 2 R 6 No.
3 -15 H Br 0 H CF2 Cl H C2 H;
3- 16 F F 0 H CF2 Cl H C 2 H s 3 -17 F C1 0 H CF2 Cl H C2 H;
3- 18 F Br 0 H CF2 Cl H C2 H 5 3 -19 H F 0 H CF2 Cl CH3 C2 H;
3 -20 H C1 0 H CF2 Cl CH3 C2 H s 3 -21 H Br 0 H CF2 Cl CH3 C2 H s 3 -22 F F 0 H CFa Cl CH3 C2 H s 3 -23 F C1 0 H CF2 Cl CH3 C2 H;
3 -24 F Br 0 H CF2 Cl CH3 C2 H s 3 -25 H F 0 H CF2 Cl CH3 CH2 Br 3 -26 H F 0 H CF2 Cl CH3 CH Br2 3 -27 H F 0 H CF2 Cl CH3 CBr 3 3 -28 H F 0 H CF2 Cl CH3 CHO
3 -29 H F 0 H CF2 Cl CH3 CN
3 -30 H F 0 H CF2 Cl CH3 COOH
3 -31 H F 0 H CF2 Cl CH3 CH2 OH
3 -32 H F 0 H CF2 Cl CH3 CH2 OCH 3 3- 33 H F 0 H CF2 Cl CH3 CH2 0C2 H 5 3 -34 H F 0 H CF2 Cl CH3 CH2 0' C a H;
3 -35 H F 0 H CF2 Cl CH3 CH2 OCH 2 OCH 3 3 -36 H F 0 H CF2 Cl CH3 CH2 OCH 2 0C2 H s 3 -37 H F 0 H CF2 Cl CHa CHa OCOCH 3 TABLE 3 (contn'd) Compound x Y Z 2 R' R' R 2 R 6 No.
3 -38 H F 0 H CF2 Cl CH3 CH2 OCOC2 H 5 3 -39 H F 0 H CF2 Cl CH3 CH2 OCO ' C 3 H
3 -40 H F 0 H CF2 Cl CH3 CH2 OCOCH 2 Cl 3- 41 H F 0 H CF2 Cl CH3 CH2 OCOCC13 3 -42 H F 0 H CF2 Cl CH3 CH2 OCOCF 3 3 -43 H F 0 H CF2 Cl CH3 COOCH3 3 -44 H F 0 H CF2 Cl CH3 COOC2 H;
3- 45 H F 0 H CF2 C1 CH3 C00 " C 3 H 7 3 -46 H F 0 H CF2 Cl CH3 C00 " C 4 H 9 3 -47 H F 0 H CF2 Cl CH3 C00 " C; H
3- 48 H F 0 H CFz C1 CH3 C00 ' C 3 H 7 3- 49 H F 0 H CF2 Cl CH3 COCH3 3- 50 H F _O H CF2 Cl CH3 COCz H;
3 -51 H C1 0 H CF2 Cl CH3 CH2 Br 3 -52 H C1 0 H CF2 Cl CH3 CH Br2 3- 53 H Cl 0 H CF2 Cl CH3 CBr3 3- 54 H C1 0 H CF2 Cl CH3 CHO
3 -55 H C1 0 H CF2 Cl CH3 CN
3 -56 H C1 0 H CF2 Cl CH3 COOH
3 -57 H C1 0 H CF2 Cl CH3 CH2 OH
3- 58 H C1 0 H CF2 Cl CH3 CH2 OCH 3 3- 59 H Cl 0 H CF2 Cl CH3 CH2 0C2 H;
3 -60 H Cl 0 H CF2 Cl CH3 CH2 0' C 3 H
TABLE 3 (contn'd) Compound X Y Z2 R a R' R 2 R6 No.
3 -61 H C1 0 H CF2 Cl CHa CH2 OCH 2 OCH a 3 -62 H C1 0 H CF2 Cl CHa CH2 OCH 2 0C2 H s 3 -63 H C1 0 H CF2 Cl CH3 CH2 OCOCH 3 3- 64 H C1 0 H CF2 Cl CHa CH2 OCOC2 H s 3- 65 H C1 0 H CF2 Cl CHa CH2 OCO ' C a H7 3 -66 H Cl 0 H CF2 Cl CHa CH2 OCOCH 2 C1 3 -67 H C1 0 H CF2 Cl CHa CH2 OCOCCI3 3 -67 H C1 0 H CF2 Cl CH3 CHz OCOCF a 3 -69 H C1 0 H CF2 Cl CHs COOCH3 3 -70 H C1 0 H CF2 C1 CHa COOC2 H s 3-71 H C1 0 H CF2 CI CHa C00 " C a H 7 3 - 72 H C1 0 H CF2 C1 CHa C00 " C, H 9 3- 73 H C1 0 H CF2 Cl CH3 COO " C s H õ
3-74 H C1 0 H CF2 Cl CHa COO ' C a H 7 3 -75 H C1 0 H CF2 Cl CH3 COCH3 3 -76 H C1 0 H CF2 Cl CH3 COC2 H s 3 -77 F F 0 H CF2 Cl CHa CH2 Br 3 -78 F F 0 H CF2 Cl CHa CH Br2 3 -79 F F 0 H CF2 Cl CHa CBr3 3 -80 F F 0 H CF2 Cl CH3 CliO
3 -81 F F 0 H CF2 Cl CHa CN
3 -82 F F 0 H CF2 Cl CH3 COOH 3 -83 F F 0 H CF2 Cl CHa CHz OH
WO 97f07104 PCT/JP96/02311 TABLE 3 (contn'd) = Compound x Y Z 2 R 3 R' R 2 R 6 No.
3 -84 F F 0 H CF2 C1 CH3 CHz 0CH 3 3- 85 F F 0 H CF2 Cl CHa CH2 0C2 H s 3 -86 F F 0 H CF2 Cl CH3 CH2 0' C 3 H, 3 -87 F F 0 H CF2 Cl CH3 CH2 OCH 2 OCH a 3 -88 F F 0 H CF2 Cl CHI CH2 0CH 2 0C2 H s 3 -89 F F 0 H CF2 Cl CH3 CH2 OCOCH 3 3- 90 F F 0 H CF2 Cl CH3 CH2 OCOC2 H
3- 91 F F 0 H CFa C1 CHa CHz OCO ' C a H 7 3- 92 F F 0 H CF2 Cl CH3 CH2 OCOCH 2 Cl 3- 93 F F 0 H CF2 Cl CH3 CH2 OCOCCI3 3 -94 F F 0 H CF2 Cl CH3 CHz OCOCF 3 3 -95 F F 0 H CF2 Cl CH3 COOCH3 3 -96 F F 0 H CF2 Cl CH3 COOC2 H;
3 -97 F F 0 H CF2 Cl CH3 C00 " C 3 H
3 - 98 F F 0 H CF2 C 1 CH3 C00 C, H 9 3- 99 F F 0 H CF2 Cl CH3 COO " C s H
3 -100 F F 0 H CF2 Cl CH3 COO ' C, H, 3- 101 F F 0 H CF2 Cl CH3 COCH3 3- 102 F F 0 H CF2 Cl CHa COC2 H s 3 -103 F C1 0 H CF2 Cl CH3 CHZ Br 3- 104 F C1 0 H CF2 Cl CH3 CH Br2 3- 105 F C1 0 H CF2 Cl CH3 CBr3 TABLE 3 (contn'd) Compound x Z 2 R 3 R' R 2 R 6 No.
3 -106 F C1 0 H CF2 Cl CH3 CHO
3 -107 F C1 0 H CF2 Cl CH3 CN
3 -108 F C1 0 H CF2 Cl CH3 COOH
3 -109 F C1 0 H CF2 Cl CH3 CHZ OH
3 -110 F Ci 0 H CF2 Cl CH3 CH2 OCH , 3 -111 F Cl 0 H CF2 Cl CH3 CH2 0CZ H s 3 -112 F Cl 0 H CF2 Cl CH3 CHZ 0' C a H
3- 113 F C1 0 H CF2 Cl CHs CHz OCH 2 OCH 3 3 -114 F C1 0 H CF2 Cl CH3 CH2 OCH 2 0C2 H s 3- 115 F Cl 0 H CF2 Cl CH3 CH2 OCOCH , 3- 116 F C1 0 H CF2 Cl CH3 CH2 OCOC2 H s 3- 117 F Ci 0 H CF2 Cl CH3 CH2 OCO ' C, H T
3 -118 F Cl 0 H CF2 Cl CHa CH2 OCOCH 2 C1 3- 119 F Cl 0 H CF2 Cl CHa CH2 OCOCCI3 3- 120 F C1 0 H CF2 Cl CH3 CH2 OCOCF 3 3 -121 F Cl 0 H CF2 Cl CH3 COOCH3 3- 122 F C1 0 H CF2 Cl CH3 COOC2 H s 3- 123 F Cl 0 H CF2 Cl CH3 C00 " C 3 H, 3 -124 F Cl 0 H CF2 Cl CH3 C00 " C, H s 3- 125 F C1 0 H CFZ Cl CH3 COO " C s H õ
3- 126 F C1 0 H CF2 Cl CH3 COO ' C, H
3- 127 F Cl 0 H CF2 Cl CH3 COCH3 3- 128 F C1 0 H CF2 Cl CH3 COC2 H
TABLE 3 (contn'd) Compound x Y Z 2 R 3 R' R 2 R 6 No.
3- 131 H Br 0 H CFs H CH3 3- 134 F Br 0 H CF3 H CH3 3- 137 H Br 0 H CF3 CH3 CH3 3 -140 F Br 0 H CF3 CH3 CH3 3 -142 H C1 0 H CF3 H C2 H s 3 -143 H Br 0 H CF3 H C2 H s 3- 146 F Br 0 H CF3 H C2 H;
3- 147 H F 0 H CF3 CH3 C2 H;
3- 149 H Br 0 H CF3 CH3 C2 H s 3- 150 F F 0 H CF3 CHa C2 H s TABLE 3 (contn'd) Compound x Y Z 2 R 3 R' R 2 R 6 No.
3 -152 F Br 0 H CF3 CH3 C2 H 5 3 -153 H F 0 H CF3 CH3 CHZ Br 3 -154 H F 0 H CF3 CH3 CH Br2 3- 155 H F 0 H CF3 CH3 CBr 3 3 -162 H F 0 H CF3 CH3 CH2 0' C 3 H;
3- 164 H F 0 H CF3 CH3 CHz OCH 2 0C2 H 5 3 -166 H F 0 H CF3 CH3 CHZ OCOC2 H;
3 -167 H F 0 H CF3 CH3 CH2 OCO ' C 3 H, 3- 168 H F 0 H CF3 CH3 CH2 OCOCH 2 Cl 3- 169 H F 0 H CF3 CH3 CHZ OCOCCI'3 3 -172 H F 0 H CF3 CH3 COOC2 H;
3 -173 H F 0 H CF3 CH3 C00 " C 3 H, 3- 174 H F 0 H CF3 CH3 C00 C, H 9 TABLE 3 (contn'd) Compound X Y ZZ Ra R' R2 R6 No.
3- 175 H F 0 H CF3 CH3 C00 " C 5 H õ
3 -176 H F 0 H CF3 CH3 COO ' C a H, 3 -179 H C1 0 H CF3 CH3 CH2 Br 3 -180 H C1 0 H CF3 CH3 CH Br2 3- 181 H C1 0 H CF3 CH3 CBr3 3 -182 H CI 0 H CF3 CHa CHO
3- 187 H C1 0 H CF3 CH3 CHa 0Ca H s 3 -188 H C1 0 H CF3 CH3 CH2 0' C 3 H, 3- 190 H C1 0 H CF3 CH3 CH2 OCH 2 0Cz H s 3- 191 H C1 0 H CF3 CH3 CHz OCOCH a 3- 192 H C1 0 H CF3 CH3 CHz OCOC2 H 5 3 -193 H Ci 0 H CF3 CH3 CH2 OCO ' C 3 H
3 -194 H C1 0 H CF3 CH3 CHz OCOCH 2 Cl 3- 196 H C1 0 H CF3 CH3 CHZ OCOCF a 3- 197 H C1 0 H CF3 CHa COOCH3 TABLE 3 (contn'd) Compound x Y Z 2 R3 R ' R 2 R G No.
3 -198 H C1 0 H CF3 CH3 COOC2 H s 3- 199 H C1 0 H CF3 CHa C00 " C 3 H, 3 -200 H C1 0 H CF3 CHa COO " C 4 H 9 3 -201 H C1 0 H CF3 CH3 C00 " C s H õ
3 -202 H C1 0 H CF3 CH3 COO ' C 3 H 7 3 -204 H C1 0 H CF3 CH3 COC2 H s 3 -205 F F 0 H CF3 CH3 CH2 Br 3 -206 F F 0 H CF3 CH3 CH Br2 3 -207 F F 0 H CF3 CH3 CBr3 3 -213 F F 0 H CF3 CH3 CH2 0C2 H b 3- 214 F F 0 H CF3 CHs CH2 0' C, H 7 3- 215 F F 0 H CF3 CH3 CH2 OCH 2 OCH , 3- 216 F F 0 H CF3 CH3 CH2 OCH 2 0C2 H s 3 -217 F F 0 H CF3 CH3 CH2 OCOCH , 3- 218 F F 0 H CF3 CH3 CH2 OCOC2 H s TABLE 3 (contn'd) Compound x y Z 2 R3 R' R 2 R 6 No.
3 -220 F F 0 H CF3 CH3 CH2 OCOCH 2 Cl 3 -222 F F 0 H CF3 CH3 CHZ OCOCF a 3 -224 F F 0 H CFa CH3 COOC2 H s 3 -225 F F 0 H CF3 CHa C00 " C 3 H 7 3 -226 F F 0 H CF3 CH3 COO " C 4 H 9 3 -227 F F 0 H CF3 CH3 C00 " C 5 H
3 -228 F F 0 H CF3 CH3 COO ' C 3 H, 3 -230 F F 0 H CF3 CH3 COC2 H;
3 -231 F C1 0 H CF3 CH3 CH2 Br 3 -232 F C1 0 H CF3 CH3 CH Br2 3 -233 F Ci 0 H CF3 CH3 CBr3 3 -234 F Cl 0 H CF3 CH3 CHO
3 -235 F Cl 0 H CF3 CH3 CN
3 -238 F C1 0 H CF3 CH3 CH2 OCH , '= 3- 239 F C1 0 H CF3 CH3 CH2 OC2 H 5 3- 240 F Cl 0 H CF3 CHa CH2 0' C a H 7 3 -241 F Cl 0 H CF3 CH3 CH2 OCH 2 OCH a 3 -242 F Cl 0 H CF3 CH3 CHz OCH 2 0C2 H s TABLE 3 (contn'd) Compound X Y Z R' R' R 2 R 6 No.
3 -244 F C1 0 H CF3 CH3 CH2 OCOCz H 5 3 -245 F C1 0 H CF3 CH3 CH2 OCO ' C 3 H, 3 -246 F C1 0 H CF3 CH3 CH2 OCOCH 2 Cl 3- 247 F Ci 0 H CF3 CH3 CH2 OCOCCI3 3 -248 F C1 0 H CF3 CH3 CH2 OCOCF , 3 -250 F C1 0 H CF3 CH3 COOC2 H s 3- 251 F C1 0 H CF3 CH3 C00 " C 3 H 7 3 -252 F C1 0 H CF3 CH3 C00 " C 4 H s 3 -253 F Cl 0 H CF3 CH3 C00 C 5 H õ
3 -254 F C1 0 H CF3 CH3 COO ' C s H 7 3 -256 F C1 0 H CF3 CH3 COC2 H;
3 -257 H F 0 H CF2 Cl H CH2 Br 3 -258 H F 0 H CF2 Cl H CH Br2 3 -259 H F 0 H CF2 Cl H CBr , 3 -260 H F 0 H CF2 Cl H CHO
3 -261 H F 0 H CF2 Cl H CN
3 -262 H F 0 H CF2 Cl H COOH
3 -263 H F 0 H CF2 Cl H CH2 OH 3 -264 H F 0 H CF2 Cl H CH2 OCH 3 3- 265 H F 0 H CF2 Cl H CH2 OC2 H 5 TABLE 3 (contn'd) Compound x y Z 2 R 3 R' R 2 R 6 No.
3-266 H F 0 H CF2 C1 H CHz 0' C 3 H, 3 -267 H F 0 H CF2 Cl H CH2 OCH 2 OCH a 3 -268 H F 0 H CF2 Cl H CH2 OCH 2 0C2 H;
3 -269 H F 0 H CF2 Cl H CH2 OCOCH 3 3 -270 H F 0 H CF2 Cl H CH2 OCOC2 H
3- 271 H F 0 H CF2 C1 H CH2 OCO ' C a H 7 3 -272 H F 0 H CF2 Cl H CH2 OCOCH 2 Cl 3 -273 H F 0 H CF2 Cl H CH2 OCOCCIa 3 -274 H F 0 H CF2 Cl H CH2 OCOCF 3 3 -275 H F 0 H CF2 Cl H COOCH3 3 -276 H F 0 H CF2 Cl H COOC2 H;
3 - 277 H F 0 H CF2 Cl H C00 C3 H, 3 - 278 H F 0 H CFZ CI H C00 C, H 9 3- 279 H F 0 H CFz Cl H C00 " C 5 H õ
3 -280 H F 0 H CF2 Cl H COO ' C, H 7 3 -281 H F 0 H CF2 Cl H COCH3 3 -282 H F 0 H CF2 Cl H COC2 H s 3 -283 H Cl 0 H CF2 Cl H CH2 Br 3 -284 H C1 0 H CF2 Cl H CH Br2 3 -285 H Cl 0 H CF2 Cl H CBr3 3 -286 H Cl 0 H CF2 Cl H CHO
3 -288 H C1 0 H CF2 Cl H COOH
TABLE 3 fcontn'dl Compound. X y Z 2 R 3 R' R Z R 6 No.
3 -289 H ci 0 H CF2 Cl H CH2 OH
3 -290 H C1 0 H CF2 Cl H CH2 OCH 3 3- 291 H ci 0 H CF2 Cl H CHZ OC2 H 5 3 - 292 H C1 0 H CFZ C l H CHz 0' C, H 7 3 -293 H C1 0 H CF2 Cl H CH2 OCH 2 OCH 3 3 -294 H Cl 0 H CF2 Cl H CH2 OCH 2 0C2 H s 3 -295 H ci 0 H CF2 Cl H CH2 OCOCH 3 3 -296 H C1 0 H CF2 Cl H CH2 OCOC2 H s 3 -297 H Cl 0 H CF2 Cl H CH2 OCO ' C 3 H 7 3 -298 H C1 0 H CF2 Cl H CH2 OCOCH 2 Cl 3- 299 H Cl 0 H CF2 Cl H CHZ OCOCC13 3 -300 H C1 0 H CF2 Cl H CH2 OCOCF 3 3 -301 H C1 0 H CF2 Cl H COOCH3 3 -302 H C1 0 H CF2 Cl H COOC2 H 5 3 -303 H C1 0 H CF2 Cl H C00 " C 3 H, 3 - 304 H C l 0 H CFz C l H C00 " C4 H 9 3 -305 H ci 0 H CF2 Cl H C00 " C 5 H 11 3 - 306 H C l 0 H CFz C1 H C00 ' C 3 H, 3 -307 H Cl 0 H CF2 Cl H COCH3 3- 308 H C1 0 H CF2 Cl H COC2 H s 3 -309 F F 0 H CF2 Cl H CH2 Br 3 -310 F F 0 H CF2 Cl H CH Br2 3 -311 F F 0 H CF2 Cl H CBr3 TABLE 3 (contn'd) Compound X Y Z Z R 3 R' R 2 R 6 No.
3 -312 F F 0 H CF2 Cl H CHO
3 -313 F F 0 H CF2 Cl H CN
3 -314 F F 0 H CF2 Cl H COOH
3 -315 F F 0 H CF2 Cl H CH2 OH
3 -316 F F 0 H CF2 Cl H CH2 OCH 3 3 -317 F F 0 H CF2 Cl H CH2 0C2 H
3 -318 F F 0 H CF2C1 H CH2 0' C3H, 3 -319 F F 0 H CF2 Cl H CH2 OCH 2 OCH , 3 -320 F F 0 H CF2 Cl H CH2 OCH 2 OC2 H 5 3 -321 F F 0 H CF2 Cl H CHz OCOCH 3 3 -322 F F 0 H CFz Cl H CH2 OCOC2 H 5 3 -323 F F 0 H CF2 Cl H CH2 OCO ' C 3 H, 3 -324 F F 0 H CF2 Cl H CHz OCOCH 2 Cl 3- 325 F F 0 H CF2 Cl H CH2 OCOCCIa 3 -326 F F 0 H CF2 Cl H CH2 OCOCF 3 3 -327 F F 0 H CF2 Cl H COOCH3 3 -328 F F 0 H CF2 Cl H COOC2 H 5 3-329 F F 0 H CF2 C1 H C00 n C 3 H, 3 -330 F F 0 H CF2 Cl H COO C, H s 3- 331 F F 0 H CF2 Cl H C00 " C 5 H õ
3 -332 F F 0 H CF2 C l H COO ' C 3 H, 3 -333 F F 0 H CF2 Cl H COCH3 TABLE 3 (contn'd) Compound X y ZZ R3 R' R 2 Rs No.
3 -334 F F 0 H CF2 C1 H COC2 H s 3 -335 F C1 0 H CF2 Cl H CH2 Br 3 -336 F C1 0 H CF2 Cl H CH Br2 3-337 F C1 0 H CF2 CI H CBr3 3 -338 F Ci 0 H CF2 Cl H CHO
3 -339 F C1 0 H CF2 Cl H CN
3 -340 F C1 0 H CF2 Cl H COOH
3 -341 F Cl 0 H CF2 Cl H CHz OH
3 -342 F C1 0 H CF2 Cl H CH2 OCH 3 3- 343 F C1 0 H CF2 Cl H CHz OCz H 5 3- 344 F C1 0 H CF2 Cl H CH2 0' C, H7 3 -345 F Cl 0 H CF2 Cl H CHz OCH 2 OCH ;
3 -346 F Cl 0 H CF2 Cl H CH2 OCH 2 0C2 H s 3 -347 F C1 0 H CF2 Cl H CH2 OCOCH , 3 -348 F Ci 0 H CF2 Cl H CHz OCOC2 H 5 3 -349 F Cl 0 H CF2 Cl H CHZ OCO ' C, H 7 3 -350 F C1 0 H CF2 Cl H CH2 OCOCH 2 Cl 3 -351 F C1 0 H CF2 Cl H CH2 OCOCCI3 3 -352 F C1 0 H CF2 Cl H CHz OCOCF 3 3 -353 F C1 0 H CF2 Cl H COOCH3 3 -354 F C1 0 H CF2 Cl H COOC2 H s 3- 355 F C1 0 H CF2 C1 H C00 " C 3 H 7 3 -356 F C1 0 H CF2 Cl H C00 " C, H fl TABLE 3 (contn'd) Compound x y Z 2 R 3 R' R 2 R 6 No.
3 -357 F C1 0 H CF2 Cl H C00 C s H
3 -358 F C1 0 H CF2 Cl H COO ' C 3 H T
3 -359 F C1 0 H CF2 Cl H COCH3 3 -360 F C1 0 H CF2 Cl H COC2 H 5 3 -361 F Br 0 H CF3 H C2 H s 3 -362 H F 0 H CF3 H CH2 Br 3 -363 H F 0 H CF3 H CH Br2 3 -364 H F 0 H CF3 H CBr 3 3 -369 H F 0 H CF3 H CHz OCH 3 3 -371 H F 0 H CF3 H CH2 0' C 3 H T
3 -373 H F 0 H CF3 H CHa OCH 2 0C2 H s 3 -374 H F 0 H CF3 H CH2 OCOCH , 3 -375 H F 0 H CF3 H CHz OCOC2 H s 3 -376 H F 0 H CF3 H CH2 OCO ' C, H T
3 -377 H F 0 H CF3 H CHZ OCOCH 2 Cl 3 -378 H F 0 H CF3 H CHz OCOCCI3 3 -379 H F 0 H CF3 H CHz OCOCF 3 TABLE 3 (contn'd) Compound X Y Z Z R' R' R 2 R 6 No. 3 -380 H F 0 H CF3 H COOCH3 3 -381 H F 0 H CF3 H COOC 2 H s 3 -382 H F 0 H CF3 H C00 " C 3 H
3 -384 H F 0 H CF3 H C00 " C H
3 -385 H F 0 H CF3 H COO ' C, H, 3 -388 H C1 0 H CF3 H CH2 Br 3 -389 H Ci 0 H CF3 H CH Br2 3 -390 H C1 0 H CF3 H CBr3 3 -391 H Ci 0 H CF3 H CHO
3 -396 H C1 0 H CF3 H CH2 0C2 H s 3-397 H C1 0 H CF3 H CH2 01 C 3 H, 3 -398 H C1 0 H CF3 H CH2 OCH 2 OCH , 3 -399 H C1 0 H CF3 H CH2 OCH 2 0C2 H s 3 -401 H C1 0 H CF3 H CH2 OCOC2 H s 3 -402 H C1 0 H CF3 H CH2 OCO ' C 3 H, WO 97/07104 PC'1'/JP96/02311 TABLE 3 fcontn'dl Compound x Y Z Z R3 R' R 2 R6 No.
3 -403 H C1 0 H CF3 H CH2 OCOCH 2 Cl 3 -407 H Ci 0 H CF3 H COOC2 H 5 3 -408 H C1 0 H CF3 H COO " C 3 H, 3 - 409 H C1 0 H CF3 H C00 " C, H 9 3 -410 H C1 0 H CF3 H COO " C H
3- 411 H C1 0 H CF3 H COO ' C 3 H
3 -413 H C1 0 H CF3 H COC2 H s 3 -414 F F 0 H CF3 H CH2 Br 3 -415 F F 0 H CF3 H CH Br2 3 -416 F F 0 H CF3 H CBr3 3 -422 F F 0 H CF3 H CHz 0C2 H s 3 - 423 F F 0 H CF3 H CH2 0' C a H 7 3 -424 F F 0 H CF3 H CH2 OCH 2 OCH , TABLE 3 (contn'd) Compound x y Z 2 R 3 R' R Z R 6 No.
3 -426 F F 0 H CF3 H CH2 OCOCH , 3 -427 F F 0 H CF3 H CH2 OCOC2 H s 3 -428 F F 0 H CF3 H CHz OCO ' C 3 H
3 -433 F F 0 H CF3 H COOC2 H s 3 -434 F F 0 H CF3 H C00 " C a H, 3 -435 F F 0 H CF3 H C00 " C4 H
3 -436 F F 0 H CF3 H C00 " C s H
3 -437 F F 0 H CF3 H COO ' C 3 H
3 -439 F F 0 H CF3 H COC2 H s 3 -440 F Ci 0 H CF3 H CH2 Br 3 -441 F Cl 0 H CF3 H CH Br2 3 -442 F Cl 0 H CF3 H CBr3 3 -443 F Cl 0 H CF3 H CHO
3 -445 F Cl 0 H CF3 H COOH
3 -446 F Cl 0 H CF3 H CH2 OH
TABLE 3 (contn'd) Compound X Y Z2 R 3 R' R2 R 6 No.
3 -447 F Cl 0 H CF3 H CH2 OCH 3 3 -448 F Cl 0 H CF3 H CH2 0C2 H s 3 - 449 F C1 0 H CF3 H CHz 0' C a H7 3- 451 F CI 0 H CF3 H CH2 OCH 2 0C2 H;
3 -453 F C1 0 H CF3 H CH2 OCOC2 H s 3 -454 F C1 0 H CF3 H CH2 OCO ' C 3 H 7 3 -455 F Cl 0 H CF3 H CH2 OCOCH 2 Cl 3 -457 F C1 0 H CF3 H CH2 OCOCF a 3 -458 F Cl 0 H CF3 H COOCH3 3 -459 F C1 0 H CF3 H COOC2 H s 3- 460 F C1 0 H CF3 H C00 " C 3 H z 3 - 461 F Cl 0 H CF3 H C00 C, H 9 3 -462 F Ci 0 H CF3 H COO " C H3- 463 F C1 0 H CF3 H COO ' C a H 7 3 -465 F Cl 0 H CF3 H COCz H 5 . 3 -466 H F 0 CH3 CF3 H CH3 3 -468 H Br 0 CHa CF3 H CHs 3 -469 F F 0 CH3 CF3 H CH.3 TABLE 3 (contn'd) Compound X Y Z 2 R' R' R 2 R e No.
3 -471 F Br 0 CHa CF3 H CH3 3 -472 H F 0 CH3 CF3 H C2 H s 3 -473 H C1 0 CH3 CF3 H C 2 H s 3 -474 H Br 0 CH3 CF3 H C 2 H;
3 -475 F F 0 CH3 CF3 H C 2 H;
3 -476 F C1 0 CH3 CF3 H C 2 H s 3 -477 F Br 0 CH3 CF3 H C 2 H 5 3 -478 F Br 0 CH3 CF3 H C 2 H s 3 -479 H F 0 CH3 CF3 H CH2 Br 3 -480 H F 0 CH3 CF3 H CH Br2 3 -481 H F 0 CH3 CF3 H CBr , 3 -486 H F 0 CH3 CF3 H CH2 OCH , 3 - 488 H F 0 CH3 CF3 H CHz 0' C, H 7 3 -489 H F 0 CHa CF3 H CH2 OCH 2 OCH 3 =
3 -490 H F 0 CH3 CF3 H CH2 OCH 2 OC2 H s 3 -492 H F 0 CH3 CF3 H CHz OCOC2 H a TABLE 3 (contn'd) Compound x y Z 2 R 3 R ' R 2 R G
No.
3 -493 H F 0 CH3 CF3 H CH2 OCO ' C 3 H7 3 -498 H F 0 CH3 CF3 H COOC2 H g 3 -499 H F 0 CH3 CF3 H C00 C 3 H, 3- 500 H F 0 CH3 CF3 H COO " C, H s 3- 501 H F 0 CH3 CF3 H C00 " C; H õ
3 -502 H F 0 CH3 CF3 H C00 ' C 3 H 7 3 -504 H F 0 CH3 CF3 H COC2 H s 3 -505 H C1 0 CH3 CF3 H CH2 Br 3 -506 H C1 0 CH3 CF3 H CH Br2 3 -507 H C1 0 CH3 CF3 H CBr3 3 -508 H Ci 0 CH3 CF3 H CHO
3 -513 H C1 0 CH3 CF3 H CH2 0C2 H s 3- 514 H C1 0 CH3 CF3 H CH2 0' C 3 H, 3 -515 H C1 0 CH3 CF3 H CHz OCH 2 OCH 3 TABLE 3 fcontn'd) Compound x Y Z 2 R3 R' R2 R 6 No.
3- 518 H C1 0 CH3 CF3 H CH2 OCOC2 H s 3- 519 H C1 0 CH3 CF3 H CH2 OCO C 3 H, 3 -520 H C1 0 CH3 CF3 H CH2 OCOCH 2 Cl 3 -521 H C1 0 CH3 CF3 H CHa OCOCC13 3 -525 H C1 0 CHa CF3 H C00 " C, H7 3 -526 H Ci 0 CH3 CF3 H C00 " C 4 H 9 3 -527 H C1 0 CH3 CF3 H COO " C s H ii 3 -528 H C1 0 CH3 CF3 H COO ' C, H7 3 -531 F F 0 CH3 CF3 H CH2 Br 3 -532 F F 0 CH3 CF3 H CH Br2 3 -533 F F 0 CH3 CF3 H CBr3 3 -535 F F 0 CHa CF3 H CN ;
3 -537 F F 0 CH3 CF3 H CHz OH
TABLE 3 (contn'd) Compound X Y Z Z R 3 R' R 2 R 6 No.
3 -540 F F 0 CH3 CF3 H CH2 0' C 3 H T
3 -542 F F 0 CH3 CF3 H CHZ OCH 2 OC2 H;
3 -543 F F 0 CH3 CF3 H CHz OCOCH 3 3 -544 F F 0 CH3 CF3 H CH2 OCOC2 H;
3 -545 F F 0 CH3 CF3 H CH2 OCO ' C 3 H, 3 -546 F F 0 CH3 CF3 H CH2 OCOCH 2 Cl 3 -547 F F 0 CH3 CF3 H CH2 OCOCCIs 3 -548 F F 0 CH3 CF3 H CHz OCOCF 3 3 -550 F F 0 CH3 CF3 H COOC2 H s 3- 551 F F 0 CH3 CF3 H C00 C 3 H, 3 -552 F F 0 CH3 CF3 H COO " C, H 9 3 -553 F F 0 CH3 CF3 H C00 C 5 H õ
3 -554 F F 0 CH3 CF3 H COO ' C 3 H, 3 -556 F F 0 CH3 CF3 H COC2 H s 3 -557 F C1 0 CH3 CF3 H CIIZ Br = 3 -558 F C1 0 CHa CF3 H CH Br2 3- 559 F C1 0 CH3 CF3 H CBr3 TABLE 3 (contn'd) Compound x y Z 2 R 3 R' R 2 R 6 No.
3 -561 F C1 0 CH3 CFs H CN
3 -563 F C1 0 CHa CF3 H CH2 OH
3 -564 F C1 0 CHa CF3 H CH2 OCH a 3 -565 F ci 0 CH3 CF3 H CH2 0C2 H 5 3- 566 F ci 0 CH3 CF3 H CH2 0' C 3 H 7 3 -568 F Cl 0 CH3 CF3 H CH2 OCH 2 0C2 H s 3 -569 F ci 0 CH3 CF3 H CH2 OCOCH 3 3 -570 F ci 0 CH3 CF3 H CH2 OCOC2 H s 3 -571 F C1 0 CH3 CF3 H CH2 OCO ' C a H7 3 -572 F C1 0 CH3 CF3 H CH2 OCOCH 2 Cl 3- 573 F Cl 0 CH3 CF3 H CHz OCOCC13 3 -575 F ci 0 CH3 CF3 H COOCH3 3 -576 F C1 0 CH3 CF3 H COOCz H;
3 -577 F Cl 0 CH3 CF3 H COO " C 3 H, 3 -578 F ci 0 CH3 CF3 H COO " C, H 9 3 -579 F C1 0 CH3 CF3 H COO " C s H,1 3 -580 F C1 0 CH3 CF3 H COO ' C s H 7 =
3 -581 F C1 0 CH3 CF3 H COCH3 3 -582 F ci 0 CH3 CF3 H COC2 H s Compounds of the formula:
X O R'-Y ~ ~ N \ Ri _ ~ Rs Compound X Y R3 R' R2 R' R8 No.
4 - 1 H Cl H CF2 Cl CH3 H CH2 Cl 4 - 2 H Cl H CF2 Cl CH3 H CH2 Br 4- 3 H Cl H CF2 Cl CH3 H CH2 OCH 3 4- 4 H Cl H CF2 Cl CH3 H CH2 0C2 H s 4 - 5 H Cl H CF2 Cl CH3 H CH2 OCH 2 OCH
4- 6 H Cl H CFZ CI CH3 H CH2 OCH 2 OC 2 Hs 4-7 H Cl H CF2 Cl CH3 H CHZ OCOCH 3 4 - 8 H Cl H CF2 Cl CH3 H CH2 OCOC 2 Hs 4 - 9 H Cl H CF2 C l CH3 H CH2 OCO ' C, H7 4- 10 H Cl H CF2 Cl CH3 H CH2 OCOCH 2 Cl 4 -11 H Cl H CF2 Cl CH3 H CH2 OCOCCI3 4- 12 H Cl H CF2 Cl CH3 H CH2 OCOCF , 4 -13 H Cl H CF2 Cl CH3 H COOH
4- 14 H Cl H CF2 Cl CH3 H COOCH3 4- 15 H Cl H CF2 Cl CH3 H COOC2 H a TABLE 4 (contn'd) Compound X Y R 3 R' R Z R' R$ No.
4 -16 H Cl H CF2 Cl CH3 H C00 " C 3 H 7 4- 17 H Cl H CF2 Cl CH3 H C00 C 4 H s 4 -18 H Cl H CF2 Cl CH3 H C00 C 5 H;
4- 19 H Cl H CF2 Cl CH3 H COO C s H 7 4- 20 H Cl H CF2 C1 CH3 H C00 ' C 5 H 9 4 -21 H Cl H CF2 Cl CH3 H COO c C s H 1, 4 -22 H Cl H CF2 Cl CH3 H COOCH2 CH = CHZ
4 -23 H Cl H CF2 Cl CH3 H COOCH2 C= CH
4 -24 H Cl H CF2 Cl CH3 H CONH2 4 -25 H C1 H CF2 Cl CH3 H CONHCH3 4 -27 H Cl H CF2 Cl CH3 H CON(CH3 ) 2 4- 28 H Cl H CF2 Cl CH3 H CON(C2 H 5) 2 4 -29 F Cl H CF2 Cl CH3 H CH2 Cl 4 -30 F Cl H CF2 Cl CH3 H CHa Br 4 -31 F Cl H CF2 Cl CH3 H CHZ OCH 3 4- 32 F Cl H CF2 Cl CH3 H CH2 0CZ H b 4 -33 F Cl H CF2 Cl CH3 H CH2 OCH 2 OCH , 4- 34 F Cl H CF2 Cl CH3 H CH2 OCH 2 OC 2 H;
4 -35 F Cl H CF2 Cl CH3 H CHz OCOCH 3 4 -36 F Cl H CF2 Cl CH3 H CHZ OCOC 2 H5 4- 37 F C1 H CF2 C1 CH3 H CHz OCO ' C 3 H 7 4- 38 F Cl H CF2 Cl CH3 H CHz OCOCH 2 Cl TABLE 4 (contn'd) Compound X Y R a R' R 2 R7 R8 No.
4 -39 F Cl H CF2 Cl CH3 H CHZ OCOCCI3 4 -40 F Cl H CF2 CI CH3 H CHZ OCOCF 3 4 -41 F Cl H CF2 Cl CH3 H COOH
4 -42 F Cl H CF2 Cl CHa H COOCH3 4 -43 F Cl H CF2 Cl CH3 H COOC2 H s 4 - 44 F Cl H CFZ C1 CH3 H C00 " C 3 H, 4- 45 F Cl H CF2 C1 CH3 H C00 C 4 H 9 4- 46 F Cl H CFz Cl CH3 H C00 C s H i, 4 - 47 F Cl H CFZ C1 CH3 H C00 ' C a H, 4- 48 F Cl H CF2 Cl CH3 H C00 ' C s H 9 4- 49 F Cl H CF2 Cl CH3 H C00 ' C 6 H õ
4 -50 F Cl H CF2 Cl CH3 H COOCH2 CH = CH2 4 -51 F Cl H CF2 Cl CH3 H COOCH2 C= CH
4 -52 F Cl H CF2 Cl CH3 H CONH2 4 -53 F Cl H CF2 C1 CH3 H CONHCH3 4 -54 F Cl H CF2 Cl CH3 H CONHC2 H s 4 -55 F Cl H CF2 Cl CH3 H CON(CH3 ) 2 4 -56 F Cl H CF2 Cl CH3 H CON(C2 H s) 2 4 -57 H Cl H CF2 Cl CH3 CH3 CH2 Cl 4 -58 H Cl H CF2 Cl CH3 CH3 CHz Br 4- 59 H Cl H CF2 Cl CH3 CH3 CHa OCH 3 4 -60 H Cl H CF2 Cl CH3 CHa CHZ 0C2 H s 4-61 H Cl H CF2 Cl CH3 CH3 CHZ OCH 2 OCH a TABLE 4 (contn'd) Compound X Y R R RZ R' R8 No.
4 -62 H Cl H CF2 Cl CH3 CH3 CH2 OCH 2 OC 2 Hs 4 -63 H Cl H CF2 Cl CH3 CH3 CHz OCOCH 3 4 -64 H Cl H CF2 C1 CH3 CH3 CH2 OCOC 2 HS
4- 65 H Cl H CF2 Cl CH3 CH3 CH2 OCO ' C 3 H 7 4 -66 H Cl H CF2 Cl CH3 CH3 CHZ OCOCH 2 Cl 4 -67 H Cl H CF2 Cl CH3 CH3 CHZ OCOCCI3 4 -68 H Cl H CF2 Cl CH3 CH3 CH2 OCOCF 3 4 -69 H Cl H CF2 Cl CH3 CH3 COOH
4 -70 H Cl H CF2 Cl CH3 CH3 COOCH3 4 -71 H Cl H CF2 Cl CH3 CH3 COOC2 H s 4- 72 H Cl H CF2 Cl CH3 CH3 C00 " C 3 H 7 4 - 73 H Cl H CF2 Cl CH3 CH3 C00 " C, H g 4 -74 H Cl H CF2 Cl CH3 CH3 C00 " C s H,t 4- 75 H Cl H CF2 Cl CH3 CH3 COO ' C 3 H 7 4- 76 H Cl H CF2 Cl CH3 CH3 COO ' C s H a 4 -77 H Cl H CF2 Cl CH3 CH3 COO ' C 6 H õ
4 -78 H Cl H CF2 Cl CH3 CH3 COOCH2 CH = CH2 4 -79 H Cl H CF2 Cl CH3 CH3 COOCH2 C= CH
4 -80 H Cl H CF2 Cl CH3 CH3 CONH2 4 -81 H Cl H CF2 Cl CH3 CH3 CONHCH3 4- 82 H Cl H CF2 Cl CH3 CH3 CONHC2 H 5 4- 83 H C1 H CF2 Cl CH3 CH3 CON(CH3 ) 2 4- 84 H Cl H CF2 Cl CH3 CH3 CON(C2 H 5 ) 2 TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R' R 8 No.
4 -85 F C1 H CF2 Cl CH3 CH3 CH2 C1 4 -86 F Cl H CF2 Cl CH3 CH3 CH2 Br 4 -87 F Cl H CF2 Cl CH3 CH3 CH2 OCH 3 4-88 F Cl H CF2 Cl CH3 CH3 CHZ 0C2 H 5 4 -89 F Cl H CF2 Cl CH3 CH3 CH2 OCH 2 OCH 3 4- 90 F Cl H CF2 Cl CH3 CH3 CHZ OCH 2 OC 2 H5 4 -91 F Cl H CF2 C1 CH3 CH3 CHZ OCOCH 3 4- 92 F Cl H CF2 Cl CH3 CH3 CH2 OCOC 2 H;
4- 93 F C1 H CF2 Cl CH3 CH3 CH2 OCO ' C 3 H, 4 -94 F Cl H CF2 Cl CH3 CH3 CH2 OCOCH 2 Cl 4 -95 F Cl H CF2 Cl CH3 CH3 CH2 OCOCCI3 4 -96 F Cl H CF2 Cl CH3 CH3 CH2 OCOCF 3 4 -97 F Cl H CF2 Cl CH3 CH3 COOH
4 -98 F Cl H CF2 Cl CH3 CH3 COOCH3 4 -99 F Cl H CF2 Cl CH3 CH3 COOC2 H 5 4- 100 F Cl H CF2 C1 CH3 CH3 COO " C 3 H, 4- 101 F Cl H CF2 Cl CH3 CH3 COO " C 4 H
4- 102 F Cl H CF2 CI CH3 CH3 COO " C 5 H4- 103 F Cl H CF2 Cl CH3 CH3 COO ' C 3 4- 104 F Cl H CF2 Cl CH3 CH3 COO ' C 5 H fl 4 -105 F Cl H CF2 Cl CH3 CH3 COO ' C 6 H,i 4 -106 F Cl H CF2 Cl CH3 CH3 COOCH2 CH= CHz TABLE 4 (contn'd) Compound X Y R3 R' R2 R' R8 No. =
4 -107 F Cl H CF2 Cl CH3 CH3 COOCH2 C= CH
4- 108 F Cl H CF2 Cl CH3 CH3 CONH2 4- 109 F Cl H CF2 Cl CH3 CH3 CONHCH3 4- 110 F Cl H CF2 Cl CH3 CH3 CONHC2 H s 4- 111 F Cl H CF2 Cl CH3 CH3 CON(CH3 ) z 4- 112 F Cl H CF2 Cl CH3 CH3 CON(C2 H;) 2 4 -113 H Cl H CF3 CH3 H CH2 Cl 4- 114 H Cl H CF3 CH3 H CH2 Br 4- 115 H Cl H CF3 CH3 H CH2 OCH 3 4- 116 H Cl H CF3 CH3 H CH2 0C2 H s 4 -117 H Cl H CF3 CH3 H CHZ OCH 2 OCH 3 4- 118 H Cl H CF3 CH3 H CH2 OCH 2 OC 2 Hs 4- 119 H Cl H CF3 CH3 H CH2 OCOCH 3 4- 120 H Cl H CF3 CH3 H CH2 OCOC 2 Hs 4- 121 H Cl H CF3 CH3 H CHZ OCO ' C 3 H, 4 -122 H Cl H CF3 CH3 H CH2 OCOCH 2 Cl 4- 123 H Cl H CF3 CH3 H CHZ OCOCCI3 4- 124 H Cl H CF3 CH3 H CH2 OCOCF 3 4- 125 H Cl H CF3 CH3 H COOH
4- 126 H Cl H CF3 CH3 H COOCH3 4- 127 H Cl H CF3 CH3 H COOCZ H 5 4- 128 H Cl H CF3 CH3 H C00 " C 3 H 7 4- 129 H Cl H CF3 CH3 H COO " C 4 H
TABLE 4 (contn'd) Compound X Y R3 R' R2 R' R8 No.
4- 130 H Cl H CF3 CH3 H C00 " C 5 H õ
4- 131 H Cl H CF3 CH3 H COO ' C a H 7 4- 132 H Cl H CF3 CH3 H C00 ' C g H 9 4 -133 H Cl H CF3 CH3 H C00 ' C 6 H 11 4 -134 H Cl H CF3 CH3 H COOCH2 CH = CH2 4 -135 H Cl H CF3 CH3 H COOCH2 C CH
4 -136 H Cl H CF3 CH3 H CONH2 4 -137 H C 1 H CF3 CH3 H CONHCH'3 4 -139 H C1 H CF3 CH3 H CON(CH3 ) 2 4- 140 H C1 H CF3 CH3 H CON(C2 H 5) 2 4 -141 F C1 H CF3 CH3 H CH2 Cl 4- 142 F C1 H CF3 CH3 H CH2 Br 4 -145 F C1 H CF3 CH3 H CH2 OCH 2 OCH , 4 -149 F Cl H CF3 CH3 H CH2 OCO ' C 3 H, 4- 150 F Cl H CF3 CH3 H CH2 OCOCH 2 Cl 4- 151 F Cl H CF3 CH3 H CH2 OCOCCla 4- 152 F Cl H CF3 CH3 H CH2 OCOCF , TABLE 4 (contn'd) Compound X Y R 3 R' R Z R' R$
No.
4 -153 F Cl H CF3 CH3 H COOH
4 -154 F Cl H CF3 CH3 H COOCH3 4 -155 F Cl H CF3 CH3 H COOC2 H s 4 - 156 F Cl H CF3 CH3 H C00 C, H7 4- 157 F Cl H CF3 CH3 H COO " C 4 H 9 4 -158 F Cl H CF3 CH3 H C00 " C 5 H õ
4 -159 F Cl H CF3 CH3 H COO ' C g H 7 4 -160 F Cl H CF3 CH3 H C00 -C 5 H0 4- 161 F Cl H CF3 CH3 H C00 ' C 6 H,1 4 -162 F Cl H CF3 CHa H COOCHz CH = CH2 4 -163 F Cl H CF3 CHs H COOCH2 C= CH
4 -164 F Cl H CF3 CH3 H CONH2 4- 165 F Cl H CF3 CH3 H CONHCH3 4 -166 F Cl H CF3 CH3 H CONHC2 H 5 4 -167 F Cl H CF3 CH3 H CON(CH3 ) 2 4- 168 F Cl H CF3 CH3 H CON(C2 H 5)2 4 -169 H Cl H CF3 CH3 CH3 CHz Cl 4- 170 H Cl H CF3 CH3 CH3 CHZ Br 4 -171 H Cl H CF3 CH3 CH3 CH2 OCH , 4 -172 H Cl H CF3 CH3 CH3 CHz 0C2 H 6 4- 173 H Cl H CF3 CH3 CH3 CHz OCH 2 OCH , 4 -174 H Cl H CF3 CH3 CH3 CH2 OCH 2 OC 2 Ha 4- 175 H Cl H CF3. CH3 CH3 CH2 OCOCH 3 TABLE 4 (contn'd) Compound X Y R 3 R' R Z R' R 8 No.
4- 176 H Cl H CF3 CH3 CH3 CH2 OCOC 2 H5 4- 177 H Cl H CF3 CH3 CH3 CHz OC0 ' C 3 H
4- 178 H Cl H CF3 CH3 CH3 CH2 OCOCH 2 Cl 4 -179 H Cl H CF3 CH3 CH3 CH2 OCOCCI3 4 -180 H Cl H CF3 CH3 CH3 CH2 OCOCF 3 4- 181 H Cl H CF3 CH3 CH3 COOH
4- 182 H Cl H CF3 CH3 CH3 COOCH3 4- 183 H Cl H CF3 CH3 CH3 COOC2 H 5 4- 184 H Cl H CF3 CH3 CH3 C00 C 3 H, 4- 185 H Cl H CF3 CH3 CH3 COO " C H
4 -186 H Cl H CF3 CH3 CH3 C00 " C H
4- 187 H Cl H CF3 CH3 CH3 COO ' C 3 H
4- 188 H Cl H CF3 CH3 CH3 COO ' C s H 9 4- 189 H Cl H CF3 CH3 CH3 COO ' C 6 H
4 -190 H Cl H CF3 CH3 CH3 COOCHa CH = CH2 4 -191 H Cl H CF3 CH3 CH3 COOCHZ C CH
4- 192 H Cl H CF3 CH3 CH3 CONH2 4 -193 H Cl H CF3 CH3 CH3 CONHCH3 4- 194 H Cl H CF3 CH3 CH3 CONHC2 H 5 4- 195 H Cl H CF3 CH3 CH3 CON(CH3 ) 2 4- 196 H Cl H CF3 CH3 CH3 CON(C2 H 2 4 -197 F Cl H CF3 CH3 CH3 CHa Cl 4- 198 F Cl H CF3 CH3 CH3 CHZ Br zHN00 'HO 'HO ~HO H IO d OZZ- V
HO = 0 zH0000 ~HO 'HO e90 H IO d 613-ZHO = HO ZH0000 eH9 'HO eH0 H IO 4 8I3-P
" H 9 0. 000 'HO 'HO e90 H IO d LIZ -~
H s 0. 000 EHO EHO 'HO H IO d 9TZ -H E 0 000 eH0 'HO EHO H 10 d 5I3-P
-~ H a 000 ~HO 'HO eH0 H IO 3 ~IZ --k a H 0 000 'HO 'HO EHO H IO J 8TZ -k H E 0 -.000 EHO EHO e90 H I9 d ZTZ- P
S H 30000 'HO 'HO e90 H IO d TTZ -~H0000 'HO eH0 ~d0 H IO d 0I3-V
H000 'HO 'HO e90 H TO d 60Z -V
E H0000 zH0 'HO 'HO ~HO H TO d 803-P
'IJJ0J0 3H0 'HO 'HO EHO H IJ d LOZ -V
IJ z H0000 zHJ 'HO EHJ EHO H IJ .3 90Z -P
H E 0, 000 3H0 EHO EHO EHO H IO d 50Z -V
'H z 0000 zH0 'HO EHO EA0 H IO 3 VOZ -k E H0000 'HO EHO e140 'HO H TO 3 E0Z -P
'-H z 00 z H00 zH0 'HO 'HO EHO H IO 3 Z0Z -P
e H00 z H00 ZHO eH0 EHO EAO H IO d 109-~
s H z90 zH0 'HO 'HO EHO H 10 3 003-P
~ HJ0 zHJ 'HO eHJ ~HJ H IJ d 66T -V
ON
~ 82i ~2~ z23 r2~ ~-d A X punodncoo p,uIuo~ 17 'AlaV1, I I~ZO/96df/.L3d b0IL0/L6 OM
OZ-ZO-8661 6610~ZZO Va TABLE 4 (contn'd) Compound X Y R3 R' R Z R7 R 8 No.
4 -221 F Cl H CF3 CH3 CH3 CONHCH3 4 -222 F Cl H CF3 CHa CH3 CONHC2 H s 4 -223 F Cl H CF3 CH3 CH3 CON(CH3 ) 2 4 -224 F C1 H CFa CH3 CH3 CON(C2 H s) 2 4 -225 H Cl H CF2 Cl CH3 H CH2 Cl 4 -226 H Cl H CF2 Cl CH3 H CH2 Br 4 -227 H Cl H CF2 Cl CH3 H CH2 OCH 3 4 -228 H Cl H CF2 C1 CH3 H CH2 OC2 H 5 4 -229 H Cl H CF2 C1 CH3 H CH2 OCH 2 OCH a 4 -230 H C1 H CF2 Cl CH3 H CH2 OCH 2 OC 2 Hs 4 -231 H Cl H CF2 Cl CH3 H CH2 OCOCH 3 4 -232 H Cl H CF2 C1 CH3 H CH2 OCOC 2 H5 4 -233 H Cl H CF2 C1 CH3 H CH2 OCO ' C 3 H, 4 -234 H Cl H CF2 Cl CH3 H CH2 OCOCH 2 C1 4 -235 H Cl H CF2 C1 CH3 H CHz OCOCCI3 4 -236 H Cl H CF2 C1 CH3 H CH2 OCOCF , 4 -238 H Cl H CF2 Cl CH3 H COOCH3 4 -239 H Cl H CF2 Cl CH3 H COOC2 H s 4- 240 H Cl H CFa Cl CH3 H C00 " C 3 H 7 4- 241 H Cl H CF2 C1 CH3 H C00 " C, H 9 4- 242 H C1 H CFZ C1 CH3 H C00 " C 5 H õ
4 -243 H C1 H CF2 Cl CH3 H COO ' C 3 H 7 TABLE 4 (contn'd) Compound X Y R' R' R 2 R' R 8 No.
4 -244 H Cl H CF2 C1 CH3 H C00 ' C 5 H s 4 -245 H Cl H CFZ Cl CH3 H COO ' C 6 H
4 -246 H Cl H CF2 Cl CH3 H COOCH2 CH = CHZ
4 -247 H Cl H CF2 Cl CH3 H COOCH2 C= CH
4 -248 H C1 H CF2 Cl CHa H CONH2 4 -249 H C1 H CF2 Cl CH3 H CONHCH3 4 -250 H C1 H CF2 C1 CH3 H CONHCz H 5 4 -251 H Cl H CF2 Cl CH3 H CON(CH3 ) 2 4- 252 H Cl H CF2 Cl CH3 H CON(C2 H 5) 2 4 -253 F Cl H CF2 Cl CH3 H CH2 Cl 4 -254 F Cl H CF2 Cl CH3 H CHZ Br 4- 255 F Cl H CF2 Cl CH3 H CHz OCH , 4- 256 F Cl H CF2 Cl CH3 H CH2 OC2 H s 4 -257 F Cl H CF2 Cl CH3 H CH2 OCH 2 OCH 3 4 -258 F Cl H CF2 Cl CH3 H CH2 OCH 2 OC 2 H5 4 -259 F Cl H CF2 Cl CH3 H CH2 OCOCH a 4 -260 F Cl H CF2 Cl CH3 H CH2 OCOC 2 HS
4 -261 F Cl H CF2 Cl CH3 H CH2 OCO ' C 3 H z 4- 262 F Cl H CF2 Cl CH3 H CH2 OCOCH 2 Cl 4- 263 F Cl H CF2 Cl CH3 H CH2 OCOCC13 4 -264 F Cl H CF2 Cl CH3 H CHz OCOCF 3 4 -265 F Cl H CF2 Cl CH3 H COOH
4 -266 F Cl H CF2 Cl CH3 H COOCH3 TABLE 4 (contn'd) = Compound X Y R 3 R' R 2 R' R 8 No.
4 -267 F C1 H CF2 Cl CHa H COOC2 H s 4- 268 F Cl H CFa C1 CH3 H C00 " C s H 7 4 - 269 F Cl H CFZ C1 CH3 H C00 " C, H s 4 -270 F Cl H CF2 Cl CH3 H COO C 5 H õ
4 -271 F Cl H CF2 Cl CH3 H COO ' C 3 H7 4 -272 F Cl H CF2 Cl CH3 H COO ' C 5 H 9 4 -273 F Cl H CF2 Cl CH3 H COO ' C 6 H õ
4 -274 F Cl H CF2 Cl CH3 H COOCH2 CH = CHZ
4 -275 F Cl H CF2 Cl CH3 H COOCH2 C= CH
4 -276 F Cl H CF2 Cl CH3 H CONH2 4- 277 F Cl H CF2 Cl CH3 H CONHCH3 4 -278 F Cl H CF2 Cl CH3 H CONHC2 H s 4 -279 F Cl H CF2 Cl CH3 H CON(CHa ) 2 4 -280 F Cl H CF2 Cl CH3 H CON(C2 H s) 2 4 -281 H Cl H CF2 Cl CH3 CH3 CHZ Cl 4 -282 H Cl H CF2 Cl CH3 CH3 CH2 Br 4 -283 H Cl H CF2 Cl CH3 CH3 CH2 OCH 3 4 -284 H Cl H CF2 Cl CH3 CHa CH2 0C2 H s 4 -285 H Cl H CF2 Cl CH3 CH3 CH2 OCH 2 OCH 3 4 -286 H Cl H CF2 Cl CH3 CH3 CHZ OCH 2 OC 2 H5 4 -287 H Cl H CF2 Cl CH3 CH3 CH2 OCOCH 3 4- 288 H Cl H CF2 Cl CHa CH3 CH2 OCOC 2 H, 4 -289 H Cl H CF2 Cl CH3 CH3 CHz OCO ' C, H, .274 TABLE 4 (contn'd) Compound X Y R' R' R 2 R' R8 No.
4 -290 H Cl H CF2 Cl CH3 CH3 CH2 OCOCH Z Cl 4 -291 H Cl H CF2 Ci 'CH3 CH3 CH2 OCOCC13 4 -292 H Cl H CF2 Cl CH3 CH3 CH2 OCOCF 3 4 -293 H Cl H CF2 Cl CH3 CH3 COOH
4 -294 H Cl H CF2 Cl CH3 CH3 COOCH3 4 -295 H C1 H CF2 Cl CH3 CH3 COOC2 H s 4 -296 H Cl H CF2 Cl CH3 CH3 C00 C 3 H, 4 -297 H Cl H CF2 Cl CH3 CH3 C00 " C, H 9 4 -298 H Cl H CF2 Cl CH3 CH3 C00 " C 5 H õ
4 -299 H Cl H CF2 C1 CH3 CH3 COO ' C, H7 4 -300 H Cl H CF2 Cl CH3 CH3 C00 C C 5 H 9 4 -301 H Cl H CF2 C1 CH3 CH3 C00 ' C 6 H,1 4 -302 H Cl H CF2 C1 CH3 CH3 COOCH2 CH = CH2 4 -303 H Cl H CF2 C1 CH3 CH3 COOCH2 C= CH
4 -304 H Cl H CF2 C1 CH3 CH3 CONH2 4 -305 H Cl H CF2 Cl CH3 CH3 CONHCH3 4 -306 H Cl H CF2 C1 CH3 CH3 CONHC2 H s 4 -307 H Cl H CF2 C1 CH3 CH3 CON(CH3 ) 2 4- 308 H Cl H CF2 C1 CH3 CH3 CON(C2 H 5) 2 4 -309 F Cl H CF2 C1 CH3 CH3 CHz Cl 4 -310 F Cl H CF2 C1 CH3 CH3 CH2 Br 4 -311 F Cl H CF2 CI CH3 CH3 CH2 OCH 3 4- 312 F Cl H CF2 Cl CH3 CH3 CH2 OC2 H 6 WO 9Wa7164 PCT/JP96102311 TABLE 4 (contn'd) Compound X Y R 3 R ' R 2 R' R e No.
4 -313 F Cl H CF2 Cl CH3 CH3 CH2 OCH 2 OCH a 4- 314 F Cl H CF2 Cl CH3 CH3 CHz OCH 2 OC 2 H5 4 -315 F Cl H CF2 C1 CH3 CH3 CH2 OCOCH , 4- 316 F Cl H CF2 Cl CHa CH3 CH2 OCOC 2 Hs 4 -317 F Cl H CF2 C1 CH3 CH3 CH2 OCO ' C 3 H, 4- 318 F Cl H CF2 C1 CH3 CH3 CH2 OCOCH 2 Cl 4 -319 F Cl H CF2 Cl CH3 CH3 CH2 OCOCCI3 4 -320 F Cl H CF2 Cl CH3 CHa CH2 OCOCF , 4 -321 F Cl H CF2 Cl CH3 CH3 COOH
4 -322 F Cl H CF2 Cl CH3 CH3 COOCH3 4 -323 F Cl H CF2 Cl CH3 CH3 COOC2 H s 4 -324 F Cl H CF2 Cl CH3 CH3 COO " C 3 H, 4- 325 F Cl H CF2 Cl CH3 CH3 COO " C, H s 4 -326 F Cl H CF2 Cl CH3 CH3 COO C 5 H õ
4 -327 F Cl H CF2 Cl CH3 CH3 COO ' C 3 H 7 4 -328 F Cl H CF2 Cl CH3 CH3 COO c C 5 H s 4 -329 F Cl H CF2 Cl CH3 CH3 COO ' C 6 H õ
4 -330 F Cl H CF2 Cl CH3 CH3 COOCH2 CH = CH2 4 -331 F Cl H CF2 Cl CH3 CH3 COOCH2 C= CH
4 -332 F Cl H CF2 C1 CH3 CH3 CONH2 4 -333 F Cl H CF2 C1 CH3 CH3 CONHCH3 4 -334 F C1 H CF2 C1 CH3 CH3 CONHC2 H a TABLE 4 (contn'd) Compound X Y R 3 R' R Z R' R 8 No.
4 -335 F Cl H CF2 Cl CHa CH3 CON(CH3 ) 2 4 -336 F Cl H CF2 Cl CH3 CH3 CON(C2 H 5) 2 4 -337 H Cl H CF3 CH3 H CH2 Cl 4 -338 H Cl H CF3 CH3 H CH2 Br 4 -339 H Cl H CF3 CH3 H CHZ OCH 3 4 -340 H Cl H CF3 CH3 H CH2 0C2 H 5 4 -341 H Cl H CF3 CH3 H CHZ OCH 2 OCH 3 4 -342 H Cl H CF3 CH3 H CH2 OCH z-OC 2 H5 4 -343 H Cl H CF3 CH3 H CH2 OCOCH 3 4 -344 H Cl H CF3 CH3 H CH2 OCOC 2 Hs 4 -345 H Cl H CF3 CH3 H CHa OCO ' C s H 7 4 -346 H Cl H CF3 CH3 H CH2 OCOCH 2 Cl 4 -347 H Cl H CF3 CH3 H CH2 OCOCC13 4 -348 H Cl H CF3 CH3 H CH2 OCOCF 3 4 -349 H Cl H CF3 CH3 H COOH
4 -350 H Cl H CF3 CH3 H COOCH3 4 -351 H Cl H CF3 CH3 H COOC2 H 6 4 -352 H Cl H CF3 CH3 H C00 " C 3 H7 4 -353 H Cl H CF3 CH3 H C00 " C 4 H 9 4 -354 H Cl H CF3 CH3 H C00 " C 5 H
4 -355 H Cl H CF3 CH3 H COO ' C s H 7 4 -356 H Cl H CF3 CH3 H C00 ' C b H 9 4 -357 H Cl H CF3 CH3 H COO ' C 6 H
TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R7 R8 No.
4 -358 H Cl H CF3 CH3 H COOCH2 CH = CH2 4 -359 H Cl H CF3 CH3 H COOCH2 C= CH
4 -360 H Cl H CF3 CHa H CONH2 4 -361 H Cl H CF3 CH3 H CONHCH3 4 -362 H Cl H CF3 CH3 H CONHC2 H s 4 -363 H C1 H CF3 CH3 H CON(CH3 ) 2 4 -364 H Cl H CF3 CH3 H CON(C2 H s) 2 4 -365 F Cl H CF3 CH3 H CH2 Ch 4 -366 F Cl H CF3 CH3 H CH2 Br 4 -367 F Cl H CF3 CH3 H CH2 OCH 3 4 -368 F Cl H CF3 CH3 H CH2 0C2 H;
4- 369 F Cl H CF3 CH3 H CH2 OCH 2 OCH 3 4 -370 F Cl H CF3 CHa H CH2 OCH 2 OC 2 Hs 4 -371 F Cl H CF3 CH3 H CH2 OCOCH 3 4 -372 F Cl H CF3 CH3 H CH2 OCOC 2 Ha 4 -373 F Cl H CF3 CH3 H CH2 OCO ' C a H, 4 -374 F Cl H CF3 CH3 H CH2 OCOCH 2 Cl 4 -375 F Cl H CF3 CH3 H CH2 OCOCCI3 4 -376 F Cl H CF3 CH3 H CHZ OCOCF 3 4 -377 F Cl H CF3 CH3 H COOH
4 -378 F Cl H CF3 CH3 H COOCH3 4 -379 F Cl H CF3 CH3 H COOCZ H s 4 -380 F Cl H CF3 CH3 H C00 C, H 7 TABLE 4 (contn'd) Compound X Y R 3 R' R Z R' R8 No.
4- 381 F Cl H CF3 CH3 H C00 " C, H 9 4 -382 F Cl H CF3 CH3 H COO " C s H i, 4 -383 F Cl H CF3 CH3 H COO ' C 3 H7 4 -384 F Cl H CF3 CH3 H C00 ' C 5 H s 4 -385 F Cl H CF3 CH3 H COO ' C 6 H õ
4 -386 F Cl H CF3 CH3 H COOCH2 CH = CH2 4 -387 F Cl H CF3 CH3 H COOCH2 C= CH
4 -388 F Cl H CF3 CH3 H CONH2 4 -389 F Cl H CF3 CH3 H CONHCH3 4 -390 F Cl H CF3 CH3 H CONHC2 H s 4 -391 F Cl H CF3 CH3 H CON(CH3 ) 2 4 -392 F Cl H CF3 CH3 H CON(C2 H;) 2 4 -393 H Cl H CF3 CH3 CH3 CH2 Cl 4 -394 H Cl H CF3 CH3 CH3 CH2 Br 4 -395 H Cl H CF3 CH3 CH3 CH2 OCH 3 4 -396 H Cl H CF3 CH3 CH3 CH2 OC2 H s 4 -397 H Cl H CF3 CH3 CH3 CH2 OCH 2 OCH 3 4 -398 H C1 H CF3 CH3 CH3 CH2 OCH 2 OC 2 Hs 4 -399 H Cl H CF3 CH3 CH3 CHz OCOCH 3 4- 400 H Cl H CF3 CH3 CH3 CH2 OCOC 2 Hs 4- 401 H Cl H CF3 CH3 CH3 CH2 OCO ' C 3 H T
4 -402 H Cl H CF3 CH3 Cli3 CH2 OCOCH 2 Cl 4 -403 H Cl H CF3 CH3 CH3 CH2 OCOCC13 TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R' R$
No. 11 1~
4 -404 H Cl H CF3 CH3 CH3 CHZ OCOCF 3 4 -405 H Cl H CF3 CH3 'CH3 COOH
4 -406 H Cl H CF3 CH3 CH3 COOCH3 4 -407 H Cl H CF3 CH3 CH3 COOC2 H s 4 -408 H Cl H CF3 CH3 CH3 C00 " C 3 H, 4 -409 H Cl H CF3 CH3 CH3 C00 " C. H n 4 -410 H Cl H CF3 CH3 CH3 C00 " C s H , , 4- 411 H C1 H CF3 CH3 CH3 COO ' C 3 H, 4- 412 H C1 H CF3 CH3 CH3 COO c C s H s 4 -413 H C1 H CF3 CH3 CH3 COO ' C 6 Hõ
4 -414 H C1 H CF3 CH3 CH3 COOCHZ CH = CHz 4 -415 H Cl H CF3 CH3 CH3 COOCH2 C CH
4 -416 H Cl H CF3 CH3 CH3 CONH2 4 -417 H Cl H CF3 CH3 CH3 CONHCH3 4 -418 H Cl H CF3 CH3 CH3 CONHC2 H s 4 -419 H Cl H CF3 CH3 CH3 CON(CH3 ) 2 4 -420 H Cl H CF3 CH3 CH3 CON(C2 H s) 2 4 -421 F Cl H CF3 CH3 CH3 CH2 Cl 4 -422 F Cl H CF3 CH3 CH3 CH2 Br 4 -423 F Cl H CF3 CH3 CH3 CHz OCH 3 4- 424 F Cl H CF3 CH3 CH3 CH2 0C2 H s 4 -425 F Cl H CF3 CH3 CH3 CHZ OCH 2 OCH 3 4 -426 F Cl H CF3 CH3 CH3 CHZ OCH 2 OC 2 H6 TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R' R B
No.
4 -427 F Cl H CF3 CH3 CH3 GHz OCOCH a 4 -428 F Cl H CF3 CH3 CH3 CH2 OCOC 2 H;
4 -429 F Cl H CF3 CH3 CH3 CH2 OCO ' C 3 H7 4 -430 F Cl H CF3 CH3 CH3 CH2 OCOCH 2 C1 4 -431 F Cl H CF3 CH3 CHs CHz OCOCCI3 4 -432 F Cl H CF3 CH3 CH3 CHZ OCOCF 3 4 -433 F Cl H CF3 CH3 CH3 COOH
4 -434 F Cl H CF3 CH3 CH3 COOCH3 4 -435 F Cl H CF3 CH3 CH3 COOC2 H 5 4 -436 F Cl H CF3 CH3 CH3 C00 C 3 H 7 4 -437 F Cl H CF3 CH3 CH3 C00 C 4 H fl 4 -438 F Cl H CF3 CH3 CH3 C00 " C s H õ
4 -439 F Cl H CF3 CHa CH3 COO ' C 3 H 7 4 -440 F Cl H CF3 CH3 CHa COO ' C s H o 4 -441 F Cl H CF3 CHa CH3 COO ' C 6 H õ
4 -442 F Cl H CF3 CH3 CH3 COOCH2 CH = CHa 4 -443 F Cl H CF3 CH3 CH3 COOCH2 C= CH
4 -444 F Cl H CF3 CH3 CH3 CONH2 4 -445 F Cl H CF3 CH3 CH3 CONHCH3 4 -446 F Cl H CF3 CH3 CH3 CONHC2 H s 4 -447 F Cl H CF3 CH3 CH3 CON(CH3 ) 2 4- 448 F Cl H CF3 CH3 CH3 CON(C2 H 6 ) 2 TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R' R g No.
4 -449 F Cl H CF3 CH3 H CH 3 4 -450 F Cl H CF3 CH3 H CH 2 OH
4 -451 F Cl H CF3 CH3 CH3 CH 3 4 -452 F Cl H CF3 CH3 CH3 CH 2 OH
4 -453 F Cl H CF3 H H CH 3 4 -454 F Cl H CF3 H H CH 2 OH
4 -455 F Cl H CF3 H CH3 CH 3 4 -456 F Cl H CF3 H CH3 CH 2 OH
4 -457 H Cl H CF3 CH3 H CH 3 4 -458 H Cl H CF3 CH3 H CH 2 OH
4 -459 H Cl H CF3 CH3 CH3 CH 3 4 -460 H Cl H CF3 CH3 CH3 CH 2 OH
4 -461 H Cl H CF3 H H CH 3 4 -462 H Cl H CF3 H H CH 2 OH
4 -463 H Cl H CF3 H CH3 CH 3 4 -464 H Cl H CF3 H CH3 CH 2 OH
4 -465 F Cl H CFz Cl CH3 H CH 3 4 -466 F Cl H CF2 Cl CH3 H CH 2 OH
4 -467 F Cl H CF2 Cl CH3 CH3 CH 3 4 -468 F Cl H CF2 C1 CH3 CH3 CH 2 OH
4 -469 F. Cl H CF2 C1 H H CH 3 4 -470 F Cl H CF2 Cl H H CH 2 OH
4 -471 F Cl H CF2 Cl H CH3 CH 3 TABLE 4 (contn'd) Compound X Y R3 R' R2 R' R8 No.
4 -472 F Cl H CF2 Cl H CH3 CH 2 OH
4 -473 H Cl H CF2 Cl CH3 H CH 3 4 -474 H Cl H CF2 Cl CH3 H CH 2 OH
4 -475 H Cl H CF2 Cl CH3 CH3 CH 3 4 -476 H Cl H CF2 Cl CH3 CH3 CH 2 OH
4 -477 H Cl H CF2 Cl H H CH , 4 -478 H Cl H CF2 Cl H H CH 2 OH
4 -479 H Cl H CFz Cl H CH3 CH , 4 -480 H Cl H CF2 Cl H CH3 CH 2 OH
4 -481 H Cl H CF3 H H CH2 Cl 4 -482 H Cl H CF3 H H CH2 Br 4 -483 H Cl H CF3 H H CH2 OCH , 4 -484 H Cl H CF3 H H CH2 0C2 H;
4 -485 H Cl H CF3 H H CH2 OCH 2 OCH 3 4 -486 H Cl H CF3 H H CH2 OCH 2 OC 2 H;
4 -487 H Cl H CF3 H H CH2 OCOCH a 4 -488 H Cl H CF3 H H CHZ OCOC 2 Hs 4 -489 H Cl H CF3 H H CH2 OCO ' C, H, 4 -490 H Cl H CF3 H H CHz OCOCH 2 Cl 4- 491 H Cl H CF3 H H CHz OCOCC13 4 -492 H Cl H CF3 H H CH2 OCOCF 3 4 -493 H Cl H CF3 H H COOH
4 -494 H Cl H CF3 H H COOCH3 TABLE 4 (contn'd) Compound X Y R 3 R ' R2 R' R B
No.
4 -495 H Cl H CF3 H H COOC2 H s 4 - 496 H C1 H CF3 H H C00 " C a H, 4- 497 H C1 H CF3 H H C00 " C 4 H y 4 -498 H Cl H CF3 H H C00 C Ht, 4 -499 H Cl H CFa H H COO C 3 H 7 4 -500 H Cl H CF3 H H C00 ' C s H s 4 -501 H Cl H CF3 H H C00 ' C 6 H 11 4 -502 H Cl H CF3 H H COOCH2 CH = CH2 4 -503 H Cl H CF3 H H COOCH2 C CH
4 -506 H Cl H CF3 H H CONHC2 H
4 -507 H Cl H CF3 H H CON(CH3 ) 2 4- 508 H Cl H CF3 H H CON(C2 H;) 2 4 -509 F Cl H CF3 H H CH2 Cl 4 -510 F Cl H CF3 H H CH2 Br 4 -512 F CI H CF3 H H CH2 0C2 H s 4 -513 F Cl H CF3 H H CH2 OCH 2 OCH 3 4 -514 F Cl H CF3 H H CHz OCH 2 OC 2 Hs r 4 -516 F Cl H CF3 H H CH2 OCOC 2 Hs 4- 517 F Cl H CF3 H H CHZ OCO ' C 3 H, TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R7 R8 No.
4 -518 F Cl H CF3 H H CH2 OCOCH 2 Cl 4- 519 F Cl H CF3 H H CH2 OCOCCI3 4 -520 F Cl H CF3 H H CH2 OCOCF , 4 -521 F Cl H CF3 H H COOH
4 -522 F Cl H CF3 H H COOCH3 4 -523 F Cl H CF3 H H COOC2 H s 4 -524 F Cl H CF3 H H C00 " C a H 1 4 -525 F Cl H CF3 H H C00 "-C H s 4 -526 F Cl H CF3 H H C00 " C 5 Hõ
4 -527 F Cl H CF3 'H H COO C a H T
4- 528 F Cl H CF3 H H C00 ' C 5 H s 4 -529 F Cl H CF3 H H COO ' C 6 Hõ
4 -530 F Cl H CF3 H H COOCH2 CH = CH2 4 -531 F Cl H CF3 H H COOCH2 C= CH
4 -532 F Cl H CF3 H H CONH2 4 -533 F Cl H CF3 H H CONHCH3 4 -534 F Cl H CF3 H H CONHC2 H s 4 -535 F Cl H CF3 H H CON(CH3 ) 2 4- 536 F Cl H CF3 H H CON(C2 H 5) 2 4 -537 H Cl H CF3 H CH3 CH2 Cl 4 -538 H Cl H CF3 H CH3 CH2 Br 4 -539 H Cl H CF3 H CH3 CH2 OCH a 4 -540 H Cl H CF3 H CH3 CH2 0C2 H 5 WO 97/07104 PCT/.bP96/02311 TABLE 4 (contn'd) Compound X Y R3 R' R2 R' R8 No.
4 -541 H Cl H CF3 H CH3 CHz OCH 2 OCH 3 4 -542 H Cl H CF3 H CH3 CH2 OCH 2 OC 2 Hs 4 -543 H Cl H CF3 H CH3 CH2 OCOCH a 4 -544 H Cl H CF3 H CHa CH2 OCOC 2 H5 4 -545 H Cl H CF3 H CH3 CH2 OCO ' C 3 H, 4 -546 H Cl H CF3 H CH3 CHZ OCOCH 2 Cl 4 -547 H Cl H CF3 H CH3 CHa OCOCC13 4 -548 H Cl H CF3 H CH3 CH2 OCOCF 3 4 -549 H Cl H CF3 H CH3 COOH
4 -550 H Cl H CF3 H CH3 COOCH3 4 -551 H Cl H CF3 H CH3 COOC2 H s 4 -552 H Cl H CF3 H CH3 C00 " C, H T
4 -553 H Cl H CF3 H CH3 C00 " C 4 H 9 4 -554 H Cl H CF3 H CH3 C00 " C s H õ
4 -555 H Cl H CF3 H CH3 COO ' C 3 H, 4 -556 H Cl H CF3 H CH3 COO ' C s H q 4 -557 H Cl H CF3 H CH3 C00 ' C 6 H,1 4 -558 H Cl H CF3 H CH3 COOCH2 CH = CHz 4 -559 H Cl H CF3 H CH3 COOCH2 C= CH
4 -560 H Cl H CF3 H CH3 CONH2 4 -561 H Cl H CF3 H CH3 CONHCH3 4 -562 H Cl H CF3 H CH3 CONHC2 H 5 TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R7 R B
No.
4 -563 H Cl H CF3 H CH3 CON(CH3 ) 2 4 -564 H Cl H CF3 H CH3 CON(C2 H s) 2 4 -565 F Cl H CF3 H CHs CH2 Cl 4 -566 F Cl H CF3 H CH3 CH2 Br 4 -567 F Cl H CF3 H CH3 CH2 0CH 3 4 -568 F Cl H CF3 H CH3 CH2 0C2 H s 4 -569 F Cl H CF3 H CH3 CH2 OCH 2 OCH 3 4 -570 F Cl H CF3 H CH3 CH2 OCH 2 OC 2 Hs 4 -571 F Cl H CF3 H CH3 CHz OCOCH a 4 -572 F Cl H CF3 H CH3 CH2 OCOC 2 H5 4 -573 F Cl H CF3 H CH3 CH2 OCO ' C a H 7 4 -574 F Cl H CF3 H CH3 CH2 OCOCH 2 Cl 4 -575 F Cl H CF3 H CH3 CH2 OCOCC13 4 -576 F Cl H CF3 H CHs CH2 OCOCF a 4 -577 F Cl H CF3 H CH3 COOH
4 -578 F Cl H CF3 H CH3 COOCH3 4 -579 F Cl H CF3 H CH3 COOC2 H s 4 -580 F Cl H CF3 H CH3 COO " C 3 H 7 4 -581 F Cl H CF3 H CH3 COO " C, H
4 -582 F Cl H CF3 H CH3 COO C s H-~
4 -583 F Cl H CF3 H CH3 COO ' C a H 7 {
4 -584 F Cl H CF3 H CH3 COO ' C s H 9 4 -585 F Cl H CF3 H CH3 COO ' C 6 H õ
WO 97/07104 PCT/.TP96/02311 TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R' R8 No.
4 -586 F Cl H CFa H CH3 COOCH2 CH = CH2 4 -587 F Cl H CF3 H CH3 COOCH2 C= CH
4 -588 F Cl H CF3 H CH3 CONH2 4 -589 F Cl H CF3 H CH3 CONHCH3 4 -590 F Cl H CF3 H CH3 CONHC2 H s 4- 591 F Cl H CF3 H CH3 CON(CH3 ) 2 4 -592 F Cl H CF3 H CH3 CON(C2 H 5) 2 4 -593 H Cl H CF3 H H CH2 Cl 4 -594 H Cl H CF3 H H CH2 Br 4 -595 H Cl H CF3 H H CH2 OCH 3 4 -596 H Cl H CF3 H H CH2 0C2 H 5 4 -597 H Cl H CF3 H H CH2 OCH 2 OCH 3 4 -598 H Cl H CF3 H H CH2 OCH 2 OC 2 Hs 4- 599 H Cl H CF3 H H CH2 OCOCH 3 4 -600 H Cl H CF3 H H CH2 OCOC 2 Hs 4 -601 H Cl H CF3 H H CH2 OCO ' C 3 H T
4 -602 H Cl H CF3 H H CH2 OCOCH 2 Cl 4 -603 H Cl H CF3 H H CH2 OCOCCI3 4 -604 H Cl H CF3 H H CHz OCOCF 3 4 -605 H C l H CF3 H H COOH
4 -606 H Cl H CF3 H H COOCH3 4 -607 H Cl H CF3 H H COOC2 H 5 4 - 608 H Cl H CF3 H H C00 " C, H, TABLE 4 (contn'd) compound X Y R' R' R Z R' R 8 No.
4 - 609 H Cl H CF3 H H C00 " C4 H o 4 - 610 H Cl H CF3 H H C00 " C 5 H,i 4 -611 H Cl H CF3 H H COO ' C 3 H, 4 -612 H Cl H CF3 H H C00 ' C 5 H 9 4 -613 H Cl H CF3 H H COO ' C 6 H ii 4 -614 H Cl H CF3 H H COOCHZ CH = CH2 4 -615 H Cl H CF3 H H COOCH2 C CH
4 -616 H Cl H CF3 H H CONH2 4 -617 H Cl H CF3 H H CONHCH3 4 -618 H Cl H CF3 H H CONHC2 H s 4 -619 H Cl H CF3 H H CON(CH3 ) 2 4 -620 H Cl H CF3 H H CON(C2 H s) 2 4 -621 F Cl H CF3 H H CH2 C1 4 -622 F Cl H CF3 H H CH2 Br 4 -623 F Cl H CF3 H H CH2 OCH 3 4 -624 F Cl H CF3 H H CH2 OC2 H s 4 -625 F Cl H CF3 H H CH2 OCH 2 OCH a 4 -626 F Cl H CF3 H H CH2 OCH 2 OC 2 Hs 4 -627 F Cl H CF3 H H CH2 OCOCH , 4 -628 F Cl H CF3 H H CH2 OCOC 2 Hs 4 -629 F Cl H CF3 H H CH2 OCO ' C 3 H T
4 -630 F Cl H CF3 H H CH2 OCOCH 2 Cl 4 -631 F Cl H CF3 H H CH2 OCOCCI3 TABLE 4 (contn'd) Compound X Y R 3 R' R Z R' R a No.
4 -633 F Cl H CF3 H H COOH
4 -635 F Cl H CF3 H H COOC2 H s 4- 636 F Cl H CF3 H H C00 " C 3 H 7 4- 638 F C1 H CF3 H H C00 " C s H õ
4 -639 F Cl H CF3 H H C00 ' C H
4- 640 F Cl H CF3 H H C00 ' C s H 9 4- 641 F Cl H CF3 H H C00 ' C 6 H 11 4 -642 F Cl H CF3 H H COOCH2 CH = CH2 4 -643 F Cl H CF3 H H COOCHa C= CH
4 -646 F C1 H CF3 H H CONHC2 H s 4 -647 F C1 H CF3 H H CON(CH3 ) 2 4 -648 F Cl H CF3 H H CON(C2 H 5) 2 4 -650 H Cl H CF3 H CH3 CH2 Br 4 -652 H Cl H CF3 H CH3 CH2 0C2 H 5 4 -653 H Cl H CF3 H CHa CH2 OCH 2 OCH 8 TABLE 4 (contn'd) Compound X Y R' R' R2 R' R B
No.
4 -655 H Cl H CF3 H CH3 CH2 OCOCH 3 4 -656 H Cl H CF3 H CH3 CH2 OCOC 2 H5 4 -657 H Cl H CF3 H CH3 CH2 OCO ' C, H 7 4 -658 H Cl H CF3 H CH3 CH2 OCOCH 2 Cl 4- 659 H Cl H CF3 H CH3 CHZ OCOCCIy 4 -660 H Cl H CF3 H CH3 CH2 OCOCF 3 4 -661 H Cl H CF3 H CH3 COOH
4 -662 H Cl H CF3 H CH3 COOCH3 4 -663 H Cl H CF3 H CH3 COOC2 H s 4 -664 H Cl H CF3 H CH3 C00 " C 3 H7 4 -665 H Cl H CF3 H CHa C00 C H
4 -666 H Cl H CF3 H CH3 C00 " C H
4 -667 H Cl H CF3 H CH3 COO C, H, 4 -668 H Cl H CF3 H CH3 COO C 5 H 9 4 -669 H Cl H CF3 H CH3 COO ' C 6 H õ
4 -670 H Cl H CF3 H CH3 COOCH2 CH = CHz 4 -671 H Cl H CF3 H CHs COOCH2 C= CH
4 -672 H Cl H CF3 H CH3 CONH2 4 -673 H Cl H CF3 H CH3 CONHCH3 4 -674 H Cl H CF3 H CH3 CONHC2 H s 4 -675 H Cl H CF3 H CH3 CON(CH3 ) 2 4 -676 H Cl H CF3 H CH3 CON(C2 H 5) 2 TABLE 4 (contn'd) Compound X y jZ 3 R 1 R 2 R7 R
No.
4 -677 F Cl H CF3 H CH3 CHz Cl 4 -678 F Cl H CF3 H CH3 CH2 Br 4 -679 F Cl H CF3 H CH3 CH2 OCH , 4 -680 F Cl H CF3 H CHa CH2 0C2 H s 4 -681 F Cl H CF3 H CH3 CHz OCH 2 OCH 3 4 -682 F Cl H CF3 H CHa CH2 OCH 2 OC 2 Hs 4 -683 F Cl H CF3 H CH3 CH2 OCOCH , 4 -684 F Cl H CF3 H CHa CH2 OCOC 2 Hs 4 -685 F Cl H CF3 H CH3 CH2 OCO ' C a H T
4 -686 F Cl H CF3 H CH3 CH2 OCOCH 2 Cl 4 -687 F Cl H CF3 H CH3 CHZ OCOCC13 4 -688 F Cl H CF3 H CH3 CHZ OCOCF , 4 -689 F Cl H CF3 H CH3 COOH
4 -690 F Cl H CF3 H CH3 COOCH3 4 -691 F Cl H CF3 H CH3 COOC2. H s 4 -692 F Cl H CF3 H CH3 C00 C a H, 4 -693 F Cl H CF3 H CH3 C00 " C 4 H 9 4 -694 F C1 H CF3 H CH3 C00 " C 5 H õ
4 -695 F Cl H CF3 H CH3 C00 ' C a H, 4 -696 F Cl H CF3 H CH3 COO c C 5 H fl 4 -697 F Cl H CF3 H CH3 COO ' C 6 H õ
4 -698 F Cl H CFa H CH3 COOCH2 CH = CH2 4 -699 F Cl H CF3 H CH3 COOCHa C CH
TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R' R 8 No.
4 -701 F Cl H CF3 H CH3 CONHCH3 4 -702 F Cl H CF3 H CHs CONHC2 H s 4 -703 F Cl H CF3 H CH3 CON(CH3 ) 2 4 -704 F Cl H CF3 H CHa CON (C2 H s) 2 4 -705 H Cl CH3 CF3 H H CH2 Cl 4 -706 H Cl CH3 CF3 H H CH2 Br 4 -707 H Cl CH3 CF3 H H CH2 OCH 3 4 -708 H Cl CH3 CF3 H H CH2 0C2 H s 4 -709 H Cl CH3 CF3 H H CH2 OCH 2 OCH 3 4 -710 H C1 CH3 CF3 H H CH2 OCH 2 OC 2 Hs 4 -711 H Cl CH3 CF3 H H CH2 OCOCH I
4 -712 H C1 CHa CF3 H H CHz OCOC.2 Hs 4- 713 H Cl CHs CF3 H H CHz OCO ' C a H 7 4 -714 H Cl CH3 CF3 H H CH2 OCOCH 2 Cl 4 -715 H Cl CH3 CF3 H H CH2 OCOCCI3 4 -716 H Cl CH3 CF3 H H CH2 OCOCF 3 4 -717 H Cl CH3 CF3 H H COOH
4 -718 H Cl CH3 CF3 H H COOCH3 4 -719 H Cl CH3 CF3 H H COOC2 H s 4 -720 H Cl CH3 CF3 H H COO " C 3 H, , 4- 721 H Cl CH3 CF3 H H C00 " C 4 H fl 4 -722 H Cl CH3 CF3 H H COO " C s H õ
VvO 97/07104 PCT/.dP96/02311 TABLE 4 (contn'd) Compound X Y R3 R' R2 R' R8 No.
4 -723 H Cl CH3 CF3 H H COO ' C, H, 4 -724 H Cl CH3 CF3 H H COO ' C 5 H y 4 -725 H Cl CH3 CF3 H H COO ' C 6 H 11 4 -726 H Cl CH3 CF3 H H COOCH2 CH = CHZ
4 -727 H Cl CH3 CF3 H H COOCH2 C= CH
4 -728 H Cl CH3 CF3 H H CONH2 4 -729 H Cl CHs CF3 H H CONHCH3 4 -730 H Cl CH3 CF3 H H CONHC2 H 5 4 -731 H Cl CH3 CF3 H H CON(CH3 ) 2 4 -732 H Cl CH3 CF3 H H CON(C2 H s) 2 4 -733 F Cl CH3 CF3 H H CHa Cl 4 -734 F Cl CH3 CF3 H H CH2 Br 4 -735 F Cl CH3 CF3 H H CHZ OCH 3 4 -736 F Cl CH3 CF3 H H CH2 0C2 H s 4 -737 F Cl CH3 CF3 H H CHZ OCH 2 OCH
4 -738 F Cl CH3 CF3 H H CH2 OCH 2 OC 2 H5 4 -739 F Cl CH3 CF3 H H CH2 OCOCH , 4 -740 F Cl CH3 CF3 H H CH2 OCOC 2 Hs 4 -741 F Cl CH3 CF3 H H CHZ OCO ' C, H
4 -742 F Cl CH3 CF3 H H CHZ OCOCH 2 Cl 4 -743 F Cl CH3 CF3 H H CH2 OCOCCI3 4 -744 F Cl CH3 CF3 H H CHZ OCOCF 3 4 -745 F Cl CH3 CF3 H H COOH
TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R' R 8 No.
4 -746 F Cl CH3 CF3 H H COOCH3 4 -747 F Cl CH3 CF3 H H COOCz. H s 4 -748 F Cl CH3 CF3 H H COO " C 3 H, 4 -749 F C1 CH3 CF3 H H COO " C, H s 4 -750 F Cl CH3 CF3 H H COO " C 5 H õ
4- 751 F Cl CH3 CF3 H H COO ' C 3 H 7 4- 752 F Cl CH3 CF3 H H C00 ' C 5 H 9 4 -753 F C1 CH3 CF3 H H COO ' C 6 H
4- 754 F Cl CH3 CF3 H H COOCHZ CH = CHz 4 -755 F Cl CH3 CF3 H H COOCH2 C= CH
4 -756 F Cl CH3 CF3 H H CONH2 4- 757 F Cl CH3 CF3 H H CONHCH3 4 -758 F Cl CH3 CF3 H H CONHC2 H s 4 -759 F Cl CH3 CF3 H H CON(CH3 ) 2 4 -760 F Cl CH3 CF3 H H CON(C2 H s) 2 4 -761 H C1 CH3 CF3 H CH3 CH2 Cl 4 -762 H C1 CH3 CF3 H CH3 CH2 Br 4 -763 H Cl CH3 CF3 H CH3 CH2 0CH 3 4 -764 H Cl CH3 CF3 H CH3 CH2 0C2 H 5 4 -765 H Cl CH3 CF3 H CH3 CH2 0CH 2 OCH 3 4 -767 H Cl CH3 CF3 H CH3 CHZ OCOCH 3 4 -768 H C1 CH3 CF3 H CH3 CH2 OCOC 2 Hs WO 97f07104 PCT/JP96/02311 TABLE 4 (contn'd) compound X Y R 3 R' R 2 R7 R8 No.
4 -769 H Cl CH3 CF3 H CH3 CH2 OCO ' C 3 H, 4 -770 H Cl CH3 CF3 H CH3 CH2 OCOCH 2 Cl 4 -771 H Cl CH3 CF3 H CH3 CHZ OCOCCI3 4 -772 H Cl CH3 CF3 H CH3 CHz OCOCF 3 4 -773 H Cl CH3. CF3 H CH3 COOH
4 -774 H Cl CH3 CF3 H CH3 COOCH3 4 -775 H Cl CH3 CF3 H CH3 COOC2 H s 4 -776 H Cl CH3 CF3 H CH3 COO " C 3 H 7 4 -777 H Cl CH3 CFa H CH3 COO C{ H g 4 -778 H Cl CH3 CF3 H CH3 COO " C s H õ
4 -779 H C1 CH3 CF3 H CH3 COO ' C 3 H7 4 -780 H Cl CH3 CF3 H CH3 COO ' C s H o 4- 781 H Cl CH3 CF3 H CH3 COO ' C 6 H õ
4 -782 H Cl CH3 CF3 H CH3 COOCH2 CH = CH2 4 -783 H Cl CH3 CF3 H CH3 COOCH2 C= CH
4 -784 H C1 CH3 CF3 H CHa CONH2 4 -786 H Cl CH3 CF3 H CH3 CONHCz H a 4 -787 H C1 CH3 CF3 H CH3 CON(CH3 ) 2 4 -788 H Cl CH3 CF3 H CH3 CON(C2 H s) 2 4 -789 F Cl CH3 CF3 H CH3 CHz Cl ,.
4 -790 F Cl CH3 CF3 H CH3 CHz Br TABLE 4 (contn'd) Compound X Y R3 R' R Z R' R 8 No.
4 -791 F Cl CH3 CF3 H CH3 CH2 OCH , 4 -792 F Cl CH3 CF3 H CH3 CH2 0C2 H;
4 -793 F Cl CH3 CF3 H CH3 CH2 OCH 2 OCH 3 4 -794 F Cl CH3 CF3 H CH3 CH2 OCH 2 OC ~ H;
4 -795 F Cl CH3. CF3 H CH3 CH2 OCOCH 3 4 -796 F Cl CH3 CF3 H CH3 CH2 OCOC 2 H;
4 -797 F Cl CH3 CF3 H CH3 CH2 OCO ' C a H 7 4 -798 F C1 CH3 CF3 H CH3 CH2 OCOCH 2 Cl 4 -799 F Cl CH3 CF3 H CH3 CH2 OCOCCI3 4 -800 F Cl CH3 CF3 H CH3 CH2 OCOCF , 4 -801 F Cl CH3 CF3 H CH3 COOH
4 -802 F Cl CH3 CF3 H CH3 COOCH3 4 -803 F Cl CH3 CF3 H CH3 COOC2 H s 4 -804 F C1 CH3 CF3 H CH3 C00 " C 3 H 7 4 -805 F Cl CH3 CF3 H CH3 COO " C 4 H 3 4 -806 F Cl CH3 CF3 H CH3 COO " C s H õ
4 -807 F C1 CH3 CF3 H CH3 COO ' C 3 H 1 4- 808 F Cl CH3 CF3 H CH3 COO ' C 5 H s 4 -809 F Cl CHa CF3 H CH3 COO c C 6 H õ
4 -810 F Cl CH3 CF3 H CH3 COOCH2 CH = CH2 4 -811 F Cl CH3 CF3 H CH3 COOCH2 C= CH
4 -812 F Cl CH3 CF3 H CH3 CONH2 4 -813 F Cl CH3 CF3 H CH3 CONHCH3 WO 97/07104 PC'H'/JP96/02311 TABLE 4 (contn'd) Compound X Y R3 R' R2 R' R8 No.
4 -814 F Cl CH3 CF3 H CH3 CONHC2 H s 4 -815 F Cl CH3 CF3 H -CH3 CON(CH3 ) Z
4- 816 F Cl CH3 CF3 H CH3 CON(C2 H s) 2 4 -817 H Cl CH3 CF3 H H CH2 Cl 4 -818 H Cl CH3 CF3 H H CH2 Br 4 -819 H Cl CH3 CF3 H H CH2 OCH , 4 -820 H Cl CH3 CF3 H H CH2 0Ca H s 4 -821 H Cl CH3 CF3 H H CH2 OCH 2 OCH 3 4 -822 H Cl CH3 CF3 H H CH2 OCH 2 OC 2 Hs 4 -823 H Cl CH3 CF3 H H CH2 OCOCH 3 4 -824 H Cl CH3 CF3 H H CH2 OCOC 2 Hs 4 -825 H Cl CH3 CF3 H H CH2 OCO ' C, H T
4 -826 H Cl CH3 CF3 H H CH2 OCOCH 2 Cl 4 -827 H Cl CH3 CF3 H H CH2 OCOCCI3 4 -828 H Cl CH3 CF3 H H CH2 OCOCF , 4 -829 H Cl CH3 CF3 H H COOH
4 -830 H Cl CHa CF3 H H COOCH3 4 -831 H Cl CHa CF3 H H COOC2 H s 4 -832 H Cl CH3 CF3 H H C00 " C 3 H, 4 -833 H C1 CH3 CF3 H H C00 " C 4 H 9 4 -834 H Cl CH3 CF3 H H C00 " C 5 H õ
4 -835 H Cl CH3 CF3 H H C00 ' C a H7 4 -836 H Cl CH3 CF3 H' H COO C 5 H 9 TABLE 4 (contn'd) Compound X Y R 3 R' R Z R7 R8 No.
4 -837 H Cl CH3 CF3 H H COO ' C 6 H
4 -838 H Cl CH3 CF3 H H COOCHZ CH = CHZ
4 -839 H Cl CH3 CF3 H H COOCHZ C= CH
4 -840 H Cl CH3 CF3 H H CONHz 4 -841 H Cl CH3 CF3 H H CONHCH3 4 -842 H Cl CH3 CF3 H H CONHC2 H s 4 -843 H Cl CH3 CF3 H H CON(CH3 ) 2 4 -844 H Cl CH3 CF3 H H CON(C2 H 2 4 -845 F Cl CH3 CF3 H H CH2 Cl 4 -846 F Cl CH3 CF3 H H CH2 Br 4 -847 F Cl CHs CF3 H H CH2 OCH 3 4 -848 F Cl CH3 CF3 H H CH2 OC2 H s 4 -849 F Cl CH3 CF3 H H CHa OCH 2 OCH 3 4 -850 F Cl CH3 CF3 H H CHa OCH 2 OC 2 H;
4 -851 F Cl CH3 CF3 H H CHa OCOCH 3 4 -852 F Cl CHa CF3 H H CHZ OCOC 2 Ha 4 -853 F Cl CH3 CF3 H H CHz OCO ' C a H 7 4 -854 F Cl CH3 CF3 H H CH2 OCOCH 2 Cl 4 -855 F Cl CH3 CF3 H H CH2 OCOCC13 4 -856 F Cl CH3 CF3 H H CH2 OCOCF , 4 -857 F Cl CH3 CF3 H H COOH
.
4 -858 F Cl CH3 CF3 H H COOCH3 4 -859 F Cl CH3 CF3 H H COOC2 H s TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R 7 R 8 No.
4 -860 F Cl CH3 CF3 H H C00 C a H 7 4- 861 F Cl CH3 CF3 H H C00 C 4 H 9 4 -862 F Cl CH3 CF3 H H C00 " C 5 H õ
4 -863 F Cl CH3 CF3 H H COO ' C a H 7 4 -864 F Cl CH3 CF3 H H C00 C C s H s 4 -865 F Cl CH3 CF3 H H COO c C 6 H õ
4 -866 F Cl CH3 CF3 H H COOCH2 CH = CHZ
4 -867 F C l CH3 CF3 H H COOCH Z-C = CH
4 -868 F Cl CH3 CF3 H H CONH2 4 -869 F Cl CH3 CF3 H H CONHCH3 4 -870 F Cl CH3 CF3 H H CONHCZ H 5 4 -871 F Cl CH3 CF3 H H CON(CH3 ) 2 4 -872 F Cl CH3 CF3 H H CON(C2 H s) 2 4 -873 H Cl CH3 CF3 H CH3 CH2 Cl 4 -874 H Cl CH3_ CF3 H CH3 CH2 Br 4 -875 H Cl CH3 CF3 H CH3 CH2 OCH a 4 -876 H Cl CH3 CF3 H CHa CH2 0C2 H 5 4 -877 H Cl CH3 CF3 H CH3 CH2 OCH 2 OCH , 4 -878 H Cl CH3 CF3 H CH3 CH2 OCH 2 OC 2 Hs 4 -879 H Cl CHa CF3 H CH3 CHz OCOCH a 4 -880 H Cl CH3 CF3 H CH3 CHz OCOC 2 Hs .
4- 881 H Cl CH3 CF3 H CH3 CHZ OCO ' C s H, 4 -882 H Cl CH3 CF3 H CH3 CHQ OCOCH 2 Cl TABLE 4 (contn'd) Compound X Y R 3 R' R2 R' R B
No.
4 -883 H Cl CH3 CF3 H CH3 CH2 OCOCCI3 4 -884 H Cl CH3 CF3 H CH3 CH2 OCOCF 3 4 -885 H Cl CH3 CF3 H CH3 COOH
4 -886 H Cl CH3 CF3 H CH3 COOCH3 4 -887 H Cl CH3 CF3 H CH3 COOC2 H 5 4 -888 H Cl CH3 CF3 H CH3 C00 " C, H 7 4 -889 H Cl CH3 CF3 H CH3 COO " C 4 H
4 -890 H Cl CH3 CF3 H CH3 C00 " C s H
4 -891 H Cl CH3 CF3 H CHa COO ' C a H 7 4 -892 H Cl CH3 CF3 H CH3 COO c C 5 H q 4 -893 H Cl CH3 CF3 H CH3 COO ' C 6 Hõ
4 -894 H Cl CHs CF3 H CH3 COOCH2 CH = CH2 4 -895 H Cl CH3 CF3 H CH3 COOCH2 C= CH
4 -896 H Cl CH3 CF3 H CHs CONH2 4 -897 H Cl CH3 CF3 H CH3 CONHCH3 4 -898 H C1 CH3 CF3 H CH3 CONHC2 H s 4 -899 H Cl CH3 CF3 H CH3 CON(CH3 ) 2 4 -900 H Cl CH3 CF3 H CH3 CON(C2.H ;) 2 4 -901 F Cl CH3 CF3 H CH3 CH2 Cl 4 -902 F Cl CH3 CF3 H CH3 CH2 Br 4 -903 F Cl CH3 CF3 H CH3 CH2 OCH 3 4 -904 F Cl CH3 CF3 H CH3 CHZ 0C2 H 5 TABLE 4 (contn'd) Compound X y R3 R' R2 R' R8 No.
4 -905 F Cl CH3 CF3 H CHa CH2 OCH 2 OCH a 4 -906 F Cl CH3 CF3 H CH3 CH2 OCH 2 OC 2 Hs 4 -907 F Cl CH3 CF3 H CH3 CH2 OCOCH , 4 -908 F C1 CH3 CF3 H CH3 CH2 OCOC 2 Hs 4 -909 F Cl CH3 CFa H CH3 CH2 OCO ' C 3 H, 4 -910 F Cl CH3 CF3 H CH3 CH2 OCOCH 2 Cl 4 -911 F Cl CH3 CF3 H CH3 CH2 OCOCC13 4 -912 F Cl CH3 CF3 H CH3 CH2 OCOCF 3 4 -913 F Cl CH3 CF3 H CH3 COOH
4 -914 F Cl CH3 CF3 H CH3 COOCH3 4 -915 F Cl CH3 CF3 H CH 3 COOC2 H;
4- 916 F Cl CH3 CF3 H CH3 C00 C 3 H 7 4- 917 F Cl CH3 CF3 H CH3 C00 " C, H 9 4 -918 F Cl CH3 CF3 H CH3 C00 " C 5 H i 4- 919 F Cl CH3 CF3 H CH3 COO ' C, H 7 4 -920 F Cl CH3 CF3 H CH3 C00 ' C 5 H9 4- 921 F Cl CH3 CF3 H CH3 COO ' C 6 H õ
4 -922 F Cl CH3 CF3 H CH3 COOCH2 CH = CHZ
4 -923 F Cl CH3 CF3 H CH3 COOCH2 C= CH
4 -924 F Cl CH3 CF3 H CH3 CONH2 4 -925 F Cl CH3 CF3 H CH3 CONHCH3 4 -926 F C1 CH3 CF3 H CH3 CONHC2 H s 4 -927 F Cl CH3 CF3 H CH3 CON(CH3 ) Z
WO 97/07104 PC'd'/JP96/02311 TABLE 4 (contn'd) Compound X Y R 3 R ' R Z R' R B
No.
4 -928 F Cl CH3 CF3 H CH3 CON(C2 H z 4 -929 F Cl CH3 CF3 H H CH 3 4 -930 F Cl CH3 CF3 H H CH z OH
4 -931 F Cl CH3 CF3 H CH3 CH 3 4 -932 F Cl CH3 CF3 H CH3 CH 2 OH
4 -933 H Cl CH3 CF3 H H CH 3 4 -934 H Cl CH3 CF3 H H CH 2 OH
4 -935 H Cl CH3 CF3 H CH3 CH 3 4 -936 H Cl CH3 CF3 H CH3 CH 2 OH
TABLE S
= Compounds of the formula:
X O R'-N ~ ~ N x R~~ -N-N
\ R;
RS
Compound X R3 R ' R 2 R S
No.
- 1 H H CF2 Cl CHa CH3 5-2 H H CF2C1 CH3 C 2 H s 5 - 3 H H CFz C1 CH3 ' C 3 H T
5- 4 H H CFZ C1 CH3 C 3 H, 5- 5 H H CF2 Cl CH3 ' C, H 9 5 - 6 H H CF2 Cl CH3 CH2 CH = CH2 5 - 7 H H CF2 Cl CH3 CH(CH3 )CH =CH2 5- 8 H H CF2 Cl CH3 CH2 C= CH
5 - 9 H H CF2 C1 CHa CH(CHa )C = CH
5- 11 F H CF2 C1 CH3 C 2 H;
5- 12 F H CF2 Cl CH3 C , H, 5 -13 F H CF2 Cl CH3 "C 3 H, 5- 14 F H CF2 C1 CH3 'C , H 9 4 5 -15 F H CF2 C1 CH3 CH2 CH=CH2 TABLE 5 (contn'd) Compound x R 3 R ' R Z R 5 No.
-16 F H CF2 Cl CH3 CH(CH3 )CH =CH2 5 -17 F H CF2 Cl CH3 CH2 C= CH
5 -18 F H CF2 Cl CH3 CH(CH3 )C=CH
5- 20 H H CF3 CH3 C z H s 5- 21 H H CF3 CH3 'C 3 H 7 5 -22 H H CF3 CH3 "C 3 H 7 5 -23 H H CF3 CH3 'C -H 9 5 -24 H H CF3 CH3 CHz CH=CH2 5 -25 H H CF3 CH3 CH(CH3 )CH =CH2 5 -26 H H CF3 CH3 CH2 C=CH
5 -27 H H CFa CH3 CH(CH3 )C -CH
5- 30 F H CF3 CH3 'C 3 H, 5-31 F H CF3 CH3 'C 4 H 9 5 -32 F H CF3 CH3 CH2 CH=CH2 5 -33 F H CF3 CH3 CH(CH3 )CH =CH2 5 -34 F H CF3 CH 3 CH 2 C= CH
5 -35 F H CF3 CH3 CH(CH3 )C=CH =
5 -36 H H CF2 Cl H CH3 5-37 H H CF2 C1 H C z H 5 5 -38 H H CF2 Cl H 'C 3 H 7 TABLE 5 (contn'd) Compound x R3 R ' R 2 R S
No.
5- 39 H H CF2 Cl H "C 3 H 7 5- 40 H H CF2 Cl H 'C H
-41 H H CF2 Cl H CH2 CH=CH2 5 -42 H H CF2 Cl H CH(CH3 )CH =CH2 5 -43 H H CF2 C l H CH a C CH
5-44 H H CF2 Cl H CH(CH3 )CCH
5- 45 F H CF2 Cl H CH3 5- 46 F H CF2 Cl H C 2-H
5 -47 F H CF2 Cl H 'C 3 H, 5 -48 F H CF2 Cl H "C 3 H
5 -49 F H CF2 Cl H ' C, H 9 5 -50 F H CF2 Cl H CH2 CH=CH2 5 -51 F H CF2 Cl H CH(CH3 )CH =CH2 5 -52 F H CF2 Cl H CH2 C=CH
5 -53 F H CF2 Cl H CH(CH3 )C=CH
5- 55 H H CF3 H C z H s 5- 56 H H CF3 H 'C 3 H5- 57 H H CF3 H "C 3 H
5- 58 H H CFa H 'C , H
5 -59 H H CF3 H CH2 CH=CH2 5 -60 H H CF3 H CH(CH3 )CH =CH2 5 -61 H H CF3 H CH2 C=CH
TABLE 5 (contn'd) Compound x R 3 R ' R 2 R 5 No.
-62 H H CF3 H. CH(CH3 )C=CH
5- 64 F H CF3 H C 2 H s 5- 65 F H CFa H C a H 7 5 -66 F H CF3 H 'C 4 H 9 5 -67 F H CF3 H CH2 CH= CH2 5 -68 F H CF3 H CH(CH3 )CH =CH2 5 -70 F H CF3 H CH(CH3 )C=CH
5 -72 H CH3 CF3 H C 2 H;
5- 73 H CH3 CF3 H 'C 3 H, 5 -74 H CH3 CF3 H C a H 7 5- 75 H CH3 CF3 H 'C 4 H fl 5 -76 H CH3 CF3 H CH2 CH=CH2 5 -77 H CH3 CF3 H CH(CH3 )CH =CH2 5 -79 H CH3 CF3 H CH(CH3 )C=CH
5 -82 F CH3 CF3 H 'C 3 H 7 5- 83 F CH3 CF3 H 'C , H o 5 -84 F CH3 CF3 H CH2 CH=CH2 TABLE 5 (contn'dl Compound X R 3 R' R Z R 5 No.
-85 F CH3 CF3 H CH(CH3 )CH = CH2 5 -87 F CH3 CF3 H CH(CH3 )C=CH
The physical properties (melting point, m.p.) or 'H-NMR (250 or 300 MHz, CDCI3, TMS, S(ppm)) data for some of the present compounds are shown below.
Compound 1-332, m.p. 97.0 C
Compound 1-335, rn.p. 80.8 C
Compound 1-337, m.p. 91.5 C
Compound 1-338, in.p. 86.1 C
Compound 1-344, m.p. 94.2 C
Compound 1-347, m.p. 80.7 C
Compound 1-350, 2.41 (3H, q, J= 1.8 Hz), 4.05-4.35 (2H, b), 6.87-6.94 (1 H, m), 7.03 (1 H, d, J= 2.4 Hz), 7.33 (1 H, d, J = 8.5 Hz), 7.98 (1 H, s) Compound 1-353, m.p. 124.0 C
Compound 1-367, 2.44 (3H, q, J = 1.9 Hz), 3.04 (3H, s), 6.88 (1 H, s), 7.37 (1 H, d, J = 9.0 Hz), 7.79 (1 H, d, J = 7.0 Hz), 8.01 (1 H, s) Compound 1-369, 2.44 (3H, q, J = 2.0 Hz), 4.57 (2H, s), 7.06 (1 H, s), 7.38 (1 H, d, J = 9.0 Hz), 7.83 (1 H, d, J = 6.9 Hz), 8.01 (1 H, s) Compound 1-391, m.p. 177.6 C
Compound 1-392, m.p. 172.5 C
Compound 1-398, m.p. 133.1 C
Compound 1-420, 1.25 (3H, t, J = 7.5 Hz), 1.51 (3H, d, J = 7.0 Hz), 2.42 (3H, q, J = 1.8 Hz), 4.0-4.18 (3H, m), 4.82 (1 H, d, J = 7.9 Hz), 6.59 (1 H, d, J = 6.3 Hz), 7.23 ( I H, d, J = 9.3 Hz), 7.97 (1H, s) Compound 1-429, 1.40 (6H, d, J = 6.3 Hz), 2.43 (3H, q, J = 2.4 Hz), 4.52-4.63 (1 H, m), 7.14 (0.5H, d, J = 2.4 Hz), 7.17 (0.5H, d, J = 2.4 Hz), 7.24 (1 H, d, J = 3.6 Hz), 7.29 (1 H, s), 7.46 (1 H, d, J = 8.4 Hz) Compound 1-439, m.p.
1 10.6 C
Compound 1-449, 1.29 (3H, t, J = 7.5 Hz), 2.42 (3H, q, J = 2.4 Hz), 4.28 (2H, q, J = 7.5 Hz), 4.73 (2H, s), 7.20-7.32 (2H, m), 7.49 (IH, d, J = 10.4 Hz), 8.00 (1H, s) Compound 1-456, 1.70 (3H, d, J = 6.9 Hz), 2.41 (3H, q, J 2.1 Hz), 3.77 (3H, s), 4.81 (1 H, q, J = 6.9 Hz), 7.21-7.28 (2H, m), 7.47 (1 H, d, J 8.7 Hz), 7.99 (IH, s) Compound 1-474, m.p. 110.6 C
Compound 1-475, 1.46 (3H, t, J = 5.8 Hz), 2.44 (3H, q, J = 1.5 Hz), 4.07 (2H, q, J = 5.8 Hz), 6.94 (1 H, d, J = 5.0 Hz), 7.29 (1 H, d, J = 7.5 Hz), 8.01 (1 H, s) Compound 1-476, 1.38 (6H, d, J = 6.3 Hz), 2.43 (3H, q, J= 2.0 Hz), 4.47 (1 H, m), 6.99 (1 H, d, J = 5.0 Hz), 7.29 (1 H, d, J = 9.5 Hz), 8.00 (1 H, s) Compound 1-482, m.p. 79_8 C
Compound 1-483, m.p. 132.7 C
Compound 1-486, m.p. 140.7 C (decomp.) Compound 1-487, m.p. 114.1 C
Compound 1-491, m.p. 82.9 C
Compound 1-495, m.p. 80.4 C
Compound 1-496, m.p. 102.0 C
Compound 1-497, m.p. 82.9 C
Compound 1-498, m.p. 75.6 C
Compound 1-499, 0.88 (3H, t, J 7 Hz), 1.2-1.4 (4H, m), 1.55-1.70 (2H, m), 2.43 (3H, q, J = 2 Hz), 4.19 (2H, t, J 7 Hz), 4.68 (2H, s), 6.98 (1H, d, J
= 7 Hz), 7.33 (1 H, d, J = 8 Hz), 7.99 (1 H, s) Compound 1-500, 1.26 (6H, d, J= 6.3 Hz), 2.43 (3H, q, J = 2 Hz), 4.65 (2H, s), 5.05-5.18 (1 H, m), 6.98 (1 H, d, J = 7 Hz), 7.33 (1 H, d, J = 8 Hz), 7.98 (1 H, s) Compound 1-501, 1.5-1.9 (8H, m), 2.43 (3H, q, J = 2 Hz), 4.65 (2H, s), 5.2-5.4 (1 H, m), 6.97 (1 H, d, J = 7 Hz), 7.33 (1 H, d, J= 8 Hz), 7.98 (1 H, s) = Compound 1-503, 1.68 (3H, d, J = 7 Hz), 2.43 (3H, q, J 2 Hz), 3.76 (3H, s), 4.73 (1 H, q, J = 7 Hz), 6.98 (1 H, d, J = 7 Hz), 7.32 (1 H, d, J 8 Hz), 7.99 (I H, s) Compound 1-504, 1.25 (3H, t, J = 7.3 Hz), 1.68 (3H, d, J = 6.8 Hz), 2.42 (3H,q,J=2.0Hz),4.21 (2H, q, J = 7.3 Hz), 4.70 (1 H, q, J = 6.8 Hz), 6.99 (1 H, d, J
= 6.8 Hz). 7.32 (1 H, d, J = 9.3 Hz), 7.98 (1 H, s) Compound 1-511, m.p. 1 10.7 C
Compound 1-518, m.p. 131.2 C (decomp.) Compound 1-576, 2.43 (3H, q, J = 1.8 Hz), 3.67 (2H, s), 3.72 (3H, s), 7.32 (1 H, d, J = 8.5 Hz), 7.59 (1 H, d, J 7.1 Hz), 8.2 (1 H, s) Compound 1-577, 1.15 (3H, t, J= 7.5 Hz), 2.36 (3H, q, J = 1.8 Hz), 3.58 (2H, s), 4.09 (2H, q, J= 7.5 Hz), 7.28 (1 H, d, J = 8.6 Hz), 7.52 (1 H, d, J=
7.1 Hz), 7.93 (1 H, s) Compound 1-579, m.p. 71.6 C
Compound 1-581, m.p. 97.5 C
Compound 1-584, 1.53 (3H, d, J= 7.2 Hz), 2.43 (3H, q, J= 1.8 Hz), 3.66 (3H, s), 3.88 (1 H, q, J = 7.2 Hz), 7.38 (IH, d, J = 9.6 Hz), 7.66 (1H, d, J =
7.5 Hz), 7.99 (1 H, s) Compound 1-585, 1.17 (3H, t, J = 6.9 Hz), 1.53 (3H, d, J = 7.2 Hz), 2.43 ( 3H, q, J = 1.8 Hz), 3.89 (1 H, q, J = 7.2 Hz), 4.11 (2H, q, J = 6.9 Hz), 7.37 (1 H, d, J
=9.6Hz),7.67(1H,d,J=9.0Hz),7.99(1H,s) Compound 1-586, 0.85 (3H, t, J = 6.8 Hz), 1.51-1.62 (5H, m), 2.43 (3H, q, J = 1.8 Hz), 3.89 (1 H, q, J = 7.2 Hz), 4.02 (2H, t, J = 6.8 Hz), 7.33 (1 H, d, J = 9.5 Hz), 7.66 (1 H, d, J= 7.5 Hz), 7.98 (1 H, s) Compound 1-587, 0.88 (3H, t, J = 7.2 Hz), 1.30-1.40 (2H, m), 1.47-1.55 (5H, m), 2.43 (3H, q, J = 1.8 Hz), 3.89 (1H, q, J = 7.1 Hz), 4.02-4.08 (2H, m), 7.36 (1 H, d, J = 9.4 Hz), 7.66 (1 H, d, J = 7.5 Hz), 7.99 (1 H, s) Compound 1-619, 2.45 (3H, q, J 1.6 Hz), 7.60 (1 H, d, J = 8.6 Hz), 7.80-7.86 (1 H, m), 8.04 (1 H, s), 8.36 (1 H, d, J 2.5 Hz) Compound 1-621, 1.40 (3H, t, J = 7.1 Hz), 2.43 (3H, q, J = 1.8 Hz), 4.41 (2H, q, J = 7.1 Hz), 7.56 (1 H, d, J = 8.6 Hz), 7.72-7.78 (1 H, m), 8.02 (1 H, s), 8.16 (1H,d,J=2.7Hz) Compound 1-625, 1.39 (6H, d, J = 6.2 Hz), 2.43 (3H, q, J = 1.6 Hz), 5.23-5.28 (1 H, m), 7.54 (1 H, d, J = 8.7 Hz), 7.70-7.76 (1 H, m), 8.02 (1 H, s), 8.10 ( l H, d, J = 2.6 Hz) Compound 1-632, m.p. 76.1 C
Compound 1-637, m.p. 102.8 C
Compound 1-641, 2.43 (3H, q, J = 2.0 Hz), 3.92 (3H, s), 7.39 (1H, d, J
9.5 Hz), 8.02 (1H, s), 8.07 (1H, d, J = 7.7 Hz) Compound 1-642, 1.39 (3H, t, J = 7.2 Hz), 2.44 (3H, q, J = 1.9 Hz), 4.40 (2H, q, J = 7.2 Hz), 7.38 (1 H, d, J= 9.5 Hz), 8.00-8.06 (2H, m) Compound 1-981, m.p. 87.1 C
Compound 1-987, 4.0-4.4 (2H, b), 6.8-6.9 (1 H, m), 7.04 (1 H, d, J = 2.4 Hz), 7.28 (1 H, q, J = 1.2 Hz), 7.35 (1H, d, J= 8.6 Hz), 8.02 (1 H, d, J = 2.2 Hz) Compound 1-1025, 5.92 (1H, s), 7.16 (0.5H, d, J= 2.4 Hz), 7.19 (0.5H, d, J = 2.4 Hz), 7.30 (1 H, q, J= 1.1 Hz), 7.34 (1 H, d, J = 5.7 Hz), 7.43 (1 H, d, J
9.0Hz),8.04(1H,q,J=3.0Hz) Compound 1-1028, m.p. 180.2 C, 5.65-5.9 (1H, br), 7.09 (1H, d, J = 7 Hz), 7.27-7.30 (2H, m), 8.10 (1H, q, J = 2.2 Hz) Compound 1-1029, 7.09 (1 H, d, J 6.4 Hz), 7.31 (1 H, q, J 1.1 Hz), 7.42 (1H,d,J8.8Hz),8.04(1H,q,J=2.2Hz) Compound 1-1035, m.p. 61.1 C
Compound 1-1057, m.p. 158 C
Compound 1-1066, m.p. 89.1 C
Compound 1-1076, m.p. 113.5 C
Compound 1-1086, m.p. 83.9 C
Compound 1-1093, m.p. 83.1 C
Compound 1-1113, m.p. 68.6 C
Compound 1-1 123, rn.p. 147.4 C
Compound 1-1 124, rn.p. 1 17.2 C
Compound 1-1133, m.p. 149.2 C (decomp.) Compound 1-1 140, rn.p. 99.1 C
Compound 1-1 141, rn.p. 80.2 C
Compound 1-1213, m.p. 85.8 C
Compound 1-1214, m.p. 65.1 C
Compound 1-1221, 1.54 (3H, d, J = 7.2 Hz), 3.66 (3H, s), 3.90 (IH, q, J
= 7.2 Hz), 7.31 (1 H, s), 7.39 (1 H, d, J = 9.0 Hz), 7.67 (1 H, d, J = 8.7 Hz), 8.04 (1 H, d, J = 3.6 Hz) Compound 1-1222, 1.16 (3H, t, J = 5.1 Hz), 1.53 (3H, d, J = 7.2 Hz), 3.89 (1 H, q, J = 7.2 Hz), 4.10 (2H, q, J = 5.1 Hz), 7.30 (1 H, q, J = 1.1 Hz), 7.38 (1H,d,J=9.0Hz),7.68(1H,d,J=7.5Hz),8.04(1H,q,J=2.2Hz) Compound 1-1226, 1.12 (3H, d, J = 6.0 Hz), 1.21 (3H, d, J = 6.0 Hz), 1.52 (3H, d, J = 3.0 Hz), 3.88 (1 H, q, J = 3.0 Hz), 4.85-5.03 (1 H, m), 7.30 (1 H, q, J
= 1.8 Hz), 7.37 (IH, d, J = 9.0 Hz), 7.67 (IH, d, J= 7.5 Hz), 8.02 (IH, q, J =
2.1 Hz) Compound 1-1256, 7.35 (IH, q, J = 1.1 Hz), 7.62 (1 H, d, J= 8.7 Hz), 7.82-7.88 (1 H, m), 8.09 (1 H, d, J = 2.2 Hz), 8.35 (1 H, d, J= 2.6 Hz) I Compound 1-1258, 1.41 (3H, t, J = 7.1 Hz), 4.42 (2H, q, J = 7.1 Hz), 7.31 (1 H, s), 7.57 (1 H, d, J = 8.7 Hz), 7.74-7.79 (1H, m), 8.07 (1 H, q, J =
2.1 Hz), 8.16(IH,d,J=2.6Hz) Compound 1-1269, in.p. 89.7 C
Compound 1-1274, m.p. 154.2 C
Compound 1-1278, m.p. 128.6 C
Compound 1-1279, 1.40 (3H, t, J = 7.1 Hz), 4.40 (2H, q, J = 7.1 Hz), 7.33 (1 H, q, J = 1.1 Hz), 7.39 (IH, d, J = 9.4 Hz), 8.05 (IH, d, J = 8.3 Hz), 8.07 (IH, s) Compound 1-1346, 2.48 (3H, s), 5.66 (1 H, s), 7.08 (1 H, d, J 7.8 Hz), 7.28 (1 H, d, J = 9.0 Hz), 7.32 (1 H, s) Compound 1-1431, rn.p. 74.5 C
Compound 1-1441, m.p. 128.2 C
Compound 1-1442, 1.73 (3H, d, J = 6.6 Hz), 2.49 (3H, q, J 1.3 Hz), 2.54 (1 H, d, J= 2.0 Hz), 4.84 (1 H, m), 7.22 (1 H, d, J= 6.5 Hz), 7.28-7.34 (2H, m) Compound 1-1451, 1.29 (3H, t, J = 7.0 Hz), 2.47 (3H, q, J = 1.4 Hz), 4.27 (2H, q, J = 7.0 Hz), 4.68 (2H, s), 6.99 (IH, d, J = 7.1 Hz), 7.32 (IH, s), 7.34 (1 H, d, J = 7.2 Hz) Compound 1-1458, 1.69 (3H, d, J = 6.8 Hz), 2.48 (3H, q, J= 1.3 Hz), 3.76 (3H, s), 4.74 (1 H, q, J = 6.8 Hz), 7.01 (1 H, d, J = 6.5 Hz), 7.29-7.34 (2H, m) Compound 1-1540, 1.17 (3H, t, J = 7.0 Hz), 1.54 (3H, d, J = 7.3 Hz), 2.48 (3H, q, J = 1.4 Hz), 3.89 (IH, q, J = 7.3 Hz), 4.11 (2H, q, J = 7.0 Hz), 7.31 (1H,s),7.37(1H,d,J=9.5Hz),7.67(1H,d,J=7.5Hz) Compound 1-1617, m.p. 105.7 C
Compound 1-1622, 1.27 (3H, t, J 7.0 Hz), 2.42 (3H, q, J = 2.0 Hz), 3.26 (0.3H, d, J 7.6 Hz), 3.32 (0.7H, d, J 7.6 Hz), 3.49 (0.7H, d, J = 7.6 Hz), 3.54 (0.3H, d, J 7.6 Hz), 4.23 (2H, q, J = 7.0 Hz), 4.54 (0.5H, d, J = 7.6 Hz), 4.57 (0.5 H, d, J = 7.6 Hz), 7.34 (1 H, d, J = 9.3 Hz), 7.40 (1 H, d, J = 7.5 Hz), 8.00 (1 H, s) Compound 1-1627, m.p. 182.2 C
Compound 1-1638, 3.66 (2H, s), 7.31 (1 H, s), 7.34 (1 H, d, J = 9.3 Hz), 7.62 (1 H, d, J = 7.2 Hz), 8.08 (1 H, s) Compound 1-1639, m.p. 158.9 C (decomp.) Compound 1-1641, 1.55 (3H, d, J = 7.2 Hz), 3.88 (IH, q, J = 7.2 Hz), 7.32 (1 H, s), 7.37 (1 H, d, J = 9.2 Hz), 7.69 (1 H, d, J = 7.1 Hz), 8.03 (1 H, s) Compound 1-1650, 1.1 1(3H, t, J = 7.5 Hz), 2.03-2.12 (2H, m), 2.43 (3H, q, J 1.8 Hz), 3.75 (3H, s), 4.58 (1 H, t, J 7.5 Hz), 6.92 0 H, d, J 8.2 Hz), 7.32 (1H, d, J 9.3 Hz), 8.00 (1 H, s) Compound 1-1655, m.p. 119.7 C, 1.29 (3H, t, J 7.1 Hz), 2.43 (3H, q, J = 1.8 Hz), 4.26 (2H, q, J = 7.1 Hz), 4.68 (2H, s), 6.91 (1 H, s), 7.99 (1H, s) Compound 1-1663, m.p. 136.2 C, 2.44 (3H, q, J = 1.8 Hz), 2.58 (1H, t, J = 2.3 Hz), 4.78 (2H, d, J = 2.3 Hz), 7.12 (1H, s), 7.59 (1H, s), 8.01 (1 H, s) Compound 1-1665, m.p. 1.23 (3H, t, J = 6.9 Hz), 1.68 (3H, d, J = 6.8 Hz), 2.42 (3H, q, J = 1.8 Hz), 4.1-4.3 (2H,m),4.72(1H,q,J=6.8Hz),6.90(1H,s),7.58.
(1 H, s), 7.97 (1 H, s) Compound 1-1670, m.p. 118.1 C
Compound 1-1673, m.p. 107.2 C
Compound 1-1678, m.p. 164.7 C
Compound 1-1679, m.p. 1.73 (3H, d, J = 6.9 Hz), 2.54 (1H, d, J = 2.1 Hz), 4.73-4.90 (1H, m), 7.20 (1H, d, J = 6.3 Hz), 7.30 (1H, s), 7.49 (1H, d, J =
8.7 Hz), 8.00 (1H, s).
Compound 1-1680, m.p. 90.1 C
Compound 1-1681, m.p. 148.1 C
Compound 1-1682, m.p. 107.0 C
Compound 1-1683, m.p. 1.73 (3H, d, J = 6.9 Hz), 2.54 (111, d, J = 6.8 Hz), 2.42 (3H, q, J = 1.5 Hz), 4.13-4.26 (2H, m), 4.70 (1H, q, J = 6.8 Hz), 6.96 (1H, d, J = 6.3 Hz), 7.48 (1 H, d, J = 9.0 Hz), 7.97 (1 H, s) Compound 1-1687, m.p. 200.1 C
Compound 1-1689, m.p. 76.3 C
Compound 1-1690, m.p. 196.1 C
Compound 1-1691, 3.06 (3H, s), 7.10-7.30 (1H, b), 7.30 (1H, s), 7.64 (1H, s), 7.74 (1 H, s), 8.06 (1 H, q, J = 2.1 Hz) Compound 1-1701, 1.39 (3H, t, J = 7.1 Hz), 4.40 (2H, q, J = 7.1 Hz), 7.33 (1 H, q, J 1.1 Hz), 7.69 (1 H, s), 7.97 (1 H, s), 8.06 (1 H, q, J 2.2 Hz) Compound 1-1718, rn.p. 63.9 C
Compound 1-1719, m.p. 189.5 C
Compound 1-1720, in.p. 117.3 C
Compound 1-1721, in.p. 156.1 C
Compound 1-1722, 2.47 (3H, q, J = 1.8 Hz), 3.05 (3H, s), 7.15-7.30 (1H, b), 7.66 (1 H, s), 7.78 (1 H, s), 8.03 (I H, s) Compound 1-1732, 1.38 (3H, t, J = 7.1 Hz), 2.44 (3H, q, J = 1.8 Hz), 4.39 (2H, q, J = 7.1 Hz), 7.68 (IH, s), 7.96 (1H, s), 8.02 ( I H, s) Compound 1-1748, 1.38 (6H, d, J = 6.0 Hz), 2.44 (3H, q, J = 1.9 Hz), 4.40-4.59 (1 H, m), 6.95 (1 H, s), 7.55 (1 H, s), 8.00 (1 H, s) Compound 1-1780, m.p. 76.4 C
Compound 1-1781. 3.51 (3H, s), 3.51 (3H, s), 7.30 (IH, q, J = 1.2 Hz), 7.59 (1 H, d, J = 6.7 Hz), 7.65 (1 H, d, J = 9.0 Hz), 8.06 (1 H, d, J = 2.1 Hz) Compound 1-1782, 3.03 (3H, s), 7.09 (1 H, s), 7.32 (1 H, q, J = 1.0 Hz), 7.53 (1 H, d, J = 8.7 Hz), 7.77 (1 H, d, J = 6.8 Hz), 8.07 (1 H, q, J = 2.2 Hz) Compound 1-1783, 1.38 (6H, d, J = 6.1 Hz), 2.43 (3H, q, J = 1.7 Hz), 4.4-4.6 (1 H, m), 6.95 (1 H, d, J = 6.4 Hz), 7.47 (1 H, d, J = 8.9 Hz), 8.00 (1 H, s) Compound 1-1785, 2.43 (3H, q, J = 1.9 Hz), 3.03 (3H, s), 7.03 (1 H, s), 7.52 (1 H, d, J = 8.8 Hz), 7.76 (1 H, d, J = 6.9 Hz), 8.02 (1 H, s) Compound 1-1789, m.p. 78.3'C
Compound 1-1790, m.p. 63.2 C
Compound 1-1879, 2.42 (3H, q, J = 1.8 Hz), 5.38 (2H, s), 7.28-7.47 (5H, m), 7.56 (1 H, d, J = 8.7 Hz), 7.72-7.79 (1 H, m), 8.00 (1 H, s), 8.18 (1 H, d, J = 2.5 Hz) Compound 1-1881, 2.20 (0.75H, s), 2.24 (2.25H, s), 2.42 (3H, q, J = 1.9 Hz), 3.82 (0.75H, s), 3.98 (2.25H, s), 7.47-7.68 (3H, m), 8.00 (IH, s) Compound 1-1901, rn.p. 99.2 C
Compound 1-1908, rn.p. 77.6 C
Compound 1-1910, rn.p. 75.3 C
Compound 1-1930, m.p. 139.7 C
Compound 1-2051, 1.25 (3H, t, J= 7.2 Hz), 2.42 (3H, q, J = 1.9 Hz), 4.17 (2H, q, J = 7.2 Hz), 4.71 (2H, s), 4.82 (2H, s), 7.10 (1 H, d, J= 6.3 Hz), 7.33 (I H, d, J = 9.1 Hz), 7.99 (1 H, s) Compound 1-2054, 1.24 (3H, t, J = 7.1 Hz), 1.51 (3H, d, J = 7.2 Hz), 2.42 (3H, q, J = 1.8 Hz), 4.15 (2H, q, J = 7.1 Hz), 4.78 (2H, s), 5.19 (1H, q, J= 7.2 Hz), 7.08 (1 H, d, J = 6.3 Hz), 7.32 (1 H, d, J = 9.1 Hz), 7.98 (1 H, s) Compound 2-203, 2.3-2.4 (1 H, m), 2.35 (3H, q, J= 1.9 Hz), 4.5-4.7 (4H, m), 7.00 ( I H, d, J = 6.5 Hz), 7.19 (1 H, m), 7.39 (IH, d, J= 2.5 Hz), 7.95 (1 H, s) Compound 2-251, m.p. 168.3 C
Compound 2-328, 0.90 (3H, t, J = 7.3 Hz), 1.54 (3H, d, J = 7.0 Hz), 1.70-1.90 (2H, m), 2.46 (3H, m), 4.50 (1 H, m), 7.18 (1 H, d, J = 5.75 Hz), 7.35 (1 H, d, J
= 8.8 Hz), 8.04 (1 H, s) Compound 2-583, m.p. 149.1 C
Compound 2-631, m.p. 168.3 C
Compound 2-708, 0.90 (3H, t, J 7.3 Hz), 1.55 (3H, d, J = 7.0 Hz), 1.75-1.95 (2H, m), 4.50 (IH, m), 7.22 (1 H, d, J 5.8 Hz), 7.30-7.40 (2H, m), 8.08 (1 H, q, J = 2.2 Hz) Compound 2-821, m.p. 162.7 C
Compound 3-139, m.p. 88.2 C
Compound 4-434, 1.67 (3H, s), 2.35 (3H, q, J = 1.7 Hz), 3.0-3.2 (IH, m), 3.4-3.7 (1 H, m), 3.71 (3H, s), 7.03 (1 H, d, J = 5.0 Hz), 7.97 (1 H, q, J =
3.3 Hz) Compound 4-451, 1.53 (6H, s), 2.43 (3H, q, J = 1.9 Hz), 2.96 (IH, d, J
16.2Hz),3.08(1H,d,J=16.2Hz),7.07(1H,d,J=9.9Hz),7.99(IH,s) Compound 4-452, 1.4-1.5 (3H, m), 2.43 (3H, q, J = 2.0 Hz), 2.7-3.0 (IH, m), 3.1-3.5 (1 H, m), 3.5-3.8 (2H, m), 7.07 (1 H, d, J = 10.0 Hz), 8.00 (1 H, q, J = 2.5 Hz) The following will describe formulation examples, in which the present compounds are designated by their compound numbers shown in Tables I to 5 and parts are by weight.
Formulation Example I
Fifty parts of each of compounds 1-1 to 1-2157, 2-1 to 2-950, 3-1 to 3-582, 4-1 to 4-936, and 5-1 to 5-87, 3 parts of calcium ligninsulfonate, 2 parts of sodium laurylsulfate, and 45 parts of synthetic hydrated silicon oxide are well pulverized and mixed to give a wettable powder for each compound.
Formulation Example 2 Ten parts of each of compounds 1-1 to 1-2157, 2-1 to 2-950, 3-1 to 3-582, 4-1 to 4-936, and 5-1 to 5-87, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 35 parts of xylene, and 35 parts of cyclohexanone are well mixed to give an emulsifiable concentrate for each compound.
Formulation Example 3 Two parts of each of compounds 1-1 to 1-2157, 2-1 to 2-950, 3-1 to 3-582, 4-1 to 4-936, and 5-1 to 5-87, 2 parts of synthetic hydrated silicon oxide, 2 parts of calcium ligninsulfonate, 30 parts of bentonite, and 64 parts of kaoline clay are well pulverized and mixed, to which water is added, and the mixture is well kneaded, granulated, and dried to give granules for each compound.
Formulation Example 4 Twenty-five parts of each of compounds 1-1 to 1-2157, 2-1 to 2-950, 3-1 to 3-582, 4-1 to 4-936, and 5-1 to 5-87, 50 parts of 10% aqueous polyvinyl alcohol solution, and 25 parts of water are mixed, and the mixture is pulverized until the average particle size becomes 5 m or less to give a flowable for each compound.
Formulation Example 5 Five parts of compound 1-1650 is added to 40 parts of 10% aqueous polyvinyl alcohol solution and dispersed by emulsion wifh a homogenizer until the mean particle size becomes 10 m or less, to which 55 parts of water is added to give a concentrated emulsion.
The following test examples will demonstrate that the present compounds are useful as active ingredients of herbicides. The present compounds are designated by their compound numbers shown in Tables I to 5.
The herbicidal activity and phytotoxicity were evaluated at 6 levels with indices of 0 to 5, i.e., designated by the numeral "0", "1", "2", "3", "4" or "5", wherein "0" means that there was no or little difference in the degree of germination or growth between the treated and the untreated test plants at the time of examination, and "5" means that the test plants died or their germination or growth was completely inhibited. The herbicidal activity is excellent when rated at "4" or "5" but insufficient when rated at "3" or lower. The phytotoxicity is not problematic for practical use when rated at "0"
or "1" but not allowed when rated at "2" or higher.
Test Example 1: Foliar treatment on upland fields Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with soil, in which the seeds of entireleaf morningglory (Ipofitoea hederacea var.
ijitegriuscitla) and velvetleaf (Abutilon theophrasti) were sown, and the test plants were grown in a greenhouse for 19 days. Each of the test compounds listed below was formulated into an emulsifiable concentrate according to Formulation Example 2, which was diluted with water containing a spreading agent to a prescribed concentration. The dilution was uniformly sprayed over the foliage of the test plants with a sprayer at a volume of 1000 liters per hectare. After the application, the test plants were grown in the greenhouse for 19 days, and the herbicidal activity was examined. The results are shown in Table 6.
Application amount of Herbicidal activity Test activeinb edient compound ~bma~ Entireleaf Velvetleaf morningglory 1-335 500 { 5 5 TABLE 6 (contn'd) Application amount of Herbicidal activity Test active ingredient compound ~gma) Entireleaf Velvetleaf morningglory 1-987 500 5 5 1-1670 500 5 5 =
TABLE 6 (contn'd) Application amount of Herbicidal activity Test active ingredient compound ~gma~ Entireleaf Velvetleaf morningglory 1-1691 500 5 5 Test Example 2: Foliar treatment on upland fields Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with soil, in which the seeds of barnyardgrass (Echinochloa crus-galli), entireleaf mom-ingglory (Ipornoea hedei-acea var. iritegriarscula), and velvetleaf (Abutilor2 theophr-asti) were sown, , and the test plants were grown in a greenhouse for 19 days. Each of the test compounds listed below was formulated into an emulsifiable concentrate according to Formulation Example 2, which was diluted with water containing a spreading agent to a prescribed concentration. The dilution was uniformly sprayed over the foliage of the test plants with a sprayer at a volume of 10001iters per hectare. After the application, the test plants were grown in the greenhouse for 19 days, apd the herbicidal activity was examined. The results are shown in Table 7.
Application amount of Herbicidal activity Test active ingredient compound (gnla) Barnyardgrass Entireleaf Velvetleaf morningglory 1-369 32 5 5 5 1-576 32 5 _5 5 1-1665 32 5 5 5, TABLE 7 (contn'd) Test Application amount of Herbicidal activity compound active ingredient Entireleaf (g/ha) Branyardgrass morningglory Velvetleaf Test Example 3: Soil surface treatment on upland fields Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with soil, in which the seeds of entireleaf morningglory (Ipanoea hederacea var.
integr=iuscula) and velvetleaf (Abutilon theophrcisti) were sown. Each of the test compounds listed below was formulated into an emulsifiable concentrate according to Formulation Example 2, which was diluted with water to a prescribed concentration. The dilution was uniformly sprayed over the soil surface in the pots with a sprayer at a volume of 10001iters per hectare. After the application, the test plants were grown in a greenhouse for 19 days, and the herbicidal activity was examined. The results are shown in Table 8.
Application amount of Herbicidal activity Test active ingredient compound (gma) Entireleaf Velvetleaf morningglory 1-347 500 5 ~ 5 TABLE 8 (contn'd) Application amount of Herbicidal activity Test active ingredient compound ~gma~ Entireleaf Velvetleaf morningglory 1-398 .500 5 5 1-4,49 500 5 5 TAB E 8 (contn'd) Application amount of Herbicidal activity Test active ingredient compound (bma) Entireleaf Velvetleaf morningglory = 326 Test Example 4: Flooding treatment on paddy fields Cylindrical plastic pots of 9 cm in diameter and 11 cm in depth were filled with soil, in which the seeds of barnyardgrass (Echinochloa oryzicola) were sown.
These pots were flooded to form a paddy field, and the test plants were grown in a green-house for 7 days. Each of the test compounds listed below was formulated into an emulsifiable concentrate according to Formulation Example 2, which was diluted with water to a prescribed concentration. The dilution was applied to the water surface in the pots at a volume of 501iters per hectare. After the application, the test plants were grown in the greenhouse for 19 days, and the herbicidal activity was examined. The results are shown in Table 9.
Test Application amount of Herbicidal activity com ound active ingredient p (giha) Barnyardgrass 1-482 250 . 5 TABLE 9 (contn'dl Test Application amount of Herbicidal activity compound active ingredient (g/ha) I Barnyardgrass TABLE 9 (contn'd) Test Application amount of Herbicidal activity compound active ingredient (g/ha) Bamyardgrass 1-1638 250 5 1-1721 500 5 "
Test Example 5: Foliar treatment on upland fields Plastic pots of 25 x 18 cm2 in area and 7 cm in depth were filled with soil, in which the seeds of soybean (Glvcine max). corn (Zea mays), entireleaf morningglory (Ipomoea hederacea var. integriuscula), common cocklebur (Xanthium pensylvanictcm), comtnon ragweed (Ambrosia artemisiifolia), and common lambsquarters (Chenopodiurn album) were sown, and the test plants were grown for 16 days. Each of the test compounds listed below was formulated into an emulsifiable concentrate according to Formulation Example 2, which was diluted with water to a prescribed concentration. The dilution was uniformly sprayed over the foliage of the test plants with a sprayer at a volume of 1000 liters per hectare. At this time, the unfavorable weeds and crop plants, although their growth state was different depending upon the weed species, were at the 1- to 4-leaf stage, and the plant height was 5 to 20 cm. After 18 days from the applica-tion, the herbicidal activity and phytotoxicity were examined. The results are shown in Table 10. This test was made in a greenhouse over the entire period.
Application Herbicidal activity and phytotoxicity Test amount of active Entireleaf Common compound ingredient Corn Soy- Common mornin Common lamb-~g~a) bean cocklebur glory g ragweed squarters Test Example 6; Foliar treatment on upland fields Plastic pots of 16 x 1 1 cm2 in area and 7 cm in depth were filled with soil, in which the seeds of wheat (Ti-itictcfia aestivuna), pale smartweed (Polygonum lapatlzi-folli[f17), catchweed bedstraw (Galium apariiie), and coinmon chickweed (Stellaria media) were sown, and the test plants were grown for 29 days. Each of the test compounds listed below was formulated into an emulsifiable concentrate according to Formulation Example 2, which was diluted with water to a prescribed concentration. The dilution was uniformly sprayed over the foliage of the test plants with a sprayer at a volume of 1000 liters per hectare. At this time, the unfavorable weeds and crop plants, although their growth state was different depending upon the weed species, were at the 1- to 4-leaf stage, and the plant height was 5 to 15 cm. After 25 days from the applica-tion, the herbicidal activity and phytotoxicity were examined. The results are shown in Table 11. This test was made in a greenhouse over the entire period.
Application Herbicidal activity and phytotoxicity Test amount of compound active Pale Catch- Common ingredient Wheat smart- weed chick-(glha) weed bedstraw weed Test Example 7: Soil surface treatment on upland fields Plastic pots of 25 x 18 cm2 in area and 7 cm in depth were filled with soil, in which the seeds of soybean (Glycine rnax), corn (Zea mays), common lambsquarters (Chenopodium album), slender amaranth (Amaranthus gracilis), and pale smartweed (Polygonum lapathifolium) were sown. Each of the test compounds listed below was formulated into an emulsifiable concentrate according to Formulation Example 2, which was diluted with water to a prescribed concentration. The dilution was uniformly sprayed over the soil surface in the pots with a sprayer at a volume of 1000 liters per hectare. After the application, the test plants were grown in a greenhouse for 19 days, and the herbicidal activity and phytotoxicity were examined. The results are shown in Table 12.
= Application Herbicidal activity and phytotoxicity Test ~"-ount of compound active Common Slender Pale ingredient Soybean Corn lamb- ~~~~ smart-(g/ha) squarters weed a
Examples of the CI-C6 haloalkyl represented by RI I and R12 include chloro-ethyl and bromoethyl.
Examples of the C3-C6 alkenyl represented by R i l and R 12 include allyl, 1-methyl-2-propenyl, and 3-butenyl.
Examples of the C3-C6 alkynyl represented by R11 and R12 include propargyl and I -methyl-2-propynyl.
Examples of the cyano C 1-C6 alkyl represented by R 11 and R 12 include cyanomethyl.
Examples of the C2-C8 alkoxyalkyl represented by R i l and R 12 include methoxymethyl and ethoxyethyl.
Examples of the C2-C8 alkylthioalkyl represented by R II and R 12 include methylthiomethyl and methylthioethyl.
Examples of the carboxy C i-C6 alkyl represented by RI I and R 12 include carboxymethyl and 1-carboxyethyl.
Examples of the (Cl-C6 alkoxy)carbonyl C1-C6 alkyl represented by R11 and R 12 include methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, butoxycarbonylmethyl, isobutoxycarbonylmethyl, t-butoxy-carbonylmethyl, amyloxycarbonyimethyl, isoamyloxycarbonylmethyl, t-amyloxycar-bonylmethyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-butoxycarbonylethyl, 1-isobutoxycarbonylethyl, 1-t-butoxycarbonylethyl, 1-amyloxycarbonylethyl, 1-isoamyloxycarbonylethyl, and I -t-amyl-oxycarbonylethyl.
Examples of the (C3-C8 cycloalkoxy)carbonyl CI-C6 alkyl represented by R i I and R12 include cyclopentyloxycarbonylmethyl.
Examples of the {(C I-C4 alkoxy) C 1-C4 alkoxy } carbonyl C 1-C6 alkyl represented by R i' and R1'' include rnethoxymethoxycarbonylmethyl and 1-methoxy-methoxycarbonylethyl.
Examples of the C i-C6 alkyl represented by R13 include methyl, ethyl, propyl, butyl, amyl, isopropyl, isobutyl, and isoamyl.
= Examples of the Ci-C6 haloalkyl represented by R13 include 2,2,2-trifluoro-ethyl.
Examples of the C3-C8 cycloalkyl represented by R13 include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
Examples of the C3-C6 alkenyl represented by R13 include allyl.
Examples of the C I-C6 alkyl represented by R 14 and R 15 include methyl, ethyl, propyl, butyl, and isopropyl.
Examples of the C I-C6 haloalkyl represented by R14 and R15 include trifluoromethyl, 2,2,2-trifluoroethyl, 2-chloroethyl, chloromethyl, and trichloromethyl.
Examples of the phenyl optionally substituted by methyl or nitro, which is represented by R14 and R 15, include phenyl, p-methylphenyl, 2-nitrophenyl, 3-nitro-phenyl, and 4-nitrophenyl.
Examples of the C 1-C6 alkyl represented by R16 include methyl, ethyl, propyl, butyl, amyl, isopropyl, isobutyl, t-butyl, isoamyl, and t-amyl.
Examples of the C i-C6 haloalkyl represented by R 16 include chloromethyl, dichloromethyl, bromomethyl, dibromomethyl, 1-chloroethyl, 1,1-dichloroethyl, 1-bromoethyl, and 1, 1 -dibromoethyl.
Examples of the C2-C6 alkenyl represented by R16 include vinyl, allyl, 1-propenyl, and I -methyl-2-propenyl.
Examples of the C2-C6 haloalkenyl represented by R16 include 3,3-dichloro-2-propenyl and 3,3-dibromo-2-propenyl.
Examples of the C2-C6 alkynyl represented by R16 include ethynyl and = 2-butynyl.
Examples of the C2-C6 haloalkynyl represented by R16 include 3-bromo-2-propynyl.
Examples of the C2-Cg alkoxyalkyl represented by R16 include methoxy-methyl, ethoxymethyl, and isopropoxymethyl.
Examples of the hydroxy Ci-C6 alkyl represented by R16 include hydroxy-methyl.
Examples of the C I -C6 alkyl represented by R 17 and R 18 include methyl.
Examples of the C 1-C6 alkyl represented by R 19 include methyl and ethyl.
Examples of the Ci-C6 alkyl represented by R33 include methyl and ethyl.
Examples of the C1-C6 haloalkyl represented by R33 include 2-chloroethyl.
Examples of the C3-C8 cycloalkyl represented by R33 include cyclopentyl.
Examples of the C3-C6 alkenyl represented by R33 include allyl.
Examples of the C3-C6 haloalkenyl represented by R33 include 2-chloro-2-propenyl.
Examples of the C3-C6 alkynyl represented by R33 include propargyl.
Examples of the C3-C6 haloalkynyl represented by R33 include 4-chloro-2-butynyl.
Examples of the cyano Ci-C6 alkyl represented by R33 include 2-cyanoethyl and cyanomethyl.
Examples of the (C I-C6 alkoxy)carbonyl C I-C6 alkyl represented by R33 include ethoxycarbonylmethyl.
Examples of the CI -C6 alkyl represented by R34 include methyl and ethyl.
Examples of the C1-C3 alkyl represented by R4 include methyl.
Examples of the CI -C6 alkyl represented by R5 include methyl, ethyl, propyl, butyl, amyl, isopropyl, isobutyl, and isoamyl.
Exarnples of the CI -C6 haloalkyl represented by R5 include 2-chloroethyl, 2-bromoethyl, 3-chlorobutyl, 3-bromobutyl, difluoromethyl, and bromodifluoromethyl.
Examples of the C3-C8 cycloalkylalkyl represented by R5 include cyclopentyl-methyl. Examples of the C3-C6 alkenyl represented by R5 include allyl, 1-methyl-2-ll propenyl, 3-butenyl, 2-butenyl, 3-methyl-2-butenyl, and 2-methyl-3-butenyl.
= Examples of the C3-C6 haloalkenyl represented by R5 include 2-chloro-2-propenyl and 3,3-dichloro-2-propenyl.
Examples of the C3-C6 alkynyl represented by R5 include propargyl, 1-methyl-2-propynyl, 2-butynyl, and 1, 1 -dimethyl-2-propynyl.
Examples of the C3-C6 haloalkynyl represented by R5 include 3-iodo-2-propynyl and 3-bromo-2-propynyl.
Examples of the cyano CI-C6 alkyl represented by R5 include cyanomethyl.
Examples of the C2-C8 alkoxyalkyl represented by R5 include methoxy-methyl, ethoxymethyl, and 1-methoxyethyl.
Examples of the C3-C8 alkoxyalkoxyalkyl represented by R5 include methoxyethoxymethyl.
Examples of the carboxy C1-C6 alkyl represented by R5 include carboxy-methyl, 1-carboxyethyl, and 2-carboxyethyl.
Examples of the (CI-C6 alkoxy)carbonyl C1-C6 alkyl represented by R5 include methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopro-poxycarbonyllnethyl, butoxycarbonylmethyl, isobutoxycarbonylmethyl, t-butoxycar-bonylmethyl, amyloxycarbonylmethyl, isoamyloxycarbonylmethyl, t-amyloxycarbonyl-methyl, I-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-propoxycarbonylethyl, I-iso-propoxycarbonylethyl, 1-butoxycarbonylethyl, 1-isobutoxycarbonylethyl, 1-t-butoxy-carbonylethyl, I-amyloxycarbonylethyl, I-isoamyloxycarbonylethyl, and 1-t-amyloxy-carbonylethyl.
Examples of the {( C 1-C4 alkoxy) C 1-C4 alkoxy } carbonyl C i-C6 alkyl represented by R5 include methoxymethoxycarbonylmethyl and 1-methoxymethoxy-carbonylethyl.
= Examples of the (C3-C8 cycloalkoxy)carbonyl CI-C6 alkyl represented by R5 include cyclobutyloxycarbonylmethyl, cyclopentyloxycarbonylmethyl, cyclohexyloxy-carbonylniethyl, 1-cyclobutyloxycarbonylethyl, 1-cyclopentyloxycarbonylethyl, and 1 -cyclohexyloxycarbonylethyl.
Examples of the C2-C8 alkylthioalkyl represented by R5 include methylthio-methyl.
Examples of the hydroxy Ci-C6 alkyl represented by R5 include hydroxy-methyl, hydroxyethyl, and hydroxypropyl.
Examples of the C I -C6 alkyl represented by R6 include methyl and ethyl.
Examples of the C1-C6 haloalkyl represented by R6 include bromomethyl, dibromomethyl, tribromomethyl, 1-bromoethyl, chloromethyl, dichloromethyl, and trichloromethyl.
Examples of the hydroxy CI-C6 a1kyI represented by R6 include hydroxy-methyl.
Examples of the CI-C6 alkoxy C 1-C6 alkyl represented by R6 include methoxymethyl, ethoxymethyl, propoxymethyl, and isopropoxymethyl.
Examples of the C I -C6 alkoxy C I -C6 alkoxy C I -C6 alkyl represented by R6 include methoxymethoxymethyl, methoxyethoxymethyl, and ethoxymethoxymethyl.
Examples of the (Cl-C6 alkyl)carbonyloxy C1-C6 alkyl represented by R6 include acetyloxymethyl, ethylcarbonyloxymethyl, and isopropylcarbonyloxymethyl.
Examples of the (C1-C6 haloalkyl)carbonyloxy C1-C6 alkyl represented by R6 include trifluoroacetyloxymethyl, chloroacetyloxymethyl, and trichloroacetyloxy-methyl.
Examples of the (C1-C6 alkoxy)carbonyl represented by R6 include methoxy-carbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, amyloxycarbonyl, isopro-poxycarbonyl, isobutoxycarbonyl, and isoamyloxycarbonyl.
Examples of the (C I -C6 alkyl)carbonyl represented by R6 include methyl-carbonyl, ethylcarbonyl, and isopropylcarbonyl.
Examples of the C1-C6 alkyl represented by R7 include methyl.
Examples of the C1-C6 alkyl represented by R8 include methyl and ethyl.
Examples of the C I -C6 haloalkyl represented by R8 include chloromethyl, bromomethyl, and fluoromethyl.
Examples of the C i-C6 hydroxyalkyl represented by R8 include hydroxy-methyl.
Examples of the C2-C8 alkoxyalkyl represented by R8 include methoxy-methyl, ethoxymethyl, isopropoxymethyl, butoxymethyl, and isobutoxymethyl.
Examples of the C3-C 1 p alkoxyalkoxyalkyl represented by R8 include methoxymethoxymethyl, methoxyethoxymethyl, and ethoxymethoxymethyl.
Examples of the (CI -C5 alkyl)carbonyloxy C1-C6 alkyl represented by R8 include acetyloxymethyl, ethylcarbonyloxymethyl, and isopropylcarbonyloxymethyl.
Examples of the (C I -C6 haloalkyl)carbonyloxy C i-C6 alkyl represented by R8 include 2-chloroethylcarbonyloxymethyl.
Examples of the carboxy Ci-C6 alkyl represented by R8 include carboxy-methyl.
Examples of the (C1-C8)alkoxycarbonyl represented by R8 include methoxy-carbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, amyloxycarbonyl, isopro-poxycarbonyl, isobutoxycarbonyl, and isoamyloxycarbonyl.
Examples of the (CI-C6 haloalkoxy)carbonyl represented by R8 include 2-chloroethoxycarbonyl, 2-bromoethoxycarbonyl, 3-chlorobutoxycarbonyl, 1-chloro-2-propoxycarbonyl, 1,3-dichloro-2-propoxycarbonyl, 2,2-dichloroethoxycarbonyl, 2,2,2-trifluoroethoxycarbonyl, 2,2,2-trichloroethoxycarbonyl, and 2,2,2-tribromoethoxy-carbonyl.
Examples of the (C3-Clp cycloalkoxy)carbonyl represented by R8 include cyclobutyloxycarbonyl, cyclopentyloxycarbonyl, and cyclohexyloxycarbonyl.
Examples of the (C3-Cg alkenyloxy)carbonyl represented by R8 include allyloxycarbonyl and 3-butenyloxycarbonyl.
Examples of the (C3-C8 alkynyloxy)carbonyl represented by R8 include propargyloxycarbonyl, 3-butynyloxycarbonyl, and 1-methyl-2-propynyloxycarbonyl.
Examples of the (CI-C6 alkyl)aminocarbonyl represented by R8 include methylaminocarbonyl, ethylaminocarbonyl, and propylaminocarbonyl.
Examples of the di(Cl-C6 alkyl)aminocarbonyl represented by R8 include dimethylaminocarbonyl, diethylaminocarbonyl, and diisopropylaminocarbonyl.
Examples of the (C1-C6 alkyl)aminocarbonyloxy C1-C6 alkyl represented by R8 include methylaminocarbonyloxymethyl, ethylaminocarbonyloxymethyl, and propyl-amin ocarbonyl oxymethyl .
Examples of the di(CI -C6 alkyl)aminocarbonyloxy C1-C6 alkyl represented by R8 include dimethylaminocarbonyloxyalkyl and diethylaminocarbonyloxyalkyl.
In the present compounds, preferred substituents from the viewpoint of their herbicidal activity are as follows:
R1 is preferably methyl substituted with one or more fluorine atoms, such as trifluoromethyl or chlorodifluoromethyl, or ethyl substituted with one or more fluorine atoms, such as pentafluoroethyl, and more preferably trifluoromethyl;
R2 is preferably CI -C3 alkyl such as methyl or ethyl, or hydrogen, and more preferably methyl or hydrogen;
R3 is preferably Ci-C3 alkyl such as methyl or ethyl, or hydrogen, and more preferably methyl or hydrogen; and Q is preferably [Q-l], [Q-2], [Q-3], or [Q-4].
Preferred examples of the present compounds from the viewpoint of their herbicidal activity are those which contain the above preferred substituents in combi-nation.
When Q is [Q-1], inore preferred compounds are those wherein X is hydrogen or fluorine and Y is chlorine. Among these compounds are more preferred ones wherein B is OR 10, S R10, N(R I I)R 12, NR 11 (S02R 14), or COOR IO.
Among these compounds are more preferred ones wherein R1a is C1-C6 alkyl, C3-C6 alkynyl, (C1-Cg alkoxy)carbonyl C I -C6 alkyl, or (C3-C8 cycloalkoxy)carbonyl C I -C6 alkyl; R
i I is hydrogen: R12 is (CI-C6 alkoxy)carbonyl Cl-C6 alkyl; and R14 is CI -C6 alkyl or Cl-C6 haloalkyl.
When Q is [Q-2], more preferred compounds are those wherein X is fluorine or hydrogen; Z1 is oxygen; R4 is hydrogen; and n is 1. Among these compounds are more preferred ones wherein R5 is C3-C6 alkynyl.
Typical examples of the preferred compounds are as follows:
7-Flu oro-6 -( 5-t ri fluoro methyl-3 -pyri dazin on -2-y l)-4 -prop arg yl -2H -1,4-benzoxazin-3-one;
7-Fluoro-6-(4-methyl-5 -trifluoromethyl-3-pyridazinon-2-yl )-4-propargyl-2H-1,4-benzoxazin-3-one;
6-(5-Trifl uoromethyl-3-pyridazinon-2-yl)-4-p ropargyl-2H- I,4-benzoxazin-3-one;
6-( 4-M ethy 1-5 -t rif luo rom et hyl -3-p y rid azi no n-2 -yl )-4-p rop argyl -2H -1,4-benzoxazin-3-one;
2-(4-Ch loro-2-fl uoro-5 -is opropoxyphen yl)-4-methyl-5-triflu oromethyl-pyridazin-3-one;
2-(4-Chloro-2-fluoro-5-methoxyphenyl)-4-methyl-5-trifluoromethyl-pyridazin-3-one;
2-(4-Chl oro-2-fl uoro-5-ethoxyph enyl)-4-meth yl-5-trifluo romethylpyridazin-3-one;
2-(4-Ch loro-2-fluoro-5 -propargylo xyphenyl )-4-methyl-5-trifl uoro methyl-pyridazin-3-one;
Methyl 2-chloro-4-fluoro-5-(4-methyl-5-tri fluoromethyl-3-pyridazinon-2-yl)-phenoxyacetate;
Ethyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-phenoxyacetate;
Propyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-phenoxyacetate;
Isopropyl 2-chloro-4-fluoro-5-(4-methyl-.5-trifluoromethyl-3-pyridazinon-2-yl)phenoxyacetate;
Butyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-phenoxyacetate;
Pentyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-phenoxyacetate;
Cyclopentyl 2-chloro-4-fl uoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxyacetate;
Ethyl 2- { 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxy }propionate;
Methyl 2- { 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxy }propionate;
Ethyl 2-chloro-4-fl uoro-5-(4-methyl-5-trifl uoromethyl-3-pyridazinon-2-yl )-phenylthioacetate;
Methyl 2-chloro-4-fluoro-5-(4-methyl -5-trifluoromethyl -3 -pyridazinon-2-yl)-phenylthioacetate;
Ethyl 2- { 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenylthio }propionate;
Methyl 2- { 2-chloro-4-fluoro-5-(4-rnethyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenylthio } propionate;
Methyl 2-{ 2-chloro-4-fluoro-5-(5-trifluoromethyl-3-pyridazinon-2-yl)phe-noxy } propionate;
Ethyl 2- { 2-chloro-4-fluoro-5-(5-trifluoromethyl-3-pyridazinon-2-yl)phe-noxy }propionate;
Ethyl 2-chloro-4-fluoro-5-(5-trifl uoromethyl-3-pyridazinon-2-yl)phenylthio-acetate;
Methyl 2-chloro-4-fluoro-5-(5-trifluoromethyl-3-pyridazinon-2-yl)phenylthio-acetate;
Ethyl 2-{ 2-chloro-4-fluoro-5-(5-trifluoromethyl-3-pyridazinon-2-yl)phenyl-thio } propionate;
Methyl 2- { 2-chloro-4-fluoro-5-(5-trifluoromethyl-3-pyridazinon-2-yl)phenyl-thio } propionate;
Isopropyl 2- { 2-chl oro -4-fluoro-5 - (5-tri fl uoromethyl -3 -pyri dazinon-2-yl)-phenylthio }propionate;
Ethyl 2- { 2-chloro-4- flu oro- 5-(4- methyl-5 -trifl uoromethyI-3-pyridazinon-yl)phenylamino }propionate;
Ethyl 2- { 2-chloro-4-fluoro-5-(5-trifluoromethyl-3 -pyridazinon-2-yl)phenyl-amino } propionate;
N- { 2-c hloro-4-f lu oro-5 -(4-methyl -5-t rifluoromethyl -3-p yri dazi non -2-yl)-phenyl }methanesulfonamide;
N- { 2-c hloro-4-f lu oro-5 -( 4-methyl -5 -t rif luoromethyl -3-p yri dazi non -2-y 1)-phenyl }chloromethanesulfonamide;
N-{ 2-chloro-5-(4-methy1-5-trifluoromethyl-3-pyridazinon-2-yl)phenyl}-methanesulfonamide;
Methyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-benzoate;
Ethyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-benzoate;
Ethyl 2-chloro-5-(4-methyl-5-trifl uoromethyl-3-pyridazinon-2-yl)benzoate;
Isopropyl 2-chloro-_5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)ben-zoate; and 2-(4-Chloro-2-fluoro-5-propargyloxyphenyl)-6-methyl-5-trifluoromethylpyri-dazin-3-one.
Among these compounds, more preferred ones from the viewpoint of their herbicidal activity are as follows:
7-F luo ro-6-(5 -triflu oro met hyl-3 -p yrid azi non -2-y 1)-4-proparyg yl-2 H-1,4-benzoxazin-3-one;
7-Fluoro-6-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-4-propargyl-2H-1,4-benzoxazin-3-one;
6-(4-Methyl -5-trifluoromethyl -3-pyridazinon-2-y 1)-4-propargyl-2H -1,4-ben-zoxazin-3-one;
Ethyl 2- { 2-chloro-4-fluoro-5-(5-trifluoromethyl-3 -pyridazinon-2-yl) phe-noxy}propionate; and Ethyl 2- { 2-chloro-4-fl u oro-5-(5-trifl uoromethyl-3-pyridazinon-2-yl )phenyl-thio }propionate.
In addition, more preferred ones from the viewpoint of their selectivity between crop plants and undesired weeds are as follows:
2-(4-Chloro-2-fl uoro-5-propargyloxyphenyl)-4-methyl-5-trifluoromethylpyri-dazin-3-one;
Ethyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-phenoxyacetate;
N- { 2-chloro-4-fluoro-5-(4-methyl-5-tri fluoromethyl-3-pyridazinon-2-yl)phen-yl } methanesulfonamide; and Ethyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-benzoate.
The present compounds can be produced, for example, according to the production processes described below.
(Production Process 1) This is the production process in which among the present compounds, a compound of the fonnula:
Q1_1~ Ri N- [3]
wherein Ri, R2, R3, and Qt are as defined above, is produced by reacting a hydrazone derivative of the formula:
QI-NHN= C~ [4]
t E- R
=
wherein R1, R3, and Q1 are as defined above, with a compound of the formula:
R?
' 1 Ar3P=C-- COOR28 [5]
wherein R2 is as defined above; R28 is Ci-C6 alkyl such as methyl or ethyl;
and Ar is an optionally substituted phenyl such as phenyl.
The reaction is usually effected in a solvent. The reaction temperature is usually in the range of -20 to 150 C, preferably 0 to 100 C. The reaction time is usually in the range of a moment to 72 hours. The amounts of the reagents to be used in the reaction, although the proportion of I mole of compound [5] to 1 mole of compound [4] is ideal, can be freely changed depending upon the reaction conditions.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; aromatic hydro-carbons such as benzene, toluene, and xylene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran (THF), and ethylene glycol dimethyl ether;
nitro compounds such as nitromethane and nitrobenzene; acid amides such as formamide, N,N-dimethylformamide, and acetamide; tertiary amines such as pyridine, triethylamine, diisopropylethylamine, N,N-dimethylaniline, N,N-diethylaniline, and N-methylmor-pholine; sulfur cornpounds such as dimethylsulfoxide and sulforane; alcohols such as methanol, ethanol, ethylene glycol, and isopropanol; water; and mixtures thereof.
= After completion of the reaction, the reaction solvent is distilled out from the reaction mixture and the residue is subjected to chromatography, or the reaction mixture is subjected to ordinary post-treatinents such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as chromatography or recrystallization. Thus the desired compound of the present invention can be isolated.
The above reaction is effected through a compound of the formula:
Qi"'NHN=~
// R [6]
R2,~~r wherein R1, R2, R3, R28, and Q1 are as defined above.
This production process can also be conducted by isolating compound [6]
and effecting intramolecular cyclization of compound [6]. The cyclization can usually be effected in a solvent. The reaction temperature is usually in the range of -20 to 150 C, preferably 50 to 150 C. The reaction time is usually in the range of a moment to 72 hours.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; aromatic hydro-carbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloromethane, dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydro-furan, and ethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; esters such as ethyl formate, ethyl acetate, butyl acetate, and diethyl carbonate; nitro compounds such as nitromethane and nitrobenzene; nitriles such as acetonitrile and isobutyronitrile; acid amides such as formamide, N,N-dimethylformamide, and acetamide; tertiary amines such as pyridine, triethylamine, diisopropylethylamine, N,N-dimethylaniline, N,N-diethylaniline, and N-methylmorpholine; sulfur compounds such as dimethylsulfoxide and sulforane;
fatty acids such as formic acid, acetic acid, and propionic acid; alcohols such as methanol, ethanol, ethylene glycol, and isopropanol; water; and mixtures thereof.
As the reaction catalyst, acids such as sulfuric acid or bases such as sodium methylate can be used.
(Production Process 2) This is the production process according to the following scheme:
x O R'- x R'-F 6 Rj ---IN F ON ~ Rj ---~ O-)N
R; R3 [7] [gJ
X O R'-R'-'OOCO ~ ~ N Rt ~ R4 ~N-N \ R3 O~N R3 O H
[9] [10]
x o R'-~ ~ N R' R5! R3 [11]
wherein R5 1 is a substituent other than hydrogen, which is included in the definition of R5; R1, R2, R3, R4, and X are as defined above; R22 is CI-C6 alkyl; and D is chlorine, bromine, iodine, methanesulfonyloxy, trifluoromethanesulfonyloxy, or p-toluenesulfonyl-oxy.
Process for Producing Compound f8l from Compound f71 = Compound [8] can be produced by reacting compound [7] with a nitrating agent in a solvent.
Nitrating agent: nitric acid or the like Amount of nitratina agent: I to 10 moles per mole of compound [7]
Solvent: sulfuric acid Temperature: -10 C to room temperature Time: a moment to 24 hours Process for Producing Compound (9l from Compound181 Compound [9] can be produced by reacting compound [8] with a compound of the formula:
HO COOR22 [12]
wherein R4 and R22 are as defined above, in the presence of potassium fluoride in a solvent.
Aniount of compound [12]: 1 to 50 moles per mole of compound [8]
Amount of potassium fluoride: 1 to 50 moles per mole of compound [8]
Solvent: 1,4-dioxane or the like Temperature: room temperature to refluxing temperature under heating Time: a moment to 96 hours Process for Producinsz Compound (101 from Compound (91 Compound [10] can be produced by reducing compound [9] with iron powder or the like in the presence of an acid in a solvent.
Amount of iron powder: 3 moles to an excess per mole of compound [9]
Acid: acetic acid or the like Amount of acid: 1 to 10 moles Solvent: water, ethyl acetate, or the like Temperature: room temperature to refluxing temperature under heating .
Time: a moment to 24 hours Process for Producina Compound (1 11 from CornQound (101 Compound [ 1 1] can be produced by reacting compound [ 10] with a compound of the formula:
R51-D [13]
wherein R51 and D are as defined above.
The reaction is usually effected in the presence of a base in a solvent. The reaction temperature is usually in the range of -20 to 150 C, preferably 0 to 50 C. The reaction time is usually in the range of a moment to 48 hours. The amounts of the reagents to be used in the reaction are usually 1 to 3 moles of compound [ 13]
and usually 1 to 2 moles of the base, per mole of compound [10].
Examples of the base which can be used include inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate; and organic bases such as triethylamine, diisopropyl-ethylamine, pyridine, 4-dimethylaminopyridine, N,N-dimethylaniline, and N,N-diethyl-aniline.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; aromatic hydro-carbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloro-benzene and dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether; nitro compounds such as nitro-benzene; acid amides such as formamide, N,N-dimethylformamide, and acetamide;
tertiary amines such as pyridine, triethylamine, diisopropylethylamine, N,N-dimethyl-amine, N,N-diethylaniline, and N-methylmorpholine; and mixtures thereof.
After completion of the reaction, the reaction mixture is poured into water, if necessary, and subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatography or recrystallization. Thus the present compound [ 1 1] can be obtained.
The above compound [9] can also be produced according to the following scheme:
X O R' R4 X O R'-HO R' ---~ R'-'-OOCIJI- ~ Ri N
[141 [ 15 ]
X O R'- R4 X O R'-H ~~ N ~ Ri R''OOCO ~~ N ~ R' _ _ O,N R3 O,N R3 [16] [9l wherein R1, R2, R3, R4, R22 , and X are as defined above.
Process for ProducinQ Compound [ 151 from Compound f 141 Compound [15] can be produced by reacting compound [14] with a compound of the formula:
Br COOR '' [17]
wherein R4 and R'-2 are as defined above, in the presence of a base in a solvent.
Amount of compound [ 17]: 1 to 2 moles per mole of compound [ 14]
Base: sodium hydride, sodium carbonate, or the like Amount of base: I to 2 moles per mole of compound [ 14]
Solvent: 1,4-dioxane, N,N-dimethylformamide, or the like Teniperature: 0 to 100 C
Time: a moment to 24 hours Process for Producing Compound f9l from Compound [ 151 Compound [9] can be produced by reacting compound [ 15] with a nitrating agent in a solvent.
Nitrating agent: nitric acid or the like Amount of nitrating agent: 1 to 10 moles per mole of compound [15]
Solvent: sulfuric acid, acetic acid, or the like Temperature: -10 C to room temperature = Time: a moment to 24 hours Process for Producing Compound j161 from Comnound f 141 Compound [ 16] can be produced by reacting compound [ 14] with a nitrating agent in a solvent.
Nitrating agent: nitric acid or the like Amount of nitrating agent: 1 to 10 moles per mole of compound [ 14]
Solvent: sulfuric acid, acetic acid, or the like Temperature: -10 C to room temperature Time: a moment to 24 hours Process for Producing Compound (91 from Compound f 161 Compound [9] can be produced by reacting compound [16] with compound[17] in the presence of a base in a solvent.
Amount of compound [ 17]: 1 to 2 moles per mole of compound [ 16]
Base: sodium hydride, potassium carbonate, or the like Ainount of base: 1 to 2 moles per mole of compound [ 16]
Solvent: 1,4-dioxane, N,N-dimethylformamide, or the like Temperature: 0 to 100 C
Time: a moment to 24 hours (Production Process 3) This is the production process according to the following scheme:
X O R'- h O R'-Y / \ N \ R ' ---o- N R i 3-- Nr- - N-O,N R3 H,N R3 [18] [ 19]
X O R'- X O R'-S Ri R1 , H,N Rj O N R3 H =
[20] [21 ]
X O R'--~ N ~ Ri ~N N-[22~
wherein X, R1, R2, R3, R51, and D are as defined above.
Process for Producin!z Compound f 191 from Compound1181 Compound [19] can be produced by reducing compound [18] with iron powder or the like in the presence of an acid in a solvent.
Amount of iron powder: 3 moles to an excess per mole of compound [18]
Acid: acetic acid or the like Amount of acid: 1 to 10 moles per mole of compound [ 18]
Solvent: water, ethyl acetate, or the like Temperature: room temperature to refluxing temperature under heating Time: a moment to 24 hours Process for Producing Compound f211 from Compound [201 Compound [20] can be produced by reacting compound [ 19] with sodium thiocyanate, potassium thiocyanate, or the like in a solvent, and then reacting it with bromine or chlorine in a solvent.
Amount of sodium thiocyanate, potassium thiocyanate, or the like: I to moles per tnole of compound [ 19]
Amount of bromine or chlorine: I to 10 moles per mole of compound [19]
Solvent: aqueous hydrochloric acid, aqueous acetic acid, aqueous sulfuric acid, or the like Temperature: 0 to 50 C
Time: a moment to 150 hours Process for Producing Compound f211 from Compound f201 Compound [21 ] can be produced by 1) reactinj compound [20] with sodium nitrite, potassium nitrite, or the like in a solvent, and then 2) heatina it in an acidic solution.
<Reaction 1)>
Amount of sodium nitrite, potassium nitrite, or the like: I to 2 moles per mole of compound [20]
Solvent: aqueous hydrochloric acid or aqueous sulfuric acid Temperature: -10 to 10 C
Time: a moment to 5 hours <Reaction 2)>
Acidic solution: aqueous hydrochloric acid, aqueous sulfuric acid, or the like Temperature: 70 C to refluxing temperature under heating Time: a moment to 24 hours Process for Producina Compound f221 from Compound i211 Compound [22] can be produced by reacting compound [21 ] with compound [ 13] in the presence of a base in a solvent.
Amount of compound [13]: 1 to 3 moles per mole of compound [21]
Base: sodium hydride, potassium carbonate, or the like Amount of base: 1 to 2 moles per mole of compound [21 ]
Solvent: 1,4-dioxane, N,N-dimethylformamide, or the like Temperature: 0 to I 00 C
Time: a moment to 48 hours (Production Process 4) This is the production process accordina to the following scheme:
WO 97/07104 PCT/.TP96/02311 X O R'- X O R ' -O _ , N N R' H2N N R~ ------~- ~
- N- -H \ R; H \ R;
[23] [24]
X O R'-~ N \ R
jl N-N-N
R;
[25]
wherein X, R I, R2, R3, and R5 are as defined above.
Process for Producing Compound L241 from Com op und [23]
Compound [24] can be produced by reducing compound [23] with iron powder or the like in the presence of an acid in a solvent.
Amount of iron powder: 3 moles to an excess per mole of compound [23]
Acid: acetic acid or the like Amount of acid: i to 10 moles per mole of compound [23]
Solvent: water, ethyl acetate, or the like Temperature: room temperature to refluxing temperature under heating Time: a moment to 24 hours Process for Producina Compound [251 from Com op und [241 Compound [25] can be produced by 1) reacting compound [24] with a nitrite salt in a solvent to form a diazonium salt, and then 2) raising the temperature to cause the cyclization of the diazonium salt in a solvent.
<Reaction 1)>
Nitrite salt: sodium nitrite, potassium nitrite, or the like Amount of nitrite salt: 1 to 2 moles per mole of compound [24]
Solvent: aqueous hydrochloric acid, aqueous sulfuric acid, or the like Temperature: -10 to 10 C
Time: a moment to 5 hours <Reaction 2)>
= Solvent: aqueous hydrochloric acid, aqueous sulfuric acid, or the like Temperature: room temperature to 80 C
Time: a moment to 24 hours (Production Process 5) This is the production process according to the following scheme:
X 0 R'- X O R'-yl 6 N \ RI yi ON \ RI R; O,N R3 [26] [27]
X O R'- X O R'-yl N R1 -~~ yt N RI
N- N-H,N W HO R3 [28] [29]
X O R'-----i- y I 0 N' R t N
RlOI-O
[30]
wherein Y~ is a substituent other than nitro, which is included in the definition of Y;
RIOi is a substituent other than hydrogen, which is included in the definition of R lO; and X, R1, R2, and R3 are as defined above.
Process for Producing Compound f271 from compound f261 Compound [27] can be produced by adding nitric acid to compound [26] in a solvent (see Organic Synthesis Collective, Vol. 1, p. 372).
The reaction temperature is usually in the range of 0 to 100 C. The reaction time is usually in the range of a moment to 24 hours. The amounts of the reagents to be used in the reaction, although the proportion of 1 mole of nitric acid to I
mole of compound [26] is ideal, can be freely changed depending upon the reaction conditions.
Examples of the solvent which can be used include acidic solvents such as sulfuric acid.
Process for Producing Compound f281 from compound1271 Compound [28] can be produced by reducing compound [27] in a solvent (see Organic Synthesis Collective, Vol. 2, p. 471, and ibid., Vol. 5, p. 829).
For example, the production can be achieved by adding compound [27], which is neat or dissolved in a solvent such as ethyl acetate, to a mixture of acetic acid, iron powder, and water. The reaction temperature is usually in the range of 0 to 100 C.
The reaction time is usually in the range of a moment to 24 hours.
After completion of the reaction, the reaction mixture is filtered to collect the crystals, which may be precipitated by the addition of water, if necessary, or the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatography or recrystallization. Thus the desired product can be isolated.
Process for Producina Compound [291 from compound [281 Compound [29] can be produced by 1) reacting compound [28] with a nitrite salt in a solvent, and then 2) heating it in an acidic solvent.
<Reaction I )>
Nitrite salt: sodium nitrite, potassium nitrite, or the like Amount of nitrite salt: I to 2 moles per inole of compound [28]
Solvent: aqueous hydrochloric acid, aqueous sulfuric acid, or the like Temperature: -10 to 10 C
Time: ainoment to 5 hours W O 97/07104 PCT/dP96/02311 <Reaction 2)>
Acidic solvent: aqueous hydrochloric acid or aqueous sulfuric acid Temperature: 70 C to refluxing temperature under heating r.
Time: a moment to 24 hours.
Process for Producing Compound (301 from Compound [29]
Compound [30] can be produced by reacting compound [29] with a compound of the formula:
R101-D [31]
wherein R101 and D are as defined above, in the presence of a base in a solvent.
The reaction is usually effected in a solvent. The reaction temperature is usually in the range of -20 to 150 C, preferably 0 to 100 C. The reaction time is usually in the range of a moment to 72 hours. The amounts of the reagents to be used in the reaction, although the proportion of I mole of compound [31] and 1 mole of a base to I mole of compound [29] is ideal, can be freely changed depending upon the reaction conditions.
Examples of the base which can be used include organic bases and inorganic bases such as potassium carbonate, sodium hydroxide, and sodium hydride.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; aromatic hydro-carbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloromethane, dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydro-furan, and ethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; esters such as ethyl formate, ethyl acetate, butyl acetate, and diethyl carbonate; nitro compounds such as nitromethane and nitrobenzene: nitriles such as acetonitrile and isobutyronitrile; acid amides such as formamide, N,N-dimethylformamide, and acetamide; tertiary amines such as pyridine, triethylamine, diisopropylethylamine, N,N-dimethylaniline, N,N-diethylaniline, and N-methylmorpholine; sulfur compounds such as dimethylsulfoxide and sulforane;
and mixtures thereof.
After completion of the reaction, the reaction mixture is filtered to collect the crystals, which may be precipitated by the addition of water, if necessary, or the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatography or recrystallization. Thus the desired product can be isolated.
(Production Process 6) This is the production process according to the following scheme:
X O R'- X O R'-1.~ N "I R' 10 1,t N RI
N- N-H,N R3 H ; R3 [28] [32]
X O R'------a Y t N ~ R ' N
R'4 R;
[33]
wherein R23 and R24 are independently a substituent other than hydrogen, which is included in the definition of RI' and R 1 2; or COR 13, S02R 14, S02R 1 5, or COOR IO, wherein R10, R13, R 14, and R 15 are as defined above; X, Y 1, R1, R2, and R3 are as defined above.
Process for Producing compound (321 from Compound 1'281 Compound [32] can be produced by reacting compound [28] with a compound of the formula:
r R20-D [34]
wherein R20 is a substituent other than hydrogen, which is included in the definition of R i l or R 1V; or COR 13, S02R 14, SO2R 15, or COOR 10, wherein R 10, R 13, R
14, and R 15 are as defined above; and D is as defined above; or with a compound of the formula:
(R21)20 [35]
wherein R21 is COR13, S02R14, S02R15, or COOR10, wherein R1o, R13, R14, and are as defined above, usually in the presence of a base and usually in a solvent.
The reaction temperature is usually in the range of -20 to 200 C, preferably 0 to 180 C. The reaction time is usually in the range of a moment to 72 hours. The amounts of the reagents to be used in the reaction, although the proportion of 1 mole of compound [34] or [35] to 1 mole of compound [28] is ideal, can be freely changed depending upon the reaction conditions.
Examples of the base which can be used include organic bases such as pyridine and triethylamine, and inorganic bases.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; aromatic hydro-carbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloromethane, dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydro-furan, and ethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; esters such as ethyl formate, ethyl acetate, butyl acetate, and diethyl carbonate; nitro compounds such as nitromethane WO 97/07104 PCT/.TP96/02311 and nitrobenzene; nitriles such as acetonitrile and isobutyronitrile; acid amides such as formamide, N,N-dimethylformamide, and acetamide; tertiary amines such as pyridine, triethylamine, diisopropylethylamine, N,N-dimethylaniline, N,N-diethylaniline, and N-methylmorpholine; sulfur compounds such as dimethylsulfoxide and sulforane;
and mixtures thereof.
After completion of the reaction, the reaction mixture is filtered to collect the precipitated crystals, or the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subse-quent purification by a technique such as column chromatography or recrystallization.
Thus the desired product can be isolated.
Process for Producin= compound f33] from Compound [321 Compound [33] can be produced by reacting compound [32] with compound [34] or [35]. This production process is based on the process for producing compound [32] from compound [28).
(Production Process 7) This is the production process according to the followin; scheme:
X O R'- X O R=' Y6 N R t R t N ~T
Rs CIOiS
R-;
[36] [37]
X O R'- X O R'-Y ON \ Rt y Rt . ~ _ R' OO, S R i t R t'-NO, S
R3 R;
[38) [39l wherein X, Y, RI, R', R3, R 10, R1i, and R12 are as defined above.
WO 97/07104 PCT/,TP96/02311 Process for Produciniz compound [371 from compound f361 Compound [37] can be produced by reacting compound [36] with chloro-sulfonic acid without any solvent or in a solvent.
Amount of chlorosulfonic acid: 1 mole to an excess per mole of compound [36]
Solvent: sulfuric acid Temperature: 0 to 70 C
Time: a moment to 24 hours (see Org. Syn. Coll., Vol. 1, 8 (1941)) Process for Producing Compound f381 from Compound [37]
Compound [38] can be produced by reacting compound [37] with a compound of the formula:
R 1 O-OH [40]
wherein R10 is as defined above, in the presence of a base without any solvent or in a solvent.
Amount of compound [24]: 1 mole to an excess per mole of compound [37]
Base: organic bases such as triethylamine or inorganic bases such as potas-sium carbonate Amount of base: 1 to 2 moles per mole of compound [37]
Solvent: N,N-dimethylformamide, 1,4-dioxane, or the like Temperature: 0 to 100 C
Time: a moment to 24 hours Process for Producina Compound [391 from Compound 571 Compound [39] can be produced by reacting compound [37] with a compound of the formula:
R11Ri2NH [41]
wherein R I 1 and R12 are as defined above, in the presence or absence of a base without any solvent or in a solvent.
Amount of compound [41]: 1 mole to an excess per mole of compound [37]
Base: organic bases such as triethylamine or inorganic bases such as potas-sium carbonate Amount of base: 1 to 2 moles per mole of compound [37]
Solvent: 1,4-dioxane, N,N-dimethylformamide, or the like Temperature: 0 to 100 C
Time: a moment to 24 hours (Production Process 8) This is the production process according to the following scheme:
X O R'- X O R'-.I \ R i ---~
_ Y~~ N R t 47R3 N
0= C, \ OH R3 [42] [43]
X 0 R'-X O R'- y N Ri y ~ ~ N ~ R!
. R17~
_ N- R3 Ri7C R3 COOR'-'- jr R1s CONR"RI' R's [44] [45]
wherein X, Y, R 1, R2, R3, R1i, R 12, R 17, R 18, and R22 are as defined above.
Process for Producing Compound [431 from Compound [421 Compound [43] can be produced from compound [42] according to the method described in JP-A 5-294920/1993, pp. 15-16.
Process for Producing Compound f441 from Compound f431 Compound [44] can be produced by reacting compound [43] with a compound of the formula:
(C6H5)3P=CR 18COOR22 [45]
or (C2H50)2P(O)CHR 18COOR22 [46]
wherein R 18 and R22 are as defined above, in a solvent, and when compound [46] is used, in the presence of a base.
Amount of compound [45] or [46]: 1 to 2 moles per mole of compound [43]
Solvent: tetrahydrofuran, toluene, or the like Base: sodium hydride or the like Amount of base: 1 to 2 moles per mole of compound [43]
Temperature: 0 to 50 C
Time: a moment to 24 hours Process for Producing Compound f451 from Compound [441 Compound[45] can be produced by reacting compound [44] with compound [41].
(Production Process 9) This is the production process according to the following scheme:
X O R'- X O R'-' ~ ~ N R' --~ Y ~ Ri - N- - H,N R~ R3 CO,R 1;
w, [48] [49]
wherein W2 is chlorine or bromine; and X, Y, RI, R2, R3, and R13 are as defined above.
The reaction conditions are described, for example, in USP 5,208,212.
s The production can be achieved by converting compound [48] into a diazonium salt in a solution of hydrochloric acid, hydrobromic acid, or the like according to the ordinary method, and then reacting it with a compound of the formula:
CH2=CHCO2R13 [50]
wherein R 13 is as defined above, in the presence of a copper salt, such as copper (II) chloride or copper (II) bromide, in a solvent such as acetonitrile.
The reaction temperature is usually in the range of -20 to 150 C, preferably 0 to 60 C. The reaction time is usually in the range of a moment to 72 hours.
After completion of the reaction, the reaction mixture is filtered to collect the crystals, which may be precipitated by the addition of water, if necessary, or the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatography or recrystallization. Thus the desired product can be isolated.
(Production Process 10) This is the production process according to the following scheme:
X O R' X O R'-Yt N ~ Rt ~,t N ~ Rt .
N-' N-H,N R.; w3 R;
[28] [51]
X O R'-yi ~ ~ N Rt _ N-R ~;OOC
[52]
wherein W3 is brornine or iodine: and X, Yl, Rl, R2, R3, and R13 are as defined above.
------------Process for Producing Compound (511 from compound f281 Compound [51 ] can be produced by 1) making a diazonium salt from compound [28] in a solvent and then 2) reacting it with potassium iodide or copper ( I) bromide in a solvent.
<Reaction 1)>
Diazotizing agent: sodium nitrite, potassium nitrite, or the like.
Amount of diazotizing agent: 1 to 2 moles per mole of compound [28]
Solvent: aqueous hydrogen bromide, aqueous sulfuric acid, or the like.
Temperature: -10 to IO C
Time: a moment to 5 hours <Reaction 2)>
Amount of potassium iodide or copper ( I) bromide: 1 mole to an excess per mole of compound [28]
Solvent: aqueous hydrogen bromide, aqueous sulfuric acid, or the like Temperature: 0 to 80 C
Time: a moment to 24 hours (see Org. Syn. Coll., Vol. 2, 604 (1943), and ibid., Vol. 1, 136 (1941)) Process for Produciniz Compound (521 from Compound (5 11 Compound [52] can be produced by reacting compound [511 with a compound of the formula:
R 1-i-OH [53]
wherein R13 is as defined above, in the presence of a transition metal catalyst and a base in a solvent under an atmosphere of carbon monoxide.
Catalyst: PdC12(PPh3)2 or the like Amount of catalyst: a catalytic amount to 0.5 mole per mole of compound [511 Amount of compound [53]: 1 mole to an excess per mole of compound [51]
Base: organic bases such as diethylamine Amount of base: 1 to 2 moles per mole of compound [51]
Solvent: N,N-dimethylformamide or the like Pressure of carbon monoxide: 1 to 150 atm.
Temperature: 0 to 100 C
Time: a moment to 72 hours (see Bull. Chem. Soc. Jpn., 48 (7) 2075 (1975)) (Production Process 11) This is the production process according to the following scheme:
X O R'- X O R'-Y~~ N ~ Ri Y~~ N ~ Ri -' N- - N-o R:s HO Rs [54] [55]
wherein X, Y, R1, R2, R3, and R 19 are as defined above.
Compound [55] can be produced by hydrolyzing compound [54] in an acid solvent such as sulfuric acid, or in the presence of an acid such as boron tribromide in a solvent such as methylene chloride.
The reaction temperature is usually in the range of -20 to 150 C, preferably 0' to 100 C. The reaction time is usually in the range of a moment to 72 hours.
The amount of the acid to be used in the reaction, although the proportion of I mole of the acid to 1 mole of compound [54] is ideal, can be freely changed depending upon the reaction conditions.
After completion of the reaction, the reaction mixture is filtered to collect the crystals, which inay be precipitated by the addition of water, if necessary, or the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatob aphy or recrystallization. Thus the desired product can be isolated.
(Production Process 12) This is the production process according to the following scheme:
X O R'- X O R'-y RI _-T 1, N \ Rt % - N- - N-Z; O R3 Z' O R3 R'-sOR' 7 R,sZsR'-e [56] [57]
wherein X, Y, R1, R2, R3, Z2, and R17 are as defined above; Z3 is oxygen or sulfur;
R25 is hydrogen or Ci-C5 alkyl; and R26 is Cl-C6 alkyl, C3-C6 alkenyl, or C3-alkynyl.
Compound [57] can be produced by reacting compound [56] with a compound of the formula:
R26Z3H [58]
wherein R26 and Z3 are as defined above, in the presence or absence of a catalyst and usually in a solvent.
The amount of compound [58] to be used in the reaction, although the proportion of 1 mole of compound [58] to I mole of compound [56] is ideal, can be freely changed depending upon the reaction conditions.
Examples of the catalyst which can be used include p-toluenesulfonic acid.
Examples of the solvent which can be used include toluene, xylene or the like, or compound [56].
The reaction temperature is usually in the range of 0 to 200 C, preferably 50 to 150 C. The reaction time is usually in the range of a moment to 72 hours.
After completion of the reaction, the reaction mixture is filtered to collect the crystals, which may be precipitated by the addition of water, if necessary, or the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatography or recrystallization. Thus the desired product can be isolated.
(Production Process 13) This is the production process according to the following scheme:
X O R'- X O R'-.
y N 1~ R' --- y N I Ri %
- N- N-HO R3 Q /i R3 ~CI
[55] [59]
X O R'- X O R'-y I'_ N ~ Ri -y R' . N- N-[60] [61 ]
wherein R61 is a substituent other than methyl, which is included in the definition of R6;
and X, Y, RI, R2, and R3 are as defined above.
Process for Producing Compound f591 from Compound f551 Compound [59] can be produced by reacting compound [55] with 2,3-di-chloropropene in the presence of a base in a solvent.
Amount of 2,3-dichloropropene: I to 3 moles per mole compound [55]
Base: inorganic bases such as potassium carbonate Amount of base: 1 to 2 moles per mole of compound [55]
Solvent: N,N-dimethylformamide or the like Temperature: 0 to 70 C
Time: a moment to 24 hours Process for Producing Compound (601 from Compound 1591 Compound [60] can be produced by heating compound [59] in a solvent.
Solvent: N,N-dimethylformamide, N,N-dimethylaniline, N,N-diethylani-line, p-diisopropylbenzene, or the like Temperature: 70 to 200 C
Time: a moment to 24 hours Process for Producina Compound [61] from Compound [601 Compound [61) can be produced from compound [62] according to the method in which the methyl group in position 2 on the benzofuran ring is replaced with another substituent, as described in USP 5,308,829, columns 2-11.
(Production Process 14) This is the production process according to the following scheme:
X O R'- X O R'-~ Rt Rt --~-.
- N-[$5] [62]
X O R'- X O R'-N
R' Y N Rt N-Y S
R; O R3 [63] [64]
wherein X, Y, RI, R2, R3, and R7 are as defined above.
Process for Producina Compound (62] from compound [55]
Compound [62] can be produced by reacting compound [55] with a compound of the formula:
CH2=CR7CH2W2 [65]
wherein W2 and R7 are as defined above, in the presence of a base in a solvent.
Amount of compound [65]: 1 to 5 moles per mole of compound [55]
Base: inorganic bases such as potassium carbonate Amount of base: I to 2 moles per mole of compound [55]
Solvent: N,N-dimethylformamide, 1,4-dioxane, or the like Temperature: 0 to 70 C
Time: a moment to 24 hours Process for Producing Compound I631 from Compound r621 Compound [64] can be produced by heating compound [62] in a solvent.
Solvent: N,N-dimethylaniline, N,N-diethylaniline, p-diisopropylbenzene, or the like Temperature: 100 to 200 C
Time: a moment to 24 hours Process for Producing Compound [641 from Compound [631 Compound [64] can be produced by heating compound [63] in the presence of an acid in a solvent.
Acid: organic acids such as p-toluenesulfonic acid; and inorganic acids such as sulfuric acid Amount of acid: a catalytic amount to 1 mole per mole of compound [63]
Solvent: toluene, xylene, or the like Temperature: 100' to 250 C
Time: a moment to 24 hours (Production Process 15) This is the production process according to the following scheme:
X O R'- X O R'-Y N R1 y N ~ Rt -HO R; HO
R-~
O R
[63] [66]
X O R'- X O R'-y i N \ R t y ~~ N R i N- N-R3 O R;
R7 CH-2OH R7 Rg 1 [67] [68]
wherein R81 is a substituent other than methyl and hydroxymethyl, which is included in the definition of R8; and X, Y, R 1, R2, R3, and R7 are as defined above.
Process for Producing Compound f661 from Compound [631 Compound [66] can be produced by reacting compound [63] with a peracid in a solvent.
Peracid: m-chloroperbenzoic acid or peracetic acid Amount of peracid: I mole to an excess per mole of compound [63]
Solvent: halogenated hydrocarbons such as dichloromethane; and organic acids such as acetic acid Temperature: -20 C to room temperature Time: a moment to 24 hours Process for Producing Compound f671 from Compound (661 Compound [67] can be produced by reacting compound [66] in the presence of a base in a solvent.
Base: potassium carbonate or the like Ainount of base: I to 2 moles per mole of compound [66]
Solvent: methanol, ethanol, or the like Temperature: 0 to 50 C
Time: a moment to 5 hours Process for ProducinQ Compound [68] from Compound r671 Compound [68] can be produced from compound [67] according to the method in which the hydroxyalkyl group in position 2 on the dihydrobenzofuran ring is replaced with another substituent, as described in USP 5,411,935, columns 5-10.
(Production Process 16) This is the production process according to the following scheme:
X O R'- X O R'-~ N Rt y ~ ~ N \ Rt --a N- - N-0= C R3 0= Rs OH wl [42] [69]
X O R'-Y ~ N R' - N
O \
CH,R3' [70]
X O R'- X O R'- X O R'-Y N R I y ~ N Ri y N. \ R I
- N- N_ Z' ~,r R3 h, ; R34 R3 ;' 0 \ R33 CH,R3' Ril~ N \ CH,R;- R R;a / Z CH,R
~
R i-[71 ] [72] [73]
wherein Wl is halogen, preferably chlorine; R32 is hydrogen or CI -C5 alkyl;
and X, Y, Z2, R1, R2, R3, R11, R12, R33, and R34 are as defined above.
Process for ProducinQ Compound f691 from compound f421 Compound [69] can be produced by reacting compound [42] with a halogenating agent such as thionyl chloride in a solvent according to the ordinary method.
Process for Producing Compound f701 from Compound f691 Compound [70] can be produced by reacting compound [69] with a compound of the formula:
M(D(E)C ~ R32 [74]
wherein M is an alkali metal cation, preferably lithium cation or sodium cation; and R 19, R22, and R32 are as defined above, to give a compound of the formula:
X O R'-y 0- N Ri 0=C N R3 [75]
~ COOR19 R;'-COOR'-'- -wherein X, Y, R t, R 2, R3, R19, R22, and R32 are as defined above, and then hydro-lyzing and decarboxylating compound [75].
The first reaction is usually effected in a solvent. The reaction temperature is usually in the range of -20 to 50 C, preferably room temperature. The reaction time is usually in the range of a moment to 72 hours.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether; acid amides such as forinamide, N,N-dimethylformamide, and acetamide;
sulfur compounds such as dimethylsulfoxide and sulforane; and mixtures thereof.
The second reaction is effected in the presence of sulfuric acid, hydrobromic acid, or the like in a solvent such as a lower carboxylic acid, e.g., acetic acid, or without any solvent. The reaction temperature is usually in the range of 80 to 140 C, preferably 100 to 120 C. The reaction time is usually in the range of a moment to 72 hours.
Process for Producin(z Compound F711 from Compound f701 Compound [71] can be produced by reacting compound [70] with a compound of the formula:
H2N-O-R33 [76]
wherein R33 is as defined above.
The reaction is effected in a lower alcohol such as methanol, ethanol or isopropanol, or in a mixed solution of such a lower alcohol and water. The reaction temperature is in the range of 0 to 80 C. The reaction time is in the range of a moment to 72 hours.
Compound [76] can be used in the form of a free base or an acid addition salt such as a hydrochloride salt or a sulfate salt.
The above reaction can also be effected with the addition of a basic catalyst such as an organic base, e.g., pyridine; an alkali metal carbonate, e.g., sodium carbonate, potassium carbonate or the like; alkali metal hydrogencarbonate; or alkaline earth metal carbonate.
Compound [71 ] can also be produced by reacting a compound of the formula:
X R' Y N ~ Ri ' [77]
CH,R;'-wherein X, Y, R', R2, R3, and R32 are as defined above, with a compound of the formula:
R33-D [78]
wherein R33 and D are as defined above, in the presence of a base, usually in a solvent.
Examples of the base which can be used include alkali metal alcoholates and alkali metal hydrides such as sodium hydride.
The amounts of the reagents to be used in the reaction, although the propor-tion of about 1 mole of compound [78] and 1 to 2 moles of the base to 1 mole of compound [77] is ideal, can be freely changed depending upon the reaction conditions.
Examples of the solvent which can be used include ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether;
acid amides such as formamide, N,N-dimethylformamide, and acetamide; sulfur compounds such as dimethylsulfoxide and sulforane; alcohols such as methanol, ethanol, ethylene glycol, and isopropanol; and mixtures thereof.
The reaction temperature in the above reaction is in the range of -10 to 100 C, preferably 0 to 80 C. The reaction time is in the range of a moment to 72 hours.
Process for Producing Compound [72] from compound f701 Compound [72] can be produced by reacting compound [70] with a compound of the formula:
H2N N~R12 [79]
wherein R11 and R12 are as defined above.
The reaction is effected in a lower alcohol such as methanol, ethanol or isopropanol, or in a mixed solution of such a lower alcohol and water. The reaction temperature is in the range of 0 to 80 C. The reaction time is in the range of a moment to 72 hours.
Compound [79] can be used in the form of a free base or an acid addition salt such as a hydrochloride salt or a sulfate salt.
The above reaction can also be effected with the addition of a basic catalyst such as an organic base, e.g., pyridine; an alkali metal carbonate, e.g., sodium carbonate, potassium carbonate or the like; alkali metal hydrogencarbonate; or alkaline earth metal carbonate.
Process for Producina Compound L731 from Compound f701 Compound [73] can be produced by reacting compound [70] with a compound of the formula:
R34-Z2H [80]
wherein Z2 and R34 are as defined above, usually in the presence of a catalytic amount to an excess of an acid such as p-toluenesulfonic acid, hydrochloric acid or sulfuric acid, in an organic solvent such as benzene or chloroform.
The reaction temperature is in the range of -30 C to the boiling temperature of the reaction mixture. The reaction time is in the range of a moment to 72 hours.
(Production Process 17) This is the production process according to the following scheme:
H
Q1-NHN--C~ Ql-N ~ R1 II R l=~-O
[81] [82]
wherein Qi and R1 are as defined above.
Compound [82] can be produced by reacting compound [81] with a compound of the formula:
2' q 9 [83]
(RO)2PCH?COR ~ ~
wherein R 19 and R22 are as defined above, in a solvent.
The reaction temperature is usually in the range of 30 to 120 C, preferably 40 to 80 C. The reaction time is usually in the range of 5 to 72 hours. The amounts of the reagents to be used in the reaction, although the proportion of 1 mole of compound [83] to 1 mole of compound [81 ] is ideal, can be changed depending upon the reaction conditions.
Examples the solvent which can be used include tertiary amines such as triethylamine.
After completion of the reaction, the reaction solvent is distilled out from the reaction mixture and the residue is subjected to chromatography, or the reaction nuxture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatography or recrystallization. Thus the desired compound of the present invention can be isolated.
(Production Process 18) This is the production process according to the following scheme:
X X O R'-Y~~ NHN-C' --~ ji N Ri ~( i N-B4 0 R $4 R3 [99] [100]
X O R'--f Y ~ ~ N_ RI
_ N_.
[101]
wherein B3 is OR35, SR35, COOR35, COR16, or CR17=CR18COR16 (wherein R35 is (C 1-C6 alkyl)carbonyl C 1-C6 alkyl (C i-C6 haloalkyl)carbonyl C 1-C6 alkyl, {(C i-C4 alkoxy) C I -C4 alkyl } carbonyl C I -C6 alkyl, or (C3-C8 cycloalkyl)carbonyl C 1-C6 alkyl;
and R16, R17, and R18 are as defined above); B4 is a substituent derived from B3 by protecting its ketone or a[dehyde moiety with an alcohol; and X, Y, R 1, R2, and R3 are as defined above.
Process for ProducingCom o~[1001 from Compound 1991 Compound [100] can be produced in the same manner as described in Produc-tion Process 1, except that compound [99] is used in place of compound [4].
Process for Producing Compound f 101 ] from Compound f 1001 Compound [ 101 ] can be= produced by deprotecting the ketal or acetal moiety of compound [100] by the ordinary method.
Compound [99] can be produced in the same manner as described below in the production process for compound [4], except that the ketone or aldehyde moiety in the substituent B3 of a compound of the formula:
X
Y O NH2 [102]
wherein X, Y, and B3 are as defined above, is protected with an alcohol such as methanol to give a compound of the formula:
X
Y O NH2 [103]
wherein X, Y, and B4 are as defined above, and compound [103] is used in place of compound [91] as described below.
Compound [5], which is one of the starting compounds in the production of the present compounds by production process 1, can be obtained from commercial sources or can be produced, for example, according to the method described in Jikken Kagaku Kouza (Maruzen K.K.), 4th ed., Vol. 24, pp. 259-260.
Compound [4], which is the other starting compound used in production process 1, can be produced by reacting a compound of the formula:
Q R1CCV2R3 [841 wherein RI and R3 are as defined above; and V is iodine, bromine, or chlorine, with water in the presence of a base to give a compound of the formula:
1 I~I I~I 3 [85]
R -C-C-R' wherein R 1 and R3 are as defined above (hereinafter referred to as reaction 1), and then reacting compound [85] with a compound of the formula:
Q1-NHNH2 [86]
wherein Q i is as defined above (hereinafter referred to as reaction 2).
Compound [85] can also be reacted as its hydmte or acetal derivative in water or an alcohol.
Reaction 1 is usually effected in a solvent. The reaction temperature is usually in the range of 20' to 100 C. The reaction time is usually in the range of a moment to 24 hours. The amounts of the reagents to be used in the reaction, although the proportion of 2 moles of water and 2 moles of a base to 1 mole of compound [84] is ideal, can be changed, if necessary.
Examples of the base which can be used include organic bases and inorganic bases such as sodium acetate and potassium acetate.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; aromatic hydro-carbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloro-benzene and dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether; esters such as ethyl formate, ethyl acetate, butyl acetate, and diethyl carbonate; nitro compounds such as nitromethane and nitrobenzene; nitriles such as acetonitrile and isobutyronitrile; acid amides such as N,N-dimethylformamide; tertiary amines such as pyridine, triethylamine, diisopropyl-ethylamine, N,N-dimethylaniline, N,N-diethylaniline, and N-methylmorpholine;
sulfur compounds such as dimethylsulfoxide and sulforane; alcohols such as methanol, ethanol, ethylene glycol, and isopropanol; water; and mixtures thereof.
Reaction 2 is usually effected in a solvent. The reaction temperature is usually in the range of -20 to 200 C. The reaction time is usually in the range of a moment to 72 hours. The amounts of the reagents to be used in the reaction, although the proportion of 1 mole of compound [86] to 1 mole of compound [84] used in reaction 1 is ideal, can be freely changed depending upon the reaction conditions. If necessary, the hydrochloride salt or sulfate salt of compound [86] can also be used.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; aromatic hydro-carbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloromethane, dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydro-furan, and ethylene glycol dimethyl ether; esters such as ethyl formate, ethyl acetate, butyl acetate, and diethyl carbonate; nitro compounds such as nitromethane and nitro-benzene; nitriles such as acetonitrile and isobutyronitrile; acid amides such as form-amide, N,N-dimethylformamide, and acetamide; tertiary amines such as pyridine, triethylamine, diisopropylethylamine, N,N-dimethylaniline, N,N-diethylaniline, and N-methylmorpholine; sulfur compounds such as dimethylsulfoxide and sulforane;
fatty acids such as formic acid, acetic acid, and propionic acid; alcohols such as methanol, ethanol, ethylene glycol, and isopropanol; water; and mixtures thereof.
After completion of the reaction, the reaction mixture is filtered to collect the crystals, which may be precipitated by the addition of water, if necessary, or the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatography or recrystallization. Thus the desired product can be isolated.
Among the examples of compound [4], a compound of the formula:
X
H
Y2 ~ ~ NHI~C..~~
' - CF3 [87]
wherein X is as defined above; Y2 is halogen; and B2 is hydrogen, halogen, C1-alkoxy, or C1-C6 alkylthio, can also be produced according to the following scheme:
X
C- O R
Y2 NH2 ---~-- Y2 NHN--< CF3 O
[887 [89]
x 0 I I
C-OH
Y 2 / 'NHI~< -~- CF3 [871 [90]
wherein X, Y2, B2, and R22 are as defined above.
Process for Producing Compound f891 from Compound f881 Compound [89] can be produced by reacting compound [88] with a nitrite salt in hydrochloric acid or sulfuric acid to convert it into a diazonium salt, and then reacting the diazonium salt with a compound of the formula:
a ~ il CF3CCH2COR22 [104]
wherein R22 is as defined above, in the presence of a base such as sodium acetate or pyridine.
(see, e.g., Tetrahedron, Vol. 35, p. 2013.(1979)) Process for Produciniz Compound [90] from Compound f891 Compound [90] can be produced by hydrolyzing compound [89] usually in the presence of a base in a solvent.
The reaction temperature is in the range of 0 to 150 C, preferably 20 to I00 C. The reaction time is in the range of I to 24 hours, preferably 1 to 10 hours. The amounts of the reagents to be used in the reaction, although the proportion of 1 mole of a base to 1 mole of compound [89] is ideal, can be changed, if necessary.
Examples of the base which can be used include inorganic bases such as potassium hydroxide, lithium hydroxide, barium hydroxide, and sodium hydroxide.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; aromatic hydro-carbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloro-benzene and dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; nitro compounds such as nitromethane and nitrobenzene; acid amides such as N,N-dimethylformamide;
tertiary amines such as pyridine, triethylamine, diisopropylethylamine, N,N-dimethyl-aniline, N,N-diethylaniline, and N-methylmorpholine; sulfur compounds such as dimethylsulfoxide and sulforane; alcohols such as methanol, ethanol, ethylene glycol, and isopropanol; water; and mixtures thereof.
Process for Producing Compound f871 from Compound [90]
Compound [87] can be produced by heating compound [90] in a solvent.
The reaction temperature is in the range of 50 to 200 C, preferably 50 to 150 C. The reaction time is in the range of a moment to 72 hours.
Examples of the solvent which can be used include aliphatic hydrocarbons such as hexane, heptane, ligroin, cyclohexane, and petroleum ether; aromatic hydro-carbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloro-form, carbon tetrachloride, dichloromethane, dichloroethane, chlorobenzene, and wo 97/07104 PCT/JP96/02311 dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydro-furan, and ethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; esters such as ethyl formate, ethyl acetate, butyl acetate, and diethyl carbonate; nitro compounds such as nitromethane and nitrobenzene; nitriles such as acetonitrile and isobutyronitrile; acid amides such as formamide, N,N-dimethylformamide, and acetamide; tertiary amines such as pyridine, triethylamine, diisopropylethylamine, N,N-dimethylaniline, N,N-diethylaniline, and N-methylmorpholine; sulfur compounds such as dimethylsulfoxide and sulforane;
fatty acids such as formic acid, acetic acid, and propionic acid; alcohols such as methanol, ethanol, ethylene glycol, and isopropanol; water; and mixtures thereof.
The above reaction can also be effected with the use of a metal, e.g., copper, as a catalyst.
After completion of the reaction, the reaction mixture is filtered to collect the precipitated crystals, or the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatography or recrystalli-zation. Thus the desired compound can be isolated.
Compound [86] can also be produced by the following scheme:
Q i -NH2 NaNO2 Q 1 -N2+Cl- a) Na2SO3 [ 91 ] HC1 [92] b) SnC12 or c) H2 / catalyst Q!-NHNH2=HCl NaOH Qi-NHNH2 [93] [86]
wherein Q~ is as defined above.
(see Organic Synthesis Collective, Vol. 1, p. 442) Compound [91 ] is known in, or can be produced according to the method as described in, EP-61741-A; USP 4,670,046, USP 4,770,695, USP 4,709,049, USP
4,640,707, USP 4,720,297, USP 5,169,43 1 and JP-A 63-156787/1988.
Some examples of compound 191] can also be produced according to the following scheme:
X x Yi -0 0,. ,t, l NO2 R'1 R3 ' [941 C951 x i Y i NHIL
R
[96]
wherein R31 is COR 16 or COOR 10.
Process for Producina Compound [951 fToin Compound 1941 Compound [95] can be produced by reacting compound [94] with nitric acid in a solvent.
The reaction terriperature is usually in the range of 0 to 100 C. The reaction time is usually in the range of a moment to 24 hours, 'The amounts of the reagents to be used in the reaction, although the proportion of I rnole of nitric acid to 1 mole of compound [94] is ideal., can be freely changed depending upon the reaction conditions.
Examples of the solvent which can be used include acidic solvents such as inixtures of nitric acid and sulfuric acid.
(see Organic Synthesis ("ollective, Vol. 1, p. 372) Process for Producing Compound j961frorn Compound [95]
Cornpound [96] can be produced by reducing compound [95] in a mixture of acetic acid, iron powder, and water.
The reaction temperature is usually in the range of 0 to 100 C. The reaction time is usually in the range of a niornent to 24 hours.
After completion of the reaction, the reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration, followed by, if necessary, subsequent purification by a technique such as column chromatography or recrystallization. Thus the desired compound can be isolated.
(see Organic Synthesis Collective, Vol. 2, p. 471, and ibid., Vol. 5, p. 829) The present compounds have excellent herbicidal activity, and some of them exhibit excellent selectivity between crop plants and unfavorable weeds. In particular, the present compounds have herbicidal activity against various unfavorable weeds as recited below, which may cause trouble in the foliar treatment and soil treatment on upland fields.
Polygonaceae:
wild buckwheat (Polygonum convolvulus), pale smartweed (Polygonum lapathifolium), Pennsylvania smartweed (Polygonum pensylvanicum), ladysthurnb (Poly-gonum persicaria), curly dock (Rumex crispus), broadleaf dock (Rumex obtusifolius), Japanese knotweed (Polygonum cuspidatum) Portulacaceae:
common purslane (Portulaca oleracea) Caryophyllaceae:
common chickweed (Stellaria media) Chenopodiaceae:
common lambsquarters (Chenopodium album), kochia (Kochia scoparia) Amaranthaceae:
redroot pigweed (Amaranthus retroflexus), smooth pigweed (Amaranthus hybridus) Crusiferae:
wild radish (Raphanus raphanistrum), wild mustard (Sinapis arvensis), shepherdspurse (Capsella bursa-pastoris) Leguminosae:
hemp sesbania (Sesbania exaltata), sicklepod (Cassia obtusifolia), Florida beggarweed (Desmodium tortuosum), white clover (Trifolium repens) Malvaceae: velvetleaf (Abutilon tlieophrasti), prickly sida (Sida spinosa) Violaceae:
field pansy (Viola arvensis), wild pansy (Viola tricolor) Rubiaceae:
catchweed bedstraw (cleavers) (Galium aparine) Convolvulaceae:
ivyleaf morningglory (Ipomoea hederacea), tall morningglory (Ipomoea purpurea), entireleaf morningglory (Ipomoea hederacea var. integriuscula), pitted morn-ingglory (Ipomoea lacunosa), field bindweed (Convolvulus arvensis) Labiatae:
red deadnettle (Lamium purpureum), henbit (Lamium amplexicaule) Solanaceae:
jimsonweed (Datura stramonium), black nightshade (Solanum nigrum) Scrophulariaceae:
birdseye speedwell (Veronica persica), ivyleaf speedwell (Veronica hederae-folia) Compositae:
common cocklebur (Xanthium pensylvanicum), common sunflower (Helian-thus annuus), scentless chamomile (Matricaria perforata or inodora), corn marigold (Chrysanthemum segetum), pineappleweed (Matricaria matricarioides), common ragweed (Ambrosia artemisiifolia), giant ragweed (Ambrosia trifida), horseweed (Erigeron canadensis), Japanese mugwort (Artemisia princeps), tall goldenrod (Solidago altissima) Boraginaceae:
field forget-me-not (Myosotis arvensis) Asclepiadaceae:
common milkweed (Asclepias syriaca) Euphorbiaceae:
sun spurge (Euphorbia helioscopia), spotted spurge (Euphorbia maculata) Gramineae:
barnyardgrass (Echinochloa crus-galli), green foxtail (Setccria viridis), giant foxtail (Setaria faberi), large crabgrass (Digitaria sanguinalis), goosegrass (Eleusine indica), annual bluegrass (Poa annua), blackgrass (Alopecurus myosuroides), wild oat (Avena fatua), johnsongrass (Sorghum halepense), quackgrass (Agropyron repens), downy brome (Bromus tectorum), bermudagrass (Cynodon dactylon), fall panicum (Panicum dichotomiforum), Texas panicum (Panicum texanum), shattercane (Sorghum vulgare) Commelinaceae:
common dayflower (Commelina communis) Equisetaceae:
field horsetail (Equisetum arvense) Cyperaceae:
rice flatsedge (Cyperus iria), purple nutsedge (Cyperus rotundus), yellow nutsedge (Cyperus esculentus) Furthermore, some of the present compounds have no problematic phyto-toxicity on main crops such as corn (Zea mays), wheat (Triticum aestivum), barley (Hordeum vulgare), rice (Oryza sativa), sorghum (Sorghum bicolor), soybean (Glycine max), cotton (Gossypium spp.), sugar beet (Beta vulgaris), peanut (Arachis hypogaea), sunflower (Helianthus annuus) and canola (Brassica napus); garden crops such as flowers and ornamental plants; and vegetable crops.
The present compounds can attain effective control of unfavorable weeds in the no-tillage cultivation of soybean (Glycine max), corn (Zea mays), and wheat (Triticum aestivum). Furthermore, some of them exhibit no problematic phytotoxicity on crop plants.
The present compounds have herbicidal activity against various unfavorable weeds as recited below under the flooding treatment on paddy fields.
Gramineae:
barnyardgrass (Echinochloa oryzicola) Scrophulariaceae:
common falsepimpernel (Lindernia procumbens) Lythraceae:
Rotala indica, Ammannia multifora Elatinaceae:
Elatine triandra Cyperaceae:
smallflower umbrellaplant (Cyperus difformis), hardstem bulrush (Scirpus juncoides), needle spikerush (Eleocharis acicularis), Cyperus serotinus, Eleocharis kuroguwai Pontederiaceae:
Monochoria vaginalis Alismataceae:
Sagittaria pygmaea, Sagittaria trifolia, Alisma canaliculatum Potamogetonaceae:
roundleaf pondweed (Potamogeton distinctus) Umbelliferae:
Oenanthejavanica Furthermore, some of the present compounds have no problematic phyto-toxicity on transplanted paddy rice.
The present compounds can attain effective control of various unfavorable weeds in orchards, grasslands, lawns, forests, waterways, canals, or other non-cultivated lands.
The present compounds also have herbicidal activity against various aquatic plants such as water hyacinth (Eichhornia crctssipes), which will grow in waterways, canals, or the like.
The present compounds have substantially the same characteristics as those of the herbicidal compounds described in the publication of International Patent Application, W095/34659. In the case where crop plants with tolerance imparted by introducing a herbicide tolerance gene described in the publication are cultivated, the present com-pounds can be used at greater doses than those used when ordinary crop plants without tolerance are cultivated, and it is, therefore, possible to attain effective control of other unfavorable plants.
When the present compounds are used as active ingredients of herbicides, they are usually mixed with solid or liquid carriers or diluents, surfactants, and other auxiliary agents to give formulations such as emulsifiable concentrates, wettable powders, flowables, granules, concentrated emulsions, and water-dispersible granules.
These formulations may contain any of the present compounds as an active ingredient at an amount of 0.001 % to 80% by weight, preferably 0.005% to 70%
by weight, based on the total weight of the formulation.
Examples of the solid carrier or diluent may include fine powders or granules of the following materials: mineral matters such as kaolin clay, attapulgite clay, bentonite, terra alba, pyrophyllite, talc, diatomaceous earth, and calcite;
organic substances such as walnut shell powder; water-soluble organic substances such as urea;
inorganic salts such as ammonium sulfate; and synthetic hydrated silicon oxide.
Examples of the liquid carrier or diluent may include aromatic hydrocarbons such as methylnaphthalene, phenylxylylethane, and alkylbenzenes (e.g., xylene);
alcohols such as isopropanol, ethylene glycol, and 2-ethoxyethanol; esters such as phthalic acid dialkyl esters; ketones such as acetone, cyclohexanone, and isophorone; mineral oils such as machine oil; vegetable oils such as soybean oil and cotton seed oil;
dimethylsulfoxide, N,N-dimethylformamide, acetonitrile, N-methylpyrrolidone, water, and the like.
Examples of the surfactant used for emulsification, dispersing, or spreading may include surfactants of the anionic type, such as alkylsulfates, alkylsulfonates, alkylarylsulfonates, dialkylsulfosuccinates, and phosphates of polyoxyethylene alkyl aryl ethers; and surfactants of the nonionic type, such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters.
Examples of the auxiliary agent used for formulation may include lignin-sulfonates, alginates, polyvinyl alcohol, gum arabic, carboxymethyl cellulose (CMC), and isopropyl acid phosphate (PAP).
The present compounds are usually formulated as described above and then used for the pre- or post-emergence soil, foliar, or flooding treatment of unfavorable weeds. The soil treatment may include soil surface treatment and soil incorporation. The foliar treatment may include application over the plants and directed application in which a chemical is applied only to the unfavorable weeds so as to keep off the crop plants.
The present compounds can be used, if necessary, in combination with other compounds having herbicidal activity. Examples of the compounds which can be used in combination with the present compounds may include various compounds described in Catalog 1995 Edition of Farm Chemicals Handbook (Meister Publishing Company);
AG
CHEM NEW COMPOUND REVIEW, VOL. 13, 1995 (AG CHEM INFORMATION
SERVICE); or JOSOUZAI KENKYU SOURAN (Hakuyu-sha). Typical examples of such compounds are as follows: atrazin, cyanazine, dimethametryn, metribuzin, pro-metryn, simazine, simetryn, chlorotoluron, diuron, dymuron, fluometuron, isoproturon, linuron, methabenzthiazuron, bromoxynil, ioxynil, ethalfluralin, pendimethalin, triflu-ralin, acifluorfen, acifluorfen-sodium, bifenox, chlomethoxynil, fomesafen, lactofen, oxa-diazon, oxyfluorfen, carfentrazone, flumiclorac-pentyl, flumioxazine, fluthiacet-methyl, sulfentrazone, thidiazimin, difenzoquat, diquat, paraquat, 2,4-D, 2,4-DB, DCPA, MCPA, MCPB, clomeprop, clopyralid, dicamba, dithiopyr, fluroxypyr, mecoprop, naploanilide, phenothiol, quinclorac, triclopyr, acetochlor, alachlor, butachlor, diethatyl-ethyl, metolachlor, pretilachlor, propachlor, bensulfuron-methyl, chlorsulfuron, chlori-_ 'WO 97/07104 PCT/JP96/02311 muron-ethyl, halosulfuron-methyl, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, sulfometuron-methyl, thifensulfuron-methyl, triasulfuron, tribe-nuron-methyl, azimsulfuron, cloransulam-methyl, cyclosulfamuron, flumeturam, flupyr-sulfuron, flazasulfuron, imazosulfuron, metosulam, prosulfuron, rimsulfuron, triflusul-furon-methyl, imazamethabenz-methyl, imazapyr, imazaquin, imazethapyr, imazameth, imazamox, bispyribac-sodium, pyriminobac-methyl, pyrithiobac-sodium, alloxydim-sodium, clethodim, sethoxydim, tralkoxydim, diclofop-methyl, fenoxaprop-ethyl, fenoxa-prop-p-ethyl, fluazifop-butyl, fluazifop-p-butyl, haloxyfop-methyl, quizalofop-p-ethyl, cyhalofop-butyl, clodinafop-propargyl, benzofenap, clomazone, diflufenican, norflura-zon, pyrazolate, pyrazoxyfen, isoxaflutole, sulcotrione, glufosinate-ammonium, glyphos-ate, bentazon, benthiocarb, bromobutide, butamifos, butylate, dimepiperate, dimethen-amid, DSMA, EPTC, esprocarb, isoxaben, mefenacet, molinate, MSMA, piperophos, pributycarb, propanil, pyridate, triallate, cafenstrol, flupoxam, and thiafluamide.
The following will describe typical examples of such a combination, where the present compounds are designated by their compound numbers shown in Tables to 5.
1. A mixture of one compound selected from the group consisting of compounds 1-495, 1-496, 1-499, 1-503 and 1-577, and one compound selected from the group consisting of atrazin, cyanazine, bromoxynil and bentazon at a weight ratio of 1: 1 to 100.
2. A mixture of one compound selected from the group consisting of compounds 1-495, 1-496, 1-499, 1-503 and 1-577, and one compound selected from the group consisting of clethodim, sethoxydim, dichlofop-methyl, quizalofop-p-ethyl, lacto-fen, acifluorfen, acifluorfen-sodium, fomesafen, flumiclorac-pentyl and dicamba at a weight ratio of I: 0.5 to 50.
3. A mixture of one compound selected from the group consisting of compounds 1-495, 1-496, 1-499, 1-503 and 1-577, and one compound selected from the group consisting of nicosulfuron, primisulfuron, prosulfuron, chlorimuran-ethyl, thifen-sulfuron, rimsulfuron, halosulfuron, oxasulfuron, isoxaflutole, imazethapyr and imaza-mox at a weight ratio of 1: 0.1 to 10.
4. A mixture of one compound selected from the group consisting of compounds 1-439, 1-482, 1-486, 1-496, 1-1076, 1-1123 and 1-1441, and one compound selected from the group consisting of isoproturon and chlorotoluron at a weight ratio of 1: 1 to 100.
5. A mixture of one compound selected from the group consisting of compounds 1-439, 1-482, 1-486, 1-496, 1-1076, 1-1123 and 1-1441, and one compound selected from the group consisting of mecoprop, fluroxypyr and ioxynil at a weight ratio of 1: 0.5 to 50.
6. A mixture of one compound selected from the group consisting of compounds 1-439, 1-482, 1-486, 1-496, 1-1076, 1-1123 and 1-1441, and one compound selected from the group consisting of diflufenican, metsulfuron-methyl, fenoxaprop-ethyl and clodinafop-propargyl at a weight ratio of 1: 0.1 to 10.
7. A mixture of one compound selected from the group consisting of compounds 1-1141, 1-1222 and 2-203, and one compound selected from the group consisting of glyphosate, glufosinate-ammonium and paraquat at a weight ratio of 1: 1 to 100.
Moreover, the present compounds may also be used in admixture with insecticides, acaricides, nematocides, fungicides, plant growth regulators, fertilizers, soil improver, and the like.
When the present compounds are used as active ingredients of herbicides, the application amount is usually in the range of 0.01 to 10,000 g, preferably 1 to 8000 g, per hectare, although it may vary depending upon the weather conditions, formulation type, application timing, application method, soil conditions, crop plants, unfavorable weeds, and the like. In the case of emulsifiable concentrates, wettable powders, flow-ables, concentrated emulsions, water-dispersible granules, or the like, the formulation is usually applied at a prescribed amount after dilution with water having a volume of about to 1000 liters per hectare, if necessary, with the addition of an adjuvant such as a spreading agent. In the case of granules or some types of flowables, the formulation is usually applied as such without any dilution.
ti Examples of the adjuvant used, if necessary, may include, in addition to the surfactants recited above, polyoxyethylene resin acids (esters), ligninsulfonates, abiet-ates, dinaphthylmethanedisulfonates, crop oil concentrates, and vegetable oils such as soybean oil, corn oil, cotton seed oil, and sunflower oil.
The present compounds can also be used as active ingredients of harvesting aids such as defoliants and desiccating agents for cotton, and desiccating agents for potato. In these cases, the present compounds are usually formulated in the same manner as the case where they are used as active ingredients of herbicides, and used alone or in combination with other harvesting aids for foliar treatment before the harvesting of crops.
The present invention will be further illustrated by the following production examples, reference examples, formulation examples, and test examples;
however, the present invention is not limited to these examples.
The following will describe production examples for the present compounds and the hydrazones of formula [2] as the intermediate compounds, where the present compounds are designated by their compound numbers shown in Tables 1 to 5.
Production Example 1(Production of Compound 2-631) To a mixed solution of 8.0 g (97.2 mmol) of sodium acetate and 50 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1,1-dibromo-3,3,3-trifluoro-acetone, and the reaction was allowed to proceed at 80 C for 30 minutes. Then, the reaction mixture was cooled to 0'C, to which 4.4 g (18.7 mmol) of 7-fluoro-6-hydra-zino-4-propargyl-2H-1,4-benzoxazin-3-one was added, and the reaction mixture was stirred at room temperature for 2 hours. The precipitated crystals were collected by filtra-tion, washed twice with 10 ml of water, and dried, which afforded 6.3 g (18.37 mmol) of 7-fluoro-6-trifluoroacetylmethylidenhydrazino-4-propargyl-2H-1,4-benzoxazin-3-one [another name: 3,3,3-trifluoro-2-oxopropanal 1-(7-fluoro-3-oxo-4-propargyl-2H-1,4-.~~ ---benzoxazin-6-ylhydrazone)], m.p. 190.6 C (decomp.).
To a mixed solution of 6.0 g (17.5 mmol) of the above compound and 50 ml of toluene was added 9.1 g (26.2 mmol) of carbethoxymethylenetriphenylphosphorane, and the mixture was heated under reflux for 1 hour. The toluene was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 1.3 g (3.5 mmol) of 7-fluoro-6-[5-trifluoromethyl-3-pyridazinon-2-yl]-4-propargyl-2H-1,4-benzoxazin-3-one (compound 2-631).
F F
O NHNH, ---~ ~ ~ NHN
~ CF3 ~--N ~_N - O
O O
F O
l N~~~///
/\f'-' N
O L.--Production Example 2 (Production of Compound 1-476) To a mixed solution of 5.3 g (53.5 mmol) of sodium acetate and about 100 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1,1-dibromo-3,3,3-tri-fluoroacetone, and the reaction was allowed to proceed at 70 C for 20 minutes.
Then, the reaction mixture was cooled to room temperature, to which a solution of 5.8 g (21.5 mmol) of 2-fluoro-4-chloro-5-isopropoxyphenylhydrazine dissolved in about 20 ml of diethyl ether was added, and the reaction mixture was stirred at room tempera-ture for 1 hour. The ether layer was separated and concentrated. Then, about 60 ml of THF was added to the residue, to which 8.3 g (23.0 mmol) of carbethoxyethylidene-triphenylphosphorane was added, and the mixture was heated under reflux for 2 hours.
The toluene was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 3.8 g (10.5 mmol) of 2-[2-fluoro-4-chloro-5-isopropoxyphenyl]-4-methyl-5-trifluoromethylpyridazin-3-one (compound 1-476).
F F
k C1 ~~ NHNH, ' Cl ~~ NHN
- =\ CFg t F O CH., CI o N \CF3 N-O
Production Example 3 (Production of Compound 1-391) First, 3.5 g (9.7 mmol) of 2-[2-fluoro-4-chloro-5-isopropoxyphenyl]-4-methyl-5-trifluoromethylpyridazin-3-one (compound 1-476) was dissolved in about ml of concentrated sulfuric acid under ice cooling, and the solution was warmed to room temperature. After 10 minutes, about 100 ml of water was added to the reaction mixture, and the precipitated crystals were collected by filtration, and washed twice with ml of water and once with 10 ml of hexane. These crystals were recrystallized from isopropanol, which afforded 3.2 g (9.0 mmol) of 2-[2-fluoro-4-chloro-5-hydroxy-phenyl] -4-methyl-5 -trifluoromethylpyridazin-3 -one (compound 1-391).
CI N CF3 Cl N ~ CF3 N
-J\
Production Example 4 (Production of Compound 1-486) First, 3.2 g (10 mmol) of compound 1-391 was dissolved in about 50 m1 of DMF, to which 2.0 g (13 mmol) of potassium carbonate was added at room temperature and 1.3 g(11 mmol) of propargyl bromide was then added, and the mixture was stirred at room temperature for 30 minutes, followed by the addition of 100 ml of water. The precipitated crystals were collected by filtration, washed with hexane, and recrystallized from isopropanol, which afforded 3.4 g (9 mmol) of compound 1-486.
F O CH; F O CH3 Cl CF3 01 Cl N, \ CFj N N _ HO O
Production Example 5 (Production of Compound 1-496) First, 3.2 g (10 mmol) of compound 1-391 was dissolved in about 50 ml of DMF, to which 0.44 g(11 mmol) of sodium hydride (60 wt.%, oil dispersion) was added, and the mixture was allowed to stand at room temperature for 30 minutes, followed by the addition of 1.8 g (11 mmol) of ethyl bromoacetate under ice cooling.
After stirring at room temperature for 1 hour, the reaction mixture was extracted with diethyl ether. The organic layer was washed with 10% aqueous HCI, aqueous sodium bicarbonate solution and then with saturated sodium chloride solution, and dried with anhydrous magnesium sulfate. The solvent was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 2.4 g (5.5 mmol) of compound 1-496.
Cl CF3 Cl O N ~\ CF3 O
HO
'- CO2 C-1 H5 Production Example 6 (Production of Compound 2-251) To a mixed solution of 5.3 g (53.5 mmol) of sodium acetate and about 50 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1, 1 -dibromo-3,3,3-trifluoro-acetone, and the reaction was allowed to proceed at 80 C for 1 hour. Then, the reaction mixture was cooled to 0 C, to which 4.4 g (18.7 mmol) of 7-fluoro-6-hydrazino-propargyl-2H-1,4-benzoxazin-3-one was added, and the reaction mixture was stirred at room temperature for 2 hours. The precipitated crystals were collected by filtration, washed twice with 10 ml of water and once with 10 ml of hexane, and then dissolved in 50 ml of toluene without drying. To this solution was added 8.8 g (24.3 mmol) of carbethoxyethylidenetriphenylphosphorane, and the mixture was heated under reflux for 1 hour, while conducting azeotropic dehydration. The toluene was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 3.5 g (9.01 mmol) of compound 2-25 1.
F F O CH, O ~~ NHNH, O N \ CF3 ~- ~-N
O O \.-Production Example 7 (Production of Compound 2-328) To a mixed solution of 5.3 g (53.5 mmol) of sodium acetate and about 50 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1, 1 -dibromo-3,3,3-trifluoro-acetone, and the reaction was allowed to proceed at 80 C for 1 hour. Then, the reaction mixture was cooled to 0 C, to which 4.8 g (18.7 mmol) of 6-fluoro-5-hydrazino-3-(sec-butyl)-1,3-benzothiazol-2-one was added, and the reaction mixture was stirred at room temperature for 2 hours. Then, 100 ml of ether was added to the reaction mixture, followed by stirring and phase separation, and the organic layer was concentrated. The residue was dissolved in 50 ml of THF, to which 8.8 g (24.3 mmol) of carbethoxyethyli-denetriphenylphosphorane was added, and the mixture was heated under reflux for 1 hour. The THF was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 3.7 g (9.6 mmol) of compound 2-328.
S NHNH2 Ni CF3 O~ O
Production Example 8 (Production of Compound 1-347) First, 50 ml of concentrated sulfuric acid was ice cooled, in which 7.0 g (22.8 mmol) of compound 1-34! was dissolved. Then, 1.51 g (24 mmol) of fuming nitric acid was added dropwise at 5 C or lower, followed by maturation at 0 to 5 C for 1 hour. The mixture was poured into 300 ml of ice-water and extracted three times with 50 ml of ether. The combined ether layer was washed with about 100 ml of water and neutralized with 100 ml of aqueous sodium bicarbonate solution, followed by phase separation. The organic layer was dried with magnesium sulfate and concentrated to half volume, and the residue was subjected to silica gel column chromatography, which afforded 6.1 g (17.4 mmol) of compound 1-347.
ci ~ ~ \ CF3 ci N CF3 - N-O,N
eroduction Examgle 9 (Production of Compound 1-353) First, 5.0 g of iron powder, 75 ml of acetic acid, and 10 ml of water were mixed, and the mixture was warmed to about 80 C, followed by maturation for about 15 minutes. Then, 6.0 g (17.1 mmol) of compound 1-347 was dissolved in 40 ml of ethyl acetate, which was added dropwise to the above mixture at 80 C or lower.
After maturation at about 80 C for 1 hour, the reaction mixture was allowed to stand for cooling to room temperature, and extracted twice with 100 ml of ethyl acetate.
The combined ethyl acetate layer was washed twice with 50 ml of water and neutralized with aqueous sodium bicarbonate solution, followed by phase separation. The organic layer was dried with magnesium sulfate, and the ethyl acetate was distilled out under reduced pressure. The residue was subjected to silica gel chromatography, which afforded 5.1 g (15.9 mmol) of compound 1-353.
CF; ci N ~\CF3 ci N-O,N H,N
Production Example 10 (Production of Compound 1-420) First, 500 mg (1.6 mmol) of compound 1-353 was mixed with 10 ml (77.3 mmol) of ethyl 2-bromopropionate, and the mixture was heated under reflux at about 160 C for about 12 hours. After allowing to stand for cooling, the reaction mixture was subjected to silica gel column chromatography, which afforded 60 mg (0.6 mmol) of compound 1-420.
CI 5~ N CF3 CI N CF3 NH2 HN
)-- CO-)CGH5 Production Example 11 (Production of Compound 1-1622) First, 6 ml (55.4 mmol) of ethyl acrylate, 0.5 g (4.8 mmol) of t-butyl nitrite, and 0.6 g (4.5 mmol) of copper (II) chloride were mixed together in 5 ml of acetonitrile, followed by ice cooling. Then, 1.0 g (3.1 mmol) of compound 1-353 dissolved in 5 ml of acetonitrile was added dropwise at 5 C or lower, followed by overnight maturation at room temperature. The reaction mixture was poured into ice-water and extracted twice with 100 ml of ethyl acetate. The combined ethyl acetate layer was washed with 50 ml of diluted hydrochloric acid and dried with magnesium sulfate. The solvent was distilled out under reduced pressure, and the residue was subjected to silica gel column chromato-graphy, which afforded 0.51 g (1.2 mmol) of compound 1-1622.
Cl ~ N CF3 Cl N CF3 -.r-H,N
- CO~C)HS
CI
Production Example 12 (Production of Compound 1-1221) To a mixed solution of 5.3 g (53.5 mmol) of sodium acetate and about 50 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1,1-dibromo-3,3,3-trifluoro-acetone, and the reaction was allowed to proceed at 80 C for 1 hour. Then, the reaction mixture was cooled to 0 C, to which 5.2 g (18.7 mmol) of methyl 2-(2-chloro-4-fluoro-5-hydrazinophenylthio)propionate was added, and the reaction mixture was stirred at room temperature for 2 hours. The precipitated crystals were collected by filtration, washed twice with 10 ml of water and once with 10 ml of hexane, and dried. The residue was dissolved in 50 ml of THF, to which 8.4 g (22.4 mmol) of carbethoxy-methylenetriphenylphosphorane was added, and the solution was stirred at room tempera-ture for 3 hours. The THF was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 3.8 g (9.0 mmol) of compound 1-1221.
F F
Cl ~ ~ NHNH, -- CI 1~ NHN-- ~- CF3 ~-- CO1CH3 ~- CO-)CHg F O
CI ~ ~ N CF3 Production Examnle 13 (Production of Compound 2-821) To a mixed solution of 8.0 g (97.2 mmol) of sodium acetate and about 50 ml of water was added under ice cooling 6.9 g (24.3 mmol) of 3,3 -dibromo- 1, 1, 1 -trifluoro-butanone, and the reaction was allowed to proceed at 80 C for 30 minutes.
Then, the reaction mixture was cooled to 0 C, to which 4.4 g (18.7 mmol) of 7-fluoro-6-hydra-zino-4-propargyl-2H-1,4-benzoxazin-3-one was added, and the reaction mixture was stirred at room temperature for 2 hours. The precipitated crystals were collected by filtration, washed twice with 10 ml of water, and dried, which afforded 6.1 g (17.0 mmol) of 1,1,1-trifluoro-2,3-butandione 3-(7-fluoro-3-oxo-4-propargyl-2H-1,4-benzoxazin-6-ylhydrazone).
To a mixed solution of 6.1 g (17.0 mmol) of the above compound and 50 ml of THF was added 7.1 g (20.4 mmol) of carbethoxymethylenetriphenylphosphorane, and the mixture was heated under reflux for 1 hour. The THF was distilled out under W O 97/07104 PC'r/JP96/02311 reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 0.61 g(1.6 mmol) of 7-fluoro-6-(6-methyl-5-trifluoromethyl-3-pyrida-zinon-2-yl)-4-propargyl-2H-1,4-benzoxazin-3-one (compound 2-821).
O F
CH; CH, ~~ O NHN
CF3~
Br Br CF3 N O
F O
---r O 0 N \ CF3 N-O
Reference Example 1 This is a production example for 3,3-dibromo-1,1,1-trifluoro-2-butanone used in Production Example 13.
First, 34.0 g of sodium acetate was dissolved in 270 ml of acetic acid, to which 25 g (0.20 mol) of 1, 1, 1 -trifluoro-2-butanone was added, and while keeping the temperature at 15 to 20'C, 66.3 g (0.42 mol) of bromine was added dropwise over 45 minutes. The reaction mixture was stirred for 5 hours, while keeping the temperature at 15 to 20'C, and then allowed to stand at room temperature for 68 hours.
The super-natant was taken and washed with 600 ml of concentrated sulfuric acid. Further washing with 307 ml of concentrated sulfuric acid and distillation under normal pressure gave 28 g (0.10 mol) of 3,3-dibromo- 1, 1, 1 -trifluoro-2-butanone.
Y""CH3 CF3-=-- CF3~ CH3 Br Br Production Exam lp e 14 (Production of Compound 1-1346) To a mixed solution of 5.3 g (53.5 mmol) of sodium acetate and about 50 ml of water was added under ice cooling 6.9 g (24.3 mmol) of 3,3-dibromo- 1, 1, 1 -trifluoro-2-butanone, and the reaction was allowed to proceed at 80 C for 1 hour. Then, the reaction mixture was cooled to 0 C, to which 3.3 g(18.7 mmol) of 2-chloro-4-fluoro-5-hydrazinophenol was added, and the reaction mixture was stirred at room temperature for 2 hours. The precipitated crystals were collected by filtration, washed twice with 10 ml of water and once with 10 ml of hexane, dried, and then dissolved in 50 n-d of THF. To this solution was added 8.8 g(24.3 mmol) of carbethoxymethylenetriphenylphos-phorane, and the mixture was stirred at room temperature for 3 hours. The THF
was distilled out under reduced pressure, and the residue was subjected to silica gel chromato-graphy, which afforded 0.51 g (1.6 mmol) of compound 1-1346.
F F
ci 0 NHNH2 --~ CI ~ 5 NHN=~_ CF3 HO HO O
F O
--= CI 0 N CF3 Production Hxamnle 15 (Production of Compound 1-1441) First, 3.2 g (10 mmol) of compound 1-1346 was dissolved in about 50 ml of DMF, to which 2.0 g (13 mmol) of potassium carbonate was added at room temperature and 1.3 g(11 mmol) of propargyl bromide was then added, and the mixture was stirred at room temperature for 30 minutes, followed by the addition of 100 ml of water. The precipitated crystals were collected by filtration, washed with hexane, and recrystallized from isopropanol, which afforded 3.2 g (8.5 mmol) of compound 1-1441.
F O F
Cl N X CF3 CF3 Production Example 16 (Production of Compound 1-499) This example followed the procedures of Production Example 5, except that 1.8 g(1.1 mmol) of n-pentyl chloroacetate was used in place of ethyl bromoacetate.
After the addition of this compound, the reaction mixture was stirred at 40 C
for 3 hours and then extracted with diethyl ether. The organic layer was washed with 10%
HCI, aqueous sodium bicarbonate solution and saturated sodium chloride solution, and dried with anhydrous magnesium sulfate. The solvent was distilled out under reduced pressure, and the residue was subjected to silica gel chromatography, which afforded 3.8 g (8.0 mmol) of compound 1-499.
Cl 0 N, \ CF3 IV ~ CF3 N
HO O
~,-COOnC5H1 I
Production Example 17 (Production of Compound 2-203) To a mixed solution of 5.3 g (53.5 mmol) of sodium acetate and about 50 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1,1-dibromo-3,3,3-trifluoro-acetone, and the reaction was allowed to proceed at 80 C for 1 hour. Then, the reaction mixture was cooled to 0 C, to which 4.0 g (18.7 mmol) of 6-hydrazino-4-propargyl-2H-1,4-benzoxazin-3-one was added, and the reaction mixture was stirred at room tempera-ture for 2 hours. The precipitated crystals were collected by filtration, washed twice with ml of water and once with 10 ml of hexane, and then dissolved in 50 ml of THF
without drying. To this solution was added 8.8 g (24.3 mmol) of carbethoxyethylidene-triphenylphosphorane, and the mixture was heated under reflux for 3 hours. The THF
was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 3.3 g (8.8 mmol) of compound 2-203.
O J~I\~ NHNH, ~-N
N O
O
Production Exam lp e 18 (Production of Compound 1-1222) To a mixed solution of 5.3 g (53.5 mmol) of sodium acetate and about 50 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1,l-dibromo-3,3,3-trifluoro-acetone, and the reaction was allowed to proceed at 80 C for 1 hour. Then, the reaction mixture was cooled to 0 C, to which 5.5 g (18.7 nunol) of ethyl 2-(2-chloro-4-fluoro-5-hydrazinophenylthio)propionate was added, and the reaction mixture was stirred at room temperature for 2 hours. The precipitated crystals were collected by filtration, washed twice with 10 ml of water and once with 10 ml of hexane, dried, and then dissolved in 50 ml of THF. To this solution was added 8.4 g (22.4 mmol) of carbethoxymethylene-triphenylphosphorane, and the mixture was stirred at room temperature for 3 hours. The THF was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 4.3 g (9.9 mmol) of cornpound 1-1222.
F F
CI NHNH, IP C1 NHN-_ CF3 O
S>- CO1C2H5 CO,C2HS
F O
--- Cl ~ ~ N \CF3 -~-- CO,C?HS
Production Example 19 (Production of Compound 1-476) To a mixed solution of 5.3 g (53.5 mmol) of sodium acetate and about 100 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1, 1 -dibromo-3,3,3-trifluoroacetone, and the reaction was allowed to proceed at 70 C for 20 minutes. Then, the reaction mixture was cooled to room temperature, to which a solution of 5.8 g (21.5 mmol) of 2-fluoro-4-chloro-5-isopropoxyphenylhydrazine dissolved in about 20 ml of diethyl ether was added, and the reaction mixture was stirred at room tempera-ture for I hour. The ether layer was separated, washed once with 10 ml of saturated sodium chloride solution, and dried with magnesium sulfate. The diethyl ether was distilled out, which afforded 6.5 g (20.0 mmol) of 3,3,3-trifluoro-2-oxo-propanal l-(4-chloro-2-fl uoro-5 -is opropoxyphenylhydrazone) .
1H-NMR (250 MHz, CDC13, TMS S(ppm)) 1.39 (6H, d, J = 6.0 Hz), 4.38-4.52 (1 H, m), 7.15 (IH, d, J = 10.5 Hz), 7.22 (1 H, d, J = 7.3 Hz), 7.43 (1 H, q, J = 1.7 Hz), 9.18 (1 H, br).
This compound was dissolved in 50 ml of THF. To this solution was added 8.3 g (23.0 mmol) of carbethoxyethylidenetriphenylphosphorane, and the mixture was heated under reflux for 2 hours. The THF was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 3.8 g (10.5 mmol) of 2-[2-fluoro-4-chloro-5-isopropoxyphenyl]-4-methyl-5-trifluoromethyl-pyridazin-3-one (compound 1-476).
F F
Cl O NHNH, ~ CI o NHN=\
, CF3 O O O
---= CI 0 N \ CF3 N
O
Production Example 20 (Production of Compound 1-642) To a mixed aqueous solution of 5.3 g (53.5 mmol) of sodium acetate and about 100 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1,1-dibromo-3,3,3-trifluoroacetone, and the reaction was allowed to proceed at 70 C for 20 minutes.
WO 97/07104 PCT/dP96/02311 Then, the reaction mixture was cooled to room temperature. Separately, 5.8 g (21.5 mmol) of crude ethyl 2-chloro-4-fluoro-5-hydrazinobenzoate hydrochloride was dissolved in 30 ml of water, to which 100 mI of diethyl ether was added, and while cooling, the mixture was neutralized by the addition of saturated sodium hydrogen-carbonate solution, followed by washing with saturated sodium chloride solution, which afforded a solution of ethyl 2-chloro-4-fluoro-5-hydrazinobenzoate in diethyl ether. This solution was added to the above reaction mixture, followed by vigorous stirring at room temperature for 2 hours. The ether layer was separated, washed once with 10 ml of saturated sodium chloride solution, and dried with magnesium sulfate. The diethyl ether was distilled out. The residue was dissolved in 50 ml of THF, to which 8.3 g (23.0 mmol) of carbethoxyethylidenetriphenylphosphorane was added, and the mixture was heated under reflux for 2 hours. The THF was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 3.8 g (10.0 mmol) of compound 1-642.
F F
CI NHNHi = HCI = Cl NHN-- - )-- CF3 CO,CGHS CO2)C,)H5 0 ----~ Cl ~ ~ CF3 - N
Reference Example 2 This is a production example for ethyl 2-chloro-4-fluoro-5-hydrazinoberizoate hydrochloride used in Production Example 20.
First, 50 g (0.29 mol) of 2-chloro-4-fluorobenzoic acid was dissolved in 150 ml of hydrochloric acid at room temperature, to which a mixed acid of 28 ml (0.31 mol) of fuming nitric acid and 56 ml of concentrated sulfuric acid was added dropwise at 35 to 45 C. Then, the solution was stirred at 40 C for 1 hour and poured into 250 ml of ice-water. The precipitated crystals were collected by filtration and recrystallized from a mixed solution of hexane and ethyl acetate, which afforded 55 g (0.25 mol) of 2-chloro-4-fluoro-5-nitrobenzoic acid. Then, 55 g (0.25 mol) of 2-chloro-4-fluoro-5-nitrobenzoic acid was dissolved in 50 ml of ethyl acetate, to which 33 g (0.28 mol) of thionyl chloride was added, and the mixture was heated under reflux for 3 hours and then allowed to stand for cooling to room temperature. Then, 20 ml of ethanol and 30 g of triethylamine were added under ice cooling, and the mixture was stirred at room temperature for 2 hours. The solvent was distilled out, and the residue was purified by silica gel chromatography, which afforded 57 g (0.23 mol) of ethyl 2-chloro-4-fluoro-5-nitrobenzoate.
F F
Cl C] NO, CO.)H CO-)H
F
CI 0 NO, Then, 60 g of iron powder and 500 ml of 10% acetic acid wvere mixed, and the mixture was heated to 40 C. Separately, 50 g (0.20 mol) of ethyl 2-chloro-4-fluoro-5-nitrobenzoate was dissolved in a mixed solution of 20 ml of acetic acid and 20 ml of ethyl acetate, and added dropwise to the above iron powder-acetic acid mixed solution.
Then, the reaction mixture was stirred at 50 C for 1 hour and filtered through CeliteT"''.
The filtrate was extracted with 100 ml of ethyl acetate. The ethyl acetate layer was washed with aqueous sodium bicarbonate solution and saturated sodium chloride solution, and dried with magnesium sulfate. The solvent was distilled out, and the residue was purified by silica gel chromatography, which afforded to 40 g(0.18 mol) of ethyl 5-amino-2-chloro-4-fluorobenzoate.
Then, 19 g (87.4 mmol) of ethyl 5-amino-2-chloro-4-fluorobenzoate was dissolved in 120 ml of hydrochloric acid, followed by cooling to 0 C, to which a solution of 6.3 g (91.7 mmol) of sodium nitrite dissolved in 10 ml of water was added dropwise at 10 C or lower. The mixture was stirred at 0 C for 30 minutes and then cooled to -30 C, into which a solution of 58 g (0.31 mol) of anhydrous tin (II) chloride dissolved in 40 ml of hydrochloric acid was poured, followed by further stirring at 0 C
for 3 hours.
The precipitated crystals were collected by filtration and then dried, which afforded 13.6 g (50.7 mmol) of crude ethyl 2-chloro-4-fluoro-5-hydrazinobenzoate hydrochloride.
Production Exam,.ple 21 (Production of Compound 1-1789) First, 5.0 g (15.5 mmol) of compound 1-391 was dissolved in about 50 ml of DMF, to which 2.8 g (20.2 mmol) of potassium carbonate was added at room temperature and then 1.5 g (17.1 mmol) of 3-bromo-2-methyl-l-propene was added, and the mixture was stirred at room temperature for 30 minutes, followed by the addition of 100 n-d of water. The precipitated crystals were collected by filtration, washed with hexane, and recrystallized from isopropanol, which afforded 4.4 g (13.2 mmol) of compound 1-1789.
CI ~N~ ~ ~ CF3 aw- CI ON~CF3 - HO O~ ~/
~-~CH3 Production Exam lp e 22 (Production of Compound 4-451) First, 4.0 g (12.0 mmol) of compound 1-1789 was dissolved in 20 ml of N,N-dimethylaniline, and the solution was heated at 180 C for 3 hours. After cooling to room temperature, 100 ml of ethyl acetate was added, and the mixture was washed with 1 N aqueous hydrochloric acid and saturated sodium chloride solution, and dried with =
magnesium sulfate. The solvent was distilled out, and the precipitated crystals were recrystallized from isopropanol, which afforded 3.4 g (10.2 mmol) of 2-[4-chloro-6-fluo ro-3-hydroxy-2 -(2-methyl-2-p ropenyl)]-4-me thyl-5-trifluo romethylpyridazin-3 -one, m.p. 133.2 C.
The product was dissolved in 30 ml of xylene, to which a catalytic amount of p-toluenesulfonic acid was added, and the mixture was heated under reflux for 1 hour.
After cooling to room temperature, 100 ml of ethyl acetate was added, and the mixture was washed with aqueous sodiuln bicarbonate solution and sodium chloride solution, and dried with magnesium sulfate. The solvent was distilled out, and the residue was purified by silica gel column chromatography, which afforded 3.0 g(9.0 mmol) of compound 4-45 1.
Cl ~~ N CF3 r Cl ~~ N ~ CF3 - - -O- ~i HO
~(\CH3 CH3 IN Cl ~ ~ N \ CF3 N
O
Production Example 23 (Production of Compound 1-483) First, 5.0 g (15.5 mmol) of compound 1-391 was dissolved in about 20 ml of DMF, to which 2.4 g (17.1 mmol) of potassium carbonate was added at room temperature. The solution was heated to about 40'C, to which 1.7 g (17.1 mmol) of 2,3-dichloropropene was added, and after 1 hour, the mixture was allowed to stand for cooling and poured into ice-water. The precipitated crystals were collected by filtration, washed with hexane, and recrystallized from isopropanol, which afforded 5.2 g (13.1 mmol) of compound 1-483.
O\ CH; F O CH3 C1 CF3 -~' CI ON ~\CF3 N-l N
HO Q /~
~'(\Cl Production Exam in e 24 (Production of Compound 3-139) First, 3.0 g (7.6 mmol) of compound 1-436 was dissolved in 10 ml of N,N-dimethylaniline, and the solution was heated under reflux for 3 hours. After cooling to room temperature, 50 ml of ethyl acetate was added, and the mixture was washed with I N aqueous hydrochloric acid and saturated sodium chloride solution, and dried with magnesium sulfate. The solvent was distilled out, and the precipitated crystals were recrystallized from isopropanol, which afforded 2.2 g (5.6 mmol) of 2-[4-chloro-6-fluoro-3-hydroxy-2-(2-chloro-2-propenyl)] -4-methyl-5-trifl uoromethylpyridazin-3-one.
IH-NMR (300 MHz, CDC13, TMS S(ppm)) 2.41 (3H, q, J= 1.9 Hz), 3.56 (1 H, d, J = 16.3 Hz), 3.72 (1 H, d, J = 16.3 Hz), 4.91 (1 H, q, J= 1.4 Hz), 5.12 (1 H, d, J = 1.5 Hz), 5.72 (1 H, s), 7.25 (1 H, d, J= 8.7 Hz), 8.00 (IH, s) The product was dissolved in 10 ml of trifluoromethanesulfonic acid cooled by ice, and the solution was stirred under ice cooling. After 30 minutes, the solution was poured into ice-water, and the precipitated crystals were collected by filtration and subjected to silica gel column chromatography, which afforded 1.9 g (5.4 mmol) of compound 3-139.
CI ON CF3 CI ~~ N CF3 N
O /~ HO
~C1 CI
--- CI ~ ~ CF3 -O /
Production Example 25 (Production of Compound 1-1744) This example followed the procedures of Production Example 20, except that 6.1 g (21.5 mmol) of ethyl 2,4-dichloro-5-hydrazinobenzoate hydrochloride was used in place of ethyl 2-chloro-4-fluoro-5-hydrazinobenzoate hydrochloride, which afforded 4.8 g (12.2 mmol) of compound 1-1744.
wo 97/07104 PCT/JP96/02311 Cl Cl 0 CH3 CI J~ NHNH, = HCl CI N ~ CF~
_ N _.
CO,Et CO,Et The ethyl 2,4-dichloro-5-hydrazinobenzoate hydrochloride used above was produced from 2,4-dichlorobenzoic acid by the same process as shown in Reference Example 2.
Production Example 26 (Production of Compound 1-1279) To a mixed aqueous solution of 5.3 g (53.5 mmol) of sodium acetate and about 100 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1,1-dibromo-3,3,3-trifluoroacetone, and the reaction was allowed to proceed at 70 C for 20 niinutes.
Then, the reaction mixture was cooled to room temperature. Separately, 5.8 g (21.5 mmol) of ethyl 2-chloro-4-fluoro-5-hydrazinobenzoate hydrochloride was dissolved in 30 ml of water, to which 100 ml of diethyl ether was added, and while cooling, the mixture was neutralized by the addition of saturated sodium hydrogen-carbonate solution, followed by washing with saturated sodium chloride solution, which afforded a solution of ethyl 2-chloro-4-fluoro-5-hydrazinobenzoate in diethyl ether. This solution was added to the above reaction mixture, followed by vigorous stirring at room temperature for 2 hours. The ether layer was separated, washed once with 10 ml of saturated sodium chloride solution, and dried with magnesium sulfate. The diethyl ether was distilled out, and a small amount of hexane was added to give 4.3 g (12.6 mmol) of ethyl 2-chloro-4-fluoro-5-(2-oxo-3,3,3-trifluoropentylidenehydrazino)benzoate.
This product was dissolved in 50 ml of THF, to which 5.0 g (14.4 mmol) of carbethoxy-methylenetriphenylphosphorane was added, and the mixture was heated under reflux for 2 hours. The THF was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 3.6 g (9.7 mmol) of compound 1-1279.
F F
CI ~~ NHNH, HCI --- CI J::~ NHN-'"- - ~CF~
CO,C,Hs CO,C~HS O
F O
--~-- CI N ~}- CF;
N-/
CO,C,H5 Production Exa=le 27 (Production of Compound 1-1780) First, 50 g (0.61 mol) of sodium acetate and 41 g(0.14 mol) of 1,1-dibromo-3,3,3-trifluoroacetone were mixed with 500 ml of water, and the mixture was stirred at 80 C for 30 minutes and then cooled to 0 C. Then, 45 g (0.14 mol) of 4-bromo-2-fluoro-5-isopropoxyphenylhydrazine hydrochloride was added at 10 C or lower, and the mixture was stirred at 10 C or lower for 3 hours. The precipitated crystals were collected by filtration and dried, which afforded 35 g (94.3 mmol) of 3,3,3-trifluoro-2-oxopro-panal 1-(4-bromo-2-fluoro-5-isopropoxyphenylhydrazone).
Then, 16 g (46.0 mmol) of carbethoxymethylenetriphenylphosphorane and 16 g (43.1 mmol) of 3,3,3-trifluoro-2-oxopropanal 1-(4-bromo-2-fluoro-5-isopropyloxy-phenylhydrazone) were stirred in 100 ml of THF at room temperature for 4 hours. After completion of the reaction, the reaction mixture was concentrated, and the residue was subjected to silica gel chromatography, which afforded 9.4 g (23.8 mmol) of compound 1-1780.
F F
Br NHNH, = HCl -- Br NHN
= CF3 T O -7"' O O
F O
--r Br N CF3 - N-Reference Example 3 ~ This is a production example for 4-bromo-2-fluoro-5-isopropoxyphenylhydra-zine hydrochloride used in Production Example 27.
First, 93 g (0.49 mol) of 2-bromo-4-fluorophenol was suspended in 200 ml of water, into which 55 g (0.59 mol) of methyl chloroformate and a solution of 21.5 g (0.51 mol) of sodium hydroxide in 60 ml of water were poured together at 10 C
or lower, and the mixture was stirred at the same temperature for 2 hours. The precipitated crystals were collected by filtration, washed with water, and dried in a vacuum oven, which afforded 111.6 g (0.45 mol) of methyl 2-bromo-4-fluorophenoxyformate.
Then, 1 10 g (0.44 mol) of methyl 2-bromo-4-fluorophenoxyformate was dissolved in 250 ml of sulfuric acid, to which a mixed acid of 30 g of fuming nitric acid and 30 ml of sulfuric acid was added dropwise at 5 C or lower, and the mixture was stirred for 2 hours. The reaction mixture was poured onto ice, and the precipitated crystals were collected by filtration, washed with water, and dried, which afforded 126 g (0.43 mol) of inethyl2-bromo-4-fluoro-5-nitrophenoxyformate.
Then, 125 g (0.43 mol) of methyl 2-bromo-4-fluoro-5-nitrophenoxyformate was suspended in 200 ml of water, to which 19 g (0.47 mol) of sodium hydroxide was added, and the mixture was stirred at 50 to 60 C for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and washed with chloro-form. The aqueous layer was acidified with aqueous hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was dried and concentrated, which afforded 104 g (0.43 mol) of 2-bromo-4-fluoro-5-nitrophenol.
F F
Br ~ ~ -----~ Br O ---~
= HO O
F F
Br o NO2 -- Br o NO2 O HO
/~-- OCH;
Then, 100 g (0.42 mol) of 2-bromo-4-fluoro-5-nitrophenol was dissolved in 400 ml of dimethylformamide, to which 70 g (0.50 mol) of potassium carbonate was added and after warming to 50 C, 94 g (0.55 mol) of isopropyl iodide was added dropwise, and the mixture was stirred at 45 to 50 C for 1 hour. After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. The ethyl acetate layer was washed with water and then with diluted hydrochloric acid, dried, and concentrated. The residue was subjected to column chromatography, which afforded 99.8 g (0.36 mol) of 2-bromo-4-fluoro-5-nitrophenyl isopropyl ether.
Then, 60 g (0.22 mol) of 2-bromo-4-fluoro-5-nitrophenyl isopropyl ether was dissolved in 300 ml of ethyl acetate, to which 1.0 g of 10% palladium-carbon was added, and the hydrogenation was effected under an atmosphere of hydrogen.
After completion of the reaction, the palladium-carbon was removed by filtration, and the filtrate was concentrated, which afforded 52 g (0.21 mol) of 4-bromo-2-fluoro-5-iso-propoxyaniline.
. Then, 108 g (0.57 mol) of tin (II) chloride was dissolved in 100 ml of concentrated hydrochloric acid, followed by cooling to -30'C, to which a diazonium solution prepared from 47 g(0.19 mol) of 4-bromo-2-fluoro-5-isopropoxyaniline, 13.5 g (0.20 mol) of sodium nitrite, and 120 ml of hydrochloric acid was added dropwise at 0 C
or lower, and the mixture was stirred at room temperature for 2 hours. The precipitated crystals were collected by filtration and dried in a vacuum oven to give 45 g(0.14 mol) of the crude product, 4-bromo-2-fluoro-5-isopropoxyphenylhydrazine hydrochloride.
F F
Br NO2 ) -- Br o NH, 77-- O '7-- O
F
Y -~- Br O NHNH,' HCl '7- O
Production Example 28 (Production of Compound 1-1783) First, 19 g (52.4 mmol) of carbethoxyethylidenetriphenylphosphorane and 19 g (63.2 mmol) of 3,3,3-trifluoro-2-oxopropanal 1-(4-bromo-2-fluoro-5-isopropyloxy-phenylhydrazone) were heated under reflux in 100 ml of THF for 5 hours. After completion of the reaction, the reaction mixture was concentrated, and the residue was subjected to silica gel chromatography, which afforded 9.1 g (22.2 n~unol) of compound 1-1783.
O
Br ~~ NH CF3 --~ Br ~~ N ~ CF3 N--7 O '7- O
Producti n Example 29 (Production of Compound 1-1748) This example followed the procedures of Production Example 27, except that 41 g (0.41 mol) of 2,4-dichloro-5-isopropoxyphenylhydrazine hydrochloride was used in place of 4-bromo-2-fluoro-5-isopropoxyphenylhydrazine hydrochloride, which afforded 31.3 g (91.3 mmol) of 3,3,3-trifluoro-2-oxopropanal 1-(2,4-dichloro-5-isopro-poxyphenylhydrazone). Then, this compound and 40 g (0.11 mol) of carbethoxy-ethylidenetriphenylphosphorane were heated under reflux in 100 ml of THF for 5 hours.
After completion of the reaction, the reaction mixture was concentrated, and the residue was subjected to silica gel column chromatography, which afforded 21 g (54.8 mmol) of compound 1-1748.
ci ci Cl NHNH, = HCl CI NHN-: - ~- CF3 /'--O -7--0 0 cl 0 cH;
-- Cl ~ ~ N \ CF.~ "
"_" -?-O
J
The 2,4-dichloro-5-isopropoxyphenylhydrazine hydrochloride used above was produced from 2,4-dichlorophenol by the same process as shown in Reference Example 3.
Production Example 30 (Production of Compound 1-1029) First, 9 g (22.8 mmol) of 2-(4-bromo-2-fluoro-5-isopropyloxyphenyl)-5-trifluoromethylpyridazin-3-one was added to 50 ml of sulfuric acid, and the mixture was stirred for 1 hour. After completion of the reaction, the reaction mixture was poured onto ice and extracted with ethyl acetate. The ethyl acetate layer was dried and concentrated, and the residue was subjected to column chromatography (eluent, hexane : ethyl acetate =
5: 1), which afforded 5.9 g (16.7 mmol) of compound 1-1029.
F O F O
\ CF3 ~ Br ~~ N CF3 Br O N N - N~~~-JJJ
-?,- O HO
Production Exam lp e 31 (Production of Compound 1-392) First, 9 g (22.0 mmol) of 2-(4-bromo-2-fluoro-5-isopropyloxyphenyl)-4-methyl-5-trifluoromethylpyridazin-3-one was added to 50 ml of sulfuric acid, and the mixture was stirred for 1 hour. After completion of the reaction, the reaction mixture was poured onto ice and extracted with ethyl acetate. The ethyl acetate layer was dried and concentrated, and the residue was subjected to column chromatography (eluent, hexane :
ethyl acetate = 5: 1), which afforded 4.2 g (11.5 mmol) of compound 1-392.
\CF3 Br O NN \CF3 ---~ Br O N, HO
'WO 97/07104 PCT/JP96/02311 Production Example 32 (Production of Compound 1-1274) First, 7.4 g (90.2 mmol) of sodium acetate and 8.0 g (28.2 mmol) of 1,1-di-bromo-3,3,3-trifluoroacetone were mixed with 70 ml of water, and the mixture was .
stirred at 80 C for 30 minutes and then cooled, to which 7.0 g of ethyl 2-chloro-5-hydrazinocinnamate was added at 10 C or lower, and the mixture was stirred for 3 hours.
The precipitated crystals were collected by filtration and dried, which afforded 9.6 g (27.5 mmol) of ethyl 2-chloro-5-(3,3,3-trifluoro-2-oxopropylidenehydrazino)cinnamate.
1H-NMR (250 MHz, CDC13, TMS S(ppm)) 1.36 (3H, t, J = 6.9 Hz), 4.30 (2H, q, J = 6.9 Hz), 6.4-6.6 (1 H, m), 7.2-7.5 (3H, m), 7.65 (1 H, d, J = 2.5 Hz), 8.0-8.1 (1H, m) Then, 1.0 g (2.9 mmol) of carbethoxymethylenetriphenylphosphorane and 1.0 g (2.9 mmol) of ethyl 2-chloro-5-(3,3,3-trifluoro-2-oxopropylidenehydrazino)-cinnamate were stirred in 10 ml of THF at room temperature for 1 hour. After comple-tion of the reaction, the reaction mixture was concentrated, and the residue was subjected to column chromatography (eluent, hexane : ethyl acetate = 5: 1), which afforded 0.43 g (11.5 mmol) of compound 1-1274.
Cl ~ ~ NHNH2 Cl NHN-- ~- CF3 O
CO,Et CO,Et O
-- Cl CF3 N-CO,Et Reference Example 4 The ethyl 2-chloro-5-hydrazinocinnamate used in Production Example 32 was produced by the following process.
First, 60 g of tin (II) chloride was dissolved in 60 ml of concentrated hydro-chloric acid, and the mixture was cooled to -30 C, to which a diazonium solution prepared from 19 g of ethyl 5-amino-2-chlorocinnamate and 6.3 g of sodium nitrite was added dropwise at 0 C or lower. The reaction mixture was stirred at room temperature for I hour, and the precipitated crystals were collected by filtration. These crystals were -added to ice-water, neutralized with 2N aqueous sodium hydroxide, and extracted with chloroform. The chloroform layer was dried and concentrated, which afforded 7.0 g of ethyl 2-chloro-5-hydrazinocinnamate.
Cl ~ NH, - Cl NHNH, CO,Et CO,Et Production Example 33 (Production of Compound 1-637) First, 1.1 g (2.9 mmol) of carbethoxyethylidenetriphenylphosphorane and 1.0 g (2.9 mmol) of ethyl 2-chloro-5-(3,3,3-trifluoro-2-oxopropylidenehydrazino)-cinnamate were heated under reflux in 10 ml of THF for 3 hours. After completion of the reaction, the reaction mixture was concentrated, and the residue was subjected to column chromatography (eluent, hexane : ethyl acetate = 5: 1), which afforded 0.66 g (1.7 mmol) of compound 1-637.
Cl NHN=~ CF3 C1 N CF3 N-JJJ
CO,Et CO.)Et Production Exam 1~ e 34 (Production of Compound 1-367) First, 0.5 g (1.6 mmol) of compound 1-353 was dissolved in 1.5 ml of pyridine, to which 0.2 g (1.7 mmol) of methanesulfonyl chloride was added dropwise, followed by stirring for 2 hours. The reaction mixture was poured into ice-water and extracted with ethyl acetate. The ethyl acetate layer was washed with diluted hydrochloric acid, dried, and concentrated. The residue was subjected to column chromatography (eluent, hexane : ethyl acetate = 3: 1), which afforded 0.42 g(1.1 mmol) of compound 1-367.
F O CH , F 0 CH3 CI CF, ~~ N ~ CF3 N- - N'-H, N HN,, SO,CH 3 Production ExampI e 35 (Production of Compound 1-369) This example followed the procedures of F'roduction Example 34, except that 0.23 g(1.6 mmol) of chloromethylsialfonyl chloride was used in place of methane-sulfonyl chloride, which afforded 0.38 g (091 mmol) of cornpound 1-369.
F 0 C'H F 0 C113 , CI CF3 C! N% CF4 N- N-H1N HN\
SO,CHzCI
Production Examnle 36 (Production of Compound 1-391) First, 32.3 g of 5-aminCy-2-chloro-4-fluoropherrolwas tnixed with 150 ml of concentrated hydrochloric acid, and the mixture was stirred at 50 C for 30 minutes, to which a solution of 15 g of sodiurn nitrite dissolved in 40 rnl of water was added drop-wise at 0 C over 10 minutes. After stirring at 0 C for 1 hour, the mixture was cooled to -50 C. Then, a solution of 132 g of tiri (11) chloride dissolveci in 132 g oi'concentrated sulfuric acid was rapidly added dropwise at --50 C., and the mixture was gradually warmed to room ternperature and stirred for 1 hour. The solids formed were collected by filtration and dried at 80 C under reduced pressure to give 75 g of the crude 2-fluoro-4-chloro-5-hydroxyphenylhydrazine hydrochloride crystals.
I H-NMR (DMS(3-d(,, TMS Fi (ppm)) 3-5 (2H, br), 6.73 (1 H, d), 7.22 (1 H, d), 8.20 (1 H, s), 9-11 (2H, br) Then, 49.2 g of sodium acetate and 40.5 g of 1,1-dibromo-3,3,3-trifluoro-acetone were dissolved in 400 ml of water, and the solution was heated at 80 to 90 C for 40 minutes. The solution was cooled to O C, to which 75 g of the crude 2-fluoro-4-chloro-5-hydroxyphenylhydrazine hydrochloride crystals obtained above was added, and the mixture was stirred at room temperature for 70 minutes. The precipitated crystals were collected by filtration and dried under reduced pressure, which afforded 35.4 g of 3,3,3-trifluoro-2-oxopropanal 1-(4-chloro-2-fluoro-5-hydroxyphenylhydrazone).
1H-NMR (300 MHz, CDC13, TMS S(ppm)) 5.49 (1H, s), 7.15 (1H, d, J
10.5Hz),7.25(1H,d,J=7.4Hz),7.38(1H,q,J=1.8Hz),8.75(1H,s) Then, 12.9 g of 3,3,3-trifluoro-2-oxopropanal 1-(4-chloro-2-fluoro-5-hydroxyphenylhydrazone) and 22.3 g of carbethoxyethylidenetriphenylphosphorane were dissolved in 110 ml of tetrahydrofuran, and the solution was heated under reflux for 3 hours. The solvent was distilled out under reduced pressure, and the residue was subjected to silica gel chromatography, which afforded 8.8 g of 2-(2-fluoro-4-chloro-5-hydroxyphenyl) -4-methyl-5-tri fluoromethylpyridazin-3-One (compound 1-391).
F F
Cl O NH, ci 0 NHNH, = HCI
HO HO
F O
~ CF3 ~ CF3 Cl NHN- - N-HO
HO
The 5-amino-2-chloro-4-fluorophenol used above can be produced by the method described in the publication of European Patent Application, EP-61741-A.
Production Example 37 (Production of Compound 1-332) First, 2 g of 3,3,3-trifluoro-2-oxo-l-propanal 1-(4-chlorophenylhydrazone) and 2 g of ethyl diethylphosphonoacetate were mixed with 20 ml of triethylamine, and the reaction was allowed to proceed at 50 C for 24 hours. The solvent was distilled out under reduced pressure, and the residue was subjected to column chromatography, which afforded 1.16 g of 2-(4-chlorophenyl)-5-tri fluoromethylpyridazin-3-one (compound 1-332).
Reference Example 5 _ The 3,3,3-trifluoro-2-oxopropanal 1-(4-chloro-2-fluoro-5-isopropoxyphenyl-hydrazone) produced in Production Example 19 can also be produced by the following process.
F F
ci NN=~ O CF3 CI 0 NH O CF3 ~ O C02Et O N~
~ C02H
5 First, 20.1 g of ethyl 4,4,4-trifluoroacetoacetate and 25 g of sodium acetate were dissolved in 150 ml of water, to which a diazonium solution in hydrochloric acid prepared from 20.3 g of 4-chloro-2-fluoro-5-isopropoxyaniline, 20 ml of concentrated hydrochloric acid, 20 ml of water, and 7.35 g of sodium nitrate was added dropwise at 10 C or lower. After stirring at room temperature for 1 hour, the precipitated crystals 10 were collected by filtration, washed with water, and dried, which afforded 34 g of the desired product as orange crystals (yield, 85%).
F F
ci ~ ~ NH2 N F;
N~/
7O -7-O CO2Et Then, 15.9 g of the ester obtained above and 1.7 g of lithium hydroxide monohydrate were added to 30 ml of 1,4-dioxane and 3 ml of water, and the mixture was heated.under reflux for 6 hours. The reaction mixture was poured into ice-water, 15 neutralized with diluted hydrochloric acid, and extracted witli ethyl acetate. The ethyl acetate layer was dried and concentrated, and the precipated crystals were washed with hexane, which afforded 11.3 g of the desired product as yellow crystals (yield, 76.3%).
F F
Cl NH O CF3 - ci ~~ NH j O N~ O ~
CO2H ~
Then, 7.4 g of the carboxylic acid obtained above was dissolved in 42 n-d of N,N-dimethylformamide, and the reaction solution was heated to 100 C and kept at the same temperature for 30 minutes. Thereafter, the reaction solution was cooled to room temperature, poured into water, and extracted with ethyl acetate. The ethyl acetate layer was washed with diluted hydrochloric acid, dried with magnesium sulfate, and concen-trated, which afforded 5.9 g of the desired product as orange crystals (yield, 90%).
iH-NMR (250 MHz, CDC13, TMS S(ppm)) 1.39 (6H, d, J = 6.0 Hz), 4.38-4.52 (1 H, m), 7.15 (1 H, d, J = 10.5 Hz), 7.22 (1 H, d, J = 7.3 Hz), 7.43 (1 H, q, J= 1.7 Hz), 9.18 (1 H, br) Reference Example 6 In the same manner as described in Reference Example 2, 3,3,3-trifluoro-2-oxopropanal 4-chlorophenylhydrazone was produced.
Cl NH CF3 Cl ~~ H
N=~ N~
CO2Et CO2H
First, 5.0 g of the ester as the starting material and 0.67 g of lithium hydroxide monohydrate were added to a mixed solution of 30 ml of 1,4-dioxane and 2 ml of water, and the mixture was heated under reflux for 1.5 hours. The reaction mixture was poured into ice-water, neutralized with diluted hydrochloric acid, and extracted with ethyl acetate. The ethyl acetate layer was dried with magnesium sulfate and concentrated, and the precipitated crystals were washed with a mixed solvent of hexane and diethyl ether (hexane : diethyl ether = 2 1), which afforded 3.3 g of the desired compound as yellow crystals (yield, 73%).
~ ~ Cl NN~CF3 Cl ~~ NH O 3 ~ CF3 N
Process 1) A solution prepared by dissolving 3.3 g of the carboxylic acid obtained by the above reaction in 10 ml of dimethylsulfoxide was heated to 100 C and kept at the same temperature for 10 minutes, followed by cooling to room temperature.
Thereafter, the reaction mixture was subjected to silica gel chromatography (eluent, hexane : ethyl acetate = 7: 1), which afforded 2.55 g of the desired product (yield, 91%).
Process 2) A reaction mixture prepared by adding 5.0 g of the carboxylic acid obtained by the above reaction, 0.5 ml of quinoline, and 0.1 g of copper powder to 40 ml of toluene was heated to 100 C and kept at the same temperature for 20 minutes.
After completion of the reaction, the reaction mixture was cooled to room temperature and subjected to silica gel chromatography (eluent, hexane : ethyl acetate = 8 :
1), which afforded 3.6 g of the desired product (yield, 86%).
Some of the present compounds are shown with their compound numbers in Tables 1 to 5, where the symbol "n" refers to normal-; "i", iso-; "s", secondary-; and "C", cyclo-.
Compounds of the formula:
X O R'-Y ~ ~ N Rt - N-Compound X Y R 3 R' R Z B
No.
1- 2 H C1 H CFZ Cl H H
1- 3 H Br H CF2 Cl H H
1- 5 H C1 H CFz C1 CH3 H
1- 6 H Br H CFa C1 CH3 H
1- 7 F F H CFZ Cl H H
1- 9 F Br H CF2 C1 H H
1 -10 F F H CF2 Cl CH3 H
1 -11 F C1 H CF2 Cl CH3 H
1 -12 F Br H CF2 Cl CH3 H
1- 13 H F H CF2 Cl CH3 NOz TABLE 1 (contn'd) Compound x y R 3 R' R 2 B
No.
1 -14 H C1 H CF2 Cl CH3 N01 1 -15 H Br H CF2 Cl CH3 N02 1 -16 F F H CF2 Cl CHa NOz 1 -18 F Br H CF2 Cl CH3 NO2 1- 19 H F H CF2 Cl CH3 NH2 1 -20 H C1 H CF2 Cl CH3 NH2 1 -21 H Br H CF2 Cl CH3 NH2 1 -22 F F H CF2 Cl CH3 NH2 1 -23 F C1 H CF2 Cl CH3 NH2 1 -24 F Br H CF2 Cl CHa NH2 1 -26 H C1 H CF2 Cl CH3 OH
1 -27 H Br H CF2 Cl CH3 OH
1 -28 F F H CF2 Cl CH3 OH
1 -29 F Cl H CF2 Cl CH3 OH
1 -30 F Br H CF2 Cl CH3 OH
1 -31 H C1 H CF2 Cl CH3 NHCH3 1 -32 H Cl H CF2 Cl CH3 NHC2 H a 1-33 H C1 H CF2 Cl CH3 NHCH2 CH= CH2 1 -34 H C1 H CF2 Cl CH3 NHCH2 C= CH
1 -35 H C1 H CF2 Cl CH3 NHCH(CH 3 )C = CH
1 -36 H C1 H CF2 Cl CH3 NHSO2 CHI
TABLE 1 (contn'd) ~
Compound X Y R3 R' R z B
No.
1- 37 H Cl H CF2 Cl GH3 NHSO2 C z H s 1 -38 H C1 H CF2 Cl CH3 NHSO2 CHZ Cl 1 -39 H C1 H CF2 Cl CH3 NHSOz CF3 1 -40 H C1 H CF2 Cl CHa N(CH3 )S0 2 CH3 1- 41 H C1 H CF2 C1 CH3 N(CH2 C CH)SO 2 CH3 1 -42 H C1 H CF2 Cl CH3 NHCOOCH 3 1 -43 H C1 H CF2 Cl CH3 NHCOOC2 H s 1 -44 H C1 H CF2 Cl CH3 NHCOO " C s H 7 1 -45 H C1 H CF2 Cl CH3 NHCOO ' C, H, 1- 46 H C1 H CF2 Cl CH3 NHCO0 C 4 H 9 1 -47 H C1 H CF2 Cl CH3 NHCOO " C s H
1 -48 H Cl H CF2 Cl CH3 NHCH2 COOCH a 1 -49 H Cl H CF2 Cl CH3 NHCH2 COOC2 H s 1 -50 H Ci H CF2 Cl CH3 NHCH2 COO C, H, 1 - 51 H Cl H CF2 Cl CH3 NHCH2 C00 " C, H g 1 -52 H Cl H CF2 Cl CH3 NHCH2 COO " C s H õ
1 -53 H Cl H CF2 Cl CHs NHCH2 COO ' C 3 H 7 1 -54 H Cl H CF2 Cl CH3 NHCH2 COO ' C s H q 1- 55 H Cl H CF2 Cl CH3 NHCH2 COO ' C 6 H õ
1 -56 H Cl H CF2 Cl CH3 NHCH(CH 3)COOCH 3 =
1 -57 H C1 H CF2 Cl CH3 NHCH(CH3 )COOC 2 H s 1 -58 H C1 H CF2 Cl CHa NHCH(CH3 )COO " C3 H, 1 -59 H C1 H CF2 Cl CH3 NHCH(CH3 )COO C, H9 TABLE 1 (contn'd) Compound X y R3 R' R Z B
No.
1 -60 H Cl H CF2 Cl CH3 NHCH(CH3 )C00 Cs Hõ
1 -61 H C1 h CF2 Cl CH3 NHCH(CH3 )C00 ' C3 H 7 1 -62 H C1 H CF2 Cl CH3 NHCH(CH3 )C00 ' C5 H g 1 -63 H C1 H CF2 Cl CHa NHCH(CH 3 )C00 ' C6 H11 1 -64 F Cl H CF2 Cl CH3 NHCHa 1 -65 F C1 H CF2 Cl CH3 NHC 2 H s 1 -66 F C1 H CF2 Cl CH3 NHCH2 CH=CH2 1 -67 F Cl H CF2 Cl CH3 NHCH2 C CH
1 -68 F Ci H CF2 Cl CH3 NHCH(CH a)C = CH
1- 69 F Cl H CF2 Cl CH3 NHSO2 CH3 1- 70 F C1 H CF2 Cl CH3 NHSOa C 2 H s 1 -71 F Ci H CF2 Cl CH3 NHSOZ CH2 Cl 1 -72 F C1 H CF2 Cl CH3 NHSO2 CF3 1 -73 F Cl H CF2 Cl CH3 N(CH3 )SO 2 CH3.
1 -74 F C1 H CF2 Cl CH3 N(CH2 C= CH)S0 2 CH3 1 -75 F Cl H CF2 Cl CH3 NHCOOCH 3 1 -76 F Cl H CF2 Cl CH3 NHCOOC2 H s 1 -77 F Ci H CF2 Cl CH3 NHCO0 " C, H 7 1 -78 F C1 H CF2 Cl CH3 NHCOO ' C 3 H T
1 -79 F Cl H CF2 Cl CH3 NHCO0 " C 4 H a 1- 80 F Ci H CF2 Cl CH3 NHCOO " C s H,1 1 -81 F C1 H CF2 Cl CH3 NHCH2 COOCH 3 1- 82 F C1 H CF2 C1 CH3 NHCH2 COOCz H s TABLE 1 (contn'd) compound X y R3 R' R 2 B
No.
1 -83 F C1 H CF2 Cl CH3 NHCH2 C00 " C 3 H 7 1- 84 F C1 H CF2 Cl CH3 NHCH2 C00 " C 4 H g 1 -85 F C1 H CF2 Cl CH3 NHCH2 C00 " C 5 H õ
1 -86 F C1 H CF2 Cl CH3 NHCH2 COO ' C 3 H 7 1- 87 F Cl . H CF2 C1 CH3 NHCH2 C00 ' C s H fl 1 -88 F Cl H CF2 Cl CH3 NH2 CH2 COO ' C 6 H õ
1 -89 F C1 H CF2 Cl CH3 NHCH(CH3 )COOCH 3 1 -90 F C1 H CF2 Cl CH3 NHCH(CH3 )COOC 2 H 5 1- 91 F C1 H CF2 Cl CH3 NHCH(CH3 )COO " C3 H 7 1 -92 F C1 H CF2 Cl CH3 NHCH(CH3 )COO " C4 H s 1 -93 F Ci H CF2 Cl CH3 NHCH(CH3 )COO " C; Hõ
1 -94 F C1 H CF2 Cl CH3 NHCH(CH3 )COO ' C3 H 7 1 -95 F C1 H CF2 Cl CH3 NHCH(CH3 )COO c C; H y 1- 96 F C1 H CF2 Cl CH3 NHCH(CH3 )COO C C6 Hõ
1 -97 H Cl H CF2 Cl CH3 OCH3 1 -98 H C1 H CF2 Cl CH3 OC 2 H 6 1 -99 H C1 H CF2 Cl CH3 0' C 3 H 7 1 -100 H Cl H CF2 Cl CH3 0" C 3 H 7 1 -101 H C1 H CF2 Cl CH3 OCH2 CH2 Cl 1 -102 H C1 H CF2 Cl CH3 OCF2 CF2 H
1-103 H C1 H CF2 Cl CH3 0' C 5= H 9 1 -104 H C1 H CF2 C1 CH3 0' C 6 H
TABLE 1 (contn'd) s Compound x Y R 3 R' R Z B
No.
1 -105 H C1 H CF2 Cl CHs OCHz CH=CHz 1- 106 H C1 R CF2 Cl CH3 OCH2 CCI = CH2 1 -107 H C1 H CF2 Cl CH3 OCH2 CCl = CHC1 1 -108 H ci H CF2 Cl CH3 OCH(CH s)CH =CH2 1 -109 H C1 H CF2 Cl CH3 OCH2 C= CH
1 -110 H C1 H CF2 Cl CH3 OCH(CH 3)C = CH
1 -111 H CI H CF2 Cl CH3 OCH2 C CBr 1 -112 H Cl H CF2 Cl CH3 OCH2 C= CC1 1- 113 H C1 H CF2 Cl CH3 OCHz C CCH 2 Cl 1 -114 H ci H CF2 Cl CH3 OCH2 CN
1- 115 H ci H CF2 Cl CH3 OCH2 OCH 3 1- 116 H ci H CF2 CI CH3 OCH2 0C2 H 5 1 -117 H ci H CF2 Cl CH3 OCH2 SCH , 1 -118 H ci H CF2 Cl CH3 OCH2 COOCH 3 1 -119 H ci H CF2 Cl CHa OCH2 COOC2 H s 1 -120 H C1 H CF2 Cl CH3 OCH2 C00 C 3 H7 1- 121 H Cl H CF2 Cl CH3 OCH2 C00 C, H 9 1 -122 H Cl H CF2 Cl CH3 OCH2 C00 " C.5 Hõ
1- 123 H C1 H CF2 Cl CH3 OCH2 COO ' C a H 7 1 -124 H C1 H CF2 Cl CH3 OCH2 COO ' C 5 H 9 1 -125 H C1 H CF2 Cl CH3 OCH2 COO ' C 6 H õ
1 -126 H C1 H CF2 Cl CH3 OCH(CH 3)COOCH 3 1 -127 H Cl H CF2 Cl CH3 OCH(CH 3)COOC 2 H s TABLE 1 (contn'd) Compound X y R 3 R' R 2 B
No.
1 -128 H C1 H CF2 Cl CH3 OCH(CH 3 )C00 " C3 H 7 1- 129 H C1 H CFz Cl CH3 OCH(CH 3 )C00 " C4 H 9 1 -130 H C1 H CF2 Cl CH3 OCH(CH 3)C00 " C5 Hõ
1- 131 H C1 H CF2 Cl CH3 OCH(CH 3 )C00 ' C3 H, 1 -132 H Cl H CF2 C1 CH3 OCH(CH 3)C00 c CS H 9 1- 133 H C1 H CF2 Cl CH3 OCH(CH 3)C00 ' C6 Hõ
1 -134 H C1 H CF2 Cl CH3 OCH2 CON(CH3 ) 2 1 -135 H C1 H CF2 Cl CH3 OCH2 CON(C 2 H s) 2 1 -136 H C1 H CF2 C1 CH3 OCH2 CON(CH3 ) C 2 H s 1 -137 H C1 H CF2 Cl CH3 OCH(CH a)CON(CH 3 2 1 -138 H C1 H CF2 C1 CH3 OCH(CH3 )CON(C 2 H;)2 1 -139 H C1 H CF2 Cl CH3 OCH(CHs )CON(CH 3)Ca H s 1 -140 H C1 H CF2 Cl CH3 OCH 2 COON(CH 3 ) 2 1 -141 H C1 H CF2 Cl CH3 OCH 2 COON(C 2 H 5- )Z
1 -142 H C1 H CF2 Cl CH3 OCH(CH3 )COON(CH3 ) 2 1 -143 H C1 H CF2 C1 CH3 OCH(CH3 )COON(C 2 H 5) 2 1 -144 F Cl H CF2 Cl CH3 OCH3 1 -145 F C1 H CF2 Cl CH3 OC 2 H 5 1- 146 F C1 H CF2 Cl CH3 0' C 3 H, 1 -147 F C1 H CF2 Cl CH3 0" C 3 H, 1 -148 F C1 H CF2 C1 CH3 OCH2 CH2 Cl 1 -149 F C1 H CF2 Cl CH3 OCF2 CF2 H
1- 150 F C1 H CFz C1 CH3 0' C 6 H 9 WO 97/07104 PCT/.BP96/02311 TABLE 1 (contn'd) Compound X Y R 3 R' R 2 B
No.
1- 151 F C1 H CF2 Cl CHs 0' C 6 H õ
1-152 F Cl H CF2 Cl CH3 OCH2, CHZ =CH2 1 -153 F C1 H CF2 Cl CHa OCHa CC1 =CH2 1 -154 F C1 H CF2 Cl CH3 OCH2 CC1 = CHCI
1 -155 F Ci H CF2 Cl CH3 OCH(CH 3)CH =CH2 1 -156 F Cl H CF2 Cl CH3 0CH2 C= CH
1 -157 F C1 H CF2 Cl CHa OCH(CH 3)C = CH
1 -158 F Cl H CF2 Cl CH3 OCH2 C CBr 1 -159 F Cl H CF2 Cl CH3 OCH2 C CC1 1 -160 F C1 11 CF2 C1 CH3 OCH2 C= CCH 2 Cl 1 -161 F C1 H CF2 Cl CH3 OCH2 CN
1 -162 F C1 H CF2 Cl CH3 OCH2 OCH 3 1 -163 F C1 H CF2 Cl CH3 OCH2 OC2 H s 1 -164 F C1 H CF2 Cl CH3 OCH2 SCH a 1 -165 F C1 H CF2 Cl CH3 OCH2 COOCH 3 1- 166 F C1 H CF2 C1CHa OCH2 COOC2 H s 1 - 168 F Cl H CFz Cl CH3 OCH2 C00 C, H fl 1- 169 F C1 H CF2 Cl CH3 OCH 2 C00 n C s H õ
1- 170 F Cl H CF2 Cl CH3 OCH2 COO ' C, H, 1- 171 F C1 H CF2 Cl CH3 OCH2 C00 ' C 5 H o 1- 172 F C1 H CF2 Cl CH3 OCH2 COO ' C e H õ
1- 173 F C1 H CF2 Cl CH3 OCH(CH 3)COOCH 3 WO 97/07104 PCT/.iP96/02311 TABLE 1 (contn'd) ~
Compound x Y R3 R' R Z B
No.
1 -174 F C1 H CF2 Cl CH3 OCH(CH a)COOC 2 H s 1 -175 F C1 H CF2 C1 CH3 OCH(CH 3 )C00 " C 3 H T
1 -176 F C1 H CF2 C1 CH3 OCH(CH 3 )C00 C, H y 1- 177 F C1 H CF2 Cl CH3 OCH(CH 3)C00 " C; H,1- 178 F C1 H CF2 Cl CH3 OCH(CH 3 )C00 ' C3 H;
1 -179 F C1 H CF2 Cl CH3 OCH(CH a)C00 ' Cs H 9 1- 180 F C1 H CF2 C1 CH3 OCH(CH 3)C00 c C6 Hõ
1 -181 F Cl H CF2 Cl CH3 OCH2 CON(CH3 ) 2 1- 182 F C1 H CF2 Cl CH3 OCH2 CON(C 2 H 5) 2 1 -183 F Cl H CF2 Cl CH3 OCH2 CON(CH3 ) C 2 H s 1 -184 F C1 H CF2 Cl CH3 OCH(CH 3)CON(CH 3) 2 1- 185 F Cl H CF2 Cl CH3 OCH(CH3 )CON(C z. H 5)2 1- 186 F C1 H CF2 Cl CH3 OCH(CH3 )CON(CH 3)C2 H 5 1 -187 F Cl H CF2 Cl CH3 OCH 2 COON(CH 3) 2 1- 188 F CI H CF2 Cl CH3 OCH 2 COON(C 2 H 5)2 1 -189 F Cl H CF2 Cl CH3 OCH(CH3 )COON(CH3 ) 2 1- 190 F C1 H CF2 Cl CH3 OCH(CH3 )COON(C 2 H$) 2 1 -191 H F H CF2 Cl CH3 SH
1 -192 H C1 H CF2 Cl CH3 SH
1 -193 H Br H CF2 Cl CH3 SH
1- 194 F F H CF2 Cl CH3 SH
1 -195 F C1 H CF2 Cl CH3 SH
1 -196 F Br H CF2 Cl CH3 SH
TABLE 1 (contn'd) Compound X y R3 R' R Z B
No.
1 -197 H C1 H CF2 Cl CH3 SCH 3 1 -198 H C1 li CF2 'C1 CHa SCz H s 1 -199 H Cl H CF2 Cl CH3 S' C, H, 1 -200 H Cl H CF2 Cl CH3 SCH2 CHZ Cl 1 - 201 H Ci H CF2 C 1 CH3 S' C; H 9 1 -202 H Cl H CF2 Cl CH3 S.' C 6 H õ
1 -203 H Ci H CF2 Cl CH3 SCH2 CH=CHz 1 -204 H Cl H CF2 Cl CH3 SCH2 CCl = CH2 1 -205 H C1 H CF2 C1 CH3 SCH2 CCl =CHCI
1 -206 H Cl H CF2 C1 CH3 SCH(CH 3)CH =CH2 1 -207 H C1 H CF2 C1 CH3 SCH2 C= CH
1 -208 H Cl H CF2 C1 CH3 SCH(CH a)C = CH
1 -209 H C1 H CF2 C1 CH3 SCHz COOCH a 1 -210 H Cl H CF2 C1 CHs SCH2 COOCZ H s 1 - 211 H C1 H CFZ C1 CH3 SCHZ C00 " C, H, 1 -212 H C1 H CF2 Cl CH3 SCH2 COO " C 4 H a 1 -213 H Cl H CF2 Cl CH3 SCH2 COO " C 3 H õ
1- 214 H Cl H CF2 C1 CHa SCH2 COO ' C a H 7 1- 215 H C1 H CF2 C1 CH3 SCHZ C00 ' C 5 H 9 = 1 -216 H C1 H CF2 C1 CH3 SCH2 COO ' C 6 H õ
1 -217 H Cl H CF2 Cl CH3 SCH(CH 3)COOCH 3 1 -218 H C1 H CF2 Cl CH3 SCH(CH a)COOC 2 H 5 TABLE 1 (contn'd) ~
Compound X y R 3 R' R 2 B
No.
1- 219 H C1 H CF2 Cl CH3 SCH(CH 3 )C00 C3 H, 1 -220 H Ci H CF2 Cl 'CH3 SCH(CH 3 )C00 " C4 H 9 1 -221 H C1 H CF2 Cl CH3 SCH(CH 3 )C00 " Cs Hõ
1 -222 H C1 H CF2 Cl CH3 SCH(CH 3)C00 C3 H, 1 -223 H C1 H CF2 Cl CH3 SCH(CH 3)C00 Cs H s 1 -224 H C1 H CF2 Cl CH3 SCH(CH 3 )C00 ' C6 H
1 -225 H C1 H CF2 Cl CH3 SCH2 CON(CH3 ) 2 1 -226 H C1 H CF2 Cl CH3 SCH2 CON(C 2'H 5) 2 1 -227 H C 1 H CF2 C 1 CH 3 SCH2CON ( tetramethylene ) 1 -228 H C 1 H CF2 C 1 CH3 SCHZCON ( pentamethylene ) 1 -229 H C1 H CF2 Cl CH3 SCH2CON
(ethyleneoxyethylene) 1- 230 H Ci H CF2 Cl CH3 SCH(CH3 )CON(CH 3) 2 1 -231 H Ci H CF2 Cl CH3 SCH(CH3 )CON(C2 H;) 2 1 -232 H C1 H CF2 Cl CHa SCH(CH3)CON
(tetramethylene) 1 -233 H Ci H CF2 Cl CH3 SCH(CH3)CON
(pentamethylene) 1 -234 F C1 H CF2 Cl CH3 SCH 3 1 -235 F C1 H CF2 C1 CH3 SC2 H s 1- 236 F C1 H CF2 Cl CH3 S' C, H
1 -237 F C1 H CF2 Cl CH3 SCH2 CH2 Cl 1- 238 F C1 H CFs CI CH3 S' C s H 9 TABLE 1 (contn'd) Compound X Y R3 R' R Z B
No.
1 -239 F C1 H CF2 CI CH3 S' C 6 H
1 -240 F Cl H CF2 Cl CH3 SCH2 CH-CH2 1 -241 F C1 H CF2 Cl CH3 SCH2 CC1 =CH2 1 -242 F C1 H CFz Cl CH3 SCH2 CCI = CHCI
1 -243 F C1 H CF2 Cl CH3 SCH(CH 3)CH = CHI
1 -245 F C1 H CF2' C1 CH3 SCH(CH )C=CH
1 -247 F Cl H CF2 Cl CH3 SCH2 COOC2 H a 1 - 248 F C1 H CFZ CI CH3 SCHZ C00 " C 3 H, 1 -249 F C1 H CF2 C1 CH3 SCH2 COO " C, H 9 1 -250 F Cl H CF2 C1 CH3 SCH2 COO " C 5 H õ
1 -251 F Cl H CF2 Cl CH3 SCH2 COO ' C a H 7 1 -252 F C1 H CF2 C1 CH3 SCH2 COO ' C 5 H 9 1 -253 F C1 H CF2 Cl CH3 SCH2 COO c C 6 H õ
1 -254 F Ci H CF2 CI CH3 SCH(CH a)COOCH , 1 -255 F C1 H CF2 Cl CH3 SCH(CH ,. )COOC 2 H 5 1 -256 F Cl H CF2 Cl CHa SCH(CH 3)C00 " C3 H 7 1 -257 F Cl H CF2 C1 CH3 SCH(CH 3)C00 " C4 H g 1 -258 F Cl H CF2 C1 CH3 SCH(CH 3)C00 " C5 Hõ
1 -259 F Cl H CF2 Cl CH3 SCH(CH 3)C00 ' C3 H, 1 -260 F C1 H CF2 C1 CH3 SCH(CH 3)C00 ' C5 H fl 1 -261 F Cl H CF2 Cl CH3 SCH(CH 3 )C00 ' C6 Hõ
TABLE I (contn'd) Compound x y R 3 R' R Z B
No.
1 -262 F- Cl H CF2 Cl CH3 SCH2 CON(CH3 ) 2 1 -263 F C1 H CF2 Cl -CH3 SCH2 CON(C 2 H s) 2 1 -264 F C 1 H CF2 C 1 CH3 SCH2CON ( tetramethylene ) 1 -265 F C l H CF2 C l CH a SCH2CON ( pentamethylene ) 1= 266 F C1 H CF2 Cl CH3 SCH2CON
(ethyleneoxyethylene) 1 -267 F C1 H CF2 Cl CHa SCH(CHa )CON(CH a) 2 1 -268 F C1 H CF2 Cl CH3 SCH(CH3 )CON(C2 H 5) 2 1 -269 F Ci H CF2 Cl CH3 SCH(CH3)COrr (tetramethylene) 1 -270 F C1 H CF2 Cl CH3 SCH(CH3)CON
(pentamethylene) 1 -271 H F H CF2 Cl CH3 SO2 Cl 1 -272 H C1 H CF2 Cl CH3 SO2 Cl 1 -273 H Br H CF2 Cl CH3 SOz Cl 1 -274 F F H CF2 Cl CHa SO2 Cl 1 -275 F C1 H CF2 Cl CH3 SOZ Ci 1 -276 F Br H CF2 Cl CH3 SOz Cl 1 -277 H C1 H CF2 Cl CH3 SOz OCH s 1- 278 H C1 H CF2 Cl CH3 SO2 OC2 H s 1 - 279 H C1 H CF2 C1 CH3 S02 0' C a H7 1 -280 H C1 H CF2 Cl CHa SO2 OCH 2 CH = CHz TABLE 1 lcontn'dl Compound X Y R3 R' R z B
No.
1 -282 F C1 H CF2 Cl CH3 SOz 0C2 H s 1- 283 F C1 H CF2 Cl CH3 SO2 0' C 3 H7 1 -284 F C1 H CF2 Cl CH3 S02 OCH 2 CH = CH2 1 -285 H Cl H CF2 Cl CH3 S02 N(CH3 ) 2 1 -286 H C1 H CF2 Cl CH3 SOz N(Ca H 5)2 1 -287 F C1 H CF2 Cl CH3 SO2 N (CH 3) 2 1 -288 F C1 H CF2 Cl CH3 SO2 N(Ca H 5) 2 1 -289 H C1 H CF2 Cl CH3 COOH
1 -290 H Cl H CF2 Cl CH3 COOCH 3 1 -291 H C1 H CF2 Cl CH3 COOC 2 H 5 1 -292 H Cl H CF2 Cl CH3 C00" C a H
1 -293 H C1 H CF2 Cl CH3 C00" C, H v 1 -294 H Cl H CF2 Cl CH3 CO0 C 5 H,, 1- 295 H C1 H CF2 Cl CH3 C00' C 3 H 7 1 -296 H C1 H CF2 Cl CH3 COOCHZ CH2 C1 1 -297 H C1 H CF2 C1 CH3 COOCH2 CH2 Br 1 -298 H C1 H CF2 C1 CH3 CON(CH a) 2 1 -299 H Cl H CF2 C1 CH3 CONHCH a 1- 300 H C1 H CF2 C1 CH3 CON(C2 H s) 2 1 -301 H Cl H CF2 C1 CH3 CONHC2 H 5 1 -302 H C1 H CF2 Cl CH3 COCH s 1 -304 H C1 H CF2 C1 CH3 COCH2 Cl TABLE 1 (contn'd) Compound X Y R 3 R' R 2 B
No.
1 -305 H Cl H CF2 Cl CH3 CHO
1 -306 H C1 H CF2 Cl CH3 CH = CHCOOCH 3 1 -307 H C1 H CF2 Cl CH3 CH = CHCOOCZ H 5 1 -308 H C1 H CF2 Cl CH3 CH2 CH2 COOCH 3 1- 309 H C1 H CF2 Cl CH3 CH2 CH2 COOC2 H s 1 -310 F C1 H CF2 Cl CH3 COOH
1 -311 F Cl H CF2 Cl CH3 COOCH a 1 -312 F C1 H CF2 Cl CH3 COOC 2 H s 1 -313 F C1 H CF2 Cl CH3 C00 C 3 H 7 1- 314 F C1 H CF2 Cl CH3 C00" C 4 H q 1- 315 F C1 H CF2 Cl CH3 CO0 C 5 H õ
1- 316 F C1 H CF2 Cl CH3 COO' C 3 H
1 -317 F Cl H CF2 Cl CH3 COOCH2 CH2 Cl 1 -318 F C1 H CF2 Cl CH3 COOCH2 CHz Br 1 -319 F CI H CF2 Cl CH3 CON(CH a) 2 1 -320 F C1 H CF2 Cl CH3 CONHCH 3 1- 321 F C1 H CF2 Cl CH3 CON(C2 H 5)2 1 -322 F Cl H CF2 Cl CHa CONHC2 H s 1 -323 F C1 H CF2 Cl CH3 COCH 3 1 -324 F Cl. H CF2 Cl CHa COC2 H s 1 -325 F C1 H CF2 Cl CH3 COCH2 Cl 1 -326 F C1 H CF2 Cl CH3 CHO
TABLE 1 (contn'd) ti Compound x y R3 R' R 2 B
No.
1 -327 F C1 H CF2 Cl CH3 CH = CHCOOCH 3 1 -328 F C1 H CF2 Cl CH3 CH = CHCOOC2 H;
1 -329 F G1 H CF2 Cl CH3 CH2 CH2 COOCH 3 1 -330 F C1 H CF2 Cl CH3 CH2 CHz COOC2 H 5 1- 333 H Br H CF3 H H
1 -336 H Br H CF3 CH3 H
1- 339 F Br H CF3 H H
1 -342 F Br H CF3 CH3 H
1 -344 H C1 H CF3 CH3 NOz 1 -345 H Br H CF3 CH3 NO2 : 1 -346 F F H CF3 CH3 NO2 1 -347 F C1 H CF3 CH3 NOz 1 -348 F Br H CF3 CH3 N02 TABLE 1 (contn'd) fi NomPound X Y R 3 R' R 2 B x 1 -351 H Br H CF3 CH3 NH2 1 -353 F Cl H CF3 CH3 NH2 1 -354 H Cl H CF3 CH3 NHCH(CH3 )COOCH 3 1 -355 H C1 H CF3 CH3 NHCH(CH3 )COOC 2 H;
1- 356 H C1 H CF3 CH3 NHCH(CH3 )C00 C3 H 7 1 -357 H C1 H CF3 CH3 NHCH(CH3 )C00 " C4 H 9 1 -358 H C1 H CF3 CH3 NHCH(CH3 )C00 " C5 Hõ
1 -359 H C1 H CF3 CH3 NHCH(CH3 )C00 ' C, H7 1- 360 H C1 H CF3 CH3 NHCH(CH3 )COO ' CS H fl 1 -361 H C1 H CF3 CH3 NHCH(CH3 )COO ' C6 Hõ
1 -363 F C1 H CF3 CH3 NHC 2 H;
1 -364 F CI H CF3 CH3 NHCH2 CH = CHZ
1 -365 F Cl H CF3 CH3 NHCH2 C CH
1 -366 F C1 H CF3 CH3 NHCH(CH 3)C=CH
1 -367 F C1 H CF3 CH3 NHSOz CH3 1- 368 F C1 H CF3 CH3 NHSOa C 2 H e 1 -369 F Cl H CF3 CH3 NHSO2 CH2 Cl 1 -371 F Cl H CF3 CH3 N(CH3 )S0 2 CH3 1 -372 F C1 H CF3 CH3 N(CH2 C= CH)SO 2 TABLE 1 (contn'd) Compound X y R 3 R' R Z B
No.
1 -373 F C1 H CF3 CHa NHCOOCH
1 -374 F C1 H CF3 CH3 NHCOOC2 H s 1 -375 F C1 H CF3 CH3 NHCOO " C 3 H 7 1 -376 F C1 H CF3 CH3 NHCOO ' C 3 H 7 1 -378 F C1 H CF3 CH3 NHCO0 " C 5 H
1 -380 F C1 H CF3 CH3 NHCH2 COOC2 H s 1 -381 F C1 H CF3 CH3 NHCH2 COO " C 3 H 7 1 -382 F CI H CF3 CH3 NHCH2 COO " C, H s 1 -383 F Cl H CF3 CH3 NHCH2 COO C 5 H õ
1 -384 F Cl H CF3 CHa NHCH2 COO ' C a H, 1 -385 F C1 H CF3 CH3 NHCH2 COO ' C 5 H 9 1 -386 F Br H CF3 CH3 NH2 1 -387 H F H CF3 CHa OH
1 -389 H Br H CF3 CH3 OH
1 -392 F Br H CF3 CH3 OH
1-393 H Cl H CF3 CH3 NHCH3 1 -395 H C1 H CF3 CH3 NHCH2 CH = CHz TABLE 1 (contn'd) Compound X Y R 3 R' R 2 B
No.
1 -396 H C1 H CF3 CH3 NHCH2 C= CH
1 -397 H C1 H CF3 CH3 NHCH(CH 3)C CH
1 -399 H Ci H CF3 CH3 NHSO2 C 2 H s 1 -401 H C1 H CF3 CH3 NHSOz CF3 1 -402 H C1 H CF3 CH3 N(CH3 )SO 2 CH3 1 -403 H Ci H CF3 CH3 N(CH2 C=CH)SO 2 CH3 1 -405 H C1 H CFa CH3 NHCOOC2 H s 1 -406 H C1 H CF3 CH3 NHCOO C s H 7 1 -407 H C1 H CF3 CH3 NHCOO C 3 H, 1 -408 H C1 H CF3 CH3 NHCO0 " C 4 H s 1 -409 H C1 H CF3 CH3 NHCOO " C s H
1 -412 H C1 H CF3 CH3 NHCH2 C00 " C, H T
1 -413 H C1 H CF3 CH3 NHCH2 C00 " C 4 H q 1 -414 H C1 H CF3 CH3 NHCH2 C00 " C s H õ
1 -415 H C1 H CF3 CH3 NHCH2 COO ' C 3 H 7 1 -416 H C1 H CF3 CH3 NHCH2 COO ' C s H a 1 -417 H C1 H CF3 CH3 NHCH2 COO ' C H
1 -418 F C1 H CF3 CH3 NH CH2 COO ' C 6 H
WO 97/07104 ]PCT/JP96/02311 TABLE 1 (contn'd) Compound X Y R3 R' R Z B
No.
1 -419 F C1 H CF3 CH3 NHCH(CH 3)COOCH 3 1 -420 F Cl H CF3 -CH3 NHCH(CH3 )COOC 2 H 5 1- 421 F C1 H CF3 CH3 NHCH(CH3 )C00 " C3 H, 1 -422 F C1 H CF3 CH3 NHCH(CH3 )C00 " C, H 9 1 -423 F C1 H CF3 CH3 NHCH(CH3 )COO C; Hõ
1 -424 F C1 H CF3 CHa NHCH(CH3 )C00 C 3 H 7 1 -425 F C1 H CF3 CHs NHCH(CH3 )COO C 5 H 9 1 -426 F Cl H CF3 CH3 NHCH(CH3 ) COO' ' CI Hõ
1 -428 H C1 H CF3 CHa OC 2 H s 1 -429 H Cl H CF3 CH3 0' C a H 7 1 -430 H Cl H CF3 CH3 0" C 3 H 7 1 -431 H Cl H CF3 CH3 OCH2 CH2 C1 1 -432 H Cl H CF3 CHa OCF2 CF2 H
1 -433 H Cl H CF3 CH3 0' C 5 H 9 1 -434 H C1 H CF3 CH3 0' C 6 H õ
1 -435 H Cl H CF3 CH3 OCH2 CH = CH2 1 -436 H C1 H CF3 CH3 OCH2 CC1 =CH2 1 -437 H C1 H CF3 CHa OCH2 CCI = CHCI
1 -438 H C1 H CF3 CH3 OCH(CH 3)CH = CHZ
1 -440 H C1 H CF3 CH3 OCH(CH 3)C=CH
TABLE 1 (contn'd) e Compound x I, R 3 R' R 2 B
No.
1 -441 H C1 H CF3 CH3 OCH2 C= CBr 1 -442 H CI H CF3 --CH3 OCH2 C=CC1 1 -443 H Cl H CF3 CH3 OCH2 C= CCH 2 Cl 1 -445 H Cl H CF3 CH3 OCH2 OCH , 1 -446 H C1 H CF3 CH3 OCH2 OC2 H s 1 -447 H Cl H CF3 CH3 OCH2 SCH 3 1 -448 H Cl H CFa CH3 OCH2 COOCH 3 1 -449 H C1 H CF3 CH3 OCH2 COOC2 H s 1 -450 H C1 H CF3 CH3 OCH2 C00 " C, H, 1 -451 H C1 H CF3 CH3 OCH2 C00 " C 4 H 9 1 -452 H Ci H CF3 CH3 OCH2 C00 " C; H õ
1 -453 H C1 H CF3 CH3 OCH2 COO ' C a H 7 1 -454 H C1 H CF3 CH3 OCH2 COO ' C s H fl 1 -455 H C1 H CF3 CH3 OCH2 COO ' C 6 H õ
1 -456 H C1 H CF3 CH3 OCH(CH 3)COOCH 3 1 -457 H Cl H CF3 CH3 OCH(CH 3)COOC 2 H s 1 -458 H C1 H CF3 CH3 OCH(CH 3)C00 C3 H7 1 -459 H C1 H CF3 CH3 OCH(CH 3 )C00 " C4 H 9 1 -460 H Cl H CF3 CH3 OCH(CH 3 )C00 " C5 Hõ
1 -461 H C1 H CF3 CH3 OCH(CH 3)C00 ' C3 H, 1 -462 H C1 H CF3 CH3 OCH(CH 3)C00 ' C5 H g 1 -463 H Cl H CF3 CH3 OCH(CH 3 )COO ' CR Hõ
TABLE 1 (contn'dl Compound X Y R 3 R1 R 2 B
No.
1 -464 H Cl H CF3 CH3 OCH 2 CON(CHa ) 2 1 -465 H Ci H CF3 CH3 OCH2 CON(C 2 H 5) 2 1 -466 H C1 H CF3 CH3 OCH2 CON(CH3 ) C 2 H;
1 -467 H C1 H CF3 CH3 OCH(CH 3)CON(CH ,) 2 1 -468 H C1 H CF3 CH3 OCH(CHs )CON(C 2 H;)=.
1 -469 H C1 H CF3 CH3 OCH(CH3. )CON(CH 3)C2 H;
1 -470 H C1 H CF3 CH3 OCH 2 COON(CH a) 2 1 -471 H Cl H CF3 CH3 OCH 2 COON(C 2 H 5)2 1 -472 H Cl H CF3 CHa OCH(CH3 )COON(CH3 ) z 1 -473 H Cl H CFa CH3 OCH(CH3 )COON(C 2 H s) 2 1 -476 F Cl H CF3 CH3 0' C 3 H 7 1 -477 F C1 H CF3 CH3 0 C, H 7 1 -478 F C1 H CF3 CH3 OCH2 CH2 Cl 1 -480 F C1 H CF3 CH3 0' C s H g 1 -481 F Cl H CF3 CH3 OC C 6 H õ
1 -482 F C l H CF3 CH3 OCH2 CH = CH 2 I -483 F Cl H CF3 CH3 OCH2 CCI = CHZ
1 -484 F C1 H CF3 CH3 OCH2 CC1 =CHCI
1 -485 F Cl H CF3 CH3 OCH(CH 3)CH = CH2 1 -486 F Cl H CF3 CH3 OCH2 C CH
TABLE 1 (contn'd) :
Compound X Y R3 R' R 2 B
No.
1 -487 F Ci H CF3 CH3 OCH(CH 3)C=CH
1 -488 F C1 H CF3 CH3 OCHZ C CBr 1 -489 F C1 H CF3 CH3 OCH2 C= CCl 1 -490 F C1 H CF3 CH3 OCH2 C= CCH 2 Cl 1 -491 F C1 H CF3 CH3 OCHz CN
1 -492 F Ci H CF3 CH3 OCH2 OCH 3 1 -493 F C1 H CF3 CH3 OCHZ 0C2 H;
1 -494 F Cl H CF3 CH3 OCH2 SCH 3 1 -496 F Cl H CF3 CH3 OCHz COOC2 H s 1 -498 F Cl H CF3 CH3 OCH2 C00 " C 4 H 9 1 -499 F C1 H CF3 CH3 OCH2 COO " C 5 H õ
1 -501 F C1 H CF3 CH3 OCHz COO C s H 9 1 -502 F C1 H CF3 CH3 OCHZ COO ' C 6 H õ
1 -503 F C1 H CF3 CH3 OCH(CH 3)COOCH 3 1 -504 F Cl H CF3 CH3 OCH(CH 3)COOC 2 H s 1 -505 F C1 H CF3 CH3 OCH(CH 3)C00 " C3 H 7 1 -506 F C1 H CF3 CH3 OCH(CH 3)C00 " C4 H9 1 -507 F Cl H CF3 CH3 OCH(CH 3)C00 " C5 H
1 -508 F Cl H CF3 CH3 OCH(CH 3-)C00 ' C3 H 7 1 -509 F C1 H CF3 CH3 OCH(CH 3 )C00 ' CS H 9 TABLE 1 (contn'd) Compound X Y R 3 R' R 2 B
No.
1 -510 F C1 H CF3 CH3 OCH(CH 3 )C00 ' C6 H
1 -511 F Ci H CF3 CH3 OCH2 CON(CH3 ) 2 1- 512 F C1 H CF3 CHa OCH2 CON(C 2 H s) 2 1- 513 F C1 H CF3 CH3 OCH2 CON(CH3 ) C 2 H;
1 -514 F Cl H CF3 CH3 OCH(CH 3)CON(CH 3) 2 1 -515 F C1 H CF3 CH3 OCH(CH3 )CON(C 2 H 5 )2 1- 516 F C1 H CF3 CH3 OCH(CH3 )CON(CH 3)C2 H;
1 -517 F C1 H CF3 CH3 OCH 2 COON(CH ,)2 1- 518 F C1 H CF3 CHa OCH 2 COON(C 2 H s)a 1 -519 F C1 H CF3 CHa OCH(CH3 )COON(CH3 ) 2 1 -520 F C1 H CF3 CHa OCH(CH3 )COON(C 2 H;) 2 1 -523 H Br H CF3 CH3 SH
1 -526 F Br H CF3 CH3 SH
1- 529 H C1 H CF3 CHI S' C s H 7 1 -530 H C1 H CF3 CH3 SCHZ CH2 Cl 1- 531 H C1 H CF3 CH3 Sc C s H s 1 -532 H C1 H CF3 CHa Sc C 6 H õ
TABLE 1 (contn'd) s Compound X Y R3 R' R 2 B
No.
1 -533 H C1 H CF3 CHa SCH2 CH = CHa 1 -534 H Cl H CF3 CHa SCH2 CC1 = CH2 1 -535 H Ci H CF3 CH3 SCH2 CCl = CHC1 1 -536 H Ci H CF3 CH3 SCH(CH a)CH = CH2 1 -537 H C1 H CF3 CH3 SCH2 C= CH
1 -538 H Cl H CF3 CH3 SCH(CH ,)C=CH
1 -539 H C1 H CF3 CH3 SCH2 COOCH , 1 -540 H C1 H CFa CH3 SCH2 COOC2 H s 1- 541 H C1 H CF3 CHa SCH2 C00 " C a H, 1 -542 H C1 H CF3 CH3 SCH2 C00 " C 4 H g 1 -543 H C1 H CF3 CH 3 SCH2 C00 C s H õ
1 -544 H C1 H CF3 CH3 SCH2 COO C a H7 1 -545 H C1 H CF3 CH3 SCH2 COO ' C s H s 1 -546 H Cl H CF3 CH3 SCH2 COO ' C 6 H õ
1 -547 H Cl H CF3 CH3 SCH(CH a)COOCH , 1 -548 H C1 H CF3 CHa SCH(CH 3)COOC 2 H s 1 -549 H C1 H CF3 CH3 SCH(CH 3 )C00 " C3 H, 1 -550 H Cl H CF3 CH3 SCH(CH 3 )C00 " C, H 9 1- 551 H Cl H CF3 CHa SCH(CH 3 )C00 " Cs Hii 1 -552 H C1 H CF3 CH3 SCH(CH 3 )C00 ' C3 H T
1 -553 H Cl H CF3 CH3 SCH(CH 3 )C00 ' C5 H 9 1 -554 H C1 H CF3 CH3 SCH(CH a)C00 ' C6 Hi i TABLE 1 (contn'd) Compound X Y R3 R' R a B
No.
1 -555 H C1 H CF3 CH3 SCH2 CON(CH3 ) 2 1 -556 H C1 H CF3 CH3 SCH2 CON(C 2 H;) 2 1- 557 H C 1 H CF3 CH3 SCHaCON ( tetramethylene ) 1 -558 H C 1 H CF3 CH 3 SCHaCON ( pentamethylene ) 1 -559 H Cl H CF3 CH3 SCH2CON
(ethyleneoxyethylene) 1 -560 H Cl H CF3 CH3 SCH(CH3 )CON(CH 3 1- 561 H C1 H CF3 CH3 SCH(CH3 )CON(C2 H;) z 1 -562 H C1 H CF3 CH3 SCH(CH3)CON
(tetramethylene) 1 -563 H C1 H CFs CH3 SCH(CH3)CON
(pentamethylene) 1 -565 F Cl H CF3 CH3 SC2 H 5 1 -566 F C1 H CF3 CHa S' C a H 7 1 -567 F C1 H CF3 CH3 SCH2 CH2 Cl 1 -568 F C1 H CF3 CH3 Sc C 5 H 9 1 -569 F C1 H CF3 CH3 S' C 6 H õ
1 -570 F Cl H CF3 CH3 SCH2 CH = CH2 1 -571 F C1 H CF3 CH3 SCH2 CCI =CH2 1 -572 F C1, H CF3 CH3 SCH2 CC1 =CHCI
1 -573 F Cl H CF3 CH3 SCH(CH 3)CH =CH2 1 -574 F C1 H CF3 CH3 SCH2 C= CH
TABLE 1 (contn'd) +
Compound x y R 3 R' R Z B
No.
1 -575 F C1, H CF3 CH3 SCH(CH 3)C=CH
1 -578 F Cl H CF3 CH3 SCH2 C00 C 3 H, 1 -579 F C1 H CF3 CH3 SCH2 COO " C 4 H 9 1 -581 F Cl. H CF3 CH3 SCH2 COO ' C 3 H 7 1 -582 F C1 H CF3 CH3 SCH2 COO ' Cs H
1 -583 F C1 H CF3 CH3 SCH2 COO ' C 6 H
1 -584 F C1 H CF3 CH3 SCH(CH 3)COOCH 3 1 -585 F Cl H CF3 CH3 SCH(CH 3)COOC 2 H 5 1 -586 F C1 H CF3 CH3 SCH(CH 3)C00 " C3 H~
1 -587 F C1 H CF3 CH3 SCH(CH 3)C00 C4 H
1- 588 F C1 H CF3 CH3 SCH(CH 3)C00 " CS H
1 -589 F C1 H CF3 CH3 SCH(CH 3)C00 ' C3 H 7 1 -590 F C1 H CF3 CH3 SCH(CH 3)C00 ' C5 H 9 1 -591 F Cl H CF3 CH3 SCH(CH 3 )C00 ' C6 Hõ
1--592 F Cl H CF3 CH3 SCH2 CON(CH3 ) 2 1- 593 F Cl H CF3 CH3 SCH2 CON(C 2 H e)2 1 -594 F C 1 H CF3 CH3 SCH2CON ( tetramethylene ) 1 -595 F C 1 H CF3 CH3 SCH2CON ( pentamethylene ) 1 -596 F C i H CF3 CH3 SCH2CON
(ethyleneoxyethylene) TABLE 1 (contn'd) Compound X Y R 3 R' R2 B
No.
1 -597 F C1 H CF3 CHa SCH(CH3 )CON(CH a) 2 1 -598 F C1 H CF3 CH3 SCH(CH3 )CON(C2 H;) 2 1 -599 F C1 H CF3 CH3 SCH(CH3)CON
(tetramethylene) 1 -600 F C1 H CF3 CH3 SCH(CH3)CON
(pentamethylene) 1 -601 H F H CF3 CH3 SOZ Ci 1 -602 H C1 H CF3 CH3 SOZ Cl 1 -603 H Br H CF3 CH3 SO2 Cl 1 -605 F C1 H CF3 CH3 SOz C1 1 -606 F Br H CF3 CH3 SO2 Cl 1 -609 H C1 H CF3 CH3 SO2 0' C 3 H T
1 -610 H C1 H CF3 CH3 SOz OCH 2 CH=CH2 1 -611 F C1 H CF3 CH3 SOz OCH s 1 -613 F C1 H CF3 CH3 SOz 0' C 3 H z 1 -614 F C1 H CF3 CH3 S02 OCH' 2 CH = CH2 1 -615 H C1 H CF3 CH3 SO2 N(CH3 ) 2 1 -616 H C1 H CF3 CHa SO2 N(Cz H b) 2 1- 617 F C1 H CF3 CH3 802 N(CH 3 ) 2 TABLE 1 (contn'd) r Compound X Y R3 R' R Z B
No.
1- 618 F C1 H CFa CHa SOz N(Cz H s) 2 1 -622 H C1 H CF3 CH3 C00" C 3 H
1 -623 H C1 H CF3 CH3 C00" C4 H 9 1 -624 H C1 H CF3 CH3 CO0 C s H õ
1- 625 H C1 H CF3 CHa COW C 3 H 7 1 -627 H C1 H CF3 CH3 COOCHZ CH2 Br 1 -628 H C1 H CF3 CH3 CON(CH a) 2 1 -630 H C1 H CF3 CH3 CON(C2 H 5) 2 1 -633 H C1 H CF3 CH3 COC2 H s 1 -634 H C1 H CF3 CH3 COCH2 Cl 1 -636 H C1 H CF3 CHa CH = CHCOOCH 3 1 -637 H C 1 H CF3 CH3 CH = CHCOOC z H s =
1 -638 H C1 H CF3 CH3 CHa CHz COOCH s TABLE 1 (contn'd) Compound x y R' R' R 2 B
No.
1 -641 F C1 H CF3 CH3 COOCH , 1 -643 F C1 H CF3 CH3 C00 C 3 H, 1 -644 F Cl H CF3 CH3 C00" C 4 H 9 1 -645 F C1 H CF3 CH3 CO0 C s H,i 1 -646 F Cl H CF3 CH3 .C00' C 3 H, 1 -648 F Cl H CF3 CH3 COOCH2 Cff Z Br 1 -649 F C1 H CF3 CH3 CON(CH a) 2 1 -651 F Cl H CF3 CH3 CON(C2 H 5) 2 1 -652 F C1 H CF3 CH3 CONHC2 H;
1 -654 F Ci H CF3 CH3 COC2 H 5 1 -655 F Ci H CF3 CH3 COCH2 Cl 1 -657 F C1 H CF3 CH3 CH = CHCOOCH 3 1 -658 F C1 H CF3 CH3 CH= CHCOOC2 H s 1 -660 F Cl H CF2 Cl CH3 CH2 CHz COOC2 H
1 -662 H F H CF2 Cl H N02 WO 97/07104 PCT/dP96/02311 TABLE 1 (contn'd) Compound x Y R 3 R' R Z B
No.
1 -663 H C1 H CF2 Cl H NO2 1 -664 H Br H CF2 Cl H NO2 1 -665 F F H CF2 Cl H NOZ
1 -666 F C1 H CF2 Cl H NOz 1 -667 F Br H CF2 C1 H NOz 1 -668 H F H CF2 Cl H NH2 1 -669 H C1 H CF2 Cl H NH2 1 -670 H Br H CF2 Cl H NH2 1 -671 F F H CF2 Cl H NH2 1 -672 F Cl H CF2 Cl H NH2 1 -673 F Br H CF2 Cl H NHZ
1 -674 H F H CF2 Cl H OH
1 -675 H C1 H CF2 Cl H OH
1 -676 H Br H CF2 Cl H OH
1 -677 F F H CF2 Cl H OH
1 -678 F Cl H CF2 Cl H OH
1 -679 F Br H CF2 C1 H OH
1 -680 H C1 H CF2 Cl H NHCH3 1 -681 H C1 H CF2 Cl H NHC2 H s 1 -682 H C1 H CF2 Cl H NHCH2 CH=CH2 1 -683 H C1 H CF2 Cl H NHCH2 C= CH
1 -684 H Cl H CF2 C1 H NHCH(CH 3)C=CH
1 -685 H C1 H CF2 Cl H NHSO2 CH3 TABLE 1 (contn'd) }
Compound x y R 3 R' R 2 B
No.
1 -686 H C1 H CF2 Cl H NHSOz C 2 H s 1 -687 H Cl H CF2 Cl H NHSOZ CH2 Cl 1 -688 H Ci H CF2 Cl H NHSO2 CF3 1 -689 H Ci H CF2 Cl H N(CH3 )SO 2 CH3 1 -690 H C1 H CF2 Cl H N(CH2 C= CH)SO 2 CH3 1 -691 H C1 H CF2 Cl H NHCOOCH 3 1 -692 H C1 H CF2 Cl H NHCOOC2 H s 1 -693 H Cl H CF2 Cl H NHCOO " C 3 H 7 1 -694 H C1 H CF2 Cl H NHCOO ' C 3 H, 1 -695 H C1 H CF2 Cl H NHCOO " C 4 H 9 1 -696 H C1 H CF2 Cl H NHCOO " C s H õ
1 -697 H C1 H CF2 Cl H NHCH2 COOCH 3 1 -698 H Cl H CF2 Cl H NHCH2 COOC2 H s 1- 699 H Cl H CF2 Cl H NHCH2 C00 " C 3 H 7 1 -700 H C1 H CF2 Cl H NHCH2 C00 " C 4 H 9 1 -701 H C1 H CF2 Cl H NHCH2 C00 " C s H
1 -702 H Ci H CF2 Cl H NHCH2 COO ' Ca H;
1 -703 H C1 H CF2 Cl H NHCH2 COO ' C s H s 1 -704 H C1 H CF2 Cl H NHCH2 COO ' C 6 H õ
1 -705 H C1 H CF2 Cl H NHCH(CH 3)COOCH , 1 -706 H Cl H CF2 C1 H NHCH(CH3 )COOC 2 H 6 1 -707 H C1 H CF2 Cl H NHCH(CH3 )COO " C3 H 7 1 -708 H Cl H CF2 Cl H NHCH(CH3 )COO " C4 H 9 TABLE 1 (contn'd) Compound x y R 3 R' R 2 B
No.
1 -709 H ci H CF2 Cl H NHCH(CH3 )C00 " C. Hõ
1- 710 H ci H CF2 Cl H NHCH(CH3 )C00 ' C3 H T
1 -711 H C1 H CF2 Cl H NHCH(CH3 )C00 ' C. H s 1 -712 H C1 H CF2 Cl H NHCH(CH3 )C00 ' C. H
1 -713 F Cl H CF2 Cl H NHCH3 1 -714 F C1 H CF2 C1 H NHC 2 H s 1 -715 F Cl H CF2 Cl H NHCH2 CH=CH2 1 -716 F ci H CF2 Cl H NHCH2 C CH
1 -717 F C1 H CF2 Cl H NHCH(CH 3)C=CH
1 -718 F C1 H CF2 Cl H NHSO2 CHa 1- 719 F Cl H CF2 Cl H NHSO2 C 2 H;
1 -720 F ci H CF2 Cl H NHSOz CH2 Cl 1 -721 F C1 H CF2 Cl H NHSO2 CF3 1 -722 F C1 H CF2 Cl H N(CH3 )S0 2 CH3 1- 723 F C1 H CF2 Cl H N(CH2 C CH)SO 2 CH3 1 -724 F C1 H CF2 Cl H NHCOOCH 3 1 -725 F C1 H CF2 Cl H NHCOOC2 H s 1 -726 F C1 H CF2 Cl H NHCOO " C 3 H, 1 -727 F C1 H CF2 Cl H NHCOO ' C a H 7 1 -728 F C1 H CF2 Cl H NHCO0 " C, H 9 1 -729 F Cl H CF2 Cl H NHCOO " C 5 H õ
1 -730 F Cl H CF2 Cl H NHCH2 COOCH 3 1 -731 F C1 H CF2 Cl H NHCH2 COOC2 H 5 TABLE 1 (contn'd) Compound X Ir R 3 R' R Z B
No.
1 -732 F Ci H CF2 Cl H NHCH2 C00 " C 3 H 7 1 -733 F C1 H CF2 Cl H NHCH2 C00 " C, H 9 1 -734 F Cl H CF2 Cl H NHCH2 C00 " C 5 H
1 -735 F Cl H CF2 Cl H NHCH2 COO ' C 3 H
1 -736 F C1 H CF2 Cl H NHCH2 COO ' C; H
1- 737 F Cl H CF2 Cl H NH2 CH2 COO ' C 6 H
1 -738 F C1 H CF2 Cl H NHCH(CH3 )COOCH 3 1 -739 F C1 H CF2 Cl H NHCH(CH3 )COOC 2 H 5 1- 740 F C1 H CF2 C1 H NHCH(CH3 )COO C 3 H 7 1 -741 F C1 H CF2 Cl H NHCH(CH3 )C00 " C 4 H 9 1 -742 F C1 H CF2 C1 H NHCH(CH3 )COO " C; Hõ
1 -743 F Cl H CF2 C1 H NHCH(CH3 )COO ' C3 H 7 1 -744 F Cl H CF2 C1 H NHCH(CH3 )COO ' CS H 9 1 -745 F Cl H C F2 Cl H NHCH (CH3 )COO c Cs Hõ
1 -747 H C1 H CF2 Cl H OC 2 H 5 1- 748 H C1 H CF2 C1 H 0' C a H 7 1- 749 H C1 H CFZ C1 H 0" C 3 H 7 1 -750 H C1 H CF2 Cl H OCH2 CH2 Cl 1 -751 H Cl H CF2 Cl H OCF2 CF2 H
1- 752 H C1 H CFz C1 H 0' C 5 H fl 1 -753 H C1 H CF2 Cl H 0' C 6 Hõ
1 -754 H C1 H CF2 Cl H OCH2 CH=CH2 TABLE 1 (contn'd) Compound X y R3 R' R z B
No.
1 -755 H Ci H CF2 Cl H OCH2 CCI =CH2 1 -756 H Ci H CF2 Cl H OCH2 CCl =CHCI
1 -757 H C1 H CF2 Cl H OCH(CH 3)CH =CH2 1 -758 H C1 H CF2 Cl H OCH2 C= CH
1 -759 H C1 H CF2 Cl H OCH(CH 3)C CH
1 -760 H Cl H CF2 Cl H OCH2 C CBr 1 -761 H C1 H CF2 C1 H OCH2 C= CC1 1 -762 H Ci H CF2 C1 H OCH2 C CCH 2 Cl 1 -763 H C1 H CF2 Cl H OCH2 CN
1 -764 H C1 H CF2 Cl H OCH2 OCH 3 1 -765 H C1 H CF2 Cl H OCH2 0C2 H s 1 -766 H C1 H CF2 Cl H OCH2 SCH '3 1 -767 H Cl H CF2 Cl H OCH2 COOCH 3 1 -768 H C1 H CF2 Cl H OCH2 COOC2 H a 1 -769 H Cl H CF2 C1 H OCH 2 C00 " C 3 H 7 1- 770 H C1 H CFz C1 H OCHa C00 " C 4 H 9 1- 771 H C1 H CF2 Cl H OCH 2 C00 " C 5 H I , 1 -772 H Cl H CF2 C1 H OCH2 COO ' C, H, 1- 773 H C1 H CF2 C1 H OCH2 C00 ' C 5 H 9 1- 774 H C1 H CFz C1 H OCHZ C00 ' C 6 H I I
1 -775 H C1 H CF2 Cl H OCH(CH 3)COOCH
1 -776 H Cl H CF2 Cl H OCH(CH 3 )COOC 2 H a WO 97/07104 PCT/.TP96/02311 TABLE 1 (contn'd) Compound x Y R 3 R' R Z B
= No.
1 -777 H CI H CF2 Cl H OCH(CH 3)C00 " C3 H 1 1 -778 H CI H CF2 Cl H OCH(CH 3)CQO C4 H9 1 -779 H C1 H CF2 Cl H OCH(CH 3 )C00 " C5 Hõ
1 -780 H Cl H CF2 Cl H OCH(CH 3 )C00 ' C3 H T
1- 781 H C1 H CF2 Cl H OCH(CH 3)COQ ' CS H s 1 -782 H C1 H CF2 Cl H OCH(CH 3)C00 ' C6 H
1 -783 H C1 H CF2 Cl H OCH2 CON(CH3 ) 2 1 -784 H C1 H CF2 Cl H OCH2 CON(C 2-H ;) 2 1 -785 H Cl H CF2 Cl H OCH2 CON(CH3 ) C 2 H s 1 -786 H C1 H CF2 Cl H OCH(CH 3)CON(CH ,) 2 1- 787 H C1 H CF2 Cl H OCH(CH3 )CON(C 2 H 5)2 1 -788 H C1 H CF2 Cl H OCH(CH3 )CON(CH 3)C2 H5 1 -789 H C1 H CF2 Cl H OCH 2 CQQN(CH 3 ) 2 1- 790 H CI H CF2 Cl H OCH 2 COON(C 2 H 5)z 1 -791 H C1 H CF2 Cl H QCH(CHa )COON(CH3 ) 2 1 -792 H C1 H CF2 Cl H OCH(CH3 )COON(C 2 H 5) 2 1 -793 F CI H CF2 Cl H OCH3 1- 794 F C1 H CFz C1 H QC 2 H s 1- 795 F C1 H CF2 Cl H 0' C a H 7 1 -796 F C1 H CF2 Cl H Q" C a H 7 1 -797 F C1 H CF2 Cl H OCH2 CH2 Cl 1- 799 F C1 H CFz C1 H Q' C 5 H 9 '134 TABLE 1 (contn'd) Compound X Y R 3 R' R2 B
No.
1 -800 F C1 H CF2 Cl H 0' C 6 H õ
1 -801 F C1 H CF2 Cl H OCH2 CH =CH2 1 -802 F C1 H CF2 Cl H OCH2 CC1 =CH2 1 -803 F C1 H CF2 Cl H OCH2 CC1 = CHCI
1 -804 F C1 H CF2 Cl H OCH(CH a)CH = CHz 1 -805 F C1 H CF2 Cl H OCH2 C CH
1 -806 F C1 H CF2 Cl H OCH(CH a)C=CH
1 -807 F C1 H CF2 Cl H OCH2 C CBr 1 -808 F Ci H CF2 C1 H OCH2 C= CC1 1 -809 F C1 H CF2 C1 H OCH2 C= CCH 2 Cl 1 -810 F Cl H CF2 C1 H OCH2 CN
1 -812 F Cl H CF2 C1 H OCH 2 0C2 H s 1 -813 F C1 H CFz' Cl H 0CH2 SCH a 1 -814 F C1 H CF2 Cl H OCH 2 COOCH , 1 -815 F Cl H CF2 Cl H 0CH2 COOC 2 H 5 1- 816 F Cl H CF2 C1 H OCH 2 COO C 3 H 7 1 - 817 F C1 H CF2 Cl H OCH2 C00 C, H 9 1 -818 F C1 H CF2 C1 H OCH2 COO " C 5 H õ
1 -819 F C1 H CFz C1 H OCH 2 COO ' C s H, 1 - 820 F C l H CFZ Cl H OCHZ C00 ' C 5 H g 1 - 821 F C1 H CFZ C1 H OCH2 C00 ' C 6 H
1 -822 F C1 H CF2 Cl H OCH(CH 3)COOCH 3 TABLE 1 (contn'd) Compound X Y R 3 R' R 2 B
No.
1 -823 F Ci H CF2 Cl H OCH(CH 3)COOC 2 H s 1 -824 F Ci H CF2 Cl H OCH(CH 3 )C00 " C3 H 7 1 -825 F C1 H CF2 Cl H OCH(CH 3)C00 " C, H 9 1 -826 F Cl H CF2 Cl H OCH(CH 3)C00 " C; Hõ
1 -827 F C1 H CF2 Cl H OCH(CH 3 )C00 ' C3 H, 1 -828 F C1 H CF2 C1 H OCH(CH 3)C00 ' Cs H 9 1 -829 F Cl H CF2 Cl H OCH(CH 3)C00 ' Cs Hõ
1 -830 F C1 H CF2 Cl H OCH2 CON(CH3 ) 2 1- 831 F C1 H CF2 Cl H OCH2 CON(C 2 H 5) 2 1 -832 F C1 H CF2 Cl H OCH2 CON(CH3 ) C 2 H s 1 -833 F C1 H CF2 Cl H OCH(CH 3)CON(CH ,) 2 1- 834 F C1 H CF2 Cl H OCH(CH3 )CON(C 2 H 5)2 1 -835 F Ci H CF2 Cl H OCH(CH3 )CON(CH 3)C2 H 5 1 -836 F C1 H CF2 Cl H OCH 2 COON(CH a) 2 1 -837 F C1 H CF2 Cl H OCH 2 COON(C 2 H 5)2 1 -838 F Ci H CF2 Cl H OCH(CH3 )COON(CH3 ) 2 1- 839 F C1 H CF2 C1 H OCH(CH3 )COON(C 2 H s) 2 1 -840 H F H CF2 Cl H SH
1 -841 H C1 H CF2 Cl H SH
1 -842 H Br H CF2 Cl H SH
1 -843 F F H CF2 Cl H SH
1 -844 F C1 H CF2 Cl H SH
1 -845 F Br H CF2 Cl H SH
WO 97/07104 PCT/.TP96/02311 TABLE 1 (contn'd) Compound X Y R 3 R' R Z B =
No.
1 -846 H Cl H CFz Cl H SCH a 1 -847 H C1 H CF2 Cl H SC2 H 5 1 -848 H Cl H CF2 Cl H S' C a H T
1 -849 H C1 H CF2 Cl H SCH2 CH2 Cl 1 -850 H C1 H CF2 Cl H SC C 5 H
1 -851 H C1 H CF2 Cl H S' C 6 H
1 -852 H C1 H CF2 Cl H SCH2 CH=CH2 1 -853 H C1 H CF2 Cl H SCH2 CC1 = CH2 1 -854 H Ci H CF2 Cl H SCH2 CC1 = CHC1 1 -855 H C1 H CF2 Cl H SCH(CH 3)CH =CH2 1 -856 H C1 H CF2 Cl H SCH2 C= CH
1 -857 H Cl H CF2 Cl H SCH(CH 3)C=CH
1 -858 H C1 H CF2 Cl H SCH2 COOCH 3 1 -859 H C1 H CF2 Cl H SCH2 COOC2 H s 1 - 860 H C1 H CFZ Cl H SCHz C00 " C, H 7 1- 861 H Cl H CF2 Cl H SCH2 COO " C 4 H 9 1- 862 H C1 H CF2 Cl H SCHZ COO C 5 H
1 -863 H C1 H CF2 Cl H SCH2 COO ' C s H 7 1 -864 H Cl H CF2 C1 H SCH2 COO c C s H s 1 -865 H C1 H CF2 C1 H SCH2 COO ' C 6 H õ
1 -866 H Cl H CF2 Cl H SCH(CH 3)COOCH s 1 -867 H C1 H CF2 C1 H SCH(CH 3)COOC 2 H s 1 -868 H C1 H CF2 Cl H SCH(CH 3 )C00 " C3 H, TABLE R (contn'd) Compound X Y R 3 R' R Z B
No.
1 -869 H C1 H CF2 Cl H SCH(CH 3 )C00 C4 H o 1 -870 H C1 H CF2 Cl H SCH(CH 3)C00 " C; Hõ
1- 871 H C1 H CF2 Cl H SCH(CH 3)C00 ' C3 H z 1 -872 H Cl H CF2 Cl H SCH(CH 3)C00 C C; H 9 1- 873 H Cl H CF2 Cl H SCH(CH 3 )C00 ' C6 Hõ
1 -874 H C1 H CF2 Cl H SCH2 CON(CH3 ) 2 1- 875 H Cl H CF2 Cl H SCH2 CON(C 2 H;)2 1 -876 H C 1 H CF2 C 1 H SCH2CON ( tetramethylene ) 1 -877 H C 1 H CF2 C l H SCH2CON ( pentamethylene ) (ethyleneoxyethylene) 1 -879 H C1 H CF2 C1 H SCH(CH3 )CON(CH 3 2 1- 880 H C1 H CF2 C1 H SCH(CH3 )CON(C2 H Z
1- 881 H C1 H CF2 Cl H SCH(CH3)CON
(tetramethylene) 1 -882 H C1 H CF2 Cl H SCH(CH3)CON
(pentamethylene) 1 -884 F Cl H CF2 C1 H SC2 H s { 1 -885 F Cl H CF2 Cl H S' C a H 7 1 -886 F Cl H CF2 Cl H SCH2 CH2 Cl TABLE 1 (contn'd) ~
Compound x y R3 R' R 2 B
No.
1- 887 F C1 H CFz C1 H S' C s H s 1- 888 F C1 H CFz C1 H S' C e H õ
1 -889 F C1 H CF2 Cl H SCHZ CH=CH2 1 -890 F C1 H CF2 Cl H SCH2 CCI = CH2 1 -891 F Cl H CF2 Cl H SCH2 CCl =CHC1 1 -892 F C1 H CF2 Cl H SCH(CH 3)CH = CH2 1 -893 F C1 H CF2 Cl H SCH2 C= CH
1 -894 F C1 H CF2 Cl H SCH(CH 3)C=CH
1 -895 F C1 H CF2 Cl H SCH2 COOCH 3 1 -896 F Cl H CF2 Cl H SCH2 COOC2 H 5 1 -897 F C1 H CF2 Cl H SCH2 COO " C 3 H 7 1 - 898 F C1 H CFz C1 H SCH2 C00 C, H 9 1 - 899 F C1 H CF2 Cl H SCH2 C00 " C; H õ
1 -900 F Cl H CF2 Cl H SCH2 COO ' C a H 7 1- 901 F Cl H CF2 Cl H SCH2 C00 ' C 5 H 9 1 -902 F C1 H CF2 Cl H SCH2 COO ' C s H õ
1 -903 F C1 H CF2 Cl H SCH(CH 3)COOCH 3 1 -904 F Cl H CF2 Cl H SCH(CH 3)COOC 2 H s 1 -905 F Cl H CF2 Cl H SCH(CH 3)C00 C3 H, 1- 906 F Cl H CF2 Cl H SCH(CH 3)C00 C4 H q 1 -907 F Ci H CF2 Cl H SCH(CH 3)C00 " C5 Hõ
1 -908 F C1 H CF2 Cl H SCH(CH 3 )C00 C3 H 7 1 -909 F C1 H CF2 Cl H SCH(CH 3)C00 ' C6 H 9 TABLE 1 (contn'd) Compound X I, R 3 R' R Z
No. B
1- 910 F C1 H CF2 Cl H SCH(CH 3 )C00 ' C6 Hõ
1 -911 F Ci H CF2 Cl H SCHz CON(CH3 ) 2 1 -912 F Cl H CF2 Cl H SCH2 CON(C 2 H 5) 2 1 -913 F C1 H CF2 Cl H SCH2CON (tetramethylene) 1 -914 F C 1 H CF2 C 1 H SCHZCON ( pentamethylene ) 1 -915 F Cl H CF2 C1 H SCH2CON
(ethyleneoxyethylene) 1 -916 F C1 H CF2 C1 H SCH(CH3 )CON(CH ,) 2 1 -917 F Cl =H CF2 Cl H SCH(CH3 )CON(C2 H 5) 2 1 -918 F C1 H CF2 Cl H SCH(CH3)CON
(tetramethylene) 1 -919 F Cl H CF2 C1 H SCH(CH3)CON
(pentamethylene) 1 -920 H F H CF2 Cl H SOZ Cl 1 -921 H C1 H CF2 Cl H SO2 Cl 1 -922 H Br H CF2 Cl H S02 Cl 1 -923 F F H CF2 C1 H SOZ Cl 1 -924 F Cl H CF2 Cl H SOZ Cl 1 -925 F Br H CF2 Cl H SOZ Cl 1 -926 H C1 H CF2 Cl H SO2 OCH 3 1 -927 H C1 H CF2 Cl H SO2 0C2 H 5 1 - 928 H C1 H CFz Cl H S02 0' C 3 H, 1 -929 H Cl H CF2 Cl H S02 OCH 2 CH=CH2 TABLE X (contn'd) Compound x y R 3 R' R 2 B
No.
1 -930 F C1 H CF2 Cl H SO2 OCH 3 1 -931 F Cl H CF2 Cl H S02 0C2 H;
1 - 932 F C1 H CFa C1 H S02 0' C 3 H r 1 -933 F ci H CF2 Cl H S02 OCH 2 CH=CH2 1 -934 H ci H CF2 Cl H SOZ N(CH3 ) 2 1 -935 H C1 H CF2 Cl H SOz N(CZ H 5) 2 1 -936 F ci H CF2 Cl H SOZ N (CH ,) 2 1 - 937 F C1 H CF2 C1 H SOz N(Cz H s) z 1 -938 H C1 H CF2 Cl H COOH
1 -939 H ci H CF2 Cl H COOCH
1 -940 H C1 H CF2 Cl H COOC 2 H 5 1- 941 H C1 H CF2 Cl H C00" C3 H 7 1 - 942 H C1 H CFZ C 1 H C00" C 4 H 9 1 -943 H C1 H CF2 C1 H C00" C s H 11 1 -944 H Cl H CF2 Cl H COO' C 3 H, 1 -945 H C1 H CF2 C1 H COOCH2 CH2 Cl 1 -946 H ci H CF2 C1 H COOCH2 CHZ Br 1 -947 H C1 H CF2 Cl H CON(CH 3) 2 1 -948 H Cl H CF2 Cl H CONHCH 3 1- 949 H Cl H CF2 Cl H CON(C2 H 2 1 -950 H Cl H CF2 Cl H CONHC2 H s 1 -951 H ci H CF2 Cl H COCH 3 1 -952 H C1 H CF2 C1 H COCz H s TABLE 1 (contn'd) :
Compound X Y R3 R' R 2 B
No.
1 -953 H C1 H CF2 Cl H COCH2 C1 1 -954 H C1 H CF2 Cl H CHO
1 -955 H C1 H CF2 Cl H CH=CHCOOCH 3 1 -956 H C l H CF2 C 1 H CH = CHCOOC 2 H;
1 -957 H C1 H CF2 Cl H CH2 CH2 COOCH 3 1 -958 H C1 H CF2 C1 H CH2 CH2 COOC2 H;
1 -959 F C1 H CF2 Cl H COOH
1 -960 F Cl H CF2 Cl H COOCH 3 1 -961 F Cl H CF2 Cl H COOC 2 H s 1- 962 F C1 H CF2 Cl H C00" C 3 H 7 1 -963 F CI H CF2 Cl H C00" C 4 H 9 1 - 964 F C1 H CF2 C1 H C00" C s Hõ
1- 965 F C1 H CF2 Cl H COO' C3 H 7 1 -966 F C1 H CF2 Cl H COOCH2 CH2 Cl 1 -967 F C1 H CF2 Cl H COOCH2 CH2 Br 1 -968 F C1 H CF2 Cl H CON(CH 3 ) 2 1 -969 F C1 H CF2 Cl H CONHCH 3 1- 970 F C1 H CF2 Cl H CON(C2 H s) 2 1 -971 F C1 H CF2 Cl H CONHC2 H s 1 -972 F C1 H CF2 Cl H COCH , 1 -973 F C1 H CF2 Cl H COC2 H s 1 -974 F Cl H CF2 Cl H COCH2 Cl 1 -975 F C1 H CF2 Cl H CHO
TABLE 1 (contn'd) Compound X Y R3 R' R Z
No. B
1 -976 F C1 H CF2 Cl H CH=CHCOOCH 3 1 -977 F C1 H CF2 Cl H CH= CHCOOC2 H s 1 -978 F Ci H CF2 Cl H CH2 CH2 COOCH , 1 -979 F C1 H CF2 Cl H CH2 CH2 COOC2 H 5 1 -982 H Br H CF3 H NO2 1 -984 F C1 H CF3 H NOz 1 -985 F Br H CF3 H NO2 1- 988 H Br H CF3 H NH2 1 -991 H C1 H CF3 H NHCH(CH3 )COOCH , 1 -992 H Ci H CF3 H NHCH(CH3 )COOC 2 H 5 1 -993 H C1 H CF3 H NHCH(CH3 )COO " C 3 H 7 1 -994 H C1 H CF3 H NHCH(CH3 )COO " C4 H 9 1 -995 H C1 H CF3 H NHCH(CH3 )COO CS Hõ
1- 996 H C1 H CF3 H NHCH(CH3 )COO ' C3 H, 1 -997 H C1 H CF3 H NHCH(CH3 )COO ' CS H 9 TABLE 1 (contn'd) Compound x Ir R 3 R' R 2 B
No.
1 -998 H Ci H CF3 H NHCH(CH3 )C00 ' C. H
1- 1000 F C1 H CF3 H NHC 2 H;
1 -1001 F C1 H CF3 H NHCH2 CH = CHz 1 -1002 F Ci H CF3 H NHCH2 C= CH
1 -1003 F C 1 H CF3 H NHCH(CH 3) C= CH
1 -1005 F C1 H CF3 H NHSO2 C z H;
1 -1006 F C1 H CF3 H NHSOz CH2 Cl 1 -1007 F C1 H CF3 H NHSOz CF3 1- 1008 F C1 H CF3 H N(CH3 )SO 2 CH3 1 -1009 F C1 H CF3 H N(CH2 C CH)SO 2 CH3 1 -1011 F C1 H CF3 H NHCOOC2 H s 1 - 1012 F C1 H CF3 H NHC00 " C, H 7 1- 1013 F C1 H CF3 H NHCOO ' C 3 H, 1 -1014 F C1 H CF3 H NHCOO " C H 9 1 -1015 F C1 H CF3 H NHCOO " C H õ
COOC2 H;
1 -1018 F C1 H CF3 H NHCH2 COO " C 3 H 7 1- 1019 F C1 H CFa H NHCHz C00 " C 4 H c 1 -1020 F C1 H CF3 H NHCH2 COO " C 5 H 11 TABLE 1 (contn'd) t Compound x y R3 R' R Z B
No.
1 -1021 F C1 H CF3 H NHCH2 COO ' C, H;
1 -1022 F C1 H CF3 H NHCH2 COO ' C s H g 1 -1023 F Br H CF3 H NH2 1 -1026 H Br H CF3 H OH
1 -1029 F Br H CF3 H OH
1 -1032 H Ci H CF3 H NHCHZ CH = CHz 1 -1034 H C1 H CF3 H NHCH(CH 3)C=CH
1 -1036 H C1 H CF3 H NHSOz C 2 H s 1 -1037 H C1 H CF3 H NHSOz CH2 Cl 1 -1039 H C1 H CF3 H N(CH3 )SO 2 CH3 1 -1040 H C1 H CF3 H N(CH2 C= CH)SO 2 CH3 1 -1041 H C1 H CF3 H NHCOOCH a 1 -1043 H C1 H CF3 H NHCOO C 3 H, TABLE 1 (contn'd) Compound x Y R 3 R ' R Z B
No.
1 -1044 H C1 H CF3 H NHCOO ' C, H 7 1 -1045 H C1 H CF3 H NHCOO " C 4 H 9 1 -1046 H C1 H CF3 H NHCOO " C s H
1 -1048 H C1 H CF3 H NHCH2 COOC2 H s 1- 1049 H C1 H CF3 H NHCH2 COO " C y H
1- 1050 H C1 H CF3 H NHCH2 COO " C 4 H
1 -1051 H C1 H CF3 H NHCH 2 C00-" C s H
1 -1052 H C1 H CF3 H NHCH2 COO C 3 H, 1 -1053 H C1 H CF3 H NHCH2 COO ' C s H 9 1 -1054 H C1 H CF3 H NHCH2 COO C C 6 H õ
1- 1055 F C1 H CF3 H NH CH2 COO c C 6 H õ
1 -1056 F C1 H CF3 H NHCH(CH 3 )COOCH 3 1 -1057 F Ci H CF3 H NHCH(CH3 )COOC 2 H.5 1 -1058 F C1 H CF3 H NHCH(CH3 )C00 "* C3 H, 1 -1059 F C1 H CF3 H NHCH(CH3 )COO " C. H fl 1 -1060 F C1 H CF3 H NHCH(CH3 )COO " C. H
1- 1061 F C1 H CF3 H NHCH(CH3 )COO ' C3 H, 1 -1062 F C1 H CF3 H NHCH(CH3 )C00 C Cs H 9 1 -1063 F C1 H CF3 H NHCH(CH3 )C00 ' C6 H
1 -1065 H C1 H CF3 H OC 2 H s 1 -1066 H C1 H CF3 H 0' C, H, TABLE 1 (contn'd) Compound x Y R 3 R' R Z B
No.
1- 1067 H C1 H CF3 H 0" C 3 H 7 1- 1068 H C1 H CF3 H OCH2 CH2 Cl 1 -1069 H Cl H CF3 H OCF2 CF2 H
1 -1070 H Cl H CF3 H 0' C s H 9 1 -1071 H ci H CF3 H 0' C 6 H õ
1-1072 H C1 H CF3 H OCH2 CH=CH2 1 -1073 H C1 H CF3 H OCH2 CC1 =CH2 1- 1074 H Cl H CF3 H OCH2 CC1 = CHC1 1 -1075 H ci H CF3 H OCH(CH 3)CH =CH2 1 -1076 H ci H CF3 H OCH2 C CH
1 -1077 H ci H CF3 H OCH(CH 3)C= CH
1 -1078 H ci H CF3 H OCH2 C CBr 1 -1079 H Cl H CF3 H OCH2 C= CCl 1 -1080 H C1 H CF3 H OCH2 C CCH 2 Cl 1- 1082 H Cl H CF3 H OCH2 OCH 3 1- 1083 H Cl H CF3 H OCH2 0Ca H s 1 -1084 H C1 H CF3 H OCH 2 SCH a 1 -1085 H ci H CF3 H OCH2 COOCH a 1- 1086 H C1 H CF3 H OCH2 COOC2 H s 1 -1087 H C1 H CF3 H OCH2 COO " C, H 7 1 -1088 H C1 H CF3 H OCH2 COO " C, H9 1 -1089 H C1 H CF3 H OCH2 COO " C 5 H
TABLE 1 (contn'dl Compound X Y R 3 R' R 2 B
No.
1 -1090 H Cl H CF3 H OCH2 COO ' C 3 H 7 1 -1091 H Ci H CF3 H OCH2 C00 ' C; H
1 -1093 H Ci H CF3 H OCH(CH 3 )COOCH 3 1 -1094 H C1 H CF3 -H OCH(CH 3)COOC 2 H 5 1- 1095 H C1 H CF3 H OCH(CH 3)C00 " C3 H 7 1 -1096 H C1 H CF3 H OCH(CH 3)C00 " C4 H 9 1 -1097 H C1 H CF3 H OCH(CH 3)C00 C5 Hõ
1 -1098 H C1 H CF3 H OCH(CH 3)C00 ' Ca H, 1 -1099 H C1 H CF3 H OCH(CH 3)C00 ' C; H 9 1 -1100 H CI H CF3 H OCH(CH 3)C00 ' C6 Hõ
1 -1101 H C1 H CF3 H OCH2 CON(CH3 ) 2 1 -1102 H C1 H CF3 H OCH2 CON(C 2 H;) 2 1- 1103 H C1 H CF3 H OCH2 CON(CH3') C 2 H5 1 -1104 H Cl H CF3 H OCH(CH 3)CON(CH ,) 2 1 -1105 H C1 H CF3 H OCH(CH3 )CON(C 2 H 5)2 1- 1106 H C1 H CF3 H OCH(CH3 )CON(CH s)Cz H s 1 -1107 H C1 H CF3 H OCH 2 COON(CH 3 ) 2 1 -1108 H C1 H CF3 H OCH 2 COON(C 2 H s)z 1 -1109 H C1 H CF3 H OCH(CH3 )COON(CH3 ) 2 1 -1110 H C1 H CF3 H OCH(CH3 )COON(C 2 H 5) 2 TABLE 1 (contn'd) ~
Compound X Y R 3 R' R 2 B
No.
1 -1112 F C1 H CF3 H OC 2 H s 1 -1113 F C1 H CF3 H 0' C 3 H, 1 -1114 F C1 H CF3 H 0" C 3 H, 1- 1117 F C1 H CF3 H 0' C s H 9 1- 1118 F C1 H CF3 H 0' C 6 H õ
1 -1119 F C1 H CF3 H OCH2 CH =CH2 1 -1120 F C1 H CF3 H OCH2 CCI =CH2 1- 1121 F C1 H CF3 H OCH2 CCI = CHC1 1 -1122 F Ci H CF3 H OCH(CH 3 )CH =CH2 1 -1124 F C1 H CF3 H OCH(CH s)C CH
1 -1125 F C1 H CF3 H OCH2 C CBr 1 -1126 F Cl H CF3 H OCH2 C= CC1 1 -1127 F C1 H CF3 H OCH2 C CCH 2 Cl 1 -1130 F C1 H CF3 H OCH2 0C2 H s 1 -1133 F C1 H CF3 H OCH2 COOC2 H a 1 - 1134 F C1 H CF3 H OCHz C00 " C 3 H, TABLE 1 (contn'd) Compound x y R 3 R' R2 B
No.
1 -1135 F C1 H CF3 H OCH2 C00 " C 4 H s 1 -1136 F Cl H CF3 H OCH2 C00 " C 5 H,1 1 -1137 F C1 H CF3 H OCH2 COO C 3 H z 1 -1138 F C1 H CF3 H OCHz COO ' C S H a 1 -1139 F C1 H CF3 H OCH2 COO ' C 6 H õ
1 -1140 F C1 H CF3 H OCH(CH 3)COOCH a 1 -1141 F C1 H CF3 H OCH(CH 3)COOC 2 H s 1 -1142 F CI H CF3 H OCH(CH 3)C00 " C3 H 7 1- 1143 F C1 H CF3 H OCH(CH 3)C00 " C4 H 9 1- 1144 F C1 H CF3 H OCH(CH 3 )C00 " C5 Hõ.
1- 1145 F C1 H CF3 H OCH(CH 3 )C00 ' C3 H, 1 -1146 F Cl H CF3 H OCH(CH 3 )C00 ' CS H o 1- 1147 F C1 H CF3 H OCH(CH 3)C00 ' C6 H,-1 -1148 F C1 H CF3 H OCH2 CON(CH3 ) 2 1 -1149 F C1 H CF3 H OCH2 CON(C 2 H s) 2 1 -1150 F C1 H CF3 H OCH2 CON(CH3 ) C 2 H s 1- 1151 F C1 H CF3 H OCH(CH 3)CON(CH 3 ) 2 1 -1152 F C1 H CF3 H OCH(CH3 )CON(C 2 H 6)2 1 -1153 F C1 H CF3 H OCH(CH3 )CON(CH 3)C2 H;
1 -1154 F C1 H CF3 H OCH 2 COON(CH ,) 2 1 -1155 F C1 H CF3 H OCH 2 COON(C 2 H s)Z
1 -1156 F C1 H CF3 H OCH(CH3 )COON(CH3 ) Q
1- 1157 F C1 H CF3 H OCH(CH3 )COON(C 2 H 5 ) 2 TABLE 1 (contn'd) Compound X Y R 3 R' R Z B
No.
1 -1160 H Br H CF3 H SH
1 -1163 F Br H CF3 H SH
1 -1165 H C1 H CF3 H SC2 H s 1 -1166 H CI H CF3 H S' C, H T
1 -1167 H C1 H CF3 H SCHZ CH2 Cl 1 -1168 H C1 H CF3 H Sc C s H fl 1- 1169 H C1 H CF3 H SC C 6 H õ
1 -1170 H Ci H CF3 H SCH2 CH=CH2 1 -1171 H C1 H CF3 H SCH2 CCI =CH2 1 -1172 H C1 H CF3 H SCH 2 CCI=CHC1 1 -1173 H C1 H CF3 H SCH(CH 9)CH = CH2 1 -1175 H C1 H CF3 H SCH(CH 3)C=CH
1 -1176 H C1 H CF3 H SCH2 COOCH , 1 -1177 H Cl H CF3 H SCH2 COOC2 H 5 :
1 -1178 H C1 H CF3 H SCH2 C00 " C 3 H, 1 -1179 H C1 H CF3 H SCH2 C00 " C< H 9 ~
1- 1180 H C1 H CF3 H SCH2 COO " C 5 H 11 TABLE 1 (contn'd) Compound x y R a R' R 2 B
No.
1 -1181 H Ci H CF3 H SCH2 COO ' C a H T
1- 1182 H C1 H CF3 H SCH2 COO ' C s H 9 1 -1183 H C1 H CF3 H SCHZ COO ' C 6 H õ
1- 1184 H C1 H CF3 H SCH(CH a)COOCH a 1 -1185 H C1 H CF3 H SCH(CH 3)COOC 2 H;
1- 1186 H C1 H CF3 H SCH(CH 3 )C00 Ca H T
1 -1187 H C1 H CF3 H SCH(CH 3 )C00 " C4 H 9 1- 1188 H C1 H CF3 H SCH(CH 3)C00 " CS Hõ
1 -1189 H C1 H CF3 H SCH(CH 3 )C00 ' C 3 H7 1- 1190 H C1 H CF3 H SCH(CH 3 )C00 ' C 5 H 9 1- 1191 H C1 H CF3 H SCH(CH 3 )C00 ' C6 Hõ
1 -1192 H C1 H CF3 H SCH2 CON(CH3 ) 2 1- 1193 H C1 H CF3 H SCHZ CON(C 2 H 5) 2 1 -1194 H C 1 H CF3 H SCHZCON ( tetramethylene ) 1 -1195 H C 1 H CF3 H SCH2CON ( pentamethylene ) 1 -1196 H Ci H CF3 H SCH2CON
(ethyleneoxyethylene) 1 -1197 H C1 H CF3 H SCH(CH3 )CON(CH a) 2 1- 1198 H C1 H CF3 H SCH(CH3 )CON(C2 H s) 2 1 -1199 H Ci H CF3 H SCH(CH3)CON
(tetramethylene) 1 -1200 H C i H CF3 H SCH ( CH3 ) CON
(pentamethylene) TABLE 1 (contn'd) Compound x Y R 3 R' R z B
No.
1 -1202 F ci H CF3 H SC2 H s 1 -1203 F C1 H CF3 H S' C 3 H T
1 -1204 F C1 H CF3 H SCH2 CH2 Cl 1 -1205 F C1 H CF3 H S' C s H
1 -1206 F C1 H CF3 H S' C 6 H õ
1 -1207 F C1 H CF3 H SCH2 CH=CH2 1 -1208 F C1 H CF3 H SCH2 CC1 = CH2 1 -1209 F ci H CF3 H SCH2 CCI =CHCI
1 -1210 F C1 H CF3 H SCH(CH 3 )CH =CH2 1 -1211 F C1 H CF3 H SCH2 C= CH
1 -1212 F CI H CF3 H SCH(CH 3)C=CH
1 -1213 F ci H CF3 H SCH2 COOCH 3 1 -1214 F C1 H CF3 H SCH2 COOCa H 5 1- 1216 F ci H CF3 H SCH2 C00 " C, H 9 1- 1217 F C1 H CF3 H SCH2 C00 C s H,i 1 -1219 F C1 H CF3 H SCH2 COO C s H o 1 -1220 F C1 H CF3 H SCH2 COO ' C 6 H11 =
1- 1221 F C1 H CF3 H SCH(CH a)COOCH a 1 -1222 F C1 H CF3 H SCH(CH 3)COOC 2 H 6 TABLE 1 fcontn'dl Compound X y R3 R' R Z B
No.
1- 1223 F C1 H CF3 H SCH(CH 3 )C00 " C. H, 1 -1224 F CI H CF3 H SCH(CH 3)C00 " C4 H 9 1 -1225 F C1 H CF3 H SCH(CH 3)C00 C5 Hõ
1 -1226 F C1 H CF3 H SCH(CH 3)C00 ' C3 H 7 1 -1227 F Cl H CF3 H SCH(CH 3)C00 c C5 H
1- 1228 F Cl H CF3 H SCH(CH 3)C00 ' C6 H
1 -1229 F C1 H CF3 H SCH2 CON(CH3 ) 2 1- 1230 F C1 H CF3 H SCH2 CON(C 2-H s) 2 1 -1231 F C 1 H CF3 H SCHZCON ( tetramethylene ) 1 -1232 F C 1 H CF3 H SCH2CON ( pentamethylene ) (ethyleneoxyethylene) 1 -1234 F C1 H CF3 H SCH(CH3 )CON(CH a) 2 1 -1235 F Ci H CF3 H SCH(CH3 )CON(C2 H 5) 2 1 -1236 F C i H CF3 H SCH ( CH3 ) CON
(tetramethylene) 1 -1237 F C l H CF3 H SCH ( CH3 ) CON
(pentamethylene) 1 -1238 H F H CF3 H SOZ Cl 1 -1239 H Cl H CF3 H SO2 Cl 1 -1240 H Br H CF3 H SOZ C1 1 -1241 F F H CF3 H SOz Cl 1 -1242 F CI H CF3 H SOZ Cl TABLE 1 (contn'd) Compound X Y R 3 R' R 2 B
No.
1 -1243 F Br H CF3 H SO2 Cl 1- 1246 H C1 H CF3 H SOz 0' C 3 H T
1 -1247 H Ci H CF3 H SO2 OCH 2 CH=CH2 1 -1248 F C1 H CF3 H SOz OCH , 1 -1249 F C1 H CF3 H SOz 0C2 H s 1-1250 F C1 H CF3 H S02 0' C 3 H 7 1 -1251 F C1 H CF3 H SO2 OCH 2 CH=CH2 1 -1252 H C1 H CF3 H SOZ N(CH3 ) 2 1- 1253 H C1 H CF3 H S02 N (C2 H s) 2 1- 1254 F Cl H CF3 H SO2 N (CH ,) 2 1 -1255 F Ci H CF3 H SOz N (C2 H 5)2 1 -1256 H Cl H CF3 H COOH
1- 1257 H C1 H CF3 H COOCH a 1 -1258 H C1 H CF3 H CoOC 2 H 5 1- 1259 H C1 H CF3 H Coo C, H, 1 -1260 H Cl H CF3 H Coo" C, H
1 -1261 H C1 H CF3 H CoO C.5 H
1 -1262 H C1 H CF3 H C00' C a H 7 1 -1263 H Cl H CF3 H COOCH2 CH2 C1 1 -1264 H Ci H CF3 H COOCHZ CH2 Br 1- 1265 H C1 H CF3 H- CON(CH 3 ) 2 TABLE 1 (contn'd) compound X y R3 R' R Z B
No.
1 -1267 H C1 H CF3 H CON(C2 H 5) 2 1 -1270 H C1 H CF3 H COC2 H s 1 -1271 H C1 H CF3 H COCH2 Cl 1 -1273 H C1 H CF3 H CH = CHCOOCH 3 1 -1274 H C 1 H CF3 H CH = CHCOOC 2 H s 1 -1276 H CI H CFa H CH2 CH2 COOC2 H 5 1 -1278 F C1 H CF3 H COOCH , 1 -1279 F C1 H CF3 H COOC2 H s 1 -1280 F C1 H CF3 H C00" C, H 7 1 -1281 F C1 H CF3 H C00 C, H s 1- 1282 F C1 H CF3 H C00" C s H õ
1 -1283 F C1 H CF3 H C00' C s H 7 1 -1284 F C1 H CF3 H COOCHz CH2 Cl 1 -1285 F C1 H CF3 H COOCHZ CH2 Br 1 -1286 F CI H CF3 H CON(CH 3 ) 2 1 -1288 F Cl H CF3 H CON(C2 H 5 ) 2 TABLE 1 (contn'd) Compound x Y R3 R' R 2 B
No.
1 -1289 F Ci H CF3 H CONHC2 H;
1 -1292 F C1 H CF3 H COCH2 Cl 1 -1294 F C1 H CF3 H CH = CHCOOCH
1 -1295 F C1 H CF3 H CH= CHCOOC2 H s 1 -1296 F C1 H CF3 H CH2 CH2 C60CH , 1 -1297 F C1 H CF3 H CH2 CH2 COOC2 H;
1 -1298 H F CH3 CF3 H NOz 1- 1300 H Br CH3 CF3 H NOz 1- 1302 F C1 CH3 CF3 H NOz 1 -1303 F Br CH3 CF3 H N02 1- 1306 H Br CH3 CF3 H NH2 1 -1308 F C1 CH3 CF3 H NH2 1 -1309 H C1 CH3 CF3 H NHCH(CH3 )COOCH 3 1 -1310 H C1 CH3 CF3 H NHCH(CH3 )COOC 2 H 5 1- 1311 H C1 CH3 CF3 H NHCH(CH3 )COO " C3 H, TABLE 1 (contn'd) Compound X Y R3 R' R Z B
= No.
1- 1312 H C1 CH3 CF3 H NHCH(CH3 )COO C, H 9 1- 1313 H C1 CHs CF3 H NHCH(CH3 )COO " C5 Hõ
1- 1314 H C1 CH3 CF3 H NHCH(CH3 )COO C3 H 7 1- 1315 H C1 CH3 CF3 H NHCH(CH3 )COO ' Cs H 9 1- 1316 H Cl CH3 CF3 H NHCH(CH3 )COO ' C6 Hõ
1 -1318 F C1 CH3 CF3 H NHC 2 H s 1 -1319 F C1 CH3 CF3 H NHCH2 CH=Cff2 1 -1321 F C1 CH3 CF3 H NHCH(CH 3)C = CH
1 -1323 F C1 CH3 CF3 H NHSOa C 2 H s 1 -1324 F CI CH3 CF3 H NHSOz CH2 C1 1 -1326 F C1 CH3 CF3 H N(CH3 )SO 2 CH3 1 -1327 F C1 CH3 CF3 H N(CH 2 C = CH)SO 2 CH3 1 -1329 F C1 CH3 CF3 H NHCOOC2 H s 1 -1331 F C1 CH3 CF3 H NHCOO ' C 3 H 7 1 -1332 F C1 CH3 CF3 H NH COO C 4 H e 1 -1333 F C1 CH3 CF3 H NHCOO C 5 H õ
TABLE 1 (contn'd) Compound x Y R 3 R' R Z B
No.
1 -1334 F C1 CH3 CF3 H NHCH2 COOCH , 1 -1335 F C1 CH3 CF3 H NHCH2 COOC2 H s 1 -1336 F C1 CH3 CF3 H NHCH2 COO C 3 H, 1 -1337 F C1 CH3 CF3 H NHCH2 COO " C, H
1= 1338 F C1 CH3 CF3 H NHCH2 COO C s H1- 1339 F C1 CH3 CFa H NHCH2 COO ' C a 1- 1340 F C1 CH3 CF3 H NHCH2 COO ' C; H
1 -1341 F Br CH3 CF3 H NH2 1 -1344 H Br CH3 CF3 H OH
1 -1347 F Br CH3 CF3 H OH
1- 1349 H C1 CH3 CF3 H NHC 2 H s 1 -1350 H C1 CH3 CF3 H NHCH2 CH = CHz 1 -1351 H C1 CH3 CF3 H NHCH 2 C= CH
1 -1352 H C1 CH3 CF3 H NHCH(CH ,)C = CH
1 -1353 H C1 CH3 CF3 H NHSOZ CH3 =
1- 1354 H C1 CH3 CF3 H NHSOZ C 2 H s 1- 1355 H C1 CH3 CF3 H NHSOz CH2 Cl 1- 1356 H Ci CH3 CF3 H NHSOZ CF3 TABLE 1 (contn'd) compound X Y R 3 R' R 2 B
No.
1 -1357 H C1 CHa CF3 H N(CH3 )SO 2 CHa 1 -1358 H C1 CH3 CF3 H N(CH2 C= CH)SO 2 CHa 1 -1360 H C1 CH3 CF3 H NHCOOC2 H s 1 -1361 H C1 CH3 CF3 H NHCOO " C 3 H, 1 -1362 H C1 CH3 CF3 H NHCOO ' C 3 H, 1- 1363 H Ci CH3 CF3 H NHCOO C, H 9 1 -1364 H C1 CH3 CF3 H NHCOO " C 5 H,t 1 -1365 H C1 CH3 CF3 H NHCH2 COOCH , 1 -1366 H C1 CH3 CF3 H NHCH2 COOC2 H;
1 -1367 H C1 CH3 CF3 H NHCH2 C00 " C, H, 1 -1368 H C1 CH3 CF3 H NHCH2 C00 " C, H 9 1 -1369 H C1 CH3 CF3 H NHCH2 C00 " C; HI1- 1370 H C1 CH3 CF3 H NHCHz COO ' C 3 H T
1 -1371 H C1 CH3 CF3 H NHCH2 COO ' C s H o 1- 1372 H C1 CH3 CF3 H NHCH2 COO ' C 6 H õ
1- 1373 F Cl CH3 CF3 H NH CHz COO ' C 6 H õ
1 -1374 F C1 CH3 CF3 H NHCH(CH 3 )COOCH , 1 -1375 F C1 CH3 CF3 H NHCH(CH3 )COOC 2 H s 1 -1376 F C1 CHa CF3 H NHCH(CH3 )COO " C3 H 7 1 -1377 F C1 CH3 CF3 H NHCH(CH3 )COO " C, H 9 = 1- 1378 F CI CH3 CF3 H NHCH(CH3 )COO " CS H,i 1- 1379 F Cl CH3 CF3 H NHCH(CH3 )COO ' C3 H, TABLE 1 (contn'd) Compound X y R 3 R' R 2 B =
No.
1 -1380 F C1 CH3 CF3 H NHCH(CH3 )C00 C CS H 9 1- 1381 F C1 CH3 CF3 H NHCH(CH3 )C00 ' C6 Hõ
1 -1383 H C1 CH3 CF3 H OC 2 H s 1- 1384 H C1 CH3 CF3 H 0' C s H 7 1 -1385 H C1 CH3 CF3 H 0" C 3 H T
1 -1386 H C1 CH3 CF3 H OCH2 CH2 Cl 1- 1388 H C1 CH3 CF3 H 0' C s H s 1 -1389 H C1 CH3 CF3 H 0' C 6 H õ
1 -1390 H Ci CH3 CF3 H OCH2 CH = CHZ
1 -1391 H C1 CHa CF3 H OCH2 CC1 =CH2 1 -1392 H C1 CH3 CF3 H OCH2 CC1 = CHC1 1 -1393 H C1 CH3 CF3 H OCH(CH 3)CH = CH2 1 -1395 H Ci CH3 CF3 H OCH(CH 3)C=CH
1 -1396 H C1 CH3 CF3 H OCH2 C CBr 1 -1398 H C1 CH3 CF3 H OCH2 C= CCH 2 Cl 1- 1399 H C1 CH3 CF3 H OCH2 CN =
1 -1402 H Ci CH3 CF3 H OCHZ SCH 3 TABLE I (contn'd) Compound x Y R3 R' R 2 B
No.
1- 1404 H C1 CH3 CF3 H OCH2 COOC2 H s 1 -1405 H C1 CH3 CF3 H OCH2 C00 " C 3 H, 1 -1406 H C1 CH3 CF3 H OCHZ C00 " C, H 9 1 -1407 H C1 CH3 CF3 H OCHZ C00 " C s H õ
1- 1408 H C1 CH3 CF3 H OCH2 COO ' C 3 H1- 1409 H C1 CH3 CF3 H OCH2 COO ' C s H
1 -1410 H C1 CH3 CF3 H OCH2 COO ' C 6 H õ
1 -1411 H C1 CH3 CF3 H OCH(CH s)COOCH 3 1 -1412 H C1 CH3 CF3 H OCH(CH 3)COOC 2 H s 1 -1413 H C1 CH3 CF3 H OCH(CH 3)C00 " C. H z 1 -1414 H CI CH3 CF3 H OCH(CH 3)C00 " C4 H fl 1- 1415 H C1 CH3 CF3 H OCH(CH 3)C00 " Cs Hõ
1- 1416 H C1 CH3 CF3 H OCH(CH 3)C00 C3 H 7 1- 1417 H C1 CH3 CF3 H OCH(CH 3)C00 C5 H 9 1 -1418 H Ci CH3 CF3 H OCH(CH 3)C00 ' C6 Hõ
1- 1419 H C1 CH3 CF3 H OCH2 CON(CH3 ) 2 1- 1420 H C1 CH3 CF3 H OCH2 CON(C 2 H s) 2 1- 1421 H Ci CH3 CF3 H OCHz CON(CH3 ) C 2 H s 1 -1422 H C1 CH3 CF3 H 0CH(CH s)CON(CH 3) 2 1 -1423 H C1 CH3 CF3 H OCH(CH3 )CON(C 2 H s )2 1 -1424 H C1 CH3 CF3 H OCH(CH3 )CON(CH 3)C2 H s 1 -1425 H C1 CH3 CF3 H OCH 2 COON(CH 3) 2 TABLE 1 (contn'd) Compound X Y R 3 R' R 2 B
No.
1 -1426 H C1 CH3 CF3 H OCH 2 COON(C 2 H 5)2 1 -1427 H C1 CH3 CF3 H OCH(CH3 )COON(CH3 ) 2 1 -1428 H C1 CH3 CF3 H OCH(CH3 )COON(C 2 H;) Z
1 -1430 F C1 CH3 CF3 H OC 2 H a 1- 1431 F C1 CH3 CF3 H 0' C a H 7 1- 1432 F C1 CH3 CF3 H 0 C, H, 1- 1433 F C1 CH3 CF3 H OCH2 CH2 Cl 1- 1435 F C1 CH3 CF3 H 0' C 5 H s 1- 1436 F Cl CH3 CF3 H 0' C 6 H.,, 1- 1437 F Cl CH3 CF3 H OCH2 CH =CH2 1 -1438 F C1 CH3 CF3 H OCH2 CC1 =CH2 1 -1439 F Ci CH3 CF3 H OCH2 CCl =CHCI
1 -1440 F Cl CH3 CF3 H OCH(CH 3)CH =CH2 1- 1441 F C1 CH3 CF3 H OCH2 C= CH
1 -1442 F Cl CH3 CF3 H OCH(CH 3)C=CH
1- 1443 F Cl CH3 CF3 H OCH2 C CBr 1 -1444 F C1 CH3 CF3 H OCH2 C= CC1 1 -1445 F C1 CH3 CF3 H OCH2 C= CCH 2 Cl 1 -1446 F Cl CH3 CF3 H OCH2 CN
TABLE 1 (contn'd) Compound X Y R 3 R' R2 B
No.
1 -1448 F C1 CH3 CF3 H OCH2 0C2 H s 1 -1451 F C1 CH3 CF3 H OCHz COOC2 H s 1 -1452 F C1 CH3 CF3 H OCHZ C00 C 3 H, 1 -1453 F C1 CH3 CF3 H OCH2 C00 C, H 9 1- 1454 F C1 CH3 CF3 H OCH2 C00 C 5 H õ
1 -1455 F C1 CH3 CF3 H OCH2 COO ' C 3 H, 1- 1456 F C1 CH3 CF3 H OCH2 COO ' C 5 H 9 1- 1457 F C1 CH3 CF3 H OCHz COO ' C 6 H õ
1 -1458 F C1 CH3 CF3 H OCH(CH 3)COOCH 3 1 -1459 F C1 CH3 CF3 H OCH(CH 3)COOC 2 H 5 1 -1460 F C1 CH3 CF3 H OCH(CH 3)C00 " C3 H T
1 -1461 F C1 CH3 - CF3 H' OCH(CH 3)C00 " C, H s 1- 1462 F C1 CH3 CF3 H OCH(CH 3)C00 C5 Hõ
1- 1463 F C1 CH3 CF3 H OCH(CH 3)C00 ' C3 H, 1 -1464 F C1 CH3 CF3 H OCH(CH 3)C00 ' CS H 9 1- 1465 F C1 CH3 CF3 H OCH(CH 3)C00 C6 Hõ
1 -1466 F C1 CH3 CF3 H OCH2 CON(CH3 ) 2 1- 1467 F C1 CH3 CF3 H OCH2 CON(C 2 H s) 2 1- 1468 F C1 CH3 CF3 H OCH2 CON(CH3 ) C 2 H 5 1 -1469 F C1 CH3 CF3 H OCH(CH 3)CON(CH 3) 2 1 -1470 F C1 CH3 CF3 H OCH(CH3 )CON(C 2 H;)2 TABLE 1 (contn'd) Compound X Y R 3 R' R Z B
No.
1 -1471 F ci CH3 CF3 H OCH(CH3 )CON(CH 3 )C2 H s 1 -1472 F C1 CH3 CF3 H OCH 2 COON(CH 3) 2 1 -1473 F C1 CH3 CF3 H OCH 2 COON(C 2 H;)2 1 -1474 F Cl CH3 CF3 H OCH(CH3 )COON(CH3 ) 2 1 -1475 F Cl CH3 CF3 H OCH(CH3 )COON(C 2 H 5) 2 1 -1477 H Cl CH3 CF3 H SH
1- 1478 H Br CHa CF3 H SH
1 -1481 F Br CH3 CF3 H SH
1 -1482 H ci CH3 CF3 H SCH 3 1 -1483 H C1 CH3 CF3 H SC2 H s 1 -1484 H C1 CHa CF3 H S' C 3 H7 1 -1485 H ci CH3 CF3 H SCH2 CH2 Cl 1 -1486 H C1 CH3 CF3 H Sc C s H s 1- 1487 H C1 CHs CF3 H S' C 6 H õ
1 -1488 H ci CHa CF3 H SCH2 CH = CH2 1 -1489 H Cl CH3 CF3 H SCH2 CC1 = CHZ
1 -1490 H ci CH3 CF3 H SCH2 CCl = CHC1 1 -1491 H C1 CH3 CF3 H SCH(CH 3 )CH = CH2 1 -1492 H C1 CH3 CF3 H SCH2 C= CH
1 -1493 H C1 CH3 CF3 H SCH(CH 3 )C=CH
TABLE 1 (contn'dl ~
; Compound x Y R 3 R' R 2 B
No.
1 -1495 H C1 CH3 CF3 H SCH2 COOC2 H;
1 -1496 H C1 CH3 CF3 H SCH2 C00 " C 3 H 7 1- 1497 H C1 CH3 CF3 H SCHZ C00 " C, H
1 -1498 H C1 CH3 CF3 H SCH2 C00 " C 5 H
1 -1499 H CI CH3 CF, H SCH2 COO ' C 3 H
1 -1500 H C1 CH3 CF3 H SCH2 COO ' C 5 H
1- 1501 H C1 CH3 CF3 H SCH2 C00 ' C 6 H
1 -1502 H C1 CH3 CF3 H SCH(CH 3 )COOCH 3 1- 1503 H C1 CH3 CF3 H SCH(CH 3 )COOC 2 H 5 1 -1504 H C1 CH3 CF3 H SCH(CH 3 )C00 " C3 H
1 -1505 H C1 CH3 CF3 H SCH(CH 3)C00 " C, H
1 -1506 H C1 CH3 CF3 H SCH(CH 3)C00 " CS H
1- 1507 H C1 CH3 CF3 H SCH(CH 3)C00 ' C3 H, 1 -1508 H C1 CH3 CF3 H SCH(CH 3)C00 ' CS H 9 1 -1509 H C1 CH3 CF3 H SCH(CH 3 )C00 ' Cs Hõ
1 -1510 H Ci CH3 CF3 H SCH2 CON(CH3 ) 2 1- 1511 H C1 CH3 CF3 H SCH2 CON(C 2 H 5) 2 1 -1512 H C 1 CH 3 CF3 H SCH2CON ( tetramethylene ) 1 -1513 H C I CH 3 CF3 H SCHZCON ( pentamethylene ) (ethyleneoxyethylene) 1 -1515 H C1 CH3 CF3 H SCH(CH3 )CON(CH 3) 2 TABLE 1 (contn'd) Compound x Y R 3 R' R 2 B
No.
1- 1516 H C1 CH3 CF3 H SCH(CH3 )CON(C2 H s) 2 1 -1517 H C1 CH3 CF3 H SCH(CH3)CON
(tetramethylene) 1 -1518 H C1 CH3 CF3 H SCH(CH3)CON
(pentamethylene) 1 -1520 F C1 CH3 CF3 H SC2 H s 1 -1521 F C1 CH3 CF3 H S' C 3 H 7 1 -1522 F C1 CH3 CF3 H SCH2 CH2 Cl 1- 1523 F C1 CH3 CF3 H Sc C s H 9 1- 1524 F Ci CH3 CF3 H S' C 6 H õ
1 -1525 F C1 CH3 CF3 H SCH2 CH = CH2 1 -1526 F C1 CH3 CF3 H SCH2 CCI =CH2 1 -1527 F Ci CH3 CF3 H SCH2 CCI =CHCI
1 -1528 F C1 CH3 CF3 H SCH(CH 3)CH = CH2 1 -1530 F C1 CH3 CF3 H SCH(CH 3)C=CH
1 -1532 F C1 CH3 CF3 H SCH2 COOC2 H s 1 -1533 F C1 CH3 CF3 H SCH2 COO " C a H 7 1 -1534 F C1 CH3 CF3 H SCH2 COO " C, H o 1- 1535 F C1 CH3 CF3 H SCH2 COO " C 6 H,t 1 -1536 F Cl CHa CF3 H SCH2 COO ' C 3 H 7 TABLE 1 (contn'd) Compound x y R 3 R' R z B
No.
1 -1537 F C1 CH3 CF3 H SCHZ COO C C; H
1 -1538 F C1 CH3 CF3 H SCH2 COO ' C 6 H
1 -1539 F C1 CH3 CF3 H SCH(CH 3)COOCH 3 1- 1540 F C1 CH3 CF3 H SCH(CH 3)COOC 2 H 5 1-1541 F C1 CH3 CF3 H SCH(CH 3)C00 " C3 H;
1 -1542 F C1 CH3 CF3 H SCH(CH 3)C00 " C4 H y 1- 1543 F C1 CH3 CF3 H SCH(CH 3)C00 " CS Hõ
1 -1544 F C1 CH3 CF3 H SCH(CH 3)C00 ' C3 H, 1 -1545 F C1 CH3 CF3 H SCH(CH 3)C00 ' C5 H s 1- 1546 F C1 CH3 CF3 H SCH(CH 3)C00 ' C6 Hõ
1 -1547 F C1 CH3 CF3 H SCH2 CON(CH3 ) 2 1 -1548 F C1 CH3 CF3 H SCH2 CON(C 2 H;)2 1 -1549 F C 1 CH3 CF3 H SCH2CON ( tetramethylene ) 1 -1550 F C 1 CH 3 CF 3 H SCH2CON ( pentamethylene ) (ethyleneoxyethylene) 1 -1552 F C1 CH3 CF3 H SCH(CH3 )CON(CH a) 2 1- 1553 F C1 CH3 CF3 H SCH(CH3 )CON(C2 H 5) 2 1 -1554 F C 1 CH3 CF3 H SCH ( CH3 ) CON
(tetramethylene) 1 -1555 F C 1 CH3 CF3 H SCH ( CH, ) CON
(pentamethylene) TABLE 1 (contn'd) Compound X Y R 3 R' R Z B
No.
1 -1557 H Ci CH3 CF3 H SOZ Cl 1 -1558 H Br CH3 CF3 H S02 Cl 1 -1559 F F CH3 CF3 H SO2 Cl 1 -1560 F Cl CH3 CF3 H SO2 C1 1 -1561 F Br CH3 CF3 H SO2 Cl 1 -1562 H C1 CH3 CF3 H SOz OCH 3 1 -1563 H C1 CH3 CF3 H SOz 0C2 H s 1- 1564 H C1 CH3 CF3 H SO2 0' C 3 H, 1 -1565 H C1 CH3 CF3 H SO2 OCH 2 CH = CH2 1 -1566 F C1 CH3 CF3 H SOz OCH 3 1 -1567 F Cl CH3 CF3 H S02 0C2 H s 1- 1568 F C1 CH3 CF3 H SOZ 0' C, H, 1 -1569 F C1 CH3 CF3 H S0Z OCH 2 CH = CH2 1 -1570 H Ci CH3 CF3 H SOZ N(CH3 ) 2 1- 1571 H C1 CH3 CF3 H SO2 N (C2 H 5) 2 1- 1572 F C1 CH3 CF3 -H SOz N (CH 3) 2 1- 1573 F C1 CH3 CF3 H S0Z N (C2 H 5) 2 1 -1575 H C1 CH3 CF3 H COOCH 3 =
1 -1576 H C1 CHa CF3 H COOC 2 H 5 1 -1577 H C1 CH3 CF3 H C00" C 3 H 7 1- 1578 H C1 CH3 CF3 H C00" C, H 9 TABLE 1 (contn'd) .
Compound x Y R3 R' R2 B
No.
1- 1579 H C1 CH3 CF3 H C00" C s H
1 -1580 H C1 CH3 CF3 H C00' C a H;
1 -1581 H C1 CH3 CF3 H COOCH2 CH2 Cl 1 -1582 H C1 CH3 CF3 H COOCH2 CHz Br 1- 1583 H Cl CH3 CF3 H CON(CH 3) 2 1 -1584 H Ci CH3 CF3 H CONHCH 3 1 -1585 H C1 CH3 CF3 H CON(C2 H s) 2 1- 1586 H C1 CH3 CF3 H CONHC2 H s 1 -1588 H C1 CH3 CF3 H COC2 H s 1 -1589 H C1 CH3 CF3 H COCHz Cl 1 -1591 H C1 CH3 CF3 H CH = CHCOOCH 3 1 -1592 H C1 CH3 CF3 H CH=CHCOOC2 H s 1 -1593 H C1 CH3 CF3 H CH2 CHz COOCH 3 1 -1594 H Cl CH3 CF3 H CH2 CHZ COOC2 H s 1 -1597 F C1 CH3 CF3 H COOC2 H s 1- 1598 F C1 CH3 CF3 H C00" C 3 H 1 1 -1599 F C1 CH3 CF3 H C00" C 4 H 9 = 1 -1600 F Cl CH3 CF3 H C00" C s H,,.
1 -1601 F C1 CH3 CF3 H COO' C, H, TABLE 1 (contn'd) Compound x Y R 3 R' R Z B
No.
1 -1602 F C1 CH3 CF3 H COOCH2 CH2 Cl 1 -1603 F Cl CH3 CF3 H COOCH2 CH2 Br 1 -1604 F Cl CH3 CF3 H CON(CH ,) 2 1 -1606 F C1 CH3 CF3 H CON(C2 H s) 2 1 -1607 F C1 CH3 CF3 H CONHC2 H s 1 -1608 F CI CH3 CF3 H COCH , 1 -1610 F CI CH3 CF3 H COCH2 Cl 1 -1612 F C1 CH3 CF3 H CH = CHCOOCH 3 1-1613 F C1 CH3 CF3 H CH=CHCOOC2 H s 1 -1614 F Ci CH3 CF3 H CH2 CH2 COOCH a 1 -1615 F C1 CH3 CF3 H CH2 CH2 COOC2 H s 1 -1618 H Br CH3 CF3 H H
1 -1620 F Cl CH3 CF3 H H
1 -1621 F Br CH3 CF3 H H
1- 1622 F C1 H CF3 CH3 CH2 CHC1CO2 C 2 H s 1- 1623 F Cl H CF3 H CH2 CHC1CO2 C 2 H b TABLE I (contn'd) compound x Y R 3 R' R Z B
= No.
1 -1628 F C1 CH3 CF3 H OCH2 COz H
1 -1629 F C1 H CF3 H OCH (CH3 ) CO2 H
1 -1630 F C1 H CF3 CH3 OCH(CH3 ) CO2 H
1 -1631 F C1 CH3 CF3 H OCH(CH3 ) COZ H
1 -1634 H C1 CH3 CF3 H OCH2 COz H
1 -1635 H C1 H CF3 H OCH(CH3 ) C02 H
1 -1636 H C1 H CF3 CH3 OCH(CH3 ) CO2 H
1- 1637 H C1 CH3 CF3 H OCH(CH3 ) COz H
1- 1639 F Ci H CF3 CH3 SCH2 CO2 H
1 -1640 F C1 CH3 CF3 H SCH2 COz H
1 -1641 F C1 H CF3 H SCH(CH3 ) CO2 H
1 -1642 F C1 H CF3 CH3 SCH(CH3 ) COz H
1 -1643 F C1 CH3 CF3 H SCH(CH3 ) CO2 H
1 -1644 H C1 H CF3 H SCHZ COz H
1 -1645 H C1 H CF3 CH3 SCH2 COz H
1- 1646 H C1 CH3 CF3 H SCH2 COz H
1 -1647 H C1 H CF3 H SCH(CH3 ) CO2 H
TABLE 1 (contn'd) Compound X Y R3 R' R 2 B
No.
1 -1648 H C1 H CF3 CH3 SCH(CH3 ) CO2 H
1 -1649 H C1 CH3 CF3 H SCH(CH3 ) CO2 H
1 -1650 F C1 H CF3 CH3 OCH (C2 H 5 )C0 2 CH3 1- 1652 C1 C1 H CF3 H OCH2C02C2Hs 1 -1653 C1 C1 H CF3 H OCH2CO2 ' C3H7 1 -1656 C1 C1 H CF3 CH3 OCH2CO2 ' C3H7 1 -1659 C1 C1 CH3 CF3 H OCH2CO2 ' C3H7 1 -1660 C1 C1 H CF3 H OCH2C = CH
1-1661 C1 Cl H CF3 H OCH(CH 3)C =CH
1- 1662 C1 C1 H CF3 H OCH(CH 3)C02C2H5 1 -1663 C1 C1 H CF3 CH3 OCH2C = CH
1 -1664 C1 C1 H CF3 CH3 OCH(CH 3)C = CH
1 -1665 C1 C1 H CF3 CH3 OCH(CH 3)C02CZHs 1 -1667 C1 C1 CH3 CF3 H OCH(CH 3)C CH
1 -1668 CI C1 CH3 CF3 H OCH(CH 3)C02C2H5 1 -1669 F Br H CF3 H OCH2CO2CH3 TABLE 1 (contn'd) Compound. x Y R 3 R' R a B
No.
1 -1670 F Br H CF3 H OCH2COzCaHs 1- 1671 F Br H CF3 H OCH2C02 C3H7 1- 1672 F Br H CFa CH3 OCH2CO2CH3 1 -1673 F Br H CFa CH3 OCH2C02C2Hs 1 -1674 F Br H CF3 CH3 OCH2CO2 C3H7 1 -1675 F Br CH3 CF3 H OCH2CO2CH3 1 -1676 F Br CH3 'CF3 H OCH2CO2CzHs 1 -1677 F Br CH3 CF3 H OCH2CO2 C3H7 1 -1678 F Br H CF3 H OCH Z C= Cff 1- 1679 F Br H CF3 H OCH(CH 3)C = CH
1 -1680 F Br H CF3 H OCH(CH 3)C0aC2Hs 1 -1681 F Br H CF3 CH3 OCH2C = CH
1 -1682 F Br H CF3 CH3 OCH(CH 3)C = CH
1- 1683 F Br H CF3 CH3 OCH(CH 3)C02CZHs 1 -1684 F Br CH3 CF3 H OCH2C CH
1 -1685 F Br CH3 CF3 H OCH(CH 3)C = CH
1- 1686 F Br CH3 CF3 H OCH(CH 3)COzC2Hs WO 97/07104 PC'E'/JP96/02311 TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No. 1-1687 C1 Cl H CF3 H H
1-1688 C1 Cl H CF3 H OH
1-1689 Cl Cl H CF3 H NO2 1-1690 C1 Cl H CF3 H NH2 1-1691 Cl C1 H CF3 H NHSO2CH3 1-1693 C1 Cl H CF3 H NHCH2CO2CH3 1-1695 C1 Cl H CF3 H NHCH2CO21C3H7 1-1696 C1 Cl H CF3 H NHCH(CH3)CO2CH3 1-1697 C1 Cl H CF3 H NHCH(CH3)CO2C2H5 1-1698 C1 C1 H CF3 H NHCH(CH3)C021C3H7 1-1699 Cl Cl H CF3 H COZH
1-1700 Ci Cl H CF3 H CO2CH3 1-1701 C1 Cl H CF3 H C02C2H5 1-1702 CI C1 H CF3 H C02nC3H7 1-1703 C1 C1 H CF3 H C02nC4H9 1-1704 Cl C1 H CF3 H C02nC5H11 1-1705 Cl Cl H CF3 H C021C3H7 1-1706 Cl C1 H CF3 H CO2CH2CH2C1 1-1707 Cl C1 H CF3 H CO2CH2CH2Br 1-1708 Cl Cl H CF3 H CON(CH3)2 1-1709 Cl Cl H CF3 H CONHCH3 1-1710 C1 Cl H CF3 H CON(C2H5)2 1-1711 Cl Cl H CF3 H CONHC2H5 1-1712 Cl C1 H CF3 H COCH3 1-1713 Cl C1 H CF3 H COC2H5 1-1715 Cl Cl H CF3 H CHO
1-1716 Cl Cl H CF3 H CH=CHCO2CH3 1-1717 Cl Ci H CF3 H 01C3H7 1-1719 Cl C1 H CF3 CH3 OH
TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No.
1-1720 C1 Ci H CF3 CH3 NO2 1-1723 Cl C1 H CF3 CH3 NHSO2CH2C1 1-1725 C1 Cl H CF3 CH3 NHCH2CO2C2H5 1-1727 C1 C1 H CF3 CH3 NHCH(CH3)CO2CH3 1-1728 C1 C1 H CF3 CH3 NHCH(CH3)C02CZH5 1-1729 Cl Cl H CF3 CH3 NHCH(CH3)CO21C3H7 1-1733 Cl Cl H CF3 CH3 C02nC3H7 1-1734 Cl Cl H CF3 CH3 C02nC4H9 1-1735 Cl C1 H CF3 CH3 C0211C5H11 1-1736 Cl Cl H CF3 CH3 C02''C3H7 1-1738 Cl C1 H CF3 CH3 CO2CH2CH2Br 1-1739 Cl C1 H CF3 CH3 CON(CH3)2 1-1741 C1 Cl H CF3 CH3 CON(C2H5)2 1-1742 Cl Cl H CF3 CH3 CONHC2H5 1-1743 Ci C1 H CF3 CH3 COCH3 1-1744 Cl Cl H CF3 CH3 COC2H5 1-1745 Cl C1 H CF3 CH3 COCH2C1 1-1747 Cl C1 H CF3 CH3 CH=CHCO2CH3 1-1748 Cl Cl H CF3 CH3 OlC3H7 1-1749 C1 Cl CH3 CF3 H H
1-1750 C1 Cl CH3 CF3 H OH
1-1751 Cl Cl CH3 CF3 H NO2 1-1752 C1 Cl CH3 CF3 H NH2 TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No.
1-1753 Cl C1 CH3 CF3 H NHSO2CH3 1-1754 Cl C1 CH3 CF3 H NHSO2CH2C1 1-1755 Ci Cl CH3 CF3 H NHCH2CO2CH3 1-1756 C1 Cl CH3 CF3 H NHCH2CO2C2H5 1-1757 Cl C1 CH3 CF3 H NHCH2CO21C3H7 1-1758 Cl C1 CH3 CF3 H NHCH(CH3)C02CH3 1-1759 Cl C1 CH3 CF3 H NHCH(CH3)C02C2H5 1-1760 Cl Cl CH3 CF3 H NHCH(CH3)CO21C3H7 1-1761 Ci C1 CH3 CF3 H CO2H
1-1762 Cl Cl CH3 CF3 H CO2CH3 1-1763 Cl Cl CH3 CF3 H C02C2H5 1-1764 Cl Cl CH3 CF3 H C02nC3H7 1-1765 Cl Cl CH3 CF3 H C02nC4Hg 1-1766 C1 C1 CH3 CF3 H C021'C5H11 1-1767 Cl Cl CH3 CF3 H C021C3H7 1-1769 C1 Cl CH3 CF3 H CO2CH2CH2Br 1-1770 C1 Cl CH3 CF3 H CON(CH3)2 1-1771 C1 Cl CH3 CF3 H CONHCH3 1-1772 Cl C1 CH3 CF3 H CON(C2H5)2 1-1773 Cl C1 CH3 CF3 H CONHC2H5 1-1774 Cl C1 CH3 CF3 H COCH3 1-1775 Cl C1 CH3 CF3 H COC2H5 1-1776 C1 Cl CH3 CF3 H COCH2C1 1-1778 C1 C1 CH3 CF3 H CH=CHCO2CH3 1-1779 Cl Cl CH3 CF3 H O''C3H7 1-1780 F Br H CF3 H 0 lC3H7 1-1781 F Br H CF3 H N(SO2CH3)2 1-1782 F Br H CF3 H NHSO2CH3 1-1783 F Br H CF3 CH3 0 1C3H7 TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No.
1-1784 F Br H CF3 CH3 N(SOZCH3)2 1-1785 F Br H CF3 CH3 NHSO2CH3 1-1786 F Br CH3 CF3 H Oi C3H7 1-1787 F Br CH3 CF3 H N(SOZCH3)Z
1-1788 F Br CH3 CF3 H NHSO2CH3 1-1789 F C1 H CF3 CH3 OCH2C(CH3)=CH2 1-1791 F C1 H CF3 CH3 OCH2CO2C$H17 1-1793 F C1 H CF3 CH3 C(CH3)=NOH
1-1794 F C1 H CF3 CH3 C(CH3)=NOCH3 1-1795 F C1 H CF3 CH3 C(CH3)=NOC2H5 1-1796 F C1 H CF3 CH3 C(CH3)=NO''C3H7 1-1797 F C1 H CF3 CH3 C(C2H5)=NOH
1-1798 F C1 H CF3 CH3 C(C2H5)=NOCH3 1-1799 F C1 H CF3 CH3 C(C2H5)=NOC2H5 1-1800 F C1 H CF3 CH3 C(C2H5)=NO1C3H7 1-1801 F C1 H CF3 CH3 C(CH3)=NNH2 1-1802 F C1 H CF3 CH3 C(CH3)=NNHCH3 1-1803 F C1 H CF3 CH3 C(CH3)=NN(CH3)2 1-1804 F C1 H CF3 CH3 C(CH3)=NNHC2H5 1-1805 F C1 H CF3 CH3 C(CH3)=NN(C2H5)2 1-1806 F C1 H CF3 CH3 C(CZHS)=NNH2 1-1807 F C1 H CF3 CH3 C(C2H5)=NNHCH3 1-1808 F C1 H CF3 CH3 C(C2H5)=NN(CH3)2 1-1809 F C1 H CF3 CH3 C(C2H5)=NNHC2H5 1-1810 F C1 H CF3 CH3 C(C2H5)=NN(C2H5)2 1-1811 F C1 H CF3 CH3 C(CH3)(OCH3)2 1-1812 F C1 H CF3 CH3 C(CHg)(OC2H5)2 1-1813 F C1 H CF3 CH3 C(CH3)(Ci C3H7)2 1-1814 F C1 H CF3 CH3 I~
O
TABLE 1 (contn'd) Compound X Y R3 R1 R2 B =
No.
O
1-1815 F C1 H CF3 CH3 iO~
C'O
~ ~o~
1-1817 F Cl H CF3 CH3 1-1818 F Cl H CF3 H OCH2C(CH3)=CH2 1-1819 F Cl H CF3 H OCH2CO2C7H15 1-1821 F Cl H CF3 H COOCH2C6H5 1-1822 F C1 H CF3 H C(CH3)=NOH
1-1823 F C1 H CF3 H C(CH3)=NOCH3 1-1824 F C1 H~ CF3 H C(CH3)=NOC2H5 1-1825 F Cl H CF3 H C(CH3)=NOlC3H7 1-1826 F C1 H CF3 H C(C2H5)=NOH
1-1827 F C1 H CF3 H C(C2H5)=NOCH3 1-1828 F C1 H CF3 H C(C2H5)=NOC2H5 1-1829 F C1 H CF3 H C(C2H5)=NOlC3H7 1-1830 F C1 H CF3 H C(CH3)=NNH2 1-1831 F Cl H CF3 H C(CH3)=NNHCH3 1-1832 F Cl H CF3 H C(CH3)=NN(CH3)2 1-1833 F C1 H CF3 H C(CH3)=NNHC2H5 1-1834 F Cl H CF3 H C(CH3)=NN(C2H5)2 1-1835 F C1 H CF3 H C(C2H5)=NNH2 1-1836 F C1 H CF3 H C(C2H5)=NNHCH3 1-1837 F C1 H CF3 H C(C2H5)=NN(CH3)2 1-1838 F C1 H CF3 H C(C2H5)=NNHC2H5 1-1839 F C1 H CF3 H C(C2H5)=NN(C2H5)2 1-1840 F C1 H CF3 H C(CH3)(OCH3)2 TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No.
1-1841 F C1 H CF3 H C(CH3)(OC2H5)2 1-1842 F C1 H CF3 H C(CH3)(C1C3H7)2 C'O~
~ ~~~
C~1O
o~
~ ~o~
1-1847 F C1 CH3 CF3 H OCH2C(CH3)=CH2 1-1851 F C1 CH3 CF3 H C(CH3)=NOH
1-1852 F C1 CH3 CF3 H C(CH3)=NOCH3 1-1853 F C1 CH3 CF3 H C(CH3)=NOC2H5 1-1854 F C1 CH3 CF3 H C(CH3)=NOlC3H7 1-1855 F C1 CH3 CF3 H C(C2H5)=NOH
1-1856 F C1 CH3 CF3 H C(C2H5)=NOCH3 1-1857 F C1 CH3 CF3 H C(C2H5)=NOC2H5 1-1858 F C1 CH3 CF3 H C(C2H5)=NO1C3H7 1-1859 F C1 CH3 CF3 H C(CH3)=NNH2 1-1860 F C1 CH3 CF3 H C(CH3)=NNHCH3 1-1861 F C1 CH3 CF3 H C(CH3)=NN(CH3)2 TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No.
1-1862 F C1 CH3 CF3 H C(CH3)=NNHC2H5 1-1863 F Cl CH3 CF3 H C(CH3)=NN(C2H5)2 1-1864 F C1 CH3 CF3 H C(C2H5)=NNH2 1-1865 F Cl CH3 CF3 H C(C2H5)=NNHCH3 1-1866 F C1 CH3 CF3 H C(C2H5)=NN(CH3)2 1-1867 F Cl CH3 CF3 H C(C2H5)=NNHC2H5 1-1868 F Cl CH3 CF3 H C(C2H5)=NN(C2H5)2 1-1869 F Cl CH3 CF3 H C(CH3)(OCH3)2 1-1870 F C1 CH3 CF3 H C(CH3)(OC2H5)2 1-1871 F C1 CH3 CF3 H C(CH3)(C1C3H7)2 C'O
1-1872 F C1 CH3 CF3 H I~O
~ ~~~
C,-O
CZHS
~~o~
1-1875 F Cl CHg CF3 H
1-1876 H C1 H CF3 CH3 OCH2C(CH3)=CH2 1-1879 H Cl H CF3 CHg COOCH2C6H5 1-1880 H C1 H CF3 CH3 C(CH3)=NOH
1-1881 H Cl H CF3 CH3 C(CH3)=NOCH3 1-1882 H C1 H CF3 CH3 C(CH3)=NOC2H5 1-1883 H C1 H CF3 CHg C(CH3)=NOlC3H7 ti TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No.
1-1884 H Cl H CF3 CH3 C(C2H5)=NOH
1-1885 H Cl H CF3 CH3 C(C2H5)=NOCH3 1-1886 H C1 H CF3 CH3 C(C2H5)=NOC2H5 1-1887 H Cl H CF3 CH3 C(C2H5)=NO1C3H7 1-1888 H Cl H CF3 CH3 C(CH3)=NNH2 1-1889 H Cl H CF3 CH3 C(CH3)=NNHCH3 1-1890 H Cl H CF3 CH3 C(CH3)=NN(CH3)2 1-1891 H Cl H CF3 CH3 C(CH3)=NNHC2H5 1-1892 H C1 H CF3 CH3 C(CH3)=NN(C2H5)2 1-1893 H Cl H CF3 CH3 C(C2H5)=NNH2 1-1894 H C1 H CF3 CH3 C(C2H5)=NNHCH3 1-1895 H Cl H CF3 CH3 C(CZHS)=NN(CH3)2 1-1896 H Cl H CF3 CH3 C(C2H5)=NNHC2H5 1-1897 H Cl H CF3 CH3 C(C2H5)=NN(C2H5)2 1-1898 H C1 H CF3 CH3 C(CH3)(OCH3)2 1-1899 H C1 H CF3 CH3 C(CH3)(OC2H5)Z
1-1900 H C1 H CF3 CH3 C(CH3)(C1C3H7)2 C'O
~
1-1901 H Cl H CF3 CH3 I -O
1-1902 H Cl H CF3 CH3 ~~~~
C'o~
1-1903 H C1 H CF3 CH3 (-O
~ ~o) 1-1904 H Cl H CF3 CH3 1-1905 H Cl H CF3 H OCH2C(CH3)=CH2 WO 97/07104 PCT/.IP96/02311 TABLE 1 (contn'd) Compound X Y R3 Rl R2 B No.
1-1907 H Cl H CF3 H OCH2C02C8H17 1-1909 H C1 H CF3 H C(CH3)=NOH
1-1910 H C1 H CF3 H C(CH3)=NOCH3 1-1911 H C1 H CF3 H C(CH3)=NOC2H5 1-1912 H C1 H CF3 H C(CHg)=NOlC3H7 1-1913 H Cl H CF3 H C(C2H5)=NOH
1-1914 H C1 H CF3 H C(C2H5)=NOCH3 1-1915 H Cl H CF3 H C(CZH5)=NOCZH5 1-1916 H C1 H CF3 H C(C2H5)=NOlC3H7 1-1917 H C1 H CF3 H C(CH3)=NNH2 1-1918 H C1 H CF3 H C(CH3)=NNHCH3 1-1919 H Cl H CF3 H C(CH3)=NN(CH3)2 1-1920 H Cl H CF3 H C(CH3)=NNHC2H5 1-1921 H C1 H CF3 H C(CH3)=NN(C2H5)2 1-1922 H Cl H CF3 H C(C2H5)=NNH2 1-1923 H Cl H CF3 H C(C2H5)=NNHCH3 1-1924 H C1 H CF3 H C(C2H5)=NN(CH3)2 1-1925 H C1 H CF3 H C(C2H5)=NNHC2H5 1-1926 H Cl H CF3 H C(C2H5)=NN(C2H5)2 1-1927 H Cl H CF3 H C(CH3)(OCH3)2 1-1928 H C1 H CF3 H C(CH3)(OC2H5)2 1-1929 H C1 H CF3 H C(CHg)(CC3H7)2 'O~
1-1930 H Cl H CF3 H i CH3 ~O
1-1931 H C1 H CF3 H i'O~
~O =
I "1 O
TABLE 1 (contn'd) Compound X y R3 Ri R2 g No.
~~o~
1-1934 H C1 CH3 CF3 H OCH2C(CH3)=CH2 1-1938 H C1 CH3 CF3 H C(CH3)=NOH
1-1939 H C1 CH3 CF3 H C(CH3)=NOCH3 1-1940 H C1 CH3 CF3 H C(CH3)=NOC2H5 1-1941 H C1 CHg CF3 H C(CH3)=N0'C3H7 1-1942 H C1 CH3 CF3 H C(C2H5)=NOH
1-1943 H C1 CH3 CF3 H C(CZH5)=NOCH3 1-1944 H C1 CH3 CF3 H C(C2H5)=NOC2H5 1-1945 H C1 CH3 CF3 H C(C2H5)=N01C3H7 1-1946 H C1 CH3 CF3 H C(CH3)=NNH2 1-1947 -H C1 CH3 CF3 H C(CH3)=NNHCH3 1-1948 H C1 CH3 CF3 H C(CH3)=NN(CH3)2 1-1949 H C1 CH3 CF3 H C(CH3)=NNHC2H5 1-1950 H C1 CH3 CF3 H C(CH3)=NN(C2H5)2 1-1951 H C1 CH3 CF3 H C(C2H5)=NNH2 1-1952 H C1 CH3 CF3 H C(C2H5)=NNHCH3 1-1953 H Cl CH3 CF3 H C(C2H5)=NN(CHg)2 1-1954 H C1 CHg CF3 H C(C2H5)=NNHC2H5 1-1955 H C1 CH3 CF3 H C(C2H5)=NN(C2H5)Z
1-1956 H C1 CH3 CF3 H C(CH3)(OCH3)2 1-1957 H C1 CH3 CF3 H C(CHg)(OC2H5)2 1-1958 H C1 CH3 CF3 H C(CH3)(C1C3H7)2 1-1959 H C1 CH3 CF3 H C~C]
Io c,o) 1-1960 H C1 CH3 CF3 H I'0 TABLE 1 (contn'd) Compound X Y R3 Rl R2 B
No.
1-1961 H Cl CH3 CF3 H C0 C'O) 1-1962 H C1 CH3 CF3 H 1\0 1-1963 Cl C1 H CF3 CH3 OCH2C(CH3)=CH2 1-1964 Cl C1 H CF3 CH3 OCH2C02C7H15 1-1966 C1 Cl H CF3 CH3 COOCH2C6H5 1-1967 Cl Cl H CF3 CH3 C(CH3)=NOH
1-1968 C1 Cl H CF3 CH3 C(CH3)=NOCH3 1-1969 Cl C1 H CF3 CH3 C(CHg)=NOC2H5 1-1970 Cl Cl H CF3 CH3 C(CH3)=NO'-C3H7 1-1971 Cl Ci H CF3 CH3 C(C2H5)=NOH
1-1972 C1 Cl H CF3 CH3 C(C2H5)=NOCH3 1-1973 Cl Cl H CF3 CH3 C(C2H5)=NOC2H5 1-1974 C1 Ci H CF3 CH3 C(C2H5)=NO1C3H7 1-1975 C1 Cl H CF3 CH3 C(CH3)=NNH2 1-1976 Cl C1 H CF3 CH3 C(CH3)=NNHCH3 1-1977 C1 Cl H CF3 CH3 C(CH3)=NN(CH3)2 1-1978 C1 C1 H CF3 CH3 C(CH3)=NNHC2H5 1-1979 C1 Cl H CF3 CH3 C(CH3)=NN(C2H5)2 1-1980 Cl C1 H CF3 CH3 C(C2H5)=NNH2 1-1981 C1 C1 H CF3 CH3 C(C2H5)=NNHCH3 1-1982 Cl C1 H CF3 CH3 C(C2H5)=NN(CH3)2 1-1983 C1 Cl H CF3 CH3 C(C2H5)=NNHC2H5 1-1984 C1 Cl H CF3 CH3 C(C2H5)=NN(C2H5)2 1-1985 C1 Cl H CF3 CH3 C(CH3)(OCH3)2 1-1986 C1 Cl H CF3 CH3 C(CH3)(OC2H5)2 1-1987 C1 C1 H CF3 CH3 C(CH3)(C1C3H7)2 '0 1-1988 C1 Cl H CF3 CH3 ~~p~
WO 97/07104 PCT/.dP96/02311 TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No.
I-O
1-1989 C1 C1 H CF3 CH3 I'C~
C'C
1-1990 C1 Cl H CF3 CH3 I",Q
~~o~
1-1992 C1 C1 H CF3 H OCH2C(CH3)=CH2 1-1995 Ci C1 H CF3 H COOCH2C6H5 1-1996 C1 C1 H CF3 H C(CH3)=NOH
1-1997 C1 C1 H CF3 H C(CH3)=NOCH3 1-1998 C1 C1 H CF3 H C(CH3)=NOC2H5 1-1999 C1 C1 H CF3 H C(CH3)=NO1C3H7 1-2000 C1 C1 H CF3 H C(C2H5)=NOH
1-2001 C1 C1 H CF3 H C(C2H5)=NOCH3 1-2002 C1 C1 H CF3 H C(C2H5)=NOC2H5 1-2003 C1 C1 H CF3 H C(C2H5)=NO'-C3H7 1-2004 C1 C1 H CF3 H C(CH3)=NNH2 1-2005 C1 C1 H CF3 H C(CH3)=NNHCH3 1-2006 C1 C1 H CF3 H C(CH3)=NN(CH3)2 1-2007 C1 C1 H CF3 H C(CH3)=NNHC2H5 1-2008 C1 C1 H CF3 H C(CH3)=NN(C2H5)2 1-2009 C1 C1 H CF3 H C(C2H5)=NNH2 1-2010 C1 C1 H CF3 H C(C2H5)=NNHCH3 1-2011 C1 C1 H CF3 H C(C2H5)=NN(CH3)2 1-2012 C1 C1 H CF3 H C(C2H5)=NNHC2H5 1-2013 C1 C1 H CF3 H C(C2H5)=NN(C2H5)2 1-2014 Cl C1 H CF3 H C(CH3)(OCH3)2 TABLE 1 (contn'd) Compound X Y R3 Ri R2 B
No. 1-2015 C1 C1 H CF3 H C(CH3)(OC2H5)Z
1-2016 C1 C1 H CF3 H C(CHg)(CCgH7)2 C'O~
1-2017 C1 C1 H CF3 H I '-, 0 ~ ~o~
C.1O
~
1-2019 C1 Ci H CF3 H 10 ~ ~o~
1-2021 C1 C1 CH3 CF3 H OCH2C(CH3)=CH2 1-2023 C1 Ci CH3 CF3 H OCH2C02C8H17 1-2025 C1 C1 CH3 CF3 H C(CH3)=NOH
1-2026 C1 C1 CH3 CF3 H C(CH3)=NOCH3 1-2027 C1 C1 CH3 CF3 H C(CH3)=NOC2H5 1-2028 C1 C1 CH3 CF3 H C(CH3)=NOlC3H7 1-2029 C1 C1 CH3 CF3 H C(C2H5)=NOH
1-2030 C1 C1 CH3 CF3 H C(C2H5)=NOCH3 1-2031 C1 C1 CH3 CF3 H C(CZH5)=NOC2H5 1-2032 C1 C1 CH3 CF3 H C(C2H5)=NO1C3H7 1-2033 C1 C1 CH3 CF3 H C(CH3)=NNH2 1-2034 C1 C1 CH3 CF3 H C(CH3)=NNHCH3 TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No.
1-2035 C1 C1 CH3 CF3 H C(CH3)=NN(CH3)2 1-2036 C1 C1 CH3 CF3 H C(CHg)=NNHC2H5 1-2037 C1 C1 CH3 CF3 H C(CH3)=NN(C2H5)2 1-2038 C1 C1 CH3 CF3 H C(C2H5)=NNH2 1-2039 C1 C1 CH3 CF3 H C(C2H5)=NNHCH3 1-2040 Ci C1 CH3 CF3 H C(C2H5)=NN(CH3)2 1-2041 C1 C1 CH3 CF3 H C(C2H5)=NNHC2H5 1-2042 C1 C1 CH3 CF3 H C(C2H5)=NN(C2H5)2 1-2043 C1 C1 CHg CF3 H C(CH3)(OCH3)2 1-2044 C1 C1 CH3 CF3 H C(CH3)(OC2H5)2 1-2045 C1 C1 CH3 CF3 H C(CH3)(C''C3H7)2 C'0 ~ ~o ~
Clo]
1-2048 C1 C1 CH3 CF3 H ~~O , ~ ~o~
1-2052 F C1 H CF3 CH3 OCH2COOCH2COOi C3H7 1-2053 F C1 H CF3 CH3 OCH2COOCH(CH3)COOCH3 1-2054 F C1 H CF3 CH3 OCH2COOCH(CH3)COOC2H5 1-2055 F C1 H CF3 CH3 OCH2COOCH(CH3)COO1C3H7 =
TABLE 1 (contn'd) Compound X Y R3 R1 R2 B =
No.
1-2056 F Cl H CF3 CH3 OCH(CH3)COOCH2COOCH3 1-2057 F Cl H CF3 CH3 OCH(CH3)COOCH2COOC2H5 1-2058 F Cl H CF3 CH3 OCH(CH3)COOCH2COOlC3H7 1-2059 F Cl H CF3 CH3 OCH(CH3)COOCH(CH3)COOCH3 1-2060 F Cl H CF3 CH3 OCH(CH3)COOCH(CH3)COOC2H5 1-2061 F Cl H CF3 CH3 OCH(CHg)COOCH(CH3)COO1C3H7 1-2062 F Cl H CF3 H OCH2COOCH2COOCH3 1-2063 F Cl H CF3 H OCH2COOCH2COOC2H5 1-2064 F Cl H CF3 H OCH2COOCH2COOlC3H7 1-2065 F Cl H CF3 H OCH2COOCH(CH3)COOCH3 1-2066 F Cl H CF3 H OCH2COOCH(CH3)COOC2H5 1-2067 F Cl H CF3 H OCH2COOCH(CH3)COOlC3H7 1-2068 F Cl H CF3 H OCH(CH3)COOCH2COOCH3 1-2069 F Cl H CF3 H OCH(CH3)COOCH2COOC2H5 1-2070 F Cl H CF3 H OCH(CH3)COOCH2COO1C3H7 1-2071 F Cl H CF3 H OCH(CH3)COOCH(CH3)COOCH3 1-2072 F Cl H CF3 H OCH(CH3)COOCH(CH3)COOC2H5 1-2073 F Cl H CF3 H OCH(CH3)COOCH(CH3)COOlC3H7 1-2074 F Cl CH3 CF3 H OCH2COOCH2COOCH3 1-2075 F Cl CH3 CF3 H OCH2COOCH2COOC2H5 1-2076 F C1 CH3 CF3 H OCH2COOCH2COOlC3H7 1-2077 F Cl CH3 CF3 H OCH2COOCH(CH3)COOCH3 1-2078 F Cl CH3 CF3 H OCH2COOCH(CH3)COOC2H5 1-2079 F Cl CH3 CF3 H OCH2COOCH(CH3)CO01C3H7 1-2080 F Cl CH3 CF3 H OCH(CH3)COOCH2COOCH3 1-2081 F Cl CH3 CF3 H OCH(CH3)COOCH2COOC2H5 1-2082 F Cl CH3 CF3 H OCH(CH3)COOCH2COO1C3H7 1-2083 F Cl CH3 CF3 H OCH(CH3)COOCH(CH3)COOCH3 1-2084 F Cl CH3 CF3 H
OCH(CH3)COOCH(CH3)COOC2H5 1-2085 F Cl CH3 CF3 H OCH(CH3)COOCH(CH3)COO'C3H7 TABLE I (contn'd) Compound X Y R3 R1 R2 g No.
1-2088 H C1 H CF3 CH3 OCH2COOCH2COOlC3H7 1-2089 H C1 H CF3 CH3 OCH2COOCH(CH3)COOCH3 1-2090 H C1 H CF3 CH3 OCH2COOCH(CH3)COOC2H5 1-2091 H C1 H CF3 CH3 OCH2COOCH(CH3)COO1C3H7 1-2092 H C1 H CF3 CH3 OCH(CH3)COOCH2COOCH3 1-2093 H C1 H CF3 CH3 OCH(CH3)COOCH2COOC2H5 1-2094 H C1 H CF3 CH3 OCH(CH3)COOCH2COOlC3H7 1-2095 H C1 H CF3 CH3 OCH(CH3)COOCH(CH3)COOCH3 1-2096 H C1 H CF3 CH3 OCH(CH3)COOCH(CH3)COOC2H5 1-2097 H C1 H CF3 CH3 OCH(CH3)COOCH(CH3)COOlC3H7 1-2100 H C1 H CF3 H OCH2COOCH2COOlC3H7 1-2101 H C1 H CF3 H OCH2COOCH(CH3)COOCH3 1-2102 H C1 H CF3 H OCH2COOCH(CH3)COOC2H5 1-2103 H C1 H CF3 H OCH2COOCH(CH3)COOlC3H7 1-2104 H C1 H CF3 H OCH(CH3)COOCH2COOCH3 1-2105 H C1 H CF3 H OCH(CH3)COOCH2COOC2H5 1-2106 H C1 H CF3 H OCH(CH3)COOCH2COO1C3H7 1-2107 H C1 H CF3 H OCH(CH3)COOCH(CH3)COOCH3 1-2108 H C1 H CF3 H OCH(CH3)COOCH(CH3)COOC2H5 1-2109 H C1 H CF3 H OCH(CH3)COOCH(CH3)COOlC3H7 1-2112 H C1 CH3 CF3 H OCH2COOCH2COOlC3H7 1-2113 H C1 CH3 CF3 H OCHZCOOCH(CH3)COOCH3 1-2114 H Ci CH3 CF3 H OCH2COOCH(CH3)COOC2H5 1-2115 H C1 CH3 CF3 H OCH2COOCH(CH3)COOlC3H7 TABLE 1 (contn'dl Compound X Y R3 R1 R2 B
No.
1-2116 H C1 CH3 CF3 H OCH(CH3)COOCH2COOCH3 1-2117 H C1 CH3 CF3 H OCH(CH3)COOCH2COOC2H5 1-2118 H C1 CH3 CF3 H OCH(CH3)COOCH2COO'-C3H7 1-2119 H C1 CH3 CF3 H OCH(CH3)COOCH(CH3)COOCH3 1-2120 H C1 CH3 CF3 H OCH(CH3)COOCH(CH3)COOC2H5 1-2121 H C1 CH3 CF3 H OCH(CH3)COOCH(CH3)COOlC3H7 1-2124 C1 C1 H CF3 CH3 OCH2COOCH2COOlC3H7 1-2125 C1 C1 H CF3 CH3 OCH2COOCH(CH3)COOCH3 1-2126 Ci C1 H CF3 CH3 OCH2COOCH(CH3)COOC2H5 1-2127 C1 C1 H CF3 CH3 OCH2COOCH(CHg)COO1C3H7 1-2128 C1 C1 H CF3 CH3 OCH(CH3)COOCH2COOCH3 1-2129 C1 C1 H CF3 CH3 OCH(CH3)COOCH2COOC2H5 1-2130 C1 C1 H CF3 CH3 OCH(CH3)COOCH2COOlC3H7 1-2131 C1 C1 H CF3 CH3 OCH(CH3)COOCH(CH3)COOCH3 1-2132 C1 C1 H CF3 CH3 OCH(CH3)COOCH(CH3)COOC2H5 1-2133 C1 C1 H CF3 CH3 OCH(CH3)COOCH(CH3)COO1C3H7 1-2136 C1 C1 H CF3 H OCH2COOCH2COOiC3H7 1-2137 C1 C1 H CF3 H OCH2COOCH(CH3)COOCH3 1-2138 Cl C1 H CF3 H OCH2COOCH(CH3)COOC2H5 1-2139 C1 Cl H CF3 H OCH2COOCH(CH3)COOlC3H7 1-2140 Ci C1 H CF3 H OCH(CH3)COOCH2COOCH3 1-2141 C1 C1 H CF3 H OCH(CH3)COOCH2COOC2H5 1-2142 C1 C1 H CF3 H OCH(CH3)COOCH2COOlC3H7 1-2143 C1 C1 H CF3 H OCH(CH3)COOCH(CH3)COOCH3 1-2144 C1 C1 H CF3 H OCH(CH3)COOCH(CH3)COOC2H5 1-2145 C1 C1 H CF3 H OCH(CH3)COOCH(CH3)CO01C3H7 TABLE 1 (contn'd) Compound X Y R3 R1 R2 B
No.
1-2148 C1 Ci CH3 CF3 H OCH2COOCH2COO1C3H7 1-2149 C1 C1 CH3 CF3 H OCH2COOCH(CH3)COOCH3 1-2150 C1 C1 CH3 CF3 H OCH2COOCH(CH3)COOC2H5 1-2151 C1 C1 CH3 CF3 H OCH2COOCH(CH3)COOlC3H7 1-2152 C1 C1 CH3 CF3 H OCH(CH3)COOCH2COOCH3 1-2153 C1 C1 CH3 CF3 H OCH(CH3)COOCH2COOC2H5 1-2154 C1 C1 CH3 CF3 H OCH(CH3)COOCH2COOlC3H7 1-2155 C1 C1 CH3 CF3 H OCH(CH3)COOCH(CH3)COOCH3 1-2156 C1 Cl CH3 CF3 H OCH(CH3)COOCH(CH3)COOC2H5 1-2157 Cl Cl CH3 CF3 H OCH(CH3)COOCH(CH3)COO1C3H7 Compounds of the formula:
X R'-Zi ~ ~ N R' (R4 - - N-' nN 3 O Rs R
Compound X Z' n R 3 R' R Z R' R 5 No.
2 - 1 H 0 1 H CF2 Cl CH3 H H
2 - 2 H 0 1 H CF2 C1 CHa H CH3 2 - 3 H' 0 1 H CF2 C1 CH3 H C 2 H 5 2 - 4 H 0 1 H CFZ C1 CH3 H "C 3 H, 2- 5 H 0 1 H CFz C1 CH3 H 'C a H 7 2- 6 H 0 1 H CF2 C1 CH3 H 'C , H 9 2-7 H 0 1 H CFZ C1 CH3 H C , H fl 2 - 9 H 0 1 H CF2.C1 CH3 H CH2 CHZ Br 2-10 H 0 1 H CF2 C1 CH3 H CH2 CH=CH2 2- 11 H 0 1 H CF2 Cl CH3 H CH(CH a)CH = CH2 2- 12 H 0 1 H CF2 Cl CHa H CH2 CC1 = CH2 2-13 H 0 1 H CF2 Cl CH3 H CH2 C=CH
2-14 H 0 1 H CF2 Cl CH3 H CH(CH a)C=CH.
TABLE 2 (contn'd) Compound X Z' n R3 R' R2 R' No. R5 2.- 15 H 0 1 H CF2 Cl CH3 H CH2 CN
2 -16 H 0 1 H-- CF2 Cl CH3 H CH2 OCH 3 2 -17 H 0 1 H CF2 Cl CH3 H CH2 0C2 H;
2 -18 H 0 1 H CF2 Cl CH3 H CH2 COOH
2 -19 H 0 1 H CF2 Cl CH3 H CH2 COOCH 3 2 -20 H 0 1 H CF2 Cl CH3 H CH2 COOCz H s 2 -21 H 0 1 H CF2 Cl CH3 H CH2 C00 " C 3 H
2 -22 H 0 1 H CF2 Cl CH3 H CH2 COO " C, H
2- 23 H 0 1 H CF2 Cl CH3 H CH2 C00 " C S H õ
2- 24 H 0 1 H CFa C1 CH3 H CHz C00 ' C 3 H, 2- 25 H 0 1 H CF2 Cl CH3 H CHz C00 ' C s H 9 2- 26 H 0 1 H CFz Cl CH3 H CHa C00 ' C 6 H õ
2 -27 H 0 1 H CF2 Cl CH3 H CH(CH 3)COOH
2 -28 H 0 1 H CF2 Cl CH3 H CH(CH 3)COOCH 3 2 -29 H 0 1 H CF2 Cl CH3 H CH(CH 3)COOC 2 H 5 2 -30 H 0 1 H CF2 Cl CH3 H CH(CH3 )CO0 C 3 H;
2 -31 H 0 1 H CF2 Cl CH3 H CH(CH3 )C00 C 4 H
2 -32 H 0 1 H CF2 Cl CH3 H CH(CH3 )C00" C s H
2 -33 H 0 1 H CF2 Cl CH3 H CH(CH3 )COO' C a H
2 -34 H 0 1 H CF2 Cl CH3 H CH(CHA COO'CjH9 2 -35 H 0 1 H CF2 Cl CH3 H CH(CH3 )C00' C 6 H
2 -36 H 0 1 H CF2 Cl CH3 CH3 H
2 -37 H 0 1 H CF2 Cl CH3 CH3 CH3 TABLE 2 (contn'd) Compound. X Z' n R' R' R 2 R' R 5 No.
2 -38 H 0 1 H CF2 Cl CH3 CH3 C2 H s 2- 39 H 0 1 H CF2 Cl CH3 CH3 "C 3 H 7 2- 40 H 0 1 H CF2 Cl CH3 GH3 'C 3 H T
2- 41 H 0 1 H CF2 Cl CH3 CH3 'C , H 9 2 -42 H 0 1 H CF2 Cl CH3 CH3 C 4 H9 2 -43 H 0 1 H CF2 Cl CH3 CH3 CH2 CH=CH2 2 -44 H 0 1 H CF2 Cl CH3 CH3 CH(CH 3 )CH = CHZ
2 -45 H 0 1 H CF2 Cl CH3 CH3 CH2 C= CH
2-46 H 0 1 H CF2 Cl CH3 CH3 CH(CH 3)C= CH
2 -47 H 0 1 H CF2 Cl CH3 CH3 CH2 OCH a 2- 48 H 0 1 H CF2 Cl CH3 CH3 CH2 0C2 H s 2 -49 F 0 1 H CF2 Cl CH3 H H
2 -50 F 0 1 H CF2 Cl CH3 H CH3 2- 51 F 0 1 H CF2 Cl CH3 H C2 H s 2- 52 F 0 1 H CF2 Cl CH3 H nC 3 H 7 2- 53 F 0 1 H CF2 Cl CH3 H 'C a H 7 2 -54 F 0 1 H CF2 Cl CH3 H 'C 4 H o 2- 55 F 0 1 H CF2 Cl CH3 H C 4 H Q
2- 56 F 0 1 H CF2 Cl CH3 H CH2 CH2 Cl 2- 57 F 0 1 H CF2 Cl CH3 H CH2 CHz Br 2 -58 F 0 1 H CF2 Cl CH3 H CH2 CH= CH2 2 -59 F 0 1 H CF2 Cl CH3 H CH(CH 3)CH =CH2 2- 60 F 0 1 H CF2 Cl CH3 H CH2 CC1 = CH2 TABLE 2 (contn'd) compound X Z' 11 R a R' R2 R' R 5 = No.
2 -61 F 0 1 H CF2 Cl CH3 H CH2 C=CH
2 -62 F 0 1 H CF2 Cl -CH3 H CH(CH a)C=CH
2 -63 F 0 1 H CF2 C1 CH3 H CHz CN
2- 65 F 0 1 H CF2 C1 CH3 H CH2 0C2 H s 2 -66 F 0 1 H CF2 CI CH3 H CHz COOH
2 -67 F 0 1 H CF2 Cl CH3 H CHZ COOCH 3 2 -68 F 0 1 H CF2 C1 CH3 H 'CH2 COOC2 -H s 2- 69 F 0 1 H CFZ CI CH3 H CH2 C00 C a H 7 2- 70 F 0 1 H CF2 C1 CH3 H CH2 COO " C, H o 2- 71 F 0 1 H CF2 C1 CH3 H CH2 C00 " C 5 H
2- 72 F 0 1 H CF2 Cl CHa H CH2 C00 ' C a H 7 2- 73 F 0 1 H CF2 CI CHa H CH2 C00 ' C s H s 2- 74 F 0 1 H CF2 CI CH3 H CH2 C00 ' C 6 H õ
2 -75 F 0 1 H CF2 C1 CH3 H CH(CH 3 )COOH
2 -76 F 0 1 H CF2 Cl CH3 H CH(CH 3)COOCH
2 -77 F 0 1 H CF2 C1 CH3 H CH(CH 3)COOC 2 H 5 2- 78 F 0 1 H CF2 C1 CH3 H CH(CH3 )C00" C 3 H T
2 -79 F 0 1 H CF2 CI CH3 H CH(CH3 )C00" C 4 H g 2 -80 F 0 1 H CF2 Cl CH3 H CH(CH3 )CO0 C; H õ
2 -81 F 0 1 H CF2 C1 CH3 H CH(CH3 )COO' C 3 H 7 2 -82 F 0 1 H CF2 CI CH3 H CH(CH3 )C00' C 6 H n 2- 83 F 0 1 H CF2 C1 CH3 H CH(CH3 )C00' C 6 H õ
TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R4 R5 No.
2 -84 F 0 1 H CF2 Cl CH3 CH3 H
2 -85 F 0 1 H CF2 C1 CHa CH3 CH3 2 -86 F 0 1 H CF2 Cl CH3 CH3 C2 H s 2- 87 F 0 1 H CF2 C1 CH3 CH3 "C , H 7 2- 88 F 0 1 H CFz C1 CH3 CH3 'C 3 H 7 2 -89 F 0 1 H CF2 C1 CH3 CH3 'C 4 H s 2- 90 F 0 1 H CF2 Cl CHa CH3 "C 4 H 9 2 -91 F 0 1 H CF2 C1 CH3 CH3 CH2 CH=CH2 2- 92 F 0 1 H CF2 C1 CH3 CH3 CH(CH 3)CH = CHz 2-94 F 0 1 H CF2 C1 CH3 CH3 CH(CH 3)C CH
2- 95 F 0 1 H CF2 C1 CH3 CH3 CH2 OCH , 2 -96 F 0 1 H CF2 C1 CH3 CHs CH2 0C2 H s 2- 97 H S 0 H CF2 Cl CH3 - H
2 -98 H S 0 H CFZ Cl CH3 - CH3 2- 100 H S 0 H CF2 Cl CH3 - "C 3 H, 2- 101 H S 0 H CF2 Cl CH3 - "C , H 9 2- 102 H S 0 H CF2 Cl CHa - 'C a H7 2-103 H S 0 H CF2 C1 CH3 - 'C , H g 2- 105 H S 0 H CF2 C1 CH3 - CHZ CHZ Br WO 97/07104 PCT/.FP96/02311 TABLE 2 (contn'd) Compound X Z' n R 3 R' R Z R' R 5 No.
2-106 H S 0 H CF2 Cl CH3 - CH2 CH=CH2 2 -107 H S 0 H CF2 Cl -CH3 - CH(CH 3)CH = CHZ
2- 108 H S 0 H CF2 CI CH3 - CHz CCI = CH2 2- 109 H S 0 H CF2 Cl CH3 - CH2 C= CH
2 -110 H S 0 H CF2 C1 CH3 - CH(CH 3)C= CH
2- 111 H S 0 H CF2 C1 CH3 - CHz CN
2- 112 H S 0 H CF2 Cl CH3 - CHz OCH 3 2- 113 H S 0 H CF2 Cl CH3 - CHZ OCZ H s 2 -115 H S 0 H CF2 C1 CH3 - CHz COOCH 3 2 - 117 H S 0 H CF2 C1 CH3 - CHZ C00 " C 3 H, 2- 118 H S 0 H CF2 Cl CH3 - CH2 COO ' C, H 9 2- 119 H S 0 H CF2 C1 CH3 - CHZ COO C; H
2- 120 H S 0 H CF2 Cl CH3 - CHz COO ' C, H
2- 121 H S 0 H CF2 Cl CH3 - CHz C00 ' C s H s 2 -122 H S 0 H CF2 Cl CH3 - CHZ COO C C 6 H,i 2- 123 'H S 0 H CF2 Cl CH3 - CH(CH 3)COOH
2- 124 H S 0 H CF2 Cl CH3 - CH(CH 3)COOCH , = 2 -125 H S 0 H CF2 Cl CH3 - CH(CH 3)COOC 2 H s 2- 126 H S 0 H CF2 C1 CH3 - CH(CH3 )C00" C 3 H, 2- 127 H S 0 H CF2 Cl CH3 - CH(CH3 )C00" C 4 H 9 2 -128 H S 0 H CF2 Cl CH3 - CH(CH3 )C00" C 5 H 11 TABLE 2 fcontn'dl Compound X Z' n R3 R' R 2 R' RS
No.
2 -129 H S 0 H CF2 Cl CH3 - CH(CH3 )C00' C 3 H T
2- 130 H S 0 H CFZ C1 CH3 - CH(CH3 )C00' C 5 H 9 2- 131 H S 0 H CF2 C1 CH3 - CH(CH3 )C00' C s H õ
2 -132 F S 0 H CF2 Cl CH3 - H
2- 133 F S 0 H CF2 Cl CH3 - CH3 2- 134 F S 0 H CF2 Cl CH3 - C2 H 5 2- 135 F S 0 H CF2 Cl CH3 - nC 3 H7 2- 136 F S 0 H CF2 Cl CH3 - C 4 H 9 2- 137 F S 0 H CFa C1 CH3 - 'C 3 H T
2- 138 F S 0 H CF2 Cl CH3 - 'C 4 H s 2- 139 F S 0 H CF2 Cl CH3 - CH2 CH2 Cl 2 -140 F S 0 H CF2 Cl CH3 - CH2 CH2 Br 2 -141 F S 0 H CF2 Cl CH3 - CH2 CH=CH2 2 -142 F S 0 H CF2 C 1 Cli 3 - CH(CH 3) )CH = CH 2 2- 143 F S 0 H CF2 Cl CH3 - CH2 CCI =CH2 2- 144 F S 0 H CF2 Cl CH3 - CH2 C= CH
2-145 F S 0 H CF2 Cl CH3 - CH(CH 3)C=CH
2 -146 F S 0 H CF2 Cl CH3 - CH2 CN
2- 147 F S 0 H CF2 Cl CH3 - CH2 OCH 3 2- 148 F S 0 H CF2 Cl CH3 - CH2 OCz H 3 2- 150 F S 0 H CFa Cl CH3 - CH2 COOCH 3 2- 151 F S 0 H CF2 Cl CH3 - CH2 COOC2 H 5 TABLE 2 (contn'd) K
Compound X Z' n R 3 R' R2 R' R5 No.
2- 152 F S 0 H CF2 Cl CH3 - CH2 C00 " C a H7 2- 153 F S 0 H CF2 Cl CH3 -- CH2 C00 " C 4 H g 2- 154 F S 0 H CF2 Cl CH3 - CH2 C00 C s H õ
2- 155 F S 0 H CF2 Cl CH3 - CH2 COO C, H, 2- 156 F S 0. H CF2 Cl CH3 - CH2 COO ' C s H 9 2- 157 F S 0 H CF2 C1 CH3 - CH2 COO C C 6 H õ
2 -158 F S 0 H CF2 Cl CH3 - CH(CH 3)COOH
2- 159 F S 0 H CF2 Cl CH3 - CH(CH 3)COOCH 3 2- 160 F S 0 H CF2 Cl CH3 - CH(CH a)COOC 2 H 5 2- 161 F S 0 H CF2 Cl CH3 - CH(CH3 )C00" C, H 7 2- 162 F S 0 H CF2 Cl CH3 - CH(CH3 )C00" C 4 H 9 2 -163 F S 0 H CF2 Cl CH3 - CH(CH3 )C00 C 5 H,1 2- 164 F S 0 H CF2 Cl CH3 - CH(CH3 )C00' C, H 7 2- 165 F S 0 H CF2 Cl CH3 - CH(CH3 )C00' C; H g 2- 166 F S 0 H CF2 Cl CH3 - CH(CH3 )COOc C 6 H
2 -167 H 0 0 H CF2 Cl CH3 - H
2- 168 H 0 0 H CF2 Cl CH3 - CH3 2- 169 H 0 0 H CF2 Cl CH3 - C2 H s 2- 170 H 0 0 H CF2 Cl CH3 - "C 3 H 7 2- 171 H 0 0 H CF2 Cl CH3 - C , H s 2 -172 H 0 0 H CF2 Cl CH3 - 'C s H 7 2 -173 H 0 0 H CF2 Cl CH3 - 'C , H, 2-174 H 0 0 H CF2 Cl CH3 - CHa CH=CHz WO 97/07104 PC'T/JP96/02311 TABLE 2 (contn'd) Compound X Z' n R' R' R 2 R' R 5 No.
2 -175 H 0 0 H CF2 Cl CH3 - CH(CH 3)CH =CH2 2 -176 H 0 0 H CF2 Cl CH3 - 'CHa C=CH
2 -177 H 0 0 H CF2 Cl CH3 - CH(CH 3)C CH
2 -178 H 0 0 H CF2 Cl CH3 - CH2 OCH 3 2 -179 H 0 0 H CFz Cl CH3 - CHz 'OCz H s 2 -180 F 0 0 H CF2 Cl CH3 - H
2 -181 F 0 0 H CF2 Cl CH3 - CH3 2- 183 F 0 0 H CF2 Cl CH3 - "C a H7 2 -184 F 0 0 H CF2 Cl CH3 - "C 4 H g 2 -185 F 0 0 H CF2 Cl CH3 - CH2 CH=CH2 2 -186 F 0 0 H CF2 Cl CH3 - CH(CH 3)CH =CH2 2- 187 F 0 0 H CF2 Cl CH3 - CH 2 C= CH
2 -188 F 0 0 H CF2 C1 CH3 - CH(CH 3)C=CH
2 -189 F 0 0 H CF2 Cl CH3 - CH2 OCH 3 2 -190 F 0 0 H CF2 Cl CH3 - CHz OCa H s 2- 194 H 0 1 H CF3 CH3 H "C 3 H, 2 -195 H 0 1 H CF3 CH3 H 'C 3 H 7 2- 196 H 0 1 H CF3 CH3 H 'C 4 H 2 2- 197 H 0 1 H CF3 CH3 H "C 4 H 9 WO 97/07104 PCTJ,6P96102311 TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R4 R 5 No.
2- 198 H 0 1 H CF3 CH3 H CH2 CH2 Cl 2- 199 H 0 1 H CF3 -CH3 H CH2 CHa Br 2 -200 H 0 1 H CF3 CH3 H CHZ CH=CH2 2 -201 H 0 1 H CF3 CH3 H CH(CH 3)CH = CH2 2 -202 H 0 1 H CF3 CH3 H CH2 CC1 =CH2 2 -203 H 0 1 H CF3 CH3 H CH2 C=CH
2 -204 H 0 1 H CF3 CH3 H CH(CH 3)C=CH
2 -205 H 0 1 H CF3 CH3 H CHz CN
2 -206 H 0 1 H CF3 CH3 H CHz OCH 3 2 -209 H 0 1 H CF3 CHa H CH2 COOCH 3 2 -211 H 0 1 H CF3 CH3 H CH2 C00 " C 3 H 7 2 -212 H 0 1 H CF3 CH3 H CH2 COO " C, H 9 2- 213 H 0 1 H CF3 CH3 H CHZ COO " C 5 H õ
2- 214 H 0 1 H CF3 CH3 H CH2 C00 ' C 3 H 7 2- 215 H 0 1 H CF3 CH3 H CH2 C00 ' C s H Q
2 -216 H 0 1 H CF3 CH3 H CHz COO ' C 6 H õ
2 -217 H 0 1 H CF3 CH3 H CH(CH 3 )COOH
2 -218 H 0 1 H CF3 CH3 H CH(CH 3)COOCH 3 2 -219 H 0 1 H CF3 CH3 H CH(CH 3)COOC 2 H 5 WO 97/07104 PC'1'/JP96/02311 TABLE 2 (contn'd) Compound X Z' n R' R' R Z R' R 5 No.
2 -220 H 0 1 H CF3 CH3 H CH(CH3 )C00" C 3 H, 2- 221 H 0 1 H CF3 CH3 H CH(CH3 )C00" C, H 9 2 -222 H 0 1 H CF3 CH3 H CH(CH3 )C00" C; H õ
2 -223 H 0 1 H CF3 CH3 H CH(CH3 )C00' C 3 H7 2 -224 H 0 1 H CF3 CH3 H CH(CH3 )COOC C s H 9 2 -225 H 0 1 H CF3 CH3 H CH(CH3 )C00' C s H õ
2- 229 H 0 1 H CF3 CH3 CH3 "C 3 H, 2 -230 H 0 1 H CF3 CH3 CH3 'C 3 H 7 2 -231 H 0 1 H CF3 CH3 CH3 'C 4 H 9 2- 232 H 0 1 H CF3 CH3 CH3 "C < H 9 2 -233 H 0 1 H CF3 CH3 CH3 CH2 CH = CH2 2 -234 H 0 1 H CF3 CH3 CH3 CH(CH 3)CH = CHZ
2 -235 H 0 1 H CF3 CH3 CH3 CH2 C= CH
2 -236 H 0 1 H CF3 CH3 CH3 CH(CH 3)C=CH
2 -238 H 0 1 H CF3 CH3 CH3 CH2 0C2 H s 2 -241 F 0 1 H CF3 CH3 H C2 H 5 2- 242 F 0 1 H CF3 CH3' H "C 3 H, TABLE 2 (contn'd) Compound X Z' n R3 R' R Z R' R s No.
2 -243 F 0 1 H CFa CHa H 'C 3 H 7 2- 244 F 0 1 H CF3 CH3 H 'C 4 H g 2- 245 F 0 1 H CF3 CH3 H "C 4 H 9 2 -246 F 0 1 H CF3 CH3 H CHZ CH2 Cl 2 -247 F 0 1 H CF3 CH3 H CH2 CHz Br 2 -248 F 0 1 H CF3 CH3 H CH2 CH=CHa 2 -249 F 0 1 H CF3 CH3 H CH(CH 3)CH = CH2 2 -250 F 0 1 H CF3 CH3 H CHz CCl = CH2 2 -251 F 0 1 H CF3 CH3 H CH2 C=CH
2 -252 F 0 1 H CF3 CH3 H CH(CH 3)C=CH
2 -258 F 0 1 H CF3 CH3 H CHz COOC2 H s 2 -259 F 0 1 H CF3 CH3 H CH2 C00 " C 3 H7 2 -260 F 0 1 H CF3 CH3 H CH2 C00 " C 4 H o 2 -261 F 0 1 H CF3 CH3 H CH2 C00 " C s H õ
2 -262 F 0 1 H CF3 CH3 H CH2 COO ' C a H 7 2 -263 F 0 1 H CF3 CH3 H CH2 COO C C 6 H s 2 -264 F 0 1 H CF3 CH3 H CH2 COO ' C 6 H õ
2 -265 F 0 1 H CF3 CH3 H CH(CH 3)COOH
TABLE 2 (contn'd) Compound. X Z' n R 3 R' R 2 R' R s No.
2 -266 F 0 1 H CFa CH3 H CH(CH 3)COOCH 3 2 -267 F 0 1 H CF3 CH3 H CH(CH 3)COOC 2 H;
2 -268 F 0 1 H CF3 CH3 H CH(CH3 )C00" C 3 H 7 2 -269 F 0 1 H CF3 CH3 H CH(CH3 )C00" C, H s 2 -270 F 0 1 H CF3 CH3 H CH(CH3 )C00" C s H 11 2- 271 F 0 1 H CF3 CH3 H CH(CH3 )C00' C 3 H 7 2 -272 F 0 1 H CF3 CH3 H CH(CH3 )C00' C; H 9 2 -273 F 0 1 H CF3 CH3 H CH(CH3 )C00' C 6 Hii 2 -275 F 0 1 H CFa CH3 CH3 CH3 2- 277 F 0 1 H CF3 CH3 CH3 "C 3 H 7 2 -278 F 0 1 H CF3 CH3 CH3 'C 3 H, 2- 279 F 0 1 H CF3 CH3 CH3 'C , H2 2- 280 F 0 1 H CF3 CH3 CH3 "C , H o 2 -281 F 0 1 H CF3 CH3 CH3 CHZ CH = CH2 2 -282 F 0 1 H CF3 CH3 CH3 CH(CH 3)CH = CHz 2 -283 F 0 1 H CF3 CH3 CH3 CHz C= CH
2 -284 F 0 1 H CF3 CH3 CH3 CH(CII 3)C=CH
2 -286 F 0 1 H CF3 CH3 CH3 CHz 0C2 H s TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R4 R 5 No.
2 -290 H S 0 H CF3 CH3 - "C 3 H 7 2- 291 H S 0 H CF3 CH3 - "C , H 9 2 -292 H S 0 H CF3 CH3 - C 3 H, 2 -293 H S 0 H CF3 CH3 - 'C 4 H 9 2 -295 H S 0 H CF3 CH3 - CH2 CH2 Br 2 -296 H S 0 H CF3 CH3 - CHz CH=CH2 2 -297 H S 0 H CF3 CH3 - CH(CH 3)CH =CH2 2 -298 H S 0.H CF3 CH3 - CH2 CC1 =CH2 2 -299 H S 0 H CF3 CH 3 - CH 2 C= CH
2 -300 H S 0 H CF3 CH3 - CH(CH 3)C=CH
2 -303 H S 0 H CF3 CH3 - CH2 0C2 H s 2 -306 H S 0 H CF3 CH3 - CH2 COOC2 H;
2 -307 H S 0 H CF3 CH3 - CHZ C00 " C 3 H 7 2 -308 H S 0 H CF3 CH3 - CH2 C00 " C, H
2 -309 H S 0 H CF3 CH3 - CH2 C00 " C 5 H
2 -311 H S 0 H CF3 CH3 - CH2 COO ' C b H
TABJLE 2 (contn'd) ;
Compound X Z' n R 3 R' R~ R' R S
No.
2 -312 H S 0 H CF3 CH3 - CH2 COO c C s H õ
2 -313 H S 0 H CF3 CH, - -CH(CH 3 )COOH
2 -314 H S 0 H CF3 CH3 - CH(CH a)COOCH a 2 -315 H S 0 H CF3 CH3 - CH(CH3 )COOC 2 H s 2- 316 H S 0 H CF3 CH3 - CH(CH3 )C00" C a H 7 2- 317 H S 0 H CF3 CH3 - CH(CH3 )C00" C 4 H 9 2 -318 H S 0 H CF3 CH3 - CH(CH3 )C00" C s H õ
2- 319 H S 0 H CF3 CH3 - CH(CH3 )C00' C 3 H 7 2 -320 H S 0 H CF3 CH3 - CH(CH3 )C00' C 5 H 9 2 -321 H S 0 H CF3 CH3 - CH(CH3 )C00' C 6 H
2- 326 F S 0 H CF3 CH3 - C , H fl 2 -327 F S 0 H CF3 CH3 - 'C 3 H, 2- 328 F S 0 H CF3 CH3 - SC 4 H s 2 -330 F S 0 H CF3 CH3 - CH2 CH2 Br 2 -331 F S 0 H CF3 CH3 - CH2 CH=CH2 2 -332 F S 0 H CF3 CH3 - CH(CH 3)CH =CH2 2 -333 F S 0 H CF3 CH3 - CH2 CC1 = CH2 TABLE 2 (contn'd) Compound X Z' n R3 R' R 2 R' R 5 No.
2 -334 F S 0 H CF3 CH3 - CH2 C=CH
2 -335 F S 0 H CF3 CH3 - CH(CH 3)C=CH
2 -338 F S 0 H CF3 CH3 - CH2 0C2 H s 2 -340 F S 0 H CF3 CH3 - CH2 COOCH , 2 -342 F S 0 H CF3 CH3 - CH2 C00 " C, H 7 2 -343 F S 0 H CF3 CH3 - CH2 C00 " C 4 H 9 2 -344 F S 0 H CF3 CH3 - CH2 C00 " C S H õ
2- 345 F S 0 H CF3 CH3 - CH2 COO ' C, H, 2 -346 F S 0 H CF3 CH3 - CH2 COO ' C s H 9 2 -347 F S 0 H CF3 CH3 - CH2 COO ' C 6 H
2 -348 F S 0 H CF3 CH3 - CH(CH 3)COOH
2 -349 F S 0 H CF3 CH3 - CH(CH 3)COOCH 3 2 -350 F S 0 H CF3 CH3 - CH(CH3 )COOC 2 H;
2 -351 F S 0 H CF3 CH3 - CH(CH3 )C00" C 3 H, 2 -352 F S 0 H CF3 CH3 - CH(CH3 )C00" C 4 H g 2 -353 F S 0 H CF3 CH3 - CH(CH3 )CQO" C s H õ
2 -354 F S 0 H CF3 CH3 - CH(CH3 )C00' C, H, 2 -355 F S 0 H CF3 CH3 - CH(CH3 )COQ' C s H fl 2- 356 F S 0 H CF3 CH3 - CH(CH3 )C00' C 6 H i TABLE 2 (contn'd) compound X Z' n R 3 R' R 2 R' R 5 No.
2 -360 H 0 0 H CF3 CH3 - "C 3 H 7 2 -361 H 0 0 H CF3 CH3 - C , H s 2 -363 H 0 0 H CF3 CH3 - C , H s 2 -364 H 0 0 H CF3 CH3 - CH2 CH=CHa 2 -365 H 0 0 H CF3 CH3 - CH(CH 3)CH = CHz 2 -366 H 0 0 H CF3 CH3 - CHz C=CH
2 -367 H 0 0 H CF3 CH3 - CH(CH 3)C=CH
2- 373 F 0 0 H CF3 CH3 - "C 3 H 7 2- 374 F 0 0 H CF3 CH3 - "C , H 9 2 -375 F 0 0 H CF3 CH3 - CH2 CH=CH2 2 -376 F 0 0 H CF3 CH3 - CH(CH 3)CH = CH2 2 -377 F 0 0 H CF3 CH 3 - CH2 C= CH
2 -378 F 0 0 H CF3 CH3 - CH(CH a)C=CH
2 -379 F 0 0 H CF3 CH3 - CHz OCH s TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R4 R g No.
2 -381 H 0 1 H CF2 Cl H H H
2 -382 H 0 1 H CF2 Cl H H CH3 2- 383 H 0 1 H CF2 Cl H H CZ H s 2 - 384 H 0 1 H CF2 C l H H C 3 H, 2-385 H 0 1 H CF2C1 H H 'C3H, 2-386 H 0 1 I1 CF2 Cl H H C , H
2 -387 H 0 1 H CF2 Cl H H "C , H 9 2- 388 H 0 1 H CF2 Cl H H CH2 CH2 Cl 2 -389 H 0 1 H CF2 Cl H H CH2 CH2 Br 2 -390 H 0 1 H CF2 Cl H H CH2 CH=CH2 2- 391 H 0 1 H CF2 Cl H H CH(CH 3)CH =CH2 2- 392 H 0 1 H CF2 Cl H H CH2 CC1 =CH2 2 -393 H 0 1 H CF2 Cl H H CH2 C=CH
2 -394 H 0 1 H CF2 Cl H H CH(CH 3)C=CH
2 -395 H 0 1 H CF2 Cl H H CH2 CN
2 -396 H 0 1 H CF2 Cl H H CH2 OCH , 2- 397 H 0 1 H CF2 Cl H H CH2 0C2 H s 2 -398 H 0 1 H CF2 Cl H H CHZ COOH
2 -399 H 0 1 H CF2 Cl H H CHz COOCH 3 2 -400 H 0 1 H CF2 Cl H H CH2 COOC2 H 5 2 - 401 H 0 1 H CF2 C1 H H CHz C00 " C a H, 2 - 402 H 0 1 H CF2 C1 H H CH2 C00 " C4 H 9 TABLE 2 (contn'd) compound X Z' n R3 R' R 2 R' RS
No.
2 -403 H 0 1 H CF2 Cl H H CH2 C00 " C 5 H õ
2 - 404 H 0 1 H CFz C1 H H CH2 C00 ' C 3 H, 2- 405 H 0 1 H CFz C1 H H CHz C00 ' C s H s 2 -406 H 0 1 H CFz Cl H H CH2 COO c C 6 H
2 -407 H 0 1 H CF2 C 1 H H CH(CH 3) )COOH
2 -408 H 0 1 H CF2 Cl H H CH(CH 3 )COOCH
2 -409 H 0 1 H CF2 Cl H H CH(CH 3)COOC 2 H;
2- 410 H 0 1 H CF2 Cl H H CH(CH3 )C00" C3 H 7 2- 411 H 0 1 H CF2 Cl H H CH(CH3 )C00" C 4 H 9 2 -412 H 0 1 H CF2 Cl H H CH(CH3 )C00" C 5 H õ
2- 413 H 0 1 H CF2 Cl H H CH(CH3 )C00' C a H 7 2 - 414 H 0 1 H CF2 C l H H CH ( CH3 ) Coo'C5SHg 2 -415 H 0 1 H CF2 Cl H H CH(CH3 )COOC C 6 H õ
2 -416 H 0 1 H CF2 Cl H CH3 H
2 -417 H 0 1 H CF2 Cl H CH3 CH3 2- 418 H 0 1 H CF2 Cl H CH3 C2 H s 2- 419 H 0 1 H CF2 Cl H CH3 "C 3 H 7 2- 420 H 0 1 H CF2 Cl H CH3 'C a H 7 2 -421 H 0 1 H CF2 Cl H CH3 'C 4 H o 2- 422 H 0 1 H CF2 Cl H CH3 "C 4 H o 2 -423 H 0 1 H CF2 Cl H CH3 CH2 CH=CH2 2 -424 H 0 1 H CF2 Cl H CH3 CH(CH a)CH =CH2 2 -425 H 0 1 H CF2 Cl H CH3 CH2 C= CH
TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R' R 5 No.
2 -426 H 0 1 H CF2 Cl H CH3 CH(CH 3)C=CH
2 -427 H 0 1 H CF2 Cl H CH3 CH2 OCH , 2 -428 H 0 1 H CFZ Cl H CH3 CH2 OC2 H 5 2 -429 F 0 1 H CF2 Cl H H H
2 -430 F 0 1 H CF2 Cl H H CH3 2- 431 F 0 1 H CF2 Cl H H C2 H s 2- 432 F 0 1 H CF2 Ci H H "C 3 H, 2 - 433 F 0 1 H CF2 Cl H H 'C 3 H, 2- 434 F 0 1 H CF2 Cl H H 'C , H 9 2 -435 F 0 1 H CF2 Cl H H "C , H 9 2 -436 F 0 1 H CF2 Cl H H CHZ CH2 C1 2- 437 F 0 1 H CF2 Cl H H CH2 CH2 Br 2 -438 F 0 1 H CF2 Cl H H CH2 CH=CH2 2 -439 F 0 1 H CF2 Cl H H CH(CH 3)CH =CH2 2- 440 F 0 1 H CF2 Cl H H CH2 CCl =CH2 2 -441 F 0 1 H CF2 Cl H H CH2 CCH
2 -442 F 0 1 H CF2 Cl H H CH(CH )C=CH
2 -443 F 0 1 H CF2 Cl H H CH2 CN
2 -444 F 0 1 H CF2 Cl H H CH2 OCH 3 2 -445 F 0 1 H CF2 Cl H H CH2 OCZ H 5 2 -446 F 0 1 H CF2 Cl H H CH2 COOH
2 -447 F 0 1 H CF2 Cl H H CH2 COOCH 3 TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R' R 5 No.
2 -448 F 0 1 H CF2 Cl H H CH2 COOC2 H s 2-449 F 0 1 H CF2 Cl - H H CH2 C00 " C 3 H;
2 - 450 F O 1 H CFZ C1 H H CH2 C00 C, H 9 2 -451 F 0 1 H CF2 Cl H H CH2 C00 " C s H õ
2-452 F 0 1 H CF2 C l H H CHZ C00 ' C 3 H, 2- 453 F 0 1 H CFa Cl H H CH2 C00 ' C s H 9 2 -454 F 0 1 H CF2 Cl H H CH2 COO C C 6 H õ
2 -455 F 0 1 H CF2 Cl H H CH(CH a)COOH
2 -456 F 0 1 H CF2 Cl H H CH(CH 3 )COOCH , 2 -457 F 0 1 H CF2 Cl H H CH(CH 3)COOC 2 H s 2 -458 F 0 1 H CF2 Cl H H CH(CH3 )C00 C 3 H, 2 -459 F 0 1 H CF2 Cl H H CH(CH3 )C00" C, H o 2 -460 F 0 1 H CF2 Cl H H CH(CH3 )C00" C 5 H õ
2- 461 F 0 1 H CF2 Cl H H CH(CH3 )C00' C 3 H, 2 -462 F 0 1 H CF2 Cl H H CH(CH3 )COOc C 5 H 9 2 -463 F 0 1 H CF2 Cl H H CH(CH3 )C00' C 6 H õ
2 -464 F 0 1 H CF2 Cl H CH3 H
2 -465 F 0 1 H CF2 Cl H CH3 CH3 2- 466 F 0 1 H CF2 Cl H CH3 C2 H s 2-467 F 0 1 H CF2 Cl H CH3 C 3 H 7 2 -468 F 0 1 H CF2 C1 H CH3 'C , H, 2-469 F 0 1 H CF2 Cl H CH3 'C 4 H 9 2- 470 F 0 1 H CF2 Cl H CH3 C 4 H 9 TABLE 2 (contn'd) Compound X Z' n R' R' R 2 No. R' R
2 -471 F 0 1 H CF2 Cl H CH3 CH2 CH=CH2 2- 472 F 0 1 H CF2 Cl H CH3 CH(CH 3)CH = CH2 2- 473 F 0 1 H CF2 Cl H CH3 CH2 C= CH
2 -474 F 0 1 H CF2 Cl H CHa CH(CH s)C=CH
2 -475 F 0 1 H CF2 Cl H CH3 CH2 OCH 3 2- 476 F 0 1 H CFZ Cl H CH3 CH2 0C2 H 5 2 -477 H S 0 H CF2 Cl H - H
2 -478 H S 0 H CF2 Cl H - CH3 2- 479 H S 0 H CF2 Cl H - C 2 H s 2- 480 H S 0 H CFZ Cl H - "C 3 H 7 2 -481 H S 0 H CF2 Cl H - "C , H 9 2 -482 H S 0 H CF2 Cl H - 'C s H 7 2-483 H S 0 I-I CF2 Cl H - 'C 4 H
2- 484 H S 0 H CF2 Cl H - CH2 CH2 Cl 2 -485 H S 0 H CF2 Cl H - CH2 CH2 Br 2 -486 H S 0 H CF2 Cl H - CH2 CH=CH2 2 -487 H S 0 H CF2 Cl H - CH(CH 3)CH =CH2 2- 488 H S 0 H CF2 C1 H - CH2 CC1 = CH2 2-489 H S 0 H CF2 Cl H - CH2 C=CH
2 -490 H S 0 H CF2 Cl H - CH(CH 3)C=CH
2 -492 H S 0 H CF2 Cl H - CH2 OCH 3 2 -493 H S 0 H CF2 Cl H - CH2 0C2 H 5 TABLE 2 (contn'd) compound X Z' n R 3 R' R 2 R' R 5 No.
2 -494 H S 0 H CF2 Cl H - CH2 COOH
2 -495 H S 0 H CF2 Cl H - CH2 COOCH , 2 -496 H S 0 H CF2 Cl H - CH2 COOC2 H s 2 - 497 H S 0 H CFZ C1 H - CHz C00 " C, H, 2 - 498 H S 0 H CF2 C l H - CHZ C00 " C, H 9 2- 499 H S 0 H CF2 C1 H - CH2 C00 " C 5 H õ
2 -500 H S 0 H CF2 C1 H - CH2 COO ' C 3 H7 2 -501 H S 0 H CF2 C1 H - CH2 COO C C s H 9 2- 502 H S 0 H CF2 C1 H - CH2 C00 ' C 6 H õ
2 -503 H S 0 H CF2 C1 H - CH(CH ,)COOH
2 -504 H S 0 H CF2 C1 H - CH(CH 3 )COOCH 3 2 -505 H S 0 H CF2 C1 H - CH(CH 3)COOC 2 H 5 2 -506 H S 0 H CF2 Cl H - CH(CH3 )C00" C a H, 2 -507 H S 0 H CF2 C1 H - CH(CH3 )C00" C, H s 2 -508 H S 0 H CF2 C1 H - CH(CH3 )C00" C 5 H õ
2- 509 H S 0 H CF2 C1 H - CH(CH3 )C00' C 3 H, 2- 510 H S 0 H CF2 Cl H - CH(CH3 )C00' C; H 9 2 -511 H S 0 H CF2 Cl H - CH(CH3 )C00' C 6 H õ
2 -512 F S 0 H CF2 Cl H - H
2 -513 F S 0 H CF2 Cl H - CH3 2 -514 F S 0 H CF2 Cl H - C2 H 5 2- 515 F S 0 H CFZ Cl H - C , H, 2- 516 F S 0 H CF2 Cl H - "C , H 9 TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R' R S
No.
2 - 517 F S 0 H CF2 C1 H - C 3 H, 2 -518 F S 0 H CF2 Cl H - 'C-, H 9 2- 519 F S 0 H CF2 Cl H - CH2 CH2 Cl 2- 520 F S 0 H CF2 Cl H - CHz CH2 Br 2 -521 F S 0 H CF2 Cl H - CH2 CH=CH2 2 -522 F S 0 H CF2 Cl H - CH(CH 3 )CH = CH2 2- 523 F S 0 H CF2 Cl H - CH2 CCl = CH2 2 -524 F S 0 H CF2 C l H - CH 2 C CH
2-525 F S 0 H CF2 Cl H - CH(CH a)C=CH
2 -526 F S 0 H CF2 Cl H - CH2 CN
2 -527 F S 0 H CF2 Cl H - CH2 OCH
2- 528 F S 0 H CF2 Cl H - CH2 0C2 H s 2 -529 F S 0 H CF2 Cl H - CH2 COOH
2 -530 F S 0 H CF2 Cl H - CH2 COOCH 3 2 -531 F S 0 H CF2 Cl H - CH2 COOC2 H 5 2 -532 F S 0 H CF2 Cl H - CH2 COO C 3 H, 2 -533 F S 0 H CF2 Cl H - CH2 COO C H
2- 534 F S 0 H CF2 Cl H - CH2 COO " C H
2 -535 F S 0 H CF2 Cl H - CH2 COO ' C a H
2 -536 F S 0 H CF2 Cl H - CHz COO ' C s H 9 2 -537 F S 0 H CF2 Cl H - CH2 COO ' C 6 H
2 -538 F S 0 H CF2 Cl H - CH(CH 3 )COOH
2 -539 F S 0 H CF2 Cl H - CH(CH 3 )COOCH 3 TABLE 2 (contn'd) Compound X Z' n R' R' R 2 R' R 5 No.
2 -540 F S 0 H CF2 Cl H - CH(CH 3)COOC 2 H;
2 -541 F S 0 H CF2 Cl H - CH(CH3 )C00" C 3 H 7 2 -542 F S 0 H CF2 Cl H - CH(CH3 )C00" C, H s 2 -543 F S 0 H CF2 Cl H - CH(CH3 )C00" C; H i, 2 -544 F S 0 H CF2 Cl H - CH(CH3 )C00' C a H 7 2 -545 F S 0 H CF2 Cl H - CH(CH3 )C00' C s H 9 2 -546 F S 0 H CF2 Cl H - CH(CH3 )C00' C 6 H õ
2 -547 H 0 0 H CF2 Cl H - H
2 -548 H 0 0 H CF2 Cl H - CH3 2- 549 H 0 0 H CF2 Cl H - C 2 H s 2 -550 H 0 0 H CF2 Cl H - "C 3 H, 2- 551 H 0 0 H CF2 Cl H - "C 4 H s 2 - 552 H 0 0 H CF2 Cl H - 'C , H, 2 -553 H 0 0 H CF2 Cl H - 'C 4 H fl 2 -554 H 0 0 H CF2 Cl H - CH2 CH=CHZ
2 -555 H 0 0 H CF2 Cl H - CH(CH 3)CH =CH2 2 -556 H 0 0 H CF2 Cl H - CH2 C=CH
2-557 H 0 0 H CF2 Cl H - CH(CH 3)C=CH
2 -558 H 0 0 H CF2 Cl H - CH2 OCH a 2- 559 H 0 0 H CF2 C1 H - CH2 0C2 H s 2- 560 F 0 0 H CF2 Cl H - H
TABLE 2 (contn'd) Compound X Z' n R 3 R' R Z R' R 5 No.
2- 562 F 0 0 H CF2 Cl H - C2 H s 2-563 F 0 0 H CF2 C1 -H - "C 3 H, 2- 564 F 0 0 H CFZ Cl H - "C , H 9 2 -565 F 0 0 H CF2 Cl H - CH2 CH=CH2 2 -566 F 0 0 H CF2 Cl H - CH(CH 3)CH = CH2 2 -567 F 0 0 H CF2 Cl H - CH2 C=CH
2 -568 F 0 0 H CF2 Cl H - CH(CH 3)C CH
2 -569 F 0 0 H CF2 Cl H - CH2 OCH , 2-570 F 0 0 H CF2 Cl H - CH2 0C2 H 5 2 -573 H 0 1 H CF3 H H C2 H s 2 -574 H 0 1 H CF3 H H "C a H
2- 575 H 0 1 H CF3 H H 'C 3 H, 2- 576 H 0 1 H CF3 H H 'C H 9 2-577 H 0 1 H CF3 H H "C t H 9 2 -578 H 0 1 H CF3 H H CH2 CH2 Cl 2 -579 H 0 1 H CF3 H H CH2 CH2 Br 2 -580 H 0 1 H CF3 H H CH2 CH=CH2 2- 581 H 0 1 H CF3 H H CH(CH 3)CH =CH2 2- 582 H 0 1 H CF3 H H CH2 CC1 = CHz 2 -583 H 0 1 H CF3 H H CH2 C= CH
2 -584 H 0 1 H CF 3 H H CH (CH 3) C= CH
TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R' R' No.
2 -587 H 0 1 H CF3 H H CH2 0C2 H s 2 -589 H 0 1 H CF3 H H CH2 COOCH , 2 -590 H 0 1 H CF3 H H CH2 COOC2 H;
2 -591 H 0 1 H CF3 H H CH2 C00 " C, H, 2 -592 H 0 1 H CF3 H H CH2 C00 " C 4 H s 2- 593 H 0 1 H CF3 H H CH2 COO C 5 H õ
2 -594 H 0 1 H CF3 H H CH2 COO ' C 3 H7 2 -595 H 0 1 H CF3 H H CH2 COO ' C s H 9 2 -596 H 0 1 H CF3 H H CH2 COO c C 6 H õ
2 -597 H 0 1 H CF3 H H CH(CH a)COOH
2 -598 H 0 1 H CF3 H H CH(CH a)COOCH 3 2 -599 H 0 1 H CF3 H H CH(CH 3)COOC 2 H s 2 -600 H 0 1 H CF3 H H CH(CH3 )COO' C 3 H 7 2- 601 H 0 1 H CF3 H H CH(CH3 )C00" C, H 9 2 -602 H 0 1 H CF3 H H CH(CH3 )C00" C 5 H õ
2 -603 H 0 1 H CF3 H H CH(CH3 )C00' C s H 7 2 -604 H 0 1 H CF3 H H CH(CH3 )COOC C s H 9 2 -605 H 0 1 H CF3 H H CH(CH3 )C00' C 6 H õ
TABLE 2 (contn'd) Compound X Z' n R' R' R 2 R~ R 5 No.
2 -608 H 0 1 H CF3 H CH3 C2 H s 2 -609 H 0 1 H CF3 H CH3 "C 3 H, 2 -610 H 0 1 H CF3 H CH3 'C 3 H, 2 -611 H 0 1 H CF3 H CH3 'C , H s 2- 612 H 0 1 H CF3 H CH3 nC , H q 2 -613 H 0 1 H CF3 H CH3 CH2 CH=CH2 2 -614 H 0 1 H CF3 H CH3 CH(CH s)CH = CHz 2 -616 H 0 1 H CF3 H CH3 CH(CH s)C=CH
2 -621 F 0 1 H CF3 H H C2 H s 2 -622 F 0 1 H CF3 H H "C 3 H, 2- 623 F 0 1 H CF3 H H 'C 3 H, 2 -624 F 0 1 H CF3 H H 'C , H 9 2 -625 F 0 1 H CF3 H H "C , H 9 2 -626 F 0 1 H CF3 H H CH2 CHZ Cl 2- 627 F 0 1 H CF3 H H CHz CH2 Br 2 -628 F 0 1 H CF3 H H CH2 CH=CH2 2 -629 F 0 1 H CF3 H H CH(CH 3)CH = CH2 2 -630 F 0 1 H CF3 H H CHZ CC1 = CH2 TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R' R s No.
2 -631 F 0 1 H CF3 H H CH Z C= CH
2 -632 F 0 1 H CF3 -H H CH(CH 3)C=CH
2 -635 F 0 1 H CF3 H H CH2 0CZ H s 2 -636 F 0 1 H CF3 H H CHz COOH
2 -637 F 0 1 H CF3 H H CHa COOCH 3 2 -638 F 0 1 H CF3 H H CHz COOC2 H s 2 -639 F 0 1 H CF3 H H CHz C00 " C, H, 2- 640 F 0 1 H CF3 H H CH2 C00 " C, H s 2- 641 F 0 1 H CF3 H H CHZ C00 " C s H õ
2 -642 F 0 1 H CF3 H H CH2 COO ' C, H, 2- 643 F 0 1 H CF3 H H CHz C00 ' C 5 H a 2 -644 F 0 1 H CF3 H H CH2 COO C C s H õ
2 -645 F 0 1 H CF3 H H CH(CH s)COOH
2 -646 F 0 1 H CF3 H H CH(CH 3)COOCH 3 2 -647 F 0 1 H CF3 H H CH(CH 3)COOC 2 H 5 2 -648 F 0 1 H CF3 H H CH(CH3 )C00" C 3 H, 2- 648 F 0 1 H CF3 H H CH(CH3 )C00" C, H o 2 -650 F 0 1 H CF3 H H CH(CH3 )C00" C s H t, 2 -651 F 0 1 H CF3 H H CH(CH3 )C00' C 3 H, 2 -652 F 0 1 H CF3 H H CH(CH3 )COOc C 5 H o 2 -653 F 0 1 H CF3 H H CH(CH3 )C00' C 6 H õ
TABLE 2 (contn'd) ~ Compound X Z' n R3 R' R2 R4 Rs No.
2 -656 F 0 1 H CF3 H CH3 C2 H;
2 -657 F 0 1 H CF3 H CH3 C a H7 2 -658 F 0 1 H CF3 H CH3 'C 3 H 7 2 -659 F 0 1 H CF3 H CH3 'C , H 9 2 -660 F 0 1 H CF3 H CH3 "C , H g 2 -661 F 0 1 H CF3 H CH3 CH2 CH=CH2 2 -662 F 0 1 H CF3 H CH3 CH(CH 3)CH =CH2 2 -664 F 0 1 H CF3 H CH3 CH(CH 3)C=CH
2 -665 F 0 1 H CF3 H CH3 CHz OCH , 2 -666 F 0 1 H CF3 H CH3 CH2 QCZ H;
2 -670 H S 0 H CF3 H - "C 3 H T
2- 671 H S 0 H CF3 H - "C 4 H 9 2 -672 H S 0 H CF3 H - C , H 7 2 -673 H S 0 H CF3 H - 'C , H
2 -674 H S 0 H CF3 H - CH2 CH2 Cl 2 -675 H S 0 H CF3 H - CH2 CH2 Br TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 No. R' R 5 2 -676 H S 0 H CF3 H - CH2 CH=CH2 2 -677 H S 0 H CF3 H - CH(CH 3)CH = CH2 2 -678 H S 0 H CF3 H - CHZ CCl = CH2 2 -679 H S 0 H CF3 H - CH 2 C= CH
2 -680 H S 0 H__CF3 H - CH(CH 3)C CH
2 -683 H S 0 H CF3 H - CH2 0C2 H;
2 -686 H S 0 H CF3 H - CH2 COOC2 H s 2 -687 H S 0 H CF3 H - CH2 C00 " C a H 7 2 -688 H S 0 H CF3 H - CHa COO " C 4 H 9 2 -689 H S 0 H CF3 H - CHZ C00 " C 5 H õ
2 -690 H S 0 H CF3 H - CH2 COO ' C 3 H7 2 -691 H S 0 H CF3 H - CHz COO ' C s H 9 2 -692 H S 0 H CF3 H - CHZ COO ' C 6 H õ
2 -693 H S 0 H CF3 H - CH(CH ,)COOH
2 -694 H S 0 H CF3 H - CH(CH 3 )COOCH , 2 -695 H S 0 H CF3 H - CH(CH3 )COOC 2 H 5 2 -696 H S 0 H CF3 H - CH(CH3 )C00" C 3 H 7 2 -697 H S 0 H CF3 H - CH(CH3 )C00" C, H 9 2 -698 H S 0 H CF3 H - CH(CH3 )C00" C 5 H õ
TABLE 2 (contn'd) :
Compound X
No. Z' n R 3 R' R Z R R
2 -699 H S 0 H CF3 H - CH(CH3 )C00' C 3 H 7 2 -700 H S 0 H CF3 H - CH(CH3 )C00' C; H 9 2 -701 H S 0 H CF3 H - CH(CH3 )C00' C 6 H õ
2 -704 F S 0 H CF3 H - C2 H s 2 - 705 F S 0 H CF3 H - C 3 H, 2- 706 F S 0 H CF3 H - C , H a 2 - 707 F S 0 H CF3 H - 'C 3 H, 2 -709 F S 0 H CF3 H - CH2 CH2 Cl 2 -710 F S 0 H CF3 H - CH2 CHZ Br 2 -711 F S 0 H CF3 H - CH2 CH=CH2 2 -712 F S 0 H CF3 H - CH(CH 3)CH = CH2 2 -713 F S 0 H CF3 H - CH2 CCI = CH2 2 -714 F S 0 H CF3 H - CH2 C=CH
2 -715 F S 0 H CF3 H - CH(CH 3)C=CH
= 2 -718 F S 0 H CF3 H - CH2 0C2 H s 2 -721 F S 0 H CF3 H - CHz COOC2 H s TABLE 2 (contn'd) Compound X Z' n R 3 R' R Z R' R 5 No.
2 - 722 F S 0 H CF3 H - CHZ C00 " C, H, 2- 723 F S 0 H CF3 H - CH2 C00 " C 4 H 9 2 -724 F S 0 H CF3 H - CH2 COO " C 5 H õ
2 -725 F S 0 H CF3 H - CH2 COO ' C, H 7 2- 726 F S 0 H CF3 H - CH2 C00 ' C s H 9 2 -727 F S 0 H CF3 H - CH2 COO C C 6 H õ
2 -728 F S 0 H CF3 H - CH(CH 3)COOH
2 -729 F S 0 H CF3 H - CH(CH 3)COOCH 3 2 -730 F S 0 H CF3 H - CH(CH3 )COOC 2 H 5 2- 731 F S 0 H CF3 H - CH(CH3 )C00" C 3 H7 2 -732 F S 0 H CF3 H - CH(CH3 )C00" C 4 H 9 2 -733 F S 0 H CF3 H - CH(CH3 )C00" C 5 H,i 2 -734 F S 0 H CF3 H - CH(CH3 )COO' C 3 H, 2 -735 F S 0 H CF3 H - CH(CH3 )COOc C a H 9 2 -736 F S 0 H CF3 H - CH(CH3 )C00' C 6 H õ
2 -739 H 0 0 H CF3 H - C2 H s 2- 740 H 0 0 H CF3 H - "C 3 H 7 2- 741 H 0 0 H CF3 H - "C , H 9 2 -742 H 0 0 H CF3 H - ' C 3 H, 2- 743 H 0 0 H CF3 H - 'C 4 H9 2 -744 H 0 0 H CF3 H - CH2 CH=CH2 TABLE 2 (contn'd) Compound X Z' n R' R' R z R' R s No.
2 -745 H 0 0 H CF3 H - CH(CH 3)CH =CH2 2 -746 H 0 0 H CF3 H - CH 2 C= CH
2 -747 H 0 0 H CF3 H - CH(CH 3)C=CH
2 -749 H 0 0 H CF3 H - CH2 0C2 H;
2 -753 F 0 0 H CF3 H - "C , H7 2 -754 F 0 0 H CF3 H - "C 4 H fl 2 -755 F 0 0 H CF3 H - CH2 CH=CH2 2 -756 F 0 0 H CF3 H - CH(CH 3)CH = CH2 2 -757 F 0 0 H CF3 H - CH2 C= CH
2 -758 F 0 0 H CF3 H - CH(CH 3)C=CH
2 -760 F 0 0 H CF3 H - CHz 0C2 H;
2 -763 H 0 1 CH3 CF3 H H C2 H s 2-764 H 0 1 CH3 CF3 H H "C a H 7 2 -765 H 0 1 CH3 CF3 H H 'C a H 7 2- 766 H 0 1 CHa CFa H H 'C 4 H s 2- 767 H 0 1 CH3 CF3 H H "C 4 H 9 TABLE 2 (contn'd) compound X Z' n R 3 R' R 2 R' R' No. 2 -768 H 0 1 CH3 CF3 H H CH2 CH2 Cl 2 -769 H O 1 CH3 CF3 H H CH2 CH2 Br 2 -770 H 0 1 CH3 CF3 H H CH2 CH = CH 2 2 -771 H 0 1 CH3 CF3 H H CH(CH 3)CH = CHZ
2 -772 H 0 1 CH3 CF3 H H CH2 CC1 =CH2 2 -773 H 0 1 CH3 CF3 H H CH2 C=CH
2 -774 H 0 1 CH3 CF3 H H CH(CH 3)C=CH
2 -777 H 0 1 CHa CF3 H H CH2 0C2 H s 2 -779 H 0 1 CH3 CF3 H H CH2 COOCH , 2 -780 H 0 1 CH3 CF3 H H CHz COOC2 H;
2- 781 H O 1 CH3 CF3 H H CH2 C00 " C 3 H 7 2 -782 H 0 1 CH3 CF3 H H CHZ C00 " C 4 H o 2 -783 H 0 1 CH3 CF3 H H CH2 C00 " C 5 H õ
2 -784 H 0 1 CHs CF3 H H CH2 COO ' C a H 7 2 -785 H 0 1 CHa CF3 H H CH2 COO ' C b H 9 2 -787 H 0 1 CH3 CF3 H H CH(CH 3)COOH
2 -788 H 0 1 CH3 CF3 H H CH(CH 3)COOCH 3 2 -789 H 0 1 CH3 CF3 H H CH(CH 3 )COOC 2 H s TABLE 2 (contn'd) Compound X Z' n R 3 R' R2 R' R 5 No.
2 -790 H 0 1 CH3 CF3 H H CH(CH3 )C00" C, H7 2 - 791 H 0 1 CH3 CF3 H H CH(CH3 )C00" C , H 9 2 -792 H 0 1 CH3 CF3 H H CH(CH3 )C00" C; H õ
2 -793 H 0 1 CH3 CF3 H H CH(CH3 )C00' C 3 H 7 2 -794 H 0 1 CH3 CF3 H H CH(CH, )C00' C 5 H g 2 -795 H 0 1 CH3 CF3 H H CH(CH3 )C00' C 6 H õ
2 -796 H 0 1 CHa CF3 H CH3 H
2 -797 H 0 1 CH3 CF3 H CHa CH3 2 -798 H 0 1 CH3 CF3 H CH3 C2 H s 2 -799 H 0 1 CH3 CF3 H CH3 C 3 H, 2 -800 H 0 1 CH3 CF3 H CH3 'C 3 H, 2- 801 H 0 1 CH3 CF3 H CH3 'C , H 9 2 -802 H 0 1 CH3 CF3 H CHa "C , H 9 2 -803 H 0 1 CH3 CF3 H CH3 CHZ CH = CH2 2 -804 H 0 1 CH3 CF3 H CH3 CH(CH a)CH = CH2 2 -805 H 0 1 CH3 CF3 H CH3 CH2 C= CH
2 -806 H 0 1 CH3 CF3 H CH3 CH(CH 3 )C=CH
2 -811 F 0 1 CH3 CF3 H H C2 H s 2-812 F 0 1 CH3 CF3 H H "C 3 H, TABLE 2 (contn'd) Compound X Z' n R' R' R 2 R' R5 No.
2- 813 F 0 1 CH3 CF3 H H 'C , H 7 2-814 F 0 1 CH3 CF3 H H 'C , H a 2- 815 F 0 1 CH3 CF3 H H "C , H 9 2 -816 F 0 1 CH3 CF3 H H CH2 CH2 Cl 2 -817 F 0 1 CH3 CF3 H H CH2 CH2 Br 2 -818 F 0 1 CH3 CF3 H H CH2 CH=CH2 2- 819 F 0 1 CH3 CF3 H H CH(CH 3)CH = CH2 2 -820 F 0 1 CH3 CF3 H H CH2 CCl =CH2 2 -821 F 0 1 CH3 CF3 H H CH2 C=CH
2 -822 F 0 1 CH3 CF3 H H CH(CH 3)C=CH
2 -824 F 0 1 CH3 CFa H H CHz OCH 3 2 -827 F 0 1 CH3 CF3 H H CHZ COOCH , 2- 828 F 0 1 CH3 CF3 H H CHz COOCz H s 2 -829 F 0 1 CH3 CF3 H H CH2 C00 " C, H 7 2 -830 F 0 1 CH3 CF3 H H CHZ COO " C4 H 9 2 -831 F 0 1 CH3 CF3 H H CH2 COO " C 5 H õ
2 -832 F 0 1 CH3 CF3 H H CHZ COO ' C, H r 2 -833 F 0 1 CH3 CF3 H H CH2 COO C C s H y 2 -835 F 0 1 CHa CF3 H H CH(CH 3)COOH
TABLE 2 (contn'd) F Compound X Z' n R3 R' R 2 R4 R 5 No.
2 -836 F 0 1 CH3 CF3 H H CH(CH 3 )COOCH
2 -837 F 0 1 CH3 CF3 H- H CH(CH 3)COOC 2 H;
2 -838 F 0 1 CH3 CF3 H H CH(CH3 )C00" C a H T
2 -839 F 0 1 CH3 CF3 H H CH(CH3 )C00" C4 H 9 2 -840 F 0 1 CH3 CF3 H H CH(CH3 )C00" C 5 H õ
2 -841 F 0 1 CH3 CF3 H H CH(CH, )C00' C, H
2 -842 F 0 1 CH3 CF3 H H CH(CH3 )C00' C 5 H
2 -843 F 0 1 CH3 CF3 H H CH(CH3 )COOc C o H 1, 2 -846 F 0 1 CH3 CF3 H CH3 C 2 H s 2- 847 F 0 1 CH3 CF3 H CH3 "C a H, 2- 848 F 0 1 CH3 CF3 H CHa 'C a H i 2 -849 F 0 1 CH3 CF3 H CH3 'C , H 9 2 -850 F 0 1 CH3 CF3 H CH3 "C 4 H 9 2 -851 F 0 1 CH3 CF3 H CH3 CH2 CH = CHz 2 -852 F 0 1 CH3 CF3 H CH3 CH(CH 3)CH = CH2 2 -853 F 0 1 CH3 CF3 H CHa CH2 C CH
2 -854 F 0 1 CH3 CF3 H CH3 CH(CH ,)C=CH
TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R' R 5 ~
No.
2- 860 H S 0 CH3 CF3 H -, "C 3 H, 2- 861 H S 0 CH3 CF3 H - "C 4 H 9 2 -862 H S 0 CH3 CF3 H 'C s H z 2 -863 H S 0 CH3 CF3 H 'C 4 H Q
2 -864 H S 0 CH3 CF3 H - CH2 CH2 Cl 2 -865 H S 0 CH3 CF3 H - CHZ CHZ Br 2 -866 H S 0 CH3 CF3 H - CH2 CH= CH2 2 -867 H S 0 CH3 CF3 H - CH(CH ,)CH = CHz 2 -868 H S 0 CH3 CF3 H - CH2 Ccl = CHz 2 -870 H S 0 CH3 CF3 H - CH(CH 3)C=CH
2 -873 H S 0 CH3 CF3 H - CH2 OC2 H s 2 -876 H S 0 CH3 CF3 H - CHz COOC2 H 5 2 -877 H S 0 CH3 CF3 H - CH2 C00 " C 3 H 7 2 -878 H S 0 CH3 CF3 H - CHz C00 " C 4 H 9 2 -879 H S 0 CH3 CF3 H - CH2 COO " C b H,i 2 -880 H S 0 CH3 CF3 H - CHz COO ' C3 H 7 WO 97/07104 PCT/Jl'96/02311 TABLE 2 (contn'd) Compound X Z' n R 3 R' R Z R' R s No.
2 -882 H S 0 CH3 CF3 H - CH2 COO C C 6 H õ
2- 883 H S 0 CH3 CF3 H - CH(CH 3)COOH
2 -884 H S 0 CH3 CF3 H - CH(CH 3)COOCH 3 2 -885 H S 0 CH3 CF3 H - CH(CH3 )COOC 2 H 5 2 -886 H S 0 CH3 CF3 H - CH(CH3 )C00" C 3 H 7 2 -887 H S 0 CH3 CF3 H - CH(CH3 )C00" C 4 H 9 2 -888 H S 0 CH3 CF3 H - CH(CH3 )CO0 C 5 H õ
2 -889 H S 0 CH3 CF3 H - CH(CH3 )COO' C 3 H 7 2 -890 H S 0 CH3 CF3 H - CH(CH3 )COOc C s H 9 2 -891 H S 0 CH3 CF3 H - CH(CH3 )COOc C 6 H õ
2- 895 F S 0 CH3 CF3 H - "C 3 H 7 2 -897 F S 0 CH3 CF3 H - 'C 3 H z 2 -899 F S 0 CH3 CF3 H - CH2 CH2 Cl 2 -900 F S 0 CH3 CF3 H - CH2 CH2 Br 2 -901 F S 0 CH3 CF3 H - CH2 CH= CH2 2 -902 F S 0 CH3 CF3 H - CH(CH 3)CH = CH2 Y =
2 -903 F S 0 CH3 CF3 H - CHZ CCl = CH2 TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R' R s No.
2-904 F S 0 CH3 CF3 H - CH2 C=CH
2 -905 F S 0 CH3 CF3 H - CH(CH 3)C=CH
2 -906 F S 0 CH3 CF3 H - CH 2. CN
2 -908 F S 0 CH3 CF3 H - CH2 0C2 H s 2 -911 F S 0 CH3 CF3 H - CHz COOC2 H;
2- 912 F S 0 CH3 CF3 H - CH2 C00 " C, H 7 2 -913 F S 0 CH3 CF3 H - CH2 C00 " C, H q 2 -914 F S 0 CH3 CF3 H - CH2 COO C s Hi, 2 -915 F S 0 CH3 CF3 H - CH2 COO ' C 3 H7 2- 916 F S 0 CH3 CF3 H - CH2 COO ' C s H 9 2 -917 F S 0 CH3 CF3 H - CH2 COO C C 6 H,1 2 -918 F S 0 CH3 CF3 H - CH(CH 3)COOH
2 -919 F S 0 CH3 CF3 H - CH(CH 3)COOCH 3 2- 920 F S 0 CH3 CF3 H - CH(CH3 )COOC 2 H s 2 -921 F S 0 CH3 CF3 H - CH(CH3 )C00" C, H 7 2 -922 F S 0 CH3 CF3 H - CH(CH3 )C00" C, H 9 2 -923 F S 0 CH3 CF3 H - CH(CH3 )C00" C s H õ
2 -924 F S 0 CH3 CF3 H - CH(CH3 )COO' C 3 H T
2 -925 F S 0 CH3 CF3 H - CH(CH3 )C00' C s H o 2 -926 F S 0 CH3 CF3 H - CH(CH3 )C00' C 6 H õ
TABLE 2 (contn'd) y Compound X Z' n R' R' R 2 R' R 5 No.
2 -929 H 0 0 CH3 CF3 H - C2 H s 2 -930 H 0 0 CH3 CF3 H - "C 3 H, 2 -932 H 0 0 CH3 CF3 H - 'C a H 1 2 -933 H 0 0 CH3 CF3 H - 'C , H a 2 -934 H 0 0 CH3 CF3 H - CH2 CH=CH2 2 -935 H 0 0 CH3 CF3 H - CH(CH 3)CH = CH2 2 -936 H 0 0 CHa CF3 H - CH2 C=CH
2 -937 H 0 0 CH3 CF3 H - CH(CH 3)C=CH
2 -938 H 0 0 CHa CF3 H - CHZ OCH a 2- 939 H 0 0 CH3 CF3 H - CH2 0C2 H;
2 -942 F 0 0 CH3 CF3 H - Cz H 5 2 -945 F 0 0 CH3 CF3 H - CH2 CH=CH2 2 -946 F 0 0 CH3 CF3 H - CH(CH 3)CH =CH2 2 -948 F 0 0 CH 3 CF 3 H - CH(CH 3 ) C= CH
TABLE 2 (contn'd) Compound X Z' n R 3 R' R 2 R' R 5 No.
2 -950 F 0 0 CH3 CF3 H - CH2 0CZ H;
WO 97f07104 PCT'/JP96/023I I
Compounds of the formula:
X O R'-Y I N Rt N-Compound X y Z2 R3 R' R 2 I~ 6 No.
3 - 1 H F 0 H CF2 Cl H CH3 3 - 2 H Cl 0 H CF2 Cl H CH3 3 - 3 H Br 0 H CF2 C1 H CH3 3 - 4 F F 0 H CF2 Cl H CH3 3 - 5 F C1 0 H CF2 Cl H CH3 3- 6 F Br 0 H CFZ C1 H CH3 3 - 7 H F 0 H CF2 Cl CHa CH3 3 - 8 H C1 0 H CF2 Cl CHa CH3 3 - 9 H Br 0 H CF2 Cl CH3 CH3 3 -10 F F 0 H CF2 Cl CH3 CH3 3- 11 F C1 0 H CF2 Cl CH3 CH3 3 -12 F Br 0 H CF2 Cl CH3 CH3 3- 13 H F 0 H CF2 Cl H C2 H
3- 14 H C1 0 H CF2 Cl H C2 H s TABLE 3 (contn'd) Compound x Y Z 2 R3 R' R 2 R 6 No.
3 -15 H Br 0 H CF2 Cl H C2 H;
3- 16 F F 0 H CF2 Cl H C 2 H s 3 -17 F C1 0 H CF2 Cl H C2 H;
3- 18 F Br 0 H CF2 Cl H C2 H 5 3 -19 H F 0 H CF2 Cl CH3 C2 H;
3 -20 H C1 0 H CF2 Cl CH3 C2 H s 3 -21 H Br 0 H CF2 Cl CH3 C2 H s 3 -22 F F 0 H CFa Cl CH3 C2 H s 3 -23 F C1 0 H CF2 Cl CH3 C2 H;
3 -24 F Br 0 H CF2 Cl CH3 C2 H s 3 -25 H F 0 H CF2 Cl CH3 CH2 Br 3 -26 H F 0 H CF2 Cl CH3 CH Br2 3 -27 H F 0 H CF2 Cl CH3 CBr 3 3 -28 H F 0 H CF2 Cl CH3 CHO
3 -29 H F 0 H CF2 Cl CH3 CN
3 -30 H F 0 H CF2 Cl CH3 COOH
3 -31 H F 0 H CF2 Cl CH3 CH2 OH
3 -32 H F 0 H CF2 Cl CH3 CH2 OCH 3 3- 33 H F 0 H CF2 Cl CH3 CH2 0C2 H 5 3 -34 H F 0 H CF2 Cl CH3 CH2 0' C a H;
3 -35 H F 0 H CF2 Cl CH3 CH2 OCH 2 OCH 3 3 -36 H F 0 H CF2 Cl CH3 CH2 OCH 2 0C2 H s 3 -37 H F 0 H CF2 Cl CHa CHa OCOCH 3 TABLE 3 (contn'd) Compound x Y Z 2 R' R' R 2 R 6 No.
3 -38 H F 0 H CF2 Cl CH3 CH2 OCOC2 H 5 3 -39 H F 0 H CF2 Cl CH3 CH2 OCO ' C 3 H
3 -40 H F 0 H CF2 Cl CH3 CH2 OCOCH 2 Cl 3- 41 H F 0 H CF2 Cl CH3 CH2 OCOCC13 3 -42 H F 0 H CF2 Cl CH3 CH2 OCOCF 3 3 -43 H F 0 H CF2 Cl CH3 COOCH3 3 -44 H F 0 H CF2 Cl CH3 COOC2 H;
3- 45 H F 0 H CF2 C1 CH3 C00 " C 3 H 7 3 -46 H F 0 H CF2 Cl CH3 C00 " C 4 H 9 3 -47 H F 0 H CF2 Cl CH3 C00 " C; H
3- 48 H F 0 H CFz C1 CH3 C00 ' C 3 H 7 3- 49 H F 0 H CF2 Cl CH3 COCH3 3- 50 H F _O H CF2 Cl CH3 COCz H;
3 -51 H C1 0 H CF2 Cl CH3 CH2 Br 3 -52 H C1 0 H CF2 Cl CH3 CH Br2 3- 53 H Cl 0 H CF2 Cl CH3 CBr3 3- 54 H C1 0 H CF2 Cl CH3 CHO
3 -55 H C1 0 H CF2 Cl CH3 CN
3 -56 H C1 0 H CF2 Cl CH3 COOH
3 -57 H C1 0 H CF2 Cl CH3 CH2 OH
3- 58 H C1 0 H CF2 Cl CH3 CH2 OCH 3 3- 59 H Cl 0 H CF2 Cl CH3 CH2 0C2 H;
3 -60 H Cl 0 H CF2 Cl CH3 CH2 0' C 3 H
TABLE 3 (contn'd) Compound X Y Z2 R a R' R 2 R6 No.
3 -61 H C1 0 H CF2 Cl CHa CH2 OCH 2 OCH a 3 -62 H C1 0 H CF2 Cl CHa CH2 OCH 2 0C2 H s 3 -63 H C1 0 H CF2 Cl CH3 CH2 OCOCH 3 3- 64 H C1 0 H CF2 Cl CHa CH2 OCOC2 H s 3- 65 H C1 0 H CF2 Cl CHa CH2 OCO ' C a H7 3 -66 H Cl 0 H CF2 Cl CHa CH2 OCOCH 2 C1 3 -67 H C1 0 H CF2 Cl CHa CH2 OCOCCI3 3 -67 H C1 0 H CF2 Cl CH3 CHz OCOCF a 3 -69 H C1 0 H CF2 Cl CHs COOCH3 3 -70 H C1 0 H CF2 C1 CHa COOC2 H s 3-71 H C1 0 H CF2 CI CHa C00 " C a H 7 3 - 72 H C1 0 H CF2 C1 CHa C00 " C, H 9 3- 73 H C1 0 H CF2 Cl CH3 COO " C s H õ
3-74 H C1 0 H CF2 Cl CHa COO ' C a H 7 3 -75 H C1 0 H CF2 Cl CH3 COCH3 3 -76 H C1 0 H CF2 Cl CH3 COC2 H s 3 -77 F F 0 H CF2 Cl CHa CH2 Br 3 -78 F F 0 H CF2 Cl CHa CH Br2 3 -79 F F 0 H CF2 Cl CHa CBr3 3 -80 F F 0 H CF2 Cl CH3 CliO
3 -81 F F 0 H CF2 Cl CHa CN
3 -82 F F 0 H CF2 Cl CH3 COOH 3 -83 F F 0 H CF2 Cl CHa CHz OH
WO 97f07104 PCT/JP96/02311 TABLE 3 (contn'd) = Compound x Y Z 2 R 3 R' R 2 R 6 No.
3 -84 F F 0 H CF2 C1 CH3 CHz 0CH 3 3- 85 F F 0 H CF2 Cl CHa CH2 0C2 H s 3 -86 F F 0 H CF2 Cl CH3 CH2 0' C 3 H, 3 -87 F F 0 H CF2 Cl CH3 CH2 OCH 2 OCH a 3 -88 F F 0 H CF2 Cl CHI CH2 0CH 2 0C2 H s 3 -89 F F 0 H CF2 Cl CH3 CH2 OCOCH 3 3- 90 F F 0 H CF2 Cl CH3 CH2 OCOC2 H
3- 91 F F 0 H CFa C1 CHa CHz OCO ' C a H 7 3- 92 F F 0 H CF2 Cl CH3 CH2 OCOCH 2 Cl 3- 93 F F 0 H CF2 Cl CH3 CH2 OCOCCI3 3 -94 F F 0 H CF2 Cl CH3 CHz OCOCF 3 3 -95 F F 0 H CF2 Cl CH3 COOCH3 3 -96 F F 0 H CF2 Cl CH3 COOC2 H;
3 -97 F F 0 H CF2 Cl CH3 C00 " C 3 H
3 - 98 F F 0 H CF2 C 1 CH3 C00 C, H 9 3- 99 F F 0 H CF2 Cl CH3 COO " C s H
3 -100 F F 0 H CF2 Cl CH3 COO ' C, H, 3- 101 F F 0 H CF2 Cl CH3 COCH3 3- 102 F F 0 H CF2 Cl CHa COC2 H s 3 -103 F C1 0 H CF2 Cl CH3 CHZ Br 3- 104 F C1 0 H CF2 Cl CH3 CH Br2 3- 105 F C1 0 H CF2 Cl CH3 CBr3 TABLE 3 (contn'd) Compound x Z 2 R 3 R' R 2 R 6 No.
3 -106 F C1 0 H CF2 Cl CH3 CHO
3 -107 F C1 0 H CF2 Cl CH3 CN
3 -108 F C1 0 H CF2 Cl CH3 COOH
3 -109 F C1 0 H CF2 Cl CH3 CHZ OH
3 -110 F Ci 0 H CF2 Cl CH3 CH2 OCH , 3 -111 F Cl 0 H CF2 Cl CH3 CH2 0CZ H s 3 -112 F Cl 0 H CF2 Cl CH3 CHZ 0' C a H
3- 113 F C1 0 H CF2 Cl CHs CHz OCH 2 OCH 3 3 -114 F C1 0 H CF2 Cl CH3 CH2 OCH 2 0C2 H s 3- 115 F Cl 0 H CF2 Cl CH3 CH2 OCOCH , 3- 116 F C1 0 H CF2 Cl CH3 CH2 OCOC2 H s 3- 117 F Ci 0 H CF2 Cl CH3 CH2 OCO ' C, H T
3 -118 F Cl 0 H CF2 Cl CHa CH2 OCOCH 2 C1 3- 119 F Cl 0 H CF2 Cl CHa CH2 OCOCCI3 3- 120 F C1 0 H CF2 Cl CH3 CH2 OCOCF 3 3 -121 F Cl 0 H CF2 Cl CH3 COOCH3 3- 122 F C1 0 H CF2 Cl CH3 COOC2 H s 3- 123 F Cl 0 H CF2 Cl CH3 C00 " C 3 H, 3 -124 F Cl 0 H CF2 Cl CH3 C00 " C, H s 3- 125 F C1 0 H CFZ Cl CH3 COO " C s H õ
3- 126 F C1 0 H CF2 Cl CH3 COO ' C, H
3- 127 F Cl 0 H CF2 Cl CH3 COCH3 3- 128 F C1 0 H CF2 Cl CH3 COC2 H
TABLE 3 (contn'd) Compound x Y Z 2 R 3 R' R 2 R 6 No.
3- 131 H Br 0 H CFs H CH3 3- 134 F Br 0 H CF3 H CH3 3- 137 H Br 0 H CF3 CH3 CH3 3 -140 F Br 0 H CF3 CH3 CH3 3 -142 H C1 0 H CF3 H C2 H s 3 -143 H Br 0 H CF3 H C2 H s 3- 146 F Br 0 H CF3 H C2 H;
3- 147 H F 0 H CF3 CH3 C2 H;
3- 149 H Br 0 H CF3 CH3 C2 H s 3- 150 F F 0 H CF3 CHa C2 H s TABLE 3 (contn'd) Compound x Y Z 2 R 3 R' R 2 R 6 No.
3 -152 F Br 0 H CF3 CH3 C2 H 5 3 -153 H F 0 H CF3 CH3 CHZ Br 3 -154 H F 0 H CF3 CH3 CH Br2 3- 155 H F 0 H CF3 CH3 CBr 3 3 -162 H F 0 H CF3 CH3 CH2 0' C 3 H;
3- 164 H F 0 H CF3 CH3 CHz OCH 2 0C2 H 5 3 -166 H F 0 H CF3 CH3 CHZ OCOC2 H;
3 -167 H F 0 H CF3 CH3 CH2 OCO ' C 3 H, 3- 168 H F 0 H CF3 CH3 CH2 OCOCH 2 Cl 3- 169 H F 0 H CF3 CH3 CHZ OCOCCI'3 3 -172 H F 0 H CF3 CH3 COOC2 H;
3 -173 H F 0 H CF3 CH3 C00 " C 3 H, 3- 174 H F 0 H CF3 CH3 C00 C, H 9 TABLE 3 (contn'd) Compound X Y ZZ Ra R' R2 R6 No.
3- 175 H F 0 H CF3 CH3 C00 " C 5 H õ
3 -176 H F 0 H CF3 CH3 COO ' C a H, 3 -179 H C1 0 H CF3 CH3 CH2 Br 3 -180 H C1 0 H CF3 CH3 CH Br2 3- 181 H C1 0 H CF3 CH3 CBr3 3 -182 H CI 0 H CF3 CHa CHO
3- 187 H C1 0 H CF3 CH3 CHa 0Ca H s 3 -188 H C1 0 H CF3 CH3 CH2 0' C 3 H, 3- 190 H C1 0 H CF3 CH3 CH2 OCH 2 0Cz H s 3- 191 H C1 0 H CF3 CH3 CHz OCOCH a 3- 192 H C1 0 H CF3 CH3 CHz OCOC2 H 5 3 -193 H Ci 0 H CF3 CH3 CH2 OCO ' C 3 H
3 -194 H C1 0 H CF3 CH3 CHz OCOCH 2 Cl 3- 196 H C1 0 H CF3 CH3 CHZ OCOCF a 3- 197 H C1 0 H CF3 CHa COOCH3 TABLE 3 (contn'd) Compound x Y Z 2 R3 R ' R 2 R G No.
3 -198 H C1 0 H CF3 CH3 COOC2 H s 3- 199 H C1 0 H CF3 CHa C00 " C 3 H, 3 -200 H C1 0 H CF3 CHa COO " C 4 H 9 3 -201 H C1 0 H CF3 CH3 C00 " C s H õ
3 -202 H C1 0 H CF3 CH3 COO ' C 3 H 7 3 -204 H C1 0 H CF3 CH3 COC2 H s 3 -205 F F 0 H CF3 CH3 CH2 Br 3 -206 F F 0 H CF3 CH3 CH Br2 3 -207 F F 0 H CF3 CH3 CBr3 3 -213 F F 0 H CF3 CH3 CH2 0C2 H b 3- 214 F F 0 H CF3 CHs CH2 0' C, H 7 3- 215 F F 0 H CF3 CH3 CH2 OCH 2 OCH , 3- 216 F F 0 H CF3 CH3 CH2 OCH 2 0C2 H s 3 -217 F F 0 H CF3 CH3 CH2 OCOCH , 3- 218 F F 0 H CF3 CH3 CH2 OCOC2 H s TABLE 3 (contn'd) Compound x y Z 2 R3 R' R 2 R 6 No.
3 -220 F F 0 H CF3 CH3 CH2 OCOCH 2 Cl 3 -222 F F 0 H CF3 CH3 CHZ OCOCF a 3 -224 F F 0 H CFa CH3 COOC2 H s 3 -225 F F 0 H CF3 CHa C00 " C 3 H 7 3 -226 F F 0 H CF3 CH3 COO " C 4 H 9 3 -227 F F 0 H CF3 CH3 C00 " C 5 H
3 -228 F F 0 H CF3 CH3 COO ' C 3 H, 3 -230 F F 0 H CF3 CH3 COC2 H;
3 -231 F C1 0 H CF3 CH3 CH2 Br 3 -232 F C1 0 H CF3 CH3 CH Br2 3 -233 F Ci 0 H CF3 CH3 CBr3 3 -234 F Cl 0 H CF3 CH3 CHO
3 -235 F Cl 0 H CF3 CH3 CN
3 -238 F C1 0 H CF3 CH3 CH2 OCH , '= 3- 239 F C1 0 H CF3 CH3 CH2 OC2 H 5 3- 240 F Cl 0 H CF3 CHa CH2 0' C a H 7 3 -241 F Cl 0 H CF3 CH3 CH2 OCH 2 OCH a 3 -242 F Cl 0 H CF3 CH3 CHz OCH 2 0C2 H s TABLE 3 (contn'd) Compound X Y Z R' R' R 2 R 6 No.
3 -244 F C1 0 H CF3 CH3 CH2 OCOCz H 5 3 -245 F C1 0 H CF3 CH3 CH2 OCO ' C 3 H, 3 -246 F C1 0 H CF3 CH3 CH2 OCOCH 2 Cl 3- 247 F Ci 0 H CF3 CH3 CH2 OCOCCI3 3 -248 F C1 0 H CF3 CH3 CH2 OCOCF , 3 -250 F C1 0 H CF3 CH3 COOC2 H s 3- 251 F C1 0 H CF3 CH3 C00 " C 3 H 7 3 -252 F C1 0 H CF3 CH3 C00 " C 4 H s 3 -253 F Cl 0 H CF3 CH3 C00 C 5 H õ
3 -254 F C1 0 H CF3 CH3 COO ' C s H 7 3 -256 F C1 0 H CF3 CH3 COC2 H;
3 -257 H F 0 H CF2 Cl H CH2 Br 3 -258 H F 0 H CF2 Cl H CH Br2 3 -259 H F 0 H CF2 Cl H CBr , 3 -260 H F 0 H CF2 Cl H CHO
3 -261 H F 0 H CF2 Cl H CN
3 -262 H F 0 H CF2 Cl H COOH
3 -263 H F 0 H CF2 Cl H CH2 OH 3 -264 H F 0 H CF2 Cl H CH2 OCH 3 3- 265 H F 0 H CF2 Cl H CH2 OC2 H 5 TABLE 3 (contn'd) Compound x y Z 2 R 3 R' R 2 R 6 No.
3-266 H F 0 H CF2 C1 H CHz 0' C 3 H, 3 -267 H F 0 H CF2 Cl H CH2 OCH 2 OCH a 3 -268 H F 0 H CF2 Cl H CH2 OCH 2 0C2 H;
3 -269 H F 0 H CF2 Cl H CH2 OCOCH 3 3 -270 H F 0 H CF2 Cl H CH2 OCOC2 H
3- 271 H F 0 H CF2 C1 H CH2 OCO ' C a H 7 3 -272 H F 0 H CF2 Cl H CH2 OCOCH 2 Cl 3 -273 H F 0 H CF2 Cl H CH2 OCOCCIa 3 -274 H F 0 H CF2 Cl H CH2 OCOCF 3 3 -275 H F 0 H CF2 Cl H COOCH3 3 -276 H F 0 H CF2 Cl H COOC2 H;
3 - 277 H F 0 H CF2 Cl H C00 C3 H, 3 - 278 H F 0 H CFZ CI H C00 C, H 9 3- 279 H F 0 H CFz Cl H C00 " C 5 H õ
3 -280 H F 0 H CF2 Cl H COO ' C, H 7 3 -281 H F 0 H CF2 Cl H COCH3 3 -282 H F 0 H CF2 Cl H COC2 H s 3 -283 H Cl 0 H CF2 Cl H CH2 Br 3 -284 H C1 0 H CF2 Cl H CH Br2 3 -285 H Cl 0 H CF2 Cl H CBr3 3 -286 H Cl 0 H CF2 Cl H CHO
3 -288 H C1 0 H CF2 Cl H COOH
TABLE 3 fcontn'dl Compound. X y Z 2 R 3 R' R Z R 6 No.
3 -289 H ci 0 H CF2 Cl H CH2 OH
3 -290 H C1 0 H CF2 Cl H CH2 OCH 3 3- 291 H ci 0 H CF2 Cl H CHZ OC2 H 5 3 - 292 H C1 0 H CFZ C l H CHz 0' C, H 7 3 -293 H C1 0 H CF2 Cl H CH2 OCH 2 OCH 3 3 -294 H Cl 0 H CF2 Cl H CH2 OCH 2 0C2 H s 3 -295 H ci 0 H CF2 Cl H CH2 OCOCH 3 3 -296 H C1 0 H CF2 Cl H CH2 OCOC2 H s 3 -297 H Cl 0 H CF2 Cl H CH2 OCO ' C 3 H 7 3 -298 H C1 0 H CF2 Cl H CH2 OCOCH 2 Cl 3- 299 H Cl 0 H CF2 Cl H CHZ OCOCC13 3 -300 H C1 0 H CF2 Cl H CH2 OCOCF 3 3 -301 H C1 0 H CF2 Cl H COOCH3 3 -302 H C1 0 H CF2 Cl H COOC2 H 5 3 -303 H C1 0 H CF2 Cl H C00 " C 3 H, 3 - 304 H C l 0 H CFz C l H C00 " C4 H 9 3 -305 H ci 0 H CF2 Cl H C00 " C 5 H 11 3 - 306 H C l 0 H CFz C1 H C00 ' C 3 H, 3 -307 H Cl 0 H CF2 Cl H COCH3 3- 308 H C1 0 H CF2 Cl H COC2 H s 3 -309 F F 0 H CF2 Cl H CH2 Br 3 -310 F F 0 H CF2 Cl H CH Br2 3 -311 F F 0 H CF2 Cl H CBr3 TABLE 3 (contn'd) Compound X Y Z Z R 3 R' R 2 R 6 No.
3 -312 F F 0 H CF2 Cl H CHO
3 -313 F F 0 H CF2 Cl H CN
3 -314 F F 0 H CF2 Cl H COOH
3 -315 F F 0 H CF2 Cl H CH2 OH
3 -316 F F 0 H CF2 Cl H CH2 OCH 3 3 -317 F F 0 H CF2 Cl H CH2 0C2 H
3 -318 F F 0 H CF2C1 H CH2 0' C3H, 3 -319 F F 0 H CF2 Cl H CH2 OCH 2 OCH , 3 -320 F F 0 H CF2 Cl H CH2 OCH 2 OC2 H 5 3 -321 F F 0 H CF2 Cl H CHz OCOCH 3 3 -322 F F 0 H CFz Cl H CH2 OCOC2 H 5 3 -323 F F 0 H CF2 Cl H CH2 OCO ' C 3 H, 3 -324 F F 0 H CF2 Cl H CHz OCOCH 2 Cl 3- 325 F F 0 H CF2 Cl H CH2 OCOCCIa 3 -326 F F 0 H CF2 Cl H CH2 OCOCF 3 3 -327 F F 0 H CF2 Cl H COOCH3 3 -328 F F 0 H CF2 Cl H COOC2 H 5 3-329 F F 0 H CF2 C1 H C00 n C 3 H, 3 -330 F F 0 H CF2 Cl H COO C, H s 3- 331 F F 0 H CF2 Cl H C00 " C 5 H õ
3 -332 F F 0 H CF2 C l H COO ' C 3 H, 3 -333 F F 0 H CF2 Cl H COCH3 TABLE 3 (contn'd) Compound X y ZZ R3 R' R 2 Rs No.
3 -334 F F 0 H CF2 C1 H COC2 H s 3 -335 F C1 0 H CF2 Cl H CH2 Br 3 -336 F C1 0 H CF2 Cl H CH Br2 3-337 F C1 0 H CF2 CI H CBr3 3 -338 F Ci 0 H CF2 Cl H CHO
3 -339 F C1 0 H CF2 Cl H CN
3 -340 F C1 0 H CF2 Cl H COOH
3 -341 F Cl 0 H CF2 Cl H CHz OH
3 -342 F C1 0 H CF2 Cl H CH2 OCH 3 3- 343 F C1 0 H CF2 Cl H CHz OCz H 5 3- 344 F C1 0 H CF2 Cl H CH2 0' C, H7 3 -345 F Cl 0 H CF2 Cl H CHz OCH 2 OCH ;
3 -346 F Cl 0 H CF2 Cl H CH2 OCH 2 0C2 H s 3 -347 F C1 0 H CF2 Cl H CH2 OCOCH , 3 -348 F Ci 0 H CF2 Cl H CHz OCOC2 H 5 3 -349 F Cl 0 H CF2 Cl H CHZ OCO ' C, H 7 3 -350 F C1 0 H CF2 Cl H CH2 OCOCH 2 Cl 3 -351 F C1 0 H CF2 Cl H CH2 OCOCCI3 3 -352 F C1 0 H CF2 Cl H CHz OCOCF 3 3 -353 F C1 0 H CF2 Cl H COOCH3 3 -354 F C1 0 H CF2 Cl H COOC2 H s 3- 355 F C1 0 H CF2 C1 H C00 " C 3 H 7 3 -356 F C1 0 H CF2 Cl H C00 " C, H fl TABLE 3 (contn'd) Compound x y Z 2 R 3 R' R 2 R 6 No.
3 -357 F C1 0 H CF2 Cl H C00 C s H
3 -358 F C1 0 H CF2 Cl H COO ' C 3 H T
3 -359 F C1 0 H CF2 Cl H COCH3 3 -360 F C1 0 H CF2 Cl H COC2 H 5 3 -361 F Br 0 H CF3 H C2 H s 3 -362 H F 0 H CF3 H CH2 Br 3 -363 H F 0 H CF3 H CH Br2 3 -364 H F 0 H CF3 H CBr 3 3 -369 H F 0 H CF3 H CHz OCH 3 3 -371 H F 0 H CF3 H CH2 0' C 3 H T
3 -373 H F 0 H CF3 H CHa OCH 2 0C2 H s 3 -374 H F 0 H CF3 H CH2 OCOCH , 3 -375 H F 0 H CF3 H CHz OCOC2 H s 3 -376 H F 0 H CF3 H CH2 OCO ' C, H T
3 -377 H F 0 H CF3 H CHZ OCOCH 2 Cl 3 -378 H F 0 H CF3 H CHz OCOCCI3 3 -379 H F 0 H CF3 H CHz OCOCF 3 TABLE 3 (contn'd) Compound X Y Z Z R' R' R 2 R 6 No. 3 -380 H F 0 H CF3 H COOCH3 3 -381 H F 0 H CF3 H COOC 2 H s 3 -382 H F 0 H CF3 H C00 " C 3 H
3 -384 H F 0 H CF3 H C00 " C H
3 -385 H F 0 H CF3 H COO ' C, H, 3 -388 H C1 0 H CF3 H CH2 Br 3 -389 H Ci 0 H CF3 H CH Br2 3 -390 H C1 0 H CF3 H CBr3 3 -391 H Ci 0 H CF3 H CHO
3 -396 H C1 0 H CF3 H CH2 0C2 H s 3-397 H C1 0 H CF3 H CH2 01 C 3 H, 3 -398 H C1 0 H CF3 H CH2 OCH 2 OCH , 3 -399 H C1 0 H CF3 H CH2 OCH 2 0C2 H s 3 -401 H C1 0 H CF3 H CH2 OCOC2 H s 3 -402 H C1 0 H CF3 H CH2 OCO ' C 3 H, WO 97/07104 PC'1'/JP96/02311 TABLE 3 fcontn'dl Compound x Y Z Z R3 R' R 2 R6 No.
3 -403 H C1 0 H CF3 H CH2 OCOCH 2 Cl 3 -407 H Ci 0 H CF3 H COOC2 H 5 3 -408 H C1 0 H CF3 H COO " C 3 H, 3 - 409 H C1 0 H CF3 H C00 " C, H 9 3 -410 H C1 0 H CF3 H COO " C H
3- 411 H C1 0 H CF3 H COO ' C 3 H
3 -413 H C1 0 H CF3 H COC2 H s 3 -414 F F 0 H CF3 H CH2 Br 3 -415 F F 0 H CF3 H CH Br2 3 -416 F F 0 H CF3 H CBr3 3 -422 F F 0 H CF3 H CHz 0C2 H s 3 - 423 F F 0 H CF3 H CH2 0' C a H 7 3 -424 F F 0 H CF3 H CH2 OCH 2 OCH , TABLE 3 (contn'd) Compound x y Z 2 R 3 R' R Z R 6 No.
3 -426 F F 0 H CF3 H CH2 OCOCH , 3 -427 F F 0 H CF3 H CH2 OCOC2 H s 3 -428 F F 0 H CF3 H CHz OCO ' C 3 H
3 -433 F F 0 H CF3 H COOC2 H s 3 -434 F F 0 H CF3 H C00 " C a H, 3 -435 F F 0 H CF3 H C00 " C4 H
3 -436 F F 0 H CF3 H C00 " C s H
3 -437 F F 0 H CF3 H COO ' C 3 H
3 -439 F F 0 H CF3 H COC2 H s 3 -440 F Ci 0 H CF3 H CH2 Br 3 -441 F Cl 0 H CF3 H CH Br2 3 -442 F Cl 0 H CF3 H CBr3 3 -443 F Cl 0 H CF3 H CHO
3 -445 F Cl 0 H CF3 H COOH
3 -446 F Cl 0 H CF3 H CH2 OH
TABLE 3 (contn'd) Compound X Y Z2 R 3 R' R2 R 6 No.
3 -447 F Cl 0 H CF3 H CH2 OCH 3 3 -448 F Cl 0 H CF3 H CH2 0C2 H s 3 - 449 F C1 0 H CF3 H CHz 0' C a H7 3- 451 F CI 0 H CF3 H CH2 OCH 2 0C2 H;
3 -453 F C1 0 H CF3 H CH2 OCOC2 H s 3 -454 F C1 0 H CF3 H CH2 OCO ' C 3 H 7 3 -455 F Cl 0 H CF3 H CH2 OCOCH 2 Cl 3 -457 F C1 0 H CF3 H CH2 OCOCF a 3 -458 F Cl 0 H CF3 H COOCH3 3 -459 F C1 0 H CF3 H COOC2 H s 3- 460 F C1 0 H CF3 H C00 " C 3 H z 3 - 461 F Cl 0 H CF3 H C00 C, H 9 3 -462 F Ci 0 H CF3 H COO " C H3- 463 F C1 0 H CF3 H COO ' C a H 7 3 -465 F Cl 0 H CF3 H COCz H 5 . 3 -466 H F 0 CH3 CF3 H CH3 3 -468 H Br 0 CHa CF3 H CHs 3 -469 F F 0 CH3 CF3 H CH.3 TABLE 3 (contn'd) Compound X Y Z 2 R' R' R 2 R e No.
3 -471 F Br 0 CHa CF3 H CH3 3 -472 H F 0 CH3 CF3 H C2 H s 3 -473 H C1 0 CH3 CF3 H C 2 H s 3 -474 H Br 0 CH3 CF3 H C 2 H;
3 -475 F F 0 CH3 CF3 H C 2 H;
3 -476 F C1 0 CH3 CF3 H C 2 H s 3 -477 F Br 0 CH3 CF3 H C 2 H 5 3 -478 F Br 0 CH3 CF3 H C 2 H s 3 -479 H F 0 CH3 CF3 H CH2 Br 3 -480 H F 0 CH3 CF3 H CH Br2 3 -481 H F 0 CH3 CF3 H CBr , 3 -486 H F 0 CH3 CF3 H CH2 OCH , 3 - 488 H F 0 CH3 CF3 H CHz 0' C, H 7 3 -489 H F 0 CHa CF3 H CH2 OCH 2 OCH 3 =
3 -490 H F 0 CH3 CF3 H CH2 OCH 2 OC2 H s 3 -492 H F 0 CH3 CF3 H CHz OCOC2 H a TABLE 3 (contn'd) Compound x y Z 2 R 3 R ' R 2 R G
No.
3 -493 H F 0 CH3 CF3 H CH2 OCO ' C 3 H7 3 -498 H F 0 CH3 CF3 H COOC2 H g 3 -499 H F 0 CH3 CF3 H C00 C 3 H, 3- 500 H F 0 CH3 CF3 H COO " C, H s 3- 501 H F 0 CH3 CF3 H C00 " C; H õ
3 -502 H F 0 CH3 CF3 H C00 ' C 3 H 7 3 -504 H F 0 CH3 CF3 H COC2 H s 3 -505 H C1 0 CH3 CF3 H CH2 Br 3 -506 H C1 0 CH3 CF3 H CH Br2 3 -507 H C1 0 CH3 CF3 H CBr3 3 -508 H Ci 0 CH3 CF3 H CHO
3 -513 H C1 0 CH3 CF3 H CH2 0C2 H s 3- 514 H C1 0 CH3 CF3 H CH2 0' C 3 H, 3 -515 H C1 0 CH3 CF3 H CHz OCH 2 OCH 3 TABLE 3 fcontn'd) Compound x Y Z 2 R3 R' R2 R 6 No.
3- 518 H C1 0 CH3 CF3 H CH2 OCOC2 H s 3- 519 H C1 0 CH3 CF3 H CH2 OCO C 3 H, 3 -520 H C1 0 CH3 CF3 H CH2 OCOCH 2 Cl 3 -521 H C1 0 CH3 CF3 H CHa OCOCC13 3 -525 H C1 0 CHa CF3 H C00 " C, H7 3 -526 H Ci 0 CH3 CF3 H C00 " C 4 H 9 3 -527 H C1 0 CH3 CF3 H COO " C s H ii 3 -528 H C1 0 CH3 CF3 H COO ' C, H7 3 -531 F F 0 CH3 CF3 H CH2 Br 3 -532 F F 0 CH3 CF3 H CH Br2 3 -533 F F 0 CH3 CF3 H CBr3 3 -535 F F 0 CHa CF3 H CN ;
3 -537 F F 0 CH3 CF3 H CHz OH
TABLE 3 (contn'd) Compound X Y Z Z R 3 R' R 2 R 6 No.
3 -540 F F 0 CH3 CF3 H CH2 0' C 3 H T
3 -542 F F 0 CH3 CF3 H CHZ OCH 2 OC2 H;
3 -543 F F 0 CH3 CF3 H CHz OCOCH 3 3 -544 F F 0 CH3 CF3 H CH2 OCOC2 H;
3 -545 F F 0 CH3 CF3 H CH2 OCO ' C 3 H, 3 -546 F F 0 CH3 CF3 H CH2 OCOCH 2 Cl 3 -547 F F 0 CH3 CF3 H CH2 OCOCCIs 3 -548 F F 0 CH3 CF3 H CHz OCOCF 3 3 -550 F F 0 CH3 CF3 H COOC2 H s 3- 551 F F 0 CH3 CF3 H C00 C 3 H, 3 -552 F F 0 CH3 CF3 H COO " C, H 9 3 -553 F F 0 CH3 CF3 H C00 C 5 H õ
3 -554 F F 0 CH3 CF3 H COO ' C 3 H, 3 -556 F F 0 CH3 CF3 H COC2 H s 3 -557 F C1 0 CH3 CF3 H CIIZ Br = 3 -558 F C1 0 CHa CF3 H CH Br2 3- 559 F C1 0 CH3 CF3 H CBr3 TABLE 3 (contn'd) Compound x y Z 2 R 3 R' R 2 R 6 No.
3 -561 F C1 0 CH3 CFs H CN
3 -563 F C1 0 CHa CF3 H CH2 OH
3 -564 F C1 0 CHa CF3 H CH2 OCH a 3 -565 F ci 0 CH3 CF3 H CH2 0C2 H 5 3- 566 F ci 0 CH3 CF3 H CH2 0' C 3 H 7 3 -568 F Cl 0 CH3 CF3 H CH2 OCH 2 0C2 H s 3 -569 F ci 0 CH3 CF3 H CH2 OCOCH 3 3 -570 F ci 0 CH3 CF3 H CH2 OCOC2 H s 3 -571 F C1 0 CH3 CF3 H CH2 OCO ' C a H7 3 -572 F C1 0 CH3 CF3 H CH2 OCOCH 2 Cl 3- 573 F Cl 0 CH3 CF3 H CHz OCOCC13 3 -575 F ci 0 CH3 CF3 H COOCH3 3 -576 F C1 0 CH3 CF3 H COOCz H;
3 -577 F Cl 0 CH3 CF3 H COO " C 3 H, 3 -578 F ci 0 CH3 CF3 H COO " C, H 9 3 -579 F C1 0 CH3 CF3 H COO " C s H,1 3 -580 F C1 0 CH3 CF3 H COO ' C s H 7 =
3 -581 F C1 0 CH3 CF3 H COCH3 3 -582 F ci 0 CH3 CF3 H COC2 H s Compounds of the formula:
X O R'-Y ~ ~ N \ Ri _ ~ Rs Compound X Y R3 R' R2 R' R8 No.
4 - 1 H Cl H CF2 Cl CH3 H CH2 Cl 4 - 2 H Cl H CF2 Cl CH3 H CH2 Br 4- 3 H Cl H CF2 Cl CH3 H CH2 OCH 3 4- 4 H Cl H CF2 Cl CH3 H CH2 0C2 H s 4 - 5 H Cl H CF2 Cl CH3 H CH2 OCH 2 OCH
4- 6 H Cl H CFZ CI CH3 H CH2 OCH 2 OC 2 Hs 4-7 H Cl H CF2 Cl CH3 H CHZ OCOCH 3 4 - 8 H Cl H CF2 Cl CH3 H CH2 OCOC 2 Hs 4 - 9 H Cl H CF2 C l CH3 H CH2 OCO ' C, H7 4- 10 H Cl H CF2 Cl CH3 H CH2 OCOCH 2 Cl 4 -11 H Cl H CF2 Cl CH3 H CH2 OCOCCI3 4- 12 H Cl H CF2 Cl CH3 H CH2 OCOCF , 4 -13 H Cl H CF2 Cl CH3 H COOH
4- 14 H Cl H CF2 Cl CH3 H COOCH3 4- 15 H Cl H CF2 Cl CH3 H COOC2 H a TABLE 4 (contn'd) Compound X Y R 3 R' R Z R' R$ No.
4 -16 H Cl H CF2 Cl CH3 H C00 " C 3 H 7 4- 17 H Cl H CF2 Cl CH3 H C00 C 4 H s 4 -18 H Cl H CF2 Cl CH3 H C00 C 5 H;
4- 19 H Cl H CF2 Cl CH3 H COO C s H 7 4- 20 H Cl H CF2 C1 CH3 H C00 ' C 5 H 9 4 -21 H Cl H CF2 Cl CH3 H COO c C s H 1, 4 -22 H Cl H CF2 Cl CH3 H COOCH2 CH = CHZ
4 -23 H Cl H CF2 Cl CH3 H COOCH2 C= CH
4 -24 H Cl H CF2 Cl CH3 H CONH2 4 -25 H C1 H CF2 Cl CH3 H CONHCH3 4 -27 H Cl H CF2 Cl CH3 H CON(CH3 ) 2 4- 28 H Cl H CF2 Cl CH3 H CON(C2 H 5) 2 4 -29 F Cl H CF2 Cl CH3 H CH2 Cl 4 -30 F Cl H CF2 Cl CH3 H CHa Br 4 -31 F Cl H CF2 Cl CH3 H CHZ OCH 3 4- 32 F Cl H CF2 Cl CH3 H CH2 0CZ H b 4 -33 F Cl H CF2 Cl CH3 H CH2 OCH 2 OCH , 4- 34 F Cl H CF2 Cl CH3 H CH2 OCH 2 OC 2 H;
4 -35 F Cl H CF2 Cl CH3 H CHz OCOCH 3 4 -36 F Cl H CF2 Cl CH3 H CHZ OCOC 2 H5 4- 37 F C1 H CF2 C1 CH3 H CHz OCO ' C 3 H 7 4- 38 F Cl H CF2 Cl CH3 H CHz OCOCH 2 Cl TABLE 4 (contn'd) Compound X Y R a R' R 2 R7 R8 No.
4 -39 F Cl H CF2 Cl CH3 H CHZ OCOCCI3 4 -40 F Cl H CF2 CI CH3 H CHZ OCOCF 3 4 -41 F Cl H CF2 Cl CH3 H COOH
4 -42 F Cl H CF2 Cl CHa H COOCH3 4 -43 F Cl H CF2 Cl CH3 H COOC2 H s 4 - 44 F Cl H CFZ C1 CH3 H C00 " C 3 H, 4- 45 F Cl H CF2 C1 CH3 H C00 C 4 H 9 4- 46 F Cl H CFz Cl CH3 H C00 C s H i, 4 - 47 F Cl H CFZ C1 CH3 H C00 ' C a H, 4- 48 F Cl H CF2 Cl CH3 H C00 ' C s H 9 4- 49 F Cl H CF2 Cl CH3 H C00 ' C 6 H õ
4 -50 F Cl H CF2 Cl CH3 H COOCH2 CH = CH2 4 -51 F Cl H CF2 Cl CH3 H COOCH2 C= CH
4 -52 F Cl H CF2 Cl CH3 H CONH2 4 -53 F Cl H CF2 C1 CH3 H CONHCH3 4 -54 F Cl H CF2 Cl CH3 H CONHC2 H s 4 -55 F Cl H CF2 Cl CH3 H CON(CH3 ) 2 4 -56 F Cl H CF2 Cl CH3 H CON(C2 H s) 2 4 -57 H Cl H CF2 Cl CH3 CH3 CH2 Cl 4 -58 H Cl H CF2 Cl CH3 CH3 CHz Br 4- 59 H Cl H CF2 Cl CH3 CH3 CHa OCH 3 4 -60 H Cl H CF2 Cl CH3 CHa CHZ 0C2 H s 4-61 H Cl H CF2 Cl CH3 CH3 CHZ OCH 2 OCH a TABLE 4 (contn'd) Compound X Y R R RZ R' R8 No.
4 -62 H Cl H CF2 Cl CH3 CH3 CH2 OCH 2 OC 2 Hs 4 -63 H Cl H CF2 Cl CH3 CH3 CHz OCOCH 3 4 -64 H Cl H CF2 C1 CH3 CH3 CH2 OCOC 2 HS
4- 65 H Cl H CF2 Cl CH3 CH3 CH2 OCO ' C 3 H 7 4 -66 H Cl H CF2 Cl CH3 CH3 CHZ OCOCH 2 Cl 4 -67 H Cl H CF2 Cl CH3 CH3 CHZ OCOCCI3 4 -68 H Cl H CF2 Cl CH3 CH3 CH2 OCOCF 3 4 -69 H Cl H CF2 Cl CH3 CH3 COOH
4 -70 H Cl H CF2 Cl CH3 CH3 COOCH3 4 -71 H Cl H CF2 Cl CH3 CH3 COOC2 H s 4- 72 H Cl H CF2 Cl CH3 CH3 C00 " C 3 H 7 4 - 73 H Cl H CF2 Cl CH3 CH3 C00 " C, H g 4 -74 H Cl H CF2 Cl CH3 CH3 C00 " C s H,t 4- 75 H Cl H CF2 Cl CH3 CH3 COO ' C 3 H 7 4- 76 H Cl H CF2 Cl CH3 CH3 COO ' C s H a 4 -77 H Cl H CF2 Cl CH3 CH3 COO ' C 6 H õ
4 -78 H Cl H CF2 Cl CH3 CH3 COOCH2 CH = CH2 4 -79 H Cl H CF2 Cl CH3 CH3 COOCH2 C= CH
4 -80 H Cl H CF2 Cl CH3 CH3 CONH2 4 -81 H Cl H CF2 Cl CH3 CH3 CONHCH3 4- 82 H Cl H CF2 Cl CH3 CH3 CONHC2 H 5 4- 83 H C1 H CF2 Cl CH3 CH3 CON(CH3 ) 2 4- 84 H Cl H CF2 Cl CH3 CH3 CON(C2 H 5 ) 2 TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R' R 8 No.
4 -85 F C1 H CF2 Cl CH3 CH3 CH2 C1 4 -86 F Cl H CF2 Cl CH3 CH3 CH2 Br 4 -87 F Cl H CF2 Cl CH3 CH3 CH2 OCH 3 4-88 F Cl H CF2 Cl CH3 CH3 CHZ 0C2 H 5 4 -89 F Cl H CF2 Cl CH3 CH3 CH2 OCH 2 OCH 3 4- 90 F Cl H CF2 Cl CH3 CH3 CHZ OCH 2 OC 2 H5 4 -91 F Cl H CF2 C1 CH3 CH3 CHZ OCOCH 3 4- 92 F Cl H CF2 Cl CH3 CH3 CH2 OCOC 2 H;
4- 93 F C1 H CF2 Cl CH3 CH3 CH2 OCO ' C 3 H, 4 -94 F Cl H CF2 Cl CH3 CH3 CH2 OCOCH 2 Cl 4 -95 F Cl H CF2 Cl CH3 CH3 CH2 OCOCCI3 4 -96 F Cl H CF2 Cl CH3 CH3 CH2 OCOCF 3 4 -97 F Cl H CF2 Cl CH3 CH3 COOH
4 -98 F Cl H CF2 Cl CH3 CH3 COOCH3 4 -99 F Cl H CF2 Cl CH3 CH3 COOC2 H 5 4- 100 F Cl H CF2 C1 CH3 CH3 COO " C 3 H, 4- 101 F Cl H CF2 Cl CH3 CH3 COO " C 4 H
4- 102 F Cl H CF2 CI CH3 CH3 COO " C 5 H4- 103 F Cl H CF2 Cl CH3 CH3 COO ' C 3 4- 104 F Cl H CF2 Cl CH3 CH3 COO ' C 5 H fl 4 -105 F Cl H CF2 Cl CH3 CH3 COO ' C 6 H,i 4 -106 F Cl H CF2 Cl CH3 CH3 COOCH2 CH= CHz TABLE 4 (contn'd) Compound X Y R3 R' R2 R' R8 No. =
4 -107 F Cl H CF2 Cl CH3 CH3 COOCH2 C= CH
4- 108 F Cl H CF2 Cl CH3 CH3 CONH2 4- 109 F Cl H CF2 Cl CH3 CH3 CONHCH3 4- 110 F Cl H CF2 Cl CH3 CH3 CONHC2 H s 4- 111 F Cl H CF2 Cl CH3 CH3 CON(CH3 ) z 4- 112 F Cl H CF2 Cl CH3 CH3 CON(C2 H;) 2 4 -113 H Cl H CF3 CH3 H CH2 Cl 4- 114 H Cl H CF3 CH3 H CH2 Br 4- 115 H Cl H CF3 CH3 H CH2 OCH 3 4- 116 H Cl H CF3 CH3 H CH2 0C2 H s 4 -117 H Cl H CF3 CH3 H CHZ OCH 2 OCH 3 4- 118 H Cl H CF3 CH3 H CH2 OCH 2 OC 2 Hs 4- 119 H Cl H CF3 CH3 H CH2 OCOCH 3 4- 120 H Cl H CF3 CH3 H CH2 OCOC 2 Hs 4- 121 H Cl H CF3 CH3 H CHZ OCO ' C 3 H, 4 -122 H Cl H CF3 CH3 H CH2 OCOCH 2 Cl 4- 123 H Cl H CF3 CH3 H CHZ OCOCCI3 4- 124 H Cl H CF3 CH3 H CH2 OCOCF 3 4- 125 H Cl H CF3 CH3 H COOH
4- 126 H Cl H CF3 CH3 H COOCH3 4- 127 H Cl H CF3 CH3 H COOCZ H 5 4- 128 H Cl H CF3 CH3 H C00 " C 3 H 7 4- 129 H Cl H CF3 CH3 H COO " C 4 H
TABLE 4 (contn'd) Compound X Y R3 R' R2 R' R8 No.
4- 130 H Cl H CF3 CH3 H C00 " C 5 H õ
4- 131 H Cl H CF3 CH3 H COO ' C a H 7 4- 132 H Cl H CF3 CH3 H C00 ' C g H 9 4 -133 H Cl H CF3 CH3 H C00 ' C 6 H 11 4 -134 H Cl H CF3 CH3 H COOCH2 CH = CH2 4 -135 H Cl H CF3 CH3 H COOCH2 C CH
4 -136 H Cl H CF3 CH3 H CONH2 4 -137 H C 1 H CF3 CH3 H CONHCH'3 4 -139 H C1 H CF3 CH3 H CON(CH3 ) 2 4- 140 H C1 H CF3 CH3 H CON(C2 H 5) 2 4 -141 F C1 H CF3 CH3 H CH2 Cl 4- 142 F C1 H CF3 CH3 H CH2 Br 4 -145 F C1 H CF3 CH3 H CH2 OCH 2 OCH , 4 -149 F Cl H CF3 CH3 H CH2 OCO ' C 3 H, 4- 150 F Cl H CF3 CH3 H CH2 OCOCH 2 Cl 4- 151 F Cl H CF3 CH3 H CH2 OCOCCla 4- 152 F Cl H CF3 CH3 H CH2 OCOCF , TABLE 4 (contn'd) Compound X Y R 3 R' R Z R' R$
No.
4 -153 F Cl H CF3 CH3 H COOH
4 -154 F Cl H CF3 CH3 H COOCH3 4 -155 F Cl H CF3 CH3 H COOC2 H s 4 - 156 F Cl H CF3 CH3 H C00 C, H7 4- 157 F Cl H CF3 CH3 H COO " C 4 H 9 4 -158 F Cl H CF3 CH3 H C00 " C 5 H õ
4 -159 F Cl H CF3 CH3 H COO ' C g H 7 4 -160 F Cl H CF3 CH3 H C00 -C 5 H0 4- 161 F Cl H CF3 CH3 H C00 ' C 6 H,1 4 -162 F Cl H CF3 CHa H COOCHz CH = CH2 4 -163 F Cl H CF3 CHs H COOCH2 C= CH
4 -164 F Cl H CF3 CH3 H CONH2 4- 165 F Cl H CF3 CH3 H CONHCH3 4 -166 F Cl H CF3 CH3 H CONHC2 H 5 4 -167 F Cl H CF3 CH3 H CON(CH3 ) 2 4- 168 F Cl H CF3 CH3 H CON(C2 H 5)2 4 -169 H Cl H CF3 CH3 CH3 CHz Cl 4- 170 H Cl H CF3 CH3 CH3 CHZ Br 4 -171 H Cl H CF3 CH3 CH3 CH2 OCH , 4 -172 H Cl H CF3 CH3 CH3 CHz 0C2 H 6 4- 173 H Cl H CF3 CH3 CH3 CHz OCH 2 OCH , 4 -174 H Cl H CF3 CH3 CH3 CH2 OCH 2 OC 2 Ha 4- 175 H Cl H CF3. CH3 CH3 CH2 OCOCH 3 TABLE 4 (contn'd) Compound X Y R 3 R' R Z R' R 8 No.
4- 176 H Cl H CF3 CH3 CH3 CH2 OCOC 2 H5 4- 177 H Cl H CF3 CH3 CH3 CHz OC0 ' C 3 H
4- 178 H Cl H CF3 CH3 CH3 CH2 OCOCH 2 Cl 4 -179 H Cl H CF3 CH3 CH3 CH2 OCOCCI3 4 -180 H Cl H CF3 CH3 CH3 CH2 OCOCF 3 4- 181 H Cl H CF3 CH3 CH3 COOH
4- 182 H Cl H CF3 CH3 CH3 COOCH3 4- 183 H Cl H CF3 CH3 CH3 COOC2 H 5 4- 184 H Cl H CF3 CH3 CH3 C00 C 3 H, 4- 185 H Cl H CF3 CH3 CH3 COO " C H
4 -186 H Cl H CF3 CH3 CH3 C00 " C H
4- 187 H Cl H CF3 CH3 CH3 COO ' C 3 H
4- 188 H Cl H CF3 CH3 CH3 COO ' C s H 9 4- 189 H Cl H CF3 CH3 CH3 COO ' C 6 H
4 -190 H Cl H CF3 CH3 CH3 COOCHa CH = CH2 4 -191 H Cl H CF3 CH3 CH3 COOCHZ C CH
4- 192 H Cl H CF3 CH3 CH3 CONH2 4 -193 H Cl H CF3 CH3 CH3 CONHCH3 4- 194 H Cl H CF3 CH3 CH3 CONHC2 H 5 4- 195 H Cl H CF3 CH3 CH3 CON(CH3 ) 2 4- 196 H Cl H CF3 CH3 CH3 CON(C2 H 2 4 -197 F Cl H CF3 CH3 CH3 CHa Cl 4- 198 F Cl H CF3 CH3 CH3 CHZ Br zHN00 'HO 'HO ~HO H IO d OZZ- V
HO = 0 zH0000 ~HO 'HO e90 H IO d 613-ZHO = HO ZH0000 eH9 'HO eH0 H IO 4 8I3-P
" H 9 0. 000 'HO 'HO e90 H IO d LIZ -~
H s 0. 000 EHO EHO 'HO H IO d 9TZ -H E 0 000 eH0 'HO EHO H 10 d 5I3-P
-~ H a 000 ~HO 'HO eH0 H IO 3 ~IZ --k a H 0 000 'HO 'HO EHO H IO J 8TZ -k H E 0 -.000 EHO EHO e90 H I9 d ZTZ- P
S H 30000 'HO 'HO e90 H IO d TTZ -~H0000 'HO eH0 ~d0 H IO d 0I3-V
H000 'HO 'HO e90 H TO d 60Z -V
E H0000 zH0 'HO 'HO ~HO H TO d 803-P
'IJJ0J0 3H0 'HO 'HO EHO H IJ d LOZ -V
IJ z H0000 zHJ 'HO EHJ EHO H IJ .3 90Z -P
H E 0, 000 3H0 EHO EHO EHO H IO d 50Z -V
'H z 0000 zH0 'HO EHO EA0 H IO 3 VOZ -k E H0000 'HO EHO e140 'HO H TO 3 E0Z -P
'-H z 00 z H00 zH0 'HO 'HO EHO H IO 3 Z0Z -P
e H00 z H00 ZHO eH0 EHO EAO H IO d 109-~
s H z90 zH0 'HO 'HO EHO H 10 3 003-P
~ HJ0 zHJ 'HO eHJ ~HJ H IJ d 66T -V
ON
~ 82i ~2~ z23 r2~ ~-d A X punodncoo p,uIuo~ 17 'AlaV1, I I~ZO/96df/.L3d b0IL0/L6 OM
OZ-ZO-8661 6610~ZZO Va TABLE 4 (contn'd) Compound X Y R3 R' R Z R7 R 8 No.
4 -221 F Cl H CF3 CH3 CH3 CONHCH3 4 -222 F Cl H CF3 CHa CH3 CONHC2 H s 4 -223 F Cl H CF3 CH3 CH3 CON(CH3 ) 2 4 -224 F C1 H CFa CH3 CH3 CON(C2 H s) 2 4 -225 H Cl H CF2 Cl CH3 H CH2 Cl 4 -226 H Cl H CF2 Cl CH3 H CH2 Br 4 -227 H Cl H CF2 Cl CH3 H CH2 OCH 3 4 -228 H Cl H CF2 C1 CH3 H CH2 OC2 H 5 4 -229 H Cl H CF2 C1 CH3 H CH2 OCH 2 OCH a 4 -230 H C1 H CF2 Cl CH3 H CH2 OCH 2 OC 2 Hs 4 -231 H Cl H CF2 Cl CH3 H CH2 OCOCH 3 4 -232 H Cl H CF2 C1 CH3 H CH2 OCOC 2 H5 4 -233 H Cl H CF2 C1 CH3 H CH2 OCO ' C 3 H, 4 -234 H Cl H CF2 Cl CH3 H CH2 OCOCH 2 C1 4 -235 H Cl H CF2 C1 CH3 H CHz OCOCCI3 4 -236 H Cl H CF2 C1 CH3 H CH2 OCOCF , 4 -238 H Cl H CF2 Cl CH3 H COOCH3 4 -239 H Cl H CF2 Cl CH3 H COOC2 H s 4- 240 H Cl H CFa Cl CH3 H C00 " C 3 H 7 4- 241 H Cl H CF2 C1 CH3 H C00 " C, H 9 4- 242 H C1 H CFZ C1 CH3 H C00 " C 5 H õ
4 -243 H C1 H CF2 Cl CH3 H COO ' C 3 H 7 TABLE 4 (contn'd) Compound X Y R' R' R 2 R' R 8 No.
4 -244 H Cl H CF2 C1 CH3 H C00 ' C 5 H s 4 -245 H Cl H CFZ Cl CH3 H COO ' C 6 H
4 -246 H Cl H CF2 Cl CH3 H COOCH2 CH = CHZ
4 -247 H Cl H CF2 Cl CH3 H COOCH2 C= CH
4 -248 H C1 H CF2 Cl CHa H CONH2 4 -249 H C1 H CF2 Cl CH3 H CONHCH3 4 -250 H C1 H CF2 C1 CH3 H CONHCz H 5 4 -251 H Cl H CF2 Cl CH3 H CON(CH3 ) 2 4- 252 H Cl H CF2 Cl CH3 H CON(C2 H 5) 2 4 -253 F Cl H CF2 Cl CH3 H CH2 Cl 4 -254 F Cl H CF2 Cl CH3 H CHZ Br 4- 255 F Cl H CF2 Cl CH3 H CHz OCH , 4- 256 F Cl H CF2 Cl CH3 H CH2 OC2 H s 4 -257 F Cl H CF2 Cl CH3 H CH2 OCH 2 OCH 3 4 -258 F Cl H CF2 Cl CH3 H CH2 OCH 2 OC 2 H5 4 -259 F Cl H CF2 Cl CH3 H CH2 OCOCH a 4 -260 F Cl H CF2 Cl CH3 H CH2 OCOC 2 HS
4 -261 F Cl H CF2 Cl CH3 H CH2 OCO ' C 3 H z 4- 262 F Cl H CF2 Cl CH3 H CH2 OCOCH 2 Cl 4- 263 F Cl H CF2 Cl CH3 H CH2 OCOCC13 4 -264 F Cl H CF2 Cl CH3 H CHz OCOCF 3 4 -265 F Cl H CF2 Cl CH3 H COOH
4 -266 F Cl H CF2 Cl CH3 H COOCH3 TABLE 4 (contn'd) = Compound X Y R 3 R' R 2 R' R 8 No.
4 -267 F C1 H CF2 Cl CHa H COOC2 H s 4- 268 F Cl H CFa C1 CH3 H C00 " C s H 7 4 - 269 F Cl H CFZ C1 CH3 H C00 " C, H s 4 -270 F Cl H CF2 Cl CH3 H COO C 5 H õ
4 -271 F Cl H CF2 Cl CH3 H COO ' C 3 H7 4 -272 F Cl H CF2 Cl CH3 H COO ' C 5 H 9 4 -273 F Cl H CF2 Cl CH3 H COO ' C 6 H õ
4 -274 F Cl H CF2 Cl CH3 H COOCH2 CH = CHZ
4 -275 F Cl H CF2 Cl CH3 H COOCH2 C= CH
4 -276 F Cl H CF2 Cl CH3 H CONH2 4- 277 F Cl H CF2 Cl CH3 H CONHCH3 4 -278 F Cl H CF2 Cl CH3 H CONHC2 H s 4 -279 F Cl H CF2 Cl CH3 H CON(CHa ) 2 4 -280 F Cl H CF2 Cl CH3 H CON(C2 H s) 2 4 -281 H Cl H CF2 Cl CH3 CH3 CHZ Cl 4 -282 H Cl H CF2 Cl CH3 CH3 CH2 Br 4 -283 H Cl H CF2 Cl CH3 CH3 CH2 OCH 3 4 -284 H Cl H CF2 Cl CH3 CHa CH2 0C2 H s 4 -285 H Cl H CF2 Cl CH3 CH3 CH2 OCH 2 OCH 3 4 -286 H Cl H CF2 Cl CH3 CH3 CHZ OCH 2 OC 2 H5 4 -287 H Cl H CF2 Cl CH3 CH3 CH2 OCOCH 3 4- 288 H Cl H CF2 Cl CHa CH3 CH2 OCOC 2 H, 4 -289 H Cl H CF2 Cl CH3 CH3 CHz OCO ' C, H, .274 TABLE 4 (contn'd) Compound X Y R' R' R 2 R' R8 No.
4 -290 H Cl H CF2 Cl CH3 CH3 CH2 OCOCH Z Cl 4 -291 H Cl H CF2 Ci 'CH3 CH3 CH2 OCOCC13 4 -292 H Cl H CF2 Cl CH3 CH3 CH2 OCOCF 3 4 -293 H Cl H CF2 Cl CH3 CH3 COOH
4 -294 H Cl H CF2 Cl CH3 CH3 COOCH3 4 -295 H C1 H CF2 Cl CH3 CH3 COOC2 H s 4 -296 H Cl H CF2 Cl CH3 CH3 C00 C 3 H, 4 -297 H Cl H CF2 Cl CH3 CH3 C00 " C, H 9 4 -298 H Cl H CF2 Cl CH3 CH3 C00 " C 5 H õ
4 -299 H Cl H CF2 C1 CH3 CH3 COO ' C, H7 4 -300 H Cl H CF2 Cl CH3 CH3 C00 C C 5 H 9 4 -301 H Cl H CF2 C1 CH3 CH3 C00 ' C 6 H,1 4 -302 H Cl H CF2 C1 CH3 CH3 COOCH2 CH = CH2 4 -303 H Cl H CF2 C1 CH3 CH3 COOCH2 C= CH
4 -304 H Cl H CF2 C1 CH3 CH3 CONH2 4 -305 H Cl H CF2 Cl CH3 CH3 CONHCH3 4 -306 H Cl H CF2 C1 CH3 CH3 CONHC2 H s 4 -307 H Cl H CF2 C1 CH3 CH3 CON(CH3 ) 2 4- 308 H Cl H CF2 C1 CH3 CH3 CON(C2 H 5) 2 4 -309 F Cl H CF2 C1 CH3 CH3 CHz Cl 4 -310 F Cl H CF2 C1 CH3 CH3 CH2 Br 4 -311 F Cl H CF2 CI CH3 CH3 CH2 OCH 3 4- 312 F Cl H CF2 Cl CH3 CH3 CH2 OC2 H 6 WO 9Wa7164 PCT/JP96102311 TABLE 4 (contn'd) Compound X Y R 3 R ' R 2 R' R e No.
4 -313 F Cl H CF2 Cl CH3 CH3 CH2 OCH 2 OCH a 4- 314 F Cl H CF2 Cl CH3 CH3 CHz OCH 2 OC 2 H5 4 -315 F Cl H CF2 C1 CH3 CH3 CH2 OCOCH , 4- 316 F Cl H CF2 Cl CHa CH3 CH2 OCOC 2 Hs 4 -317 F Cl H CF2 C1 CH3 CH3 CH2 OCO ' C 3 H, 4- 318 F Cl H CF2 C1 CH3 CH3 CH2 OCOCH 2 Cl 4 -319 F Cl H CF2 Cl CH3 CH3 CH2 OCOCCI3 4 -320 F Cl H CF2 Cl CH3 CHa CH2 OCOCF , 4 -321 F Cl H CF2 Cl CH3 CH3 COOH
4 -322 F Cl H CF2 Cl CH3 CH3 COOCH3 4 -323 F Cl H CF2 Cl CH3 CH3 COOC2 H s 4 -324 F Cl H CF2 Cl CH3 CH3 COO " C 3 H, 4- 325 F Cl H CF2 Cl CH3 CH3 COO " C, H s 4 -326 F Cl H CF2 Cl CH3 CH3 COO C 5 H õ
4 -327 F Cl H CF2 Cl CH3 CH3 COO ' C 3 H 7 4 -328 F Cl H CF2 Cl CH3 CH3 COO c C 5 H s 4 -329 F Cl H CF2 Cl CH3 CH3 COO ' C 6 H õ
4 -330 F Cl H CF2 Cl CH3 CH3 COOCH2 CH = CH2 4 -331 F Cl H CF2 Cl CH3 CH3 COOCH2 C= CH
4 -332 F Cl H CF2 C1 CH3 CH3 CONH2 4 -333 F Cl H CF2 C1 CH3 CH3 CONHCH3 4 -334 F C1 H CF2 C1 CH3 CH3 CONHC2 H a TABLE 4 (contn'd) Compound X Y R 3 R' R Z R' R 8 No.
4 -335 F Cl H CF2 Cl CHa CH3 CON(CH3 ) 2 4 -336 F Cl H CF2 Cl CH3 CH3 CON(C2 H 5) 2 4 -337 H Cl H CF3 CH3 H CH2 Cl 4 -338 H Cl H CF3 CH3 H CH2 Br 4 -339 H Cl H CF3 CH3 H CHZ OCH 3 4 -340 H Cl H CF3 CH3 H CH2 0C2 H 5 4 -341 H Cl H CF3 CH3 H CHZ OCH 2 OCH 3 4 -342 H Cl H CF3 CH3 H CH2 OCH z-OC 2 H5 4 -343 H Cl H CF3 CH3 H CH2 OCOCH 3 4 -344 H Cl H CF3 CH3 H CH2 OCOC 2 Hs 4 -345 H Cl H CF3 CH3 H CHa OCO ' C s H 7 4 -346 H Cl H CF3 CH3 H CH2 OCOCH 2 Cl 4 -347 H Cl H CF3 CH3 H CH2 OCOCC13 4 -348 H Cl H CF3 CH3 H CH2 OCOCF 3 4 -349 H Cl H CF3 CH3 H COOH
4 -350 H Cl H CF3 CH3 H COOCH3 4 -351 H Cl H CF3 CH3 H COOC2 H 6 4 -352 H Cl H CF3 CH3 H C00 " C 3 H7 4 -353 H Cl H CF3 CH3 H C00 " C 4 H 9 4 -354 H Cl H CF3 CH3 H C00 " C 5 H
4 -355 H Cl H CF3 CH3 H COO ' C s H 7 4 -356 H Cl H CF3 CH3 H C00 ' C b H 9 4 -357 H Cl H CF3 CH3 H COO ' C 6 H
TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R7 R8 No.
4 -358 H Cl H CF3 CH3 H COOCH2 CH = CH2 4 -359 H Cl H CF3 CH3 H COOCH2 C= CH
4 -360 H Cl H CF3 CHa H CONH2 4 -361 H Cl H CF3 CH3 H CONHCH3 4 -362 H Cl H CF3 CH3 H CONHC2 H s 4 -363 H C1 H CF3 CH3 H CON(CH3 ) 2 4 -364 H Cl H CF3 CH3 H CON(C2 H s) 2 4 -365 F Cl H CF3 CH3 H CH2 Ch 4 -366 F Cl H CF3 CH3 H CH2 Br 4 -367 F Cl H CF3 CH3 H CH2 OCH 3 4 -368 F Cl H CF3 CH3 H CH2 0C2 H;
4- 369 F Cl H CF3 CH3 H CH2 OCH 2 OCH 3 4 -370 F Cl H CF3 CHa H CH2 OCH 2 OC 2 Hs 4 -371 F Cl H CF3 CH3 H CH2 OCOCH 3 4 -372 F Cl H CF3 CH3 H CH2 OCOC 2 Ha 4 -373 F Cl H CF3 CH3 H CH2 OCO ' C a H, 4 -374 F Cl H CF3 CH3 H CH2 OCOCH 2 Cl 4 -375 F Cl H CF3 CH3 H CH2 OCOCCI3 4 -376 F Cl H CF3 CH3 H CHZ OCOCF 3 4 -377 F Cl H CF3 CH3 H COOH
4 -378 F Cl H CF3 CH3 H COOCH3 4 -379 F Cl H CF3 CH3 H COOCZ H s 4 -380 F Cl H CF3 CH3 H C00 C, H 7 TABLE 4 (contn'd) Compound X Y R 3 R' R Z R' R8 No.
4- 381 F Cl H CF3 CH3 H C00 " C, H 9 4 -382 F Cl H CF3 CH3 H COO " C s H i, 4 -383 F Cl H CF3 CH3 H COO ' C 3 H7 4 -384 F Cl H CF3 CH3 H C00 ' C 5 H s 4 -385 F Cl H CF3 CH3 H COO ' C 6 H õ
4 -386 F Cl H CF3 CH3 H COOCH2 CH = CH2 4 -387 F Cl H CF3 CH3 H COOCH2 C= CH
4 -388 F Cl H CF3 CH3 H CONH2 4 -389 F Cl H CF3 CH3 H CONHCH3 4 -390 F Cl H CF3 CH3 H CONHC2 H s 4 -391 F Cl H CF3 CH3 H CON(CH3 ) 2 4 -392 F Cl H CF3 CH3 H CON(C2 H;) 2 4 -393 H Cl H CF3 CH3 CH3 CH2 Cl 4 -394 H Cl H CF3 CH3 CH3 CH2 Br 4 -395 H Cl H CF3 CH3 CH3 CH2 OCH 3 4 -396 H Cl H CF3 CH3 CH3 CH2 OC2 H s 4 -397 H Cl H CF3 CH3 CH3 CH2 OCH 2 OCH 3 4 -398 H C1 H CF3 CH3 CH3 CH2 OCH 2 OC 2 Hs 4 -399 H Cl H CF3 CH3 CH3 CHz OCOCH 3 4- 400 H Cl H CF3 CH3 CH3 CH2 OCOC 2 Hs 4- 401 H Cl H CF3 CH3 CH3 CH2 OCO ' C 3 H T
4 -402 H Cl H CF3 CH3 Cli3 CH2 OCOCH 2 Cl 4 -403 H Cl H CF3 CH3 CH3 CH2 OCOCC13 TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R' R$
No. 11 1~
4 -404 H Cl H CF3 CH3 CH3 CHZ OCOCF 3 4 -405 H Cl H CF3 CH3 'CH3 COOH
4 -406 H Cl H CF3 CH3 CH3 COOCH3 4 -407 H Cl H CF3 CH3 CH3 COOC2 H s 4 -408 H Cl H CF3 CH3 CH3 C00 " C 3 H, 4 -409 H Cl H CF3 CH3 CH3 C00 " C. H n 4 -410 H Cl H CF3 CH3 CH3 C00 " C s H , , 4- 411 H C1 H CF3 CH3 CH3 COO ' C 3 H, 4- 412 H C1 H CF3 CH3 CH3 COO c C s H s 4 -413 H C1 H CF3 CH3 CH3 COO ' C 6 Hõ
4 -414 H C1 H CF3 CH3 CH3 COOCHZ CH = CHz 4 -415 H Cl H CF3 CH3 CH3 COOCH2 C CH
4 -416 H Cl H CF3 CH3 CH3 CONH2 4 -417 H Cl H CF3 CH3 CH3 CONHCH3 4 -418 H Cl H CF3 CH3 CH3 CONHC2 H s 4 -419 H Cl H CF3 CH3 CH3 CON(CH3 ) 2 4 -420 H Cl H CF3 CH3 CH3 CON(C2 H s) 2 4 -421 F Cl H CF3 CH3 CH3 CH2 Cl 4 -422 F Cl H CF3 CH3 CH3 CH2 Br 4 -423 F Cl H CF3 CH3 CH3 CHz OCH 3 4- 424 F Cl H CF3 CH3 CH3 CH2 0C2 H s 4 -425 F Cl H CF3 CH3 CH3 CHZ OCH 2 OCH 3 4 -426 F Cl H CF3 CH3 CH3 CHZ OCH 2 OC 2 H6 TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R' R B
No.
4 -427 F Cl H CF3 CH3 CH3 GHz OCOCH a 4 -428 F Cl H CF3 CH3 CH3 CH2 OCOC 2 H;
4 -429 F Cl H CF3 CH3 CH3 CH2 OCO ' C 3 H7 4 -430 F Cl H CF3 CH3 CH3 CH2 OCOCH 2 C1 4 -431 F Cl H CF3 CH3 CHs CHz OCOCCI3 4 -432 F Cl H CF3 CH3 CH3 CHZ OCOCF 3 4 -433 F Cl H CF3 CH3 CH3 COOH
4 -434 F Cl H CF3 CH3 CH3 COOCH3 4 -435 F Cl H CF3 CH3 CH3 COOC2 H 5 4 -436 F Cl H CF3 CH3 CH3 C00 C 3 H 7 4 -437 F Cl H CF3 CH3 CH3 C00 C 4 H fl 4 -438 F Cl H CF3 CH3 CH3 C00 " C s H õ
4 -439 F Cl H CF3 CHa CH3 COO ' C 3 H 7 4 -440 F Cl H CF3 CH3 CHa COO ' C s H o 4 -441 F Cl H CF3 CHa CH3 COO ' C 6 H õ
4 -442 F Cl H CF3 CH3 CH3 COOCH2 CH = CHa 4 -443 F Cl H CF3 CH3 CH3 COOCH2 C= CH
4 -444 F Cl H CF3 CH3 CH3 CONH2 4 -445 F Cl H CF3 CH3 CH3 CONHCH3 4 -446 F Cl H CF3 CH3 CH3 CONHC2 H s 4 -447 F Cl H CF3 CH3 CH3 CON(CH3 ) 2 4- 448 F Cl H CF3 CH3 CH3 CON(C2 H 6 ) 2 TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R' R g No.
4 -449 F Cl H CF3 CH3 H CH 3 4 -450 F Cl H CF3 CH3 H CH 2 OH
4 -451 F Cl H CF3 CH3 CH3 CH 3 4 -452 F Cl H CF3 CH3 CH3 CH 2 OH
4 -453 F Cl H CF3 H H CH 3 4 -454 F Cl H CF3 H H CH 2 OH
4 -455 F Cl H CF3 H CH3 CH 3 4 -456 F Cl H CF3 H CH3 CH 2 OH
4 -457 H Cl H CF3 CH3 H CH 3 4 -458 H Cl H CF3 CH3 H CH 2 OH
4 -459 H Cl H CF3 CH3 CH3 CH 3 4 -460 H Cl H CF3 CH3 CH3 CH 2 OH
4 -461 H Cl H CF3 H H CH 3 4 -462 H Cl H CF3 H H CH 2 OH
4 -463 H Cl H CF3 H CH3 CH 3 4 -464 H Cl H CF3 H CH3 CH 2 OH
4 -465 F Cl H CFz Cl CH3 H CH 3 4 -466 F Cl H CF2 Cl CH3 H CH 2 OH
4 -467 F Cl H CF2 Cl CH3 CH3 CH 3 4 -468 F Cl H CF2 C1 CH3 CH3 CH 2 OH
4 -469 F. Cl H CF2 C1 H H CH 3 4 -470 F Cl H CF2 Cl H H CH 2 OH
4 -471 F Cl H CF2 Cl H CH3 CH 3 TABLE 4 (contn'd) Compound X Y R3 R' R2 R' R8 No.
4 -472 F Cl H CF2 Cl H CH3 CH 2 OH
4 -473 H Cl H CF2 Cl CH3 H CH 3 4 -474 H Cl H CF2 Cl CH3 H CH 2 OH
4 -475 H Cl H CF2 Cl CH3 CH3 CH 3 4 -476 H Cl H CF2 Cl CH3 CH3 CH 2 OH
4 -477 H Cl H CF2 Cl H H CH , 4 -478 H Cl H CF2 Cl H H CH 2 OH
4 -479 H Cl H CFz Cl H CH3 CH , 4 -480 H Cl H CF2 Cl H CH3 CH 2 OH
4 -481 H Cl H CF3 H H CH2 Cl 4 -482 H Cl H CF3 H H CH2 Br 4 -483 H Cl H CF3 H H CH2 OCH , 4 -484 H Cl H CF3 H H CH2 0C2 H;
4 -485 H Cl H CF3 H H CH2 OCH 2 OCH 3 4 -486 H Cl H CF3 H H CH2 OCH 2 OC 2 H;
4 -487 H Cl H CF3 H H CH2 OCOCH a 4 -488 H Cl H CF3 H H CHZ OCOC 2 Hs 4 -489 H Cl H CF3 H H CH2 OCO ' C, H, 4 -490 H Cl H CF3 H H CHz OCOCH 2 Cl 4- 491 H Cl H CF3 H H CHz OCOCC13 4 -492 H Cl H CF3 H H CH2 OCOCF 3 4 -493 H Cl H CF3 H H COOH
4 -494 H Cl H CF3 H H COOCH3 TABLE 4 (contn'd) Compound X Y R 3 R ' R2 R' R B
No.
4 -495 H Cl H CF3 H H COOC2 H s 4 - 496 H C1 H CF3 H H C00 " C a H, 4- 497 H C1 H CF3 H H C00 " C 4 H y 4 -498 H Cl H CF3 H H C00 C Ht, 4 -499 H Cl H CFa H H COO C 3 H 7 4 -500 H Cl H CF3 H H C00 ' C s H s 4 -501 H Cl H CF3 H H C00 ' C 6 H 11 4 -502 H Cl H CF3 H H COOCH2 CH = CH2 4 -503 H Cl H CF3 H H COOCH2 C CH
4 -506 H Cl H CF3 H H CONHC2 H
4 -507 H Cl H CF3 H H CON(CH3 ) 2 4- 508 H Cl H CF3 H H CON(C2 H;) 2 4 -509 F Cl H CF3 H H CH2 Cl 4 -510 F Cl H CF3 H H CH2 Br 4 -512 F CI H CF3 H H CH2 0C2 H s 4 -513 F Cl H CF3 H H CH2 OCH 2 OCH 3 4 -514 F Cl H CF3 H H CHz OCH 2 OC 2 Hs r 4 -516 F Cl H CF3 H H CH2 OCOC 2 Hs 4- 517 F Cl H CF3 H H CHZ OCO ' C 3 H, TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R7 R8 No.
4 -518 F Cl H CF3 H H CH2 OCOCH 2 Cl 4- 519 F Cl H CF3 H H CH2 OCOCCI3 4 -520 F Cl H CF3 H H CH2 OCOCF , 4 -521 F Cl H CF3 H H COOH
4 -522 F Cl H CF3 H H COOCH3 4 -523 F Cl H CF3 H H COOC2 H s 4 -524 F Cl H CF3 H H C00 " C a H 1 4 -525 F Cl H CF3 H H C00 "-C H s 4 -526 F Cl H CF3 H H C00 " C 5 Hõ
4 -527 F Cl H CF3 'H H COO C a H T
4- 528 F Cl H CF3 H H C00 ' C 5 H s 4 -529 F Cl H CF3 H H COO ' C 6 Hõ
4 -530 F Cl H CF3 H H COOCH2 CH = CH2 4 -531 F Cl H CF3 H H COOCH2 C= CH
4 -532 F Cl H CF3 H H CONH2 4 -533 F Cl H CF3 H H CONHCH3 4 -534 F Cl H CF3 H H CONHC2 H s 4 -535 F Cl H CF3 H H CON(CH3 ) 2 4- 536 F Cl H CF3 H H CON(C2 H 5) 2 4 -537 H Cl H CF3 H CH3 CH2 Cl 4 -538 H Cl H CF3 H CH3 CH2 Br 4 -539 H Cl H CF3 H CH3 CH2 OCH a 4 -540 H Cl H CF3 H CH3 CH2 0C2 H 5 WO 97/07104 PCT/.bP96/02311 TABLE 4 (contn'd) Compound X Y R3 R' R2 R' R8 No.
4 -541 H Cl H CF3 H CH3 CHz OCH 2 OCH 3 4 -542 H Cl H CF3 H CH3 CH2 OCH 2 OC 2 Hs 4 -543 H Cl H CF3 H CH3 CH2 OCOCH a 4 -544 H Cl H CF3 H CHa CH2 OCOC 2 H5 4 -545 H Cl H CF3 H CH3 CH2 OCO ' C 3 H, 4 -546 H Cl H CF3 H CH3 CHZ OCOCH 2 Cl 4 -547 H Cl H CF3 H CH3 CHa OCOCC13 4 -548 H Cl H CF3 H CH3 CH2 OCOCF 3 4 -549 H Cl H CF3 H CH3 COOH
4 -550 H Cl H CF3 H CH3 COOCH3 4 -551 H Cl H CF3 H CH3 COOC2 H s 4 -552 H Cl H CF3 H CH3 C00 " C, H T
4 -553 H Cl H CF3 H CH3 C00 " C 4 H 9 4 -554 H Cl H CF3 H CH3 C00 " C s H õ
4 -555 H Cl H CF3 H CH3 COO ' C 3 H, 4 -556 H Cl H CF3 H CH3 COO ' C s H q 4 -557 H Cl H CF3 H CH3 C00 ' C 6 H,1 4 -558 H Cl H CF3 H CH3 COOCH2 CH = CHz 4 -559 H Cl H CF3 H CH3 COOCH2 C= CH
4 -560 H Cl H CF3 H CH3 CONH2 4 -561 H Cl H CF3 H CH3 CONHCH3 4 -562 H Cl H CF3 H CH3 CONHC2 H 5 TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R7 R B
No.
4 -563 H Cl H CF3 H CH3 CON(CH3 ) 2 4 -564 H Cl H CF3 H CH3 CON(C2 H s) 2 4 -565 F Cl H CF3 H CHs CH2 Cl 4 -566 F Cl H CF3 H CH3 CH2 Br 4 -567 F Cl H CF3 H CH3 CH2 0CH 3 4 -568 F Cl H CF3 H CH3 CH2 0C2 H s 4 -569 F Cl H CF3 H CH3 CH2 OCH 2 OCH 3 4 -570 F Cl H CF3 H CH3 CH2 OCH 2 OC 2 Hs 4 -571 F Cl H CF3 H CH3 CHz OCOCH a 4 -572 F Cl H CF3 H CH3 CH2 OCOC 2 H5 4 -573 F Cl H CF3 H CH3 CH2 OCO ' C a H 7 4 -574 F Cl H CF3 H CH3 CH2 OCOCH 2 Cl 4 -575 F Cl H CF3 H CH3 CH2 OCOCC13 4 -576 F Cl H CF3 H CHs CH2 OCOCF a 4 -577 F Cl H CF3 H CH3 COOH
4 -578 F Cl H CF3 H CH3 COOCH3 4 -579 F Cl H CF3 H CH3 COOC2 H s 4 -580 F Cl H CF3 H CH3 COO " C 3 H 7 4 -581 F Cl H CF3 H CH3 COO " C, H
4 -582 F Cl H CF3 H CH3 COO C s H-~
4 -583 F Cl H CF3 H CH3 COO ' C a H 7 {
4 -584 F Cl H CF3 H CH3 COO ' C s H 9 4 -585 F Cl H CF3 H CH3 COO ' C 6 H õ
WO 97/07104 PCT/.TP96/02311 TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R' R8 No.
4 -586 F Cl H CFa H CH3 COOCH2 CH = CH2 4 -587 F Cl H CF3 H CH3 COOCH2 C= CH
4 -588 F Cl H CF3 H CH3 CONH2 4 -589 F Cl H CF3 H CH3 CONHCH3 4 -590 F Cl H CF3 H CH3 CONHC2 H s 4- 591 F Cl H CF3 H CH3 CON(CH3 ) 2 4 -592 F Cl H CF3 H CH3 CON(C2 H 5) 2 4 -593 H Cl H CF3 H H CH2 Cl 4 -594 H Cl H CF3 H H CH2 Br 4 -595 H Cl H CF3 H H CH2 OCH 3 4 -596 H Cl H CF3 H H CH2 0C2 H 5 4 -597 H Cl H CF3 H H CH2 OCH 2 OCH 3 4 -598 H Cl H CF3 H H CH2 OCH 2 OC 2 Hs 4- 599 H Cl H CF3 H H CH2 OCOCH 3 4 -600 H Cl H CF3 H H CH2 OCOC 2 Hs 4 -601 H Cl H CF3 H H CH2 OCO ' C 3 H T
4 -602 H Cl H CF3 H H CH2 OCOCH 2 Cl 4 -603 H Cl H CF3 H H CH2 OCOCCI3 4 -604 H Cl H CF3 H H CHz OCOCF 3 4 -605 H C l H CF3 H H COOH
4 -606 H Cl H CF3 H H COOCH3 4 -607 H Cl H CF3 H H COOC2 H 5 4 - 608 H Cl H CF3 H H C00 " C, H, TABLE 4 (contn'd) compound X Y R' R' R Z R' R 8 No.
4 - 609 H Cl H CF3 H H C00 " C4 H o 4 - 610 H Cl H CF3 H H C00 " C 5 H,i 4 -611 H Cl H CF3 H H COO ' C 3 H, 4 -612 H Cl H CF3 H H C00 ' C 5 H 9 4 -613 H Cl H CF3 H H COO ' C 6 H ii 4 -614 H Cl H CF3 H H COOCHZ CH = CH2 4 -615 H Cl H CF3 H H COOCH2 C CH
4 -616 H Cl H CF3 H H CONH2 4 -617 H Cl H CF3 H H CONHCH3 4 -618 H Cl H CF3 H H CONHC2 H s 4 -619 H Cl H CF3 H H CON(CH3 ) 2 4 -620 H Cl H CF3 H H CON(C2 H s) 2 4 -621 F Cl H CF3 H H CH2 C1 4 -622 F Cl H CF3 H H CH2 Br 4 -623 F Cl H CF3 H H CH2 OCH 3 4 -624 F Cl H CF3 H H CH2 OC2 H s 4 -625 F Cl H CF3 H H CH2 OCH 2 OCH a 4 -626 F Cl H CF3 H H CH2 OCH 2 OC 2 Hs 4 -627 F Cl H CF3 H H CH2 OCOCH , 4 -628 F Cl H CF3 H H CH2 OCOC 2 Hs 4 -629 F Cl H CF3 H H CH2 OCO ' C 3 H T
4 -630 F Cl H CF3 H H CH2 OCOCH 2 Cl 4 -631 F Cl H CF3 H H CH2 OCOCCI3 TABLE 4 (contn'd) Compound X Y R 3 R' R Z R' R a No.
4 -633 F Cl H CF3 H H COOH
4 -635 F Cl H CF3 H H COOC2 H s 4- 636 F Cl H CF3 H H C00 " C 3 H 7 4- 638 F C1 H CF3 H H C00 " C s H õ
4 -639 F Cl H CF3 H H C00 ' C H
4- 640 F Cl H CF3 H H C00 ' C s H 9 4- 641 F Cl H CF3 H H C00 ' C 6 H 11 4 -642 F Cl H CF3 H H COOCH2 CH = CH2 4 -643 F Cl H CF3 H H COOCHa C= CH
4 -646 F C1 H CF3 H H CONHC2 H s 4 -647 F C1 H CF3 H H CON(CH3 ) 2 4 -648 F Cl H CF3 H H CON(C2 H 5) 2 4 -650 H Cl H CF3 H CH3 CH2 Br 4 -652 H Cl H CF3 H CH3 CH2 0C2 H 5 4 -653 H Cl H CF3 H CHa CH2 OCH 2 OCH 8 TABLE 4 (contn'd) Compound X Y R' R' R2 R' R B
No.
4 -655 H Cl H CF3 H CH3 CH2 OCOCH 3 4 -656 H Cl H CF3 H CH3 CH2 OCOC 2 H5 4 -657 H Cl H CF3 H CH3 CH2 OCO ' C, H 7 4 -658 H Cl H CF3 H CH3 CH2 OCOCH 2 Cl 4- 659 H Cl H CF3 H CH3 CHZ OCOCCIy 4 -660 H Cl H CF3 H CH3 CH2 OCOCF 3 4 -661 H Cl H CF3 H CH3 COOH
4 -662 H Cl H CF3 H CH3 COOCH3 4 -663 H Cl H CF3 H CH3 COOC2 H s 4 -664 H Cl H CF3 H CH3 C00 " C 3 H7 4 -665 H Cl H CF3 H CHa C00 C H
4 -666 H Cl H CF3 H CH3 C00 " C H
4 -667 H Cl H CF3 H CH3 COO C, H, 4 -668 H Cl H CF3 H CH3 COO C 5 H 9 4 -669 H Cl H CF3 H CH3 COO ' C 6 H õ
4 -670 H Cl H CF3 H CH3 COOCH2 CH = CHz 4 -671 H Cl H CF3 H CHs COOCH2 C= CH
4 -672 H Cl H CF3 H CH3 CONH2 4 -673 H Cl H CF3 H CH3 CONHCH3 4 -674 H Cl H CF3 H CH3 CONHC2 H s 4 -675 H Cl H CF3 H CH3 CON(CH3 ) 2 4 -676 H Cl H CF3 H CH3 CON(C2 H 5) 2 TABLE 4 (contn'd) Compound X y jZ 3 R 1 R 2 R7 R
No.
4 -677 F Cl H CF3 H CH3 CHz Cl 4 -678 F Cl H CF3 H CH3 CH2 Br 4 -679 F Cl H CF3 H CH3 CH2 OCH , 4 -680 F Cl H CF3 H CHa CH2 0C2 H s 4 -681 F Cl H CF3 H CH3 CHz OCH 2 OCH 3 4 -682 F Cl H CF3 H CHa CH2 OCH 2 OC 2 Hs 4 -683 F Cl H CF3 H CH3 CH2 OCOCH , 4 -684 F Cl H CF3 H CHa CH2 OCOC 2 Hs 4 -685 F Cl H CF3 H CH3 CH2 OCO ' C a H T
4 -686 F Cl H CF3 H CH3 CH2 OCOCH 2 Cl 4 -687 F Cl H CF3 H CH3 CHZ OCOCC13 4 -688 F Cl H CF3 H CH3 CHZ OCOCF , 4 -689 F Cl H CF3 H CH3 COOH
4 -690 F Cl H CF3 H CH3 COOCH3 4 -691 F Cl H CF3 H CH3 COOC2. H s 4 -692 F Cl H CF3 H CH3 C00 C a H, 4 -693 F Cl H CF3 H CH3 C00 " C 4 H 9 4 -694 F C1 H CF3 H CH3 C00 " C 5 H õ
4 -695 F Cl H CF3 H CH3 C00 ' C a H, 4 -696 F Cl H CF3 H CH3 COO c C 5 H fl 4 -697 F Cl H CF3 H CH3 COO ' C 6 H õ
4 -698 F Cl H CFa H CH3 COOCH2 CH = CH2 4 -699 F Cl H CF3 H CH3 COOCHa C CH
TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R' R 8 No.
4 -701 F Cl H CF3 H CH3 CONHCH3 4 -702 F Cl H CF3 H CHs CONHC2 H s 4 -703 F Cl H CF3 H CH3 CON(CH3 ) 2 4 -704 F Cl H CF3 H CHa CON (C2 H s) 2 4 -705 H Cl CH3 CF3 H H CH2 Cl 4 -706 H Cl CH3 CF3 H H CH2 Br 4 -707 H Cl CH3 CF3 H H CH2 OCH 3 4 -708 H Cl CH3 CF3 H H CH2 0C2 H s 4 -709 H Cl CH3 CF3 H H CH2 OCH 2 OCH 3 4 -710 H C1 CH3 CF3 H H CH2 OCH 2 OC 2 Hs 4 -711 H Cl CH3 CF3 H H CH2 OCOCH I
4 -712 H C1 CHa CF3 H H CHz OCOC.2 Hs 4- 713 H Cl CHs CF3 H H CHz OCO ' C a H 7 4 -714 H Cl CH3 CF3 H H CH2 OCOCH 2 Cl 4 -715 H Cl CH3 CF3 H H CH2 OCOCCI3 4 -716 H Cl CH3 CF3 H H CH2 OCOCF 3 4 -717 H Cl CH3 CF3 H H COOH
4 -718 H Cl CH3 CF3 H H COOCH3 4 -719 H Cl CH3 CF3 H H COOC2 H s 4 -720 H Cl CH3 CF3 H H COO " C 3 H, , 4- 721 H Cl CH3 CF3 H H C00 " C 4 H fl 4 -722 H Cl CH3 CF3 H H COO " C s H õ
VvO 97/07104 PCT/.dP96/02311 TABLE 4 (contn'd) Compound X Y R3 R' R2 R' R8 No.
4 -723 H Cl CH3 CF3 H H COO ' C, H, 4 -724 H Cl CH3 CF3 H H COO ' C 5 H y 4 -725 H Cl CH3 CF3 H H COO ' C 6 H 11 4 -726 H Cl CH3 CF3 H H COOCH2 CH = CHZ
4 -727 H Cl CH3 CF3 H H COOCH2 C= CH
4 -728 H Cl CH3 CF3 H H CONH2 4 -729 H Cl CHs CF3 H H CONHCH3 4 -730 H Cl CH3 CF3 H H CONHC2 H 5 4 -731 H Cl CH3 CF3 H H CON(CH3 ) 2 4 -732 H Cl CH3 CF3 H H CON(C2 H s) 2 4 -733 F Cl CH3 CF3 H H CHa Cl 4 -734 F Cl CH3 CF3 H H CH2 Br 4 -735 F Cl CH3 CF3 H H CHZ OCH 3 4 -736 F Cl CH3 CF3 H H CH2 0C2 H s 4 -737 F Cl CH3 CF3 H H CHZ OCH 2 OCH
4 -738 F Cl CH3 CF3 H H CH2 OCH 2 OC 2 H5 4 -739 F Cl CH3 CF3 H H CH2 OCOCH , 4 -740 F Cl CH3 CF3 H H CH2 OCOC 2 Hs 4 -741 F Cl CH3 CF3 H H CHZ OCO ' C, H
4 -742 F Cl CH3 CF3 H H CHZ OCOCH 2 Cl 4 -743 F Cl CH3 CF3 H H CH2 OCOCCI3 4 -744 F Cl CH3 CF3 H H CHZ OCOCF 3 4 -745 F Cl CH3 CF3 H H COOH
TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R' R 8 No.
4 -746 F Cl CH3 CF3 H H COOCH3 4 -747 F Cl CH3 CF3 H H COOCz. H s 4 -748 F Cl CH3 CF3 H H COO " C 3 H, 4 -749 F C1 CH3 CF3 H H COO " C, H s 4 -750 F Cl CH3 CF3 H H COO " C 5 H õ
4- 751 F Cl CH3 CF3 H H COO ' C 3 H 7 4- 752 F Cl CH3 CF3 H H C00 ' C 5 H 9 4 -753 F C1 CH3 CF3 H H COO ' C 6 H
4- 754 F Cl CH3 CF3 H H COOCHZ CH = CHz 4 -755 F Cl CH3 CF3 H H COOCH2 C= CH
4 -756 F Cl CH3 CF3 H H CONH2 4- 757 F Cl CH3 CF3 H H CONHCH3 4 -758 F Cl CH3 CF3 H H CONHC2 H s 4 -759 F Cl CH3 CF3 H H CON(CH3 ) 2 4 -760 F Cl CH3 CF3 H H CON(C2 H s) 2 4 -761 H C1 CH3 CF3 H CH3 CH2 Cl 4 -762 H C1 CH3 CF3 H CH3 CH2 Br 4 -763 H Cl CH3 CF3 H CH3 CH2 0CH 3 4 -764 H Cl CH3 CF3 H CH3 CH2 0C2 H 5 4 -765 H Cl CH3 CF3 H CH3 CH2 0CH 2 OCH 3 4 -767 H Cl CH3 CF3 H CH3 CHZ OCOCH 3 4 -768 H C1 CH3 CF3 H CH3 CH2 OCOC 2 Hs WO 97f07104 PCT/JP96/02311 TABLE 4 (contn'd) compound X Y R 3 R' R 2 R7 R8 No.
4 -769 H Cl CH3 CF3 H CH3 CH2 OCO ' C 3 H, 4 -770 H Cl CH3 CF3 H CH3 CH2 OCOCH 2 Cl 4 -771 H Cl CH3 CF3 H CH3 CHZ OCOCCI3 4 -772 H Cl CH3 CF3 H CH3 CHz OCOCF 3 4 -773 H Cl CH3. CF3 H CH3 COOH
4 -774 H Cl CH3 CF3 H CH3 COOCH3 4 -775 H Cl CH3 CF3 H CH3 COOC2 H s 4 -776 H Cl CH3 CF3 H CH3 COO " C 3 H 7 4 -777 H Cl CH3 CFa H CH3 COO C{ H g 4 -778 H Cl CH3 CF3 H CH3 COO " C s H õ
4 -779 H C1 CH3 CF3 H CH3 COO ' C 3 H7 4 -780 H Cl CH3 CF3 H CH3 COO ' C s H o 4- 781 H Cl CH3 CF3 H CH3 COO ' C 6 H õ
4 -782 H Cl CH3 CF3 H CH3 COOCH2 CH = CH2 4 -783 H Cl CH3 CF3 H CH3 COOCH2 C= CH
4 -784 H C1 CH3 CF3 H CHa CONH2 4 -786 H Cl CH3 CF3 H CH3 CONHCz H a 4 -787 H C1 CH3 CF3 H CH3 CON(CH3 ) 2 4 -788 H Cl CH3 CF3 H CH3 CON(C2 H s) 2 4 -789 F Cl CH3 CF3 H CH3 CHz Cl ,.
4 -790 F Cl CH3 CF3 H CH3 CHz Br TABLE 4 (contn'd) Compound X Y R3 R' R Z R' R 8 No.
4 -791 F Cl CH3 CF3 H CH3 CH2 OCH , 4 -792 F Cl CH3 CF3 H CH3 CH2 0C2 H;
4 -793 F Cl CH3 CF3 H CH3 CH2 OCH 2 OCH 3 4 -794 F Cl CH3 CF3 H CH3 CH2 OCH 2 OC ~ H;
4 -795 F Cl CH3. CF3 H CH3 CH2 OCOCH 3 4 -796 F Cl CH3 CF3 H CH3 CH2 OCOC 2 H;
4 -797 F Cl CH3 CF3 H CH3 CH2 OCO ' C a H 7 4 -798 F C1 CH3 CF3 H CH3 CH2 OCOCH 2 Cl 4 -799 F Cl CH3 CF3 H CH3 CH2 OCOCCI3 4 -800 F Cl CH3 CF3 H CH3 CH2 OCOCF , 4 -801 F Cl CH3 CF3 H CH3 COOH
4 -802 F Cl CH3 CF3 H CH3 COOCH3 4 -803 F Cl CH3 CF3 H CH3 COOC2 H s 4 -804 F C1 CH3 CF3 H CH3 C00 " C 3 H 7 4 -805 F Cl CH3 CF3 H CH3 COO " C 4 H 3 4 -806 F Cl CH3 CF3 H CH3 COO " C s H õ
4 -807 F C1 CH3 CF3 H CH3 COO ' C 3 H 1 4- 808 F Cl CH3 CF3 H CH3 COO ' C 5 H s 4 -809 F Cl CHa CF3 H CH3 COO c C 6 H õ
4 -810 F Cl CH3 CF3 H CH3 COOCH2 CH = CH2 4 -811 F Cl CH3 CF3 H CH3 COOCH2 C= CH
4 -812 F Cl CH3 CF3 H CH3 CONH2 4 -813 F Cl CH3 CF3 H CH3 CONHCH3 WO 97/07104 PC'H'/JP96/02311 TABLE 4 (contn'd) Compound X Y R3 R' R2 R' R8 No.
4 -814 F Cl CH3 CF3 H CH3 CONHC2 H s 4 -815 F Cl CH3 CF3 H -CH3 CON(CH3 ) Z
4- 816 F Cl CH3 CF3 H CH3 CON(C2 H s) 2 4 -817 H Cl CH3 CF3 H H CH2 Cl 4 -818 H Cl CH3 CF3 H H CH2 Br 4 -819 H Cl CH3 CF3 H H CH2 OCH , 4 -820 H Cl CH3 CF3 H H CH2 0Ca H s 4 -821 H Cl CH3 CF3 H H CH2 OCH 2 OCH 3 4 -822 H Cl CH3 CF3 H H CH2 OCH 2 OC 2 Hs 4 -823 H Cl CH3 CF3 H H CH2 OCOCH 3 4 -824 H Cl CH3 CF3 H H CH2 OCOC 2 Hs 4 -825 H Cl CH3 CF3 H H CH2 OCO ' C, H T
4 -826 H Cl CH3 CF3 H H CH2 OCOCH 2 Cl 4 -827 H Cl CH3 CF3 H H CH2 OCOCCI3 4 -828 H Cl CH3 CF3 H H CH2 OCOCF , 4 -829 H Cl CH3 CF3 H H COOH
4 -830 H Cl CHa CF3 H H COOCH3 4 -831 H Cl CHa CF3 H H COOC2 H s 4 -832 H Cl CH3 CF3 H H C00 " C 3 H, 4 -833 H C1 CH3 CF3 H H C00 " C 4 H 9 4 -834 H Cl CH3 CF3 H H C00 " C 5 H õ
4 -835 H Cl CH3 CF3 H H C00 ' C a H7 4 -836 H Cl CH3 CF3 H' H COO C 5 H 9 TABLE 4 (contn'd) Compound X Y R 3 R' R Z R7 R8 No.
4 -837 H Cl CH3 CF3 H H COO ' C 6 H
4 -838 H Cl CH3 CF3 H H COOCHZ CH = CHZ
4 -839 H Cl CH3 CF3 H H COOCHZ C= CH
4 -840 H Cl CH3 CF3 H H CONHz 4 -841 H Cl CH3 CF3 H H CONHCH3 4 -842 H Cl CH3 CF3 H H CONHC2 H s 4 -843 H Cl CH3 CF3 H H CON(CH3 ) 2 4 -844 H Cl CH3 CF3 H H CON(C2 H 2 4 -845 F Cl CH3 CF3 H H CH2 Cl 4 -846 F Cl CH3 CF3 H H CH2 Br 4 -847 F Cl CHs CF3 H H CH2 OCH 3 4 -848 F Cl CH3 CF3 H H CH2 OC2 H s 4 -849 F Cl CH3 CF3 H H CHa OCH 2 OCH 3 4 -850 F Cl CH3 CF3 H H CHa OCH 2 OC 2 H;
4 -851 F Cl CH3 CF3 H H CHa OCOCH 3 4 -852 F Cl CHa CF3 H H CHZ OCOC 2 Ha 4 -853 F Cl CH3 CF3 H H CHz OCO ' C a H 7 4 -854 F Cl CH3 CF3 H H CH2 OCOCH 2 Cl 4 -855 F Cl CH3 CF3 H H CH2 OCOCC13 4 -856 F Cl CH3 CF3 H H CH2 OCOCF , 4 -857 F Cl CH3 CF3 H H COOH
.
4 -858 F Cl CH3 CF3 H H COOCH3 4 -859 F Cl CH3 CF3 H H COOC2 H s TABLE 4 (contn'd) Compound X Y R 3 R' R 2 R 7 R 8 No.
4 -860 F Cl CH3 CF3 H H C00 C a H 7 4- 861 F Cl CH3 CF3 H H C00 C 4 H 9 4 -862 F Cl CH3 CF3 H H C00 " C 5 H õ
4 -863 F Cl CH3 CF3 H H COO ' C a H 7 4 -864 F Cl CH3 CF3 H H C00 C C s H s 4 -865 F Cl CH3 CF3 H H COO c C 6 H õ
4 -866 F Cl CH3 CF3 H H COOCH2 CH = CHZ
4 -867 F C l CH3 CF3 H H COOCH Z-C = CH
4 -868 F Cl CH3 CF3 H H CONH2 4 -869 F Cl CH3 CF3 H H CONHCH3 4 -870 F Cl CH3 CF3 H H CONHCZ H 5 4 -871 F Cl CH3 CF3 H H CON(CH3 ) 2 4 -872 F Cl CH3 CF3 H H CON(C2 H s) 2 4 -873 H Cl CH3 CF3 H CH3 CH2 Cl 4 -874 H Cl CH3_ CF3 H CH3 CH2 Br 4 -875 H Cl CH3 CF3 H CH3 CH2 OCH a 4 -876 H Cl CH3 CF3 H CHa CH2 0C2 H 5 4 -877 H Cl CH3 CF3 H CH3 CH2 OCH 2 OCH , 4 -878 H Cl CH3 CF3 H CH3 CH2 OCH 2 OC 2 Hs 4 -879 H Cl CHa CF3 H CH3 CHz OCOCH a 4 -880 H Cl CH3 CF3 H CH3 CHz OCOC 2 Hs .
4- 881 H Cl CH3 CF3 H CH3 CHZ OCO ' C s H, 4 -882 H Cl CH3 CF3 H CH3 CHQ OCOCH 2 Cl TABLE 4 (contn'd) Compound X Y R 3 R' R2 R' R B
No.
4 -883 H Cl CH3 CF3 H CH3 CH2 OCOCCI3 4 -884 H Cl CH3 CF3 H CH3 CH2 OCOCF 3 4 -885 H Cl CH3 CF3 H CH3 COOH
4 -886 H Cl CH3 CF3 H CH3 COOCH3 4 -887 H Cl CH3 CF3 H CH3 COOC2 H 5 4 -888 H Cl CH3 CF3 H CH3 C00 " C, H 7 4 -889 H Cl CH3 CF3 H CH3 COO " C 4 H
4 -890 H Cl CH3 CF3 H CH3 C00 " C s H
4 -891 H Cl CH3 CF3 H CHa COO ' C a H 7 4 -892 H Cl CH3 CF3 H CH3 COO c C 5 H q 4 -893 H Cl CH3 CF3 H CH3 COO ' C 6 Hõ
4 -894 H Cl CHs CF3 H CH3 COOCH2 CH = CH2 4 -895 H Cl CH3 CF3 H CH3 COOCH2 C= CH
4 -896 H Cl CH3 CF3 H CHs CONH2 4 -897 H Cl CH3 CF3 H CH3 CONHCH3 4 -898 H C1 CH3 CF3 H CH3 CONHC2 H s 4 -899 H Cl CH3 CF3 H CH3 CON(CH3 ) 2 4 -900 H Cl CH3 CF3 H CH3 CON(C2.H ;) 2 4 -901 F Cl CH3 CF3 H CH3 CH2 Cl 4 -902 F Cl CH3 CF3 H CH3 CH2 Br 4 -903 F Cl CH3 CF3 H CH3 CH2 OCH 3 4 -904 F Cl CH3 CF3 H CH3 CHZ 0C2 H 5 TABLE 4 (contn'd) Compound X y R3 R' R2 R' R8 No.
4 -905 F Cl CH3 CF3 H CHa CH2 OCH 2 OCH a 4 -906 F Cl CH3 CF3 H CH3 CH2 OCH 2 OC 2 Hs 4 -907 F Cl CH3 CF3 H CH3 CH2 OCOCH , 4 -908 F C1 CH3 CF3 H CH3 CH2 OCOC 2 Hs 4 -909 F Cl CH3 CFa H CH3 CH2 OCO ' C 3 H, 4 -910 F Cl CH3 CF3 H CH3 CH2 OCOCH 2 Cl 4 -911 F Cl CH3 CF3 H CH3 CH2 OCOCC13 4 -912 F Cl CH3 CF3 H CH3 CH2 OCOCF 3 4 -913 F Cl CH3 CF3 H CH3 COOH
4 -914 F Cl CH3 CF3 H CH3 COOCH3 4 -915 F Cl CH3 CF3 H CH 3 COOC2 H;
4- 916 F Cl CH3 CF3 H CH3 C00 C 3 H 7 4- 917 F Cl CH3 CF3 H CH3 C00 " C, H 9 4 -918 F Cl CH3 CF3 H CH3 C00 " C 5 H i 4- 919 F Cl CH3 CF3 H CH3 COO ' C, H 7 4 -920 F Cl CH3 CF3 H CH3 C00 ' C 5 H9 4- 921 F Cl CH3 CF3 H CH3 COO ' C 6 H õ
4 -922 F Cl CH3 CF3 H CH3 COOCH2 CH = CHZ
4 -923 F Cl CH3 CF3 H CH3 COOCH2 C= CH
4 -924 F Cl CH3 CF3 H CH3 CONH2 4 -925 F Cl CH3 CF3 H CH3 CONHCH3 4 -926 F C1 CH3 CF3 H CH3 CONHC2 H s 4 -927 F Cl CH3 CF3 H CH3 CON(CH3 ) Z
WO 97/07104 PC'd'/JP96/02311 TABLE 4 (contn'd) Compound X Y R 3 R ' R Z R' R B
No.
4 -928 F Cl CH3 CF3 H CH3 CON(C2 H z 4 -929 F Cl CH3 CF3 H H CH 3 4 -930 F Cl CH3 CF3 H H CH z OH
4 -931 F Cl CH3 CF3 H CH3 CH 3 4 -932 F Cl CH3 CF3 H CH3 CH 2 OH
4 -933 H Cl CH3 CF3 H H CH 3 4 -934 H Cl CH3 CF3 H H CH 2 OH
4 -935 H Cl CH3 CF3 H CH3 CH 3 4 -936 H Cl CH3 CF3 H CH3 CH 2 OH
TABLE S
= Compounds of the formula:
X O R'-N ~ ~ N x R~~ -N-N
\ R;
RS
Compound X R3 R ' R 2 R S
No.
- 1 H H CF2 Cl CHa CH3 5-2 H H CF2C1 CH3 C 2 H s 5 - 3 H H CFz C1 CH3 ' C 3 H T
5- 4 H H CFZ C1 CH3 C 3 H, 5- 5 H H CF2 Cl CH3 ' C, H 9 5 - 6 H H CF2 Cl CH3 CH2 CH = CH2 5 - 7 H H CF2 Cl CH3 CH(CH3 )CH =CH2 5- 8 H H CF2 Cl CH3 CH2 C= CH
5 - 9 H H CF2 C1 CHa CH(CHa )C = CH
5- 11 F H CF2 C1 CH3 C 2 H;
5- 12 F H CF2 Cl CH3 C , H, 5 -13 F H CF2 Cl CH3 "C 3 H, 5- 14 F H CF2 C1 CH3 'C , H 9 4 5 -15 F H CF2 C1 CH3 CH2 CH=CH2 TABLE 5 (contn'd) Compound x R 3 R ' R Z R 5 No.
-16 F H CF2 Cl CH3 CH(CH3 )CH =CH2 5 -17 F H CF2 Cl CH3 CH2 C= CH
5 -18 F H CF2 Cl CH3 CH(CH3 )C=CH
5- 20 H H CF3 CH3 C z H s 5- 21 H H CF3 CH3 'C 3 H 7 5 -22 H H CF3 CH3 "C 3 H 7 5 -23 H H CF3 CH3 'C -H 9 5 -24 H H CF3 CH3 CHz CH=CH2 5 -25 H H CF3 CH3 CH(CH3 )CH =CH2 5 -26 H H CF3 CH3 CH2 C=CH
5 -27 H H CFa CH3 CH(CH3 )C -CH
5- 30 F H CF3 CH3 'C 3 H, 5-31 F H CF3 CH3 'C 4 H 9 5 -32 F H CF3 CH3 CH2 CH=CH2 5 -33 F H CF3 CH3 CH(CH3 )CH =CH2 5 -34 F H CF3 CH 3 CH 2 C= CH
5 -35 F H CF3 CH3 CH(CH3 )C=CH =
5 -36 H H CF2 Cl H CH3 5-37 H H CF2 C1 H C z H 5 5 -38 H H CF2 Cl H 'C 3 H 7 TABLE 5 (contn'd) Compound x R3 R ' R 2 R S
No.
5- 39 H H CF2 Cl H "C 3 H 7 5- 40 H H CF2 Cl H 'C H
-41 H H CF2 Cl H CH2 CH=CH2 5 -42 H H CF2 Cl H CH(CH3 )CH =CH2 5 -43 H H CF2 C l H CH a C CH
5-44 H H CF2 Cl H CH(CH3 )CCH
5- 45 F H CF2 Cl H CH3 5- 46 F H CF2 Cl H C 2-H
5 -47 F H CF2 Cl H 'C 3 H, 5 -48 F H CF2 Cl H "C 3 H
5 -49 F H CF2 Cl H ' C, H 9 5 -50 F H CF2 Cl H CH2 CH=CH2 5 -51 F H CF2 Cl H CH(CH3 )CH =CH2 5 -52 F H CF2 Cl H CH2 C=CH
5 -53 F H CF2 Cl H CH(CH3 )C=CH
5- 55 H H CF3 H C z H s 5- 56 H H CF3 H 'C 3 H5- 57 H H CF3 H "C 3 H
5- 58 H H CFa H 'C , H
5 -59 H H CF3 H CH2 CH=CH2 5 -60 H H CF3 H CH(CH3 )CH =CH2 5 -61 H H CF3 H CH2 C=CH
TABLE 5 (contn'd) Compound x R 3 R ' R 2 R 5 No.
-62 H H CF3 H. CH(CH3 )C=CH
5- 64 F H CF3 H C 2 H s 5- 65 F H CFa H C a H 7 5 -66 F H CF3 H 'C 4 H 9 5 -67 F H CF3 H CH2 CH= CH2 5 -68 F H CF3 H CH(CH3 )CH =CH2 5 -70 F H CF3 H CH(CH3 )C=CH
5 -72 H CH3 CF3 H C 2 H;
5- 73 H CH3 CF3 H 'C 3 H, 5 -74 H CH3 CF3 H C a H 7 5- 75 H CH3 CF3 H 'C 4 H fl 5 -76 H CH3 CF3 H CH2 CH=CH2 5 -77 H CH3 CF3 H CH(CH3 )CH =CH2 5 -79 H CH3 CF3 H CH(CH3 )C=CH
5 -82 F CH3 CF3 H 'C 3 H 7 5- 83 F CH3 CF3 H 'C , H o 5 -84 F CH3 CF3 H CH2 CH=CH2 TABLE 5 (contn'dl Compound X R 3 R' R Z R 5 No.
-85 F CH3 CF3 H CH(CH3 )CH = CH2 5 -87 F CH3 CF3 H CH(CH3 )C=CH
The physical properties (melting point, m.p.) or 'H-NMR (250 or 300 MHz, CDCI3, TMS, S(ppm)) data for some of the present compounds are shown below.
Compound 1-332, m.p. 97.0 C
Compound 1-335, rn.p. 80.8 C
Compound 1-337, m.p. 91.5 C
Compound 1-338, in.p. 86.1 C
Compound 1-344, m.p. 94.2 C
Compound 1-347, m.p. 80.7 C
Compound 1-350, 2.41 (3H, q, J= 1.8 Hz), 4.05-4.35 (2H, b), 6.87-6.94 (1 H, m), 7.03 (1 H, d, J= 2.4 Hz), 7.33 (1 H, d, J = 8.5 Hz), 7.98 (1 H, s) Compound 1-353, m.p. 124.0 C
Compound 1-367, 2.44 (3H, q, J = 1.9 Hz), 3.04 (3H, s), 6.88 (1 H, s), 7.37 (1 H, d, J = 9.0 Hz), 7.79 (1 H, d, J = 7.0 Hz), 8.01 (1 H, s) Compound 1-369, 2.44 (3H, q, J = 2.0 Hz), 4.57 (2H, s), 7.06 (1 H, s), 7.38 (1 H, d, J = 9.0 Hz), 7.83 (1 H, d, J = 6.9 Hz), 8.01 (1 H, s) Compound 1-391, m.p. 177.6 C
Compound 1-392, m.p. 172.5 C
Compound 1-398, m.p. 133.1 C
Compound 1-420, 1.25 (3H, t, J = 7.5 Hz), 1.51 (3H, d, J = 7.0 Hz), 2.42 (3H, q, J = 1.8 Hz), 4.0-4.18 (3H, m), 4.82 (1 H, d, J = 7.9 Hz), 6.59 (1 H, d, J = 6.3 Hz), 7.23 ( I H, d, J = 9.3 Hz), 7.97 (1H, s) Compound 1-429, 1.40 (6H, d, J = 6.3 Hz), 2.43 (3H, q, J = 2.4 Hz), 4.52-4.63 (1 H, m), 7.14 (0.5H, d, J = 2.4 Hz), 7.17 (0.5H, d, J = 2.4 Hz), 7.24 (1 H, d, J = 3.6 Hz), 7.29 (1 H, s), 7.46 (1 H, d, J = 8.4 Hz) Compound 1-439, m.p.
1 10.6 C
Compound 1-449, 1.29 (3H, t, J = 7.5 Hz), 2.42 (3H, q, J = 2.4 Hz), 4.28 (2H, q, J = 7.5 Hz), 4.73 (2H, s), 7.20-7.32 (2H, m), 7.49 (IH, d, J = 10.4 Hz), 8.00 (1H, s) Compound 1-456, 1.70 (3H, d, J = 6.9 Hz), 2.41 (3H, q, J 2.1 Hz), 3.77 (3H, s), 4.81 (1 H, q, J = 6.9 Hz), 7.21-7.28 (2H, m), 7.47 (1 H, d, J 8.7 Hz), 7.99 (IH, s) Compound 1-474, m.p. 110.6 C
Compound 1-475, 1.46 (3H, t, J = 5.8 Hz), 2.44 (3H, q, J = 1.5 Hz), 4.07 (2H, q, J = 5.8 Hz), 6.94 (1 H, d, J = 5.0 Hz), 7.29 (1 H, d, J = 7.5 Hz), 8.01 (1 H, s) Compound 1-476, 1.38 (6H, d, J = 6.3 Hz), 2.43 (3H, q, J= 2.0 Hz), 4.47 (1 H, m), 6.99 (1 H, d, J = 5.0 Hz), 7.29 (1 H, d, J = 9.5 Hz), 8.00 (1 H, s) Compound 1-482, m.p. 79_8 C
Compound 1-483, m.p. 132.7 C
Compound 1-486, m.p. 140.7 C (decomp.) Compound 1-487, m.p. 114.1 C
Compound 1-491, m.p. 82.9 C
Compound 1-495, m.p. 80.4 C
Compound 1-496, m.p. 102.0 C
Compound 1-497, m.p. 82.9 C
Compound 1-498, m.p. 75.6 C
Compound 1-499, 0.88 (3H, t, J 7 Hz), 1.2-1.4 (4H, m), 1.55-1.70 (2H, m), 2.43 (3H, q, J = 2 Hz), 4.19 (2H, t, J 7 Hz), 4.68 (2H, s), 6.98 (1H, d, J
= 7 Hz), 7.33 (1 H, d, J = 8 Hz), 7.99 (1 H, s) Compound 1-500, 1.26 (6H, d, J= 6.3 Hz), 2.43 (3H, q, J = 2 Hz), 4.65 (2H, s), 5.05-5.18 (1 H, m), 6.98 (1 H, d, J = 7 Hz), 7.33 (1 H, d, J = 8 Hz), 7.98 (1 H, s) Compound 1-501, 1.5-1.9 (8H, m), 2.43 (3H, q, J = 2 Hz), 4.65 (2H, s), 5.2-5.4 (1 H, m), 6.97 (1 H, d, J = 7 Hz), 7.33 (1 H, d, J= 8 Hz), 7.98 (1 H, s) = Compound 1-503, 1.68 (3H, d, J = 7 Hz), 2.43 (3H, q, J 2 Hz), 3.76 (3H, s), 4.73 (1 H, q, J = 7 Hz), 6.98 (1 H, d, J = 7 Hz), 7.32 (1 H, d, J 8 Hz), 7.99 (I H, s) Compound 1-504, 1.25 (3H, t, J = 7.3 Hz), 1.68 (3H, d, J = 6.8 Hz), 2.42 (3H,q,J=2.0Hz),4.21 (2H, q, J = 7.3 Hz), 4.70 (1 H, q, J = 6.8 Hz), 6.99 (1 H, d, J
= 6.8 Hz). 7.32 (1 H, d, J = 9.3 Hz), 7.98 (1 H, s) Compound 1-511, m.p. 1 10.7 C
Compound 1-518, m.p. 131.2 C (decomp.) Compound 1-576, 2.43 (3H, q, J = 1.8 Hz), 3.67 (2H, s), 3.72 (3H, s), 7.32 (1 H, d, J = 8.5 Hz), 7.59 (1 H, d, J 7.1 Hz), 8.2 (1 H, s) Compound 1-577, 1.15 (3H, t, J= 7.5 Hz), 2.36 (3H, q, J = 1.8 Hz), 3.58 (2H, s), 4.09 (2H, q, J= 7.5 Hz), 7.28 (1 H, d, J = 8.6 Hz), 7.52 (1 H, d, J=
7.1 Hz), 7.93 (1 H, s) Compound 1-579, m.p. 71.6 C
Compound 1-581, m.p. 97.5 C
Compound 1-584, 1.53 (3H, d, J= 7.2 Hz), 2.43 (3H, q, J= 1.8 Hz), 3.66 (3H, s), 3.88 (1 H, q, J = 7.2 Hz), 7.38 (IH, d, J = 9.6 Hz), 7.66 (1H, d, J =
7.5 Hz), 7.99 (1 H, s) Compound 1-585, 1.17 (3H, t, J = 6.9 Hz), 1.53 (3H, d, J = 7.2 Hz), 2.43 ( 3H, q, J = 1.8 Hz), 3.89 (1 H, q, J = 7.2 Hz), 4.11 (2H, q, J = 6.9 Hz), 7.37 (1 H, d, J
=9.6Hz),7.67(1H,d,J=9.0Hz),7.99(1H,s) Compound 1-586, 0.85 (3H, t, J = 6.8 Hz), 1.51-1.62 (5H, m), 2.43 (3H, q, J = 1.8 Hz), 3.89 (1 H, q, J = 7.2 Hz), 4.02 (2H, t, J = 6.8 Hz), 7.33 (1 H, d, J = 9.5 Hz), 7.66 (1 H, d, J= 7.5 Hz), 7.98 (1 H, s) Compound 1-587, 0.88 (3H, t, J = 7.2 Hz), 1.30-1.40 (2H, m), 1.47-1.55 (5H, m), 2.43 (3H, q, J = 1.8 Hz), 3.89 (1H, q, J = 7.1 Hz), 4.02-4.08 (2H, m), 7.36 (1 H, d, J = 9.4 Hz), 7.66 (1 H, d, J = 7.5 Hz), 7.99 (1 H, s) Compound 1-619, 2.45 (3H, q, J 1.6 Hz), 7.60 (1 H, d, J = 8.6 Hz), 7.80-7.86 (1 H, m), 8.04 (1 H, s), 8.36 (1 H, d, J 2.5 Hz) Compound 1-621, 1.40 (3H, t, J = 7.1 Hz), 2.43 (3H, q, J = 1.8 Hz), 4.41 (2H, q, J = 7.1 Hz), 7.56 (1 H, d, J = 8.6 Hz), 7.72-7.78 (1 H, m), 8.02 (1 H, s), 8.16 (1H,d,J=2.7Hz) Compound 1-625, 1.39 (6H, d, J = 6.2 Hz), 2.43 (3H, q, J = 1.6 Hz), 5.23-5.28 (1 H, m), 7.54 (1 H, d, J = 8.7 Hz), 7.70-7.76 (1 H, m), 8.02 (1 H, s), 8.10 ( l H, d, J = 2.6 Hz) Compound 1-632, m.p. 76.1 C
Compound 1-637, m.p. 102.8 C
Compound 1-641, 2.43 (3H, q, J = 2.0 Hz), 3.92 (3H, s), 7.39 (1H, d, J
9.5 Hz), 8.02 (1H, s), 8.07 (1H, d, J = 7.7 Hz) Compound 1-642, 1.39 (3H, t, J = 7.2 Hz), 2.44 (3H, q, J = 1.9 Hz), 4.40 (2H, q, J = 7.2 Hz), 7.38 (1 H, d, J= 9.5 Hz), 8.00-8.06 (2H, m) Compound 1-981, m.p. 87.1 C
Compound 1-987, 4.0-4.4 (2H, b), 6.8-6.9 (1 H, m), 7.04 (1 H, d, J = 2.4 Hz), 7.28 (1 H, q, J = 1.2 Hz), 7.35 (1H, d, J= 8.6 Hz), 8.02 (1 H, d, J = 2.2 Hz) Compound 1-1025, 5.92 (1H, s), 7.16 (0.5H, d, J= 2.4 Hz), 7.19 (0.5H, d, J = 2.4 Hz), 7.30 (1 H, q, J= 1.1 Hz), 7.34 (1 H, d, J = 5.7 Hz), 7.43 (1 H, d, J
9.0Hz),8.04(1H,q,J=3.0Hz) Compound 1-1028, m.p. 180.2 C, 5.65-5.9 (1H, br), 7.09 (1H, d, J = 7 Hz), 7.27-7.30 (2H, m), 8.10 (1H, q, J = 2.2 Hz) Compound 1-1029, 7.09 (1 H, d, J 6.4 Hz), 7.31 (1 H, q, J 1.1 Hz), 7.42 (1H,d,J8.8Hz),8.04(1H,q,J=2.2Hz) Compound 1-1035, m.p. 61.1 C
Compound 1-1057, m.p. 158 C
Compound 1-1066, m.p. 89.1 C
Compound 1-1076, m.p. 113.5 C
Compound 1-1086, m.p. 83.9 C
Compound 1-1093, m.p. 83.1 C
Compound 1-1113, m.p. 68.6 C
Compound 1-1 123, rn.p. 147.4 C
Compound 1-1 124, rn.p. 1 17.2 C
Compound 1-1133, m.p. 149.2 C (decomp.) Compound 1-1 140, rn.p. 99.1 C
Compound 1-1 141, rn.p. 80.2 C
Compound 1-1213, m.p. 85.8 C
Compound 1-1214, m.p. 65.1 C
Compound 1-1221, 1.54 (3H, d, J = 7.2 Hz), 3.66 (3H, s), 3.90 (IH, q, J
= 7.2 Hz), 7.31 (1 H, s), 7.39 (1 H, d, J = 9.0 Hz), 7.67 (1 H, d, J = 8.7 Hz), 8.04 (1 H, d, J = 3.6 Hz) Compound 1-1222, 1.16 (3H, t, J = 5.1 Hz), 1.53 (3H, d, J = 7.2 Hz), 3.89 (1 H, q, J = 7.2 Hz), 4.10 (2H, q, J = 5.1 Hz), 7.30 (1 H, q, J = 1.1 Hz), 7.38 (1H,d,J=9.0Hz),7.68(1H,d,J=7.5Hz),8.04(1H,q,J=2.2Hz) Compound 1-1226, 1.12 (3H, d, J = 6.0 Hz), 1.21 (3H, d, J = 6.0 Hz), 1.52 (3H, d, J = 3.0 Hz), 3.88 (1 H, q, J = 3.0 Hz), 4.85-5.03 (1 H, m), 7.30 (1 H, q, J
= 1.8 Hz), 7.37 (IH, d, J = 9.0 Hz), 7.67 (IH, d, J= 7.5 Hz), 8.02 (IH, q, J =
2.1 Hz) Compound 1-1256, 7.35 (IH, q, J = 1.1 Hz), 7.62 (1 H, d, J= 8.7 Hz), 7.82-7.88 (1 H, m), 8.09 (1 H, d, J = 2.2 Hz), 8.35 (1 H, d, J= 2.6 Hz) I Compound 1-1258, 1.41 (3H, t, J = 7.1 Hz), 4.42 (2H, q, J = 7.1 Hz), 7.31 (1 H, s), 7.57 (1 H, d, J = 8.7 Hz), 7.74-7.79 (1H, m), 8.07 (1 H, q, J =
2.1 Hz), 8.16(IH,d,J=2.6Hz) Compound 1-1269, in.p. 89.7 C
Compound 1-1274, m.p. 154.2 C
Compound 1-1278, m.p. 128.6 C
Compound 1-1279, 1.40 (3H, t, J = 7.1 Hz), 4.40 (2H, q, J = 7.1 Hz), 7.33 (1 H, q, J = 1.1 Hz), 7.39 (IH, d, J = 9.4 Hz), 8.05 (IH, d, J = 8.3 Hz), 8.07 (IH, s) Compound 1-1346, 2.48 (3H, s), 5.66 (1 H, s), 7.08 (1 H, d, J 7.8 Hz), 7.28 (1 H, d, J = 9.0 Hz), 7.32 (1 H, s) Compound 1-1431, rn.p. 74.5 C
Compound 1-1441, m.p. 128.2 C
Compound 1-1442, 1.73 (3H, d, J = 6.6 Hz), 2.49 (3H, q, J 1.3 Hz), 2.54 (1 H, d, J= 2.0 Hz), 4.84 (1 H, m), 7.22 (1 H, d, J= 6.5 Hz), 7.28-7.34 (2H, m) Compound 1-1451, 1.29 (3H, t, J = 7.0 Hz), 2.47 (3H, q, J = 1.4 Hz), 4.27 (2H, q, J = 7.0 Hz), 4.68 (2H, s), 6.99 (IH, d, J = 7.1 Hz), 7.32 (IH, s), 7.34 (1 H, d, J = 7.2 Hz) Compound 1-1458, 1.69 (3H, d, J = 6.8 Hz), 2.48 (3H, q, J= 1.3 Hz), 3.76 (3H, s), 4.74 (1 H, q, J = 6.8 Hz), 7.01 (1 H, d, J = 6.5 Hz), 7.29-7.34 (2H, m) Compound 1-1540, 1.17 (3H, t, J = 7.0 Hz), 1.54 (3H, d, J = 7.3 Hz), 2.48 (3H, q, J = 1.4 Hz), 3.89 (IH, q, J = 7.3 Hz), 4.11 (2H, q, J = 7.0 Hz), 7.31 (1H,s),7.37(1H,d,J=9.5Hz),7.67(1H,d,J=7.5Hz) Compound 1-1617, m.p. 105.7 C
Compound 1-1622, 1.27 (3H, t, J 7.0 Hz), 2.42 (3H, q, J = 2.0 Hz), 3.26 (0.3H, d, J 7.6 Hz), 3.32 (0.7H, d, J 7.6 Hz), 3.49 (0.7H, d, J = 7.6 Hz), 3.54 (0.3H, d, J 7.6 Hz), 4.23 (2H, q, J = 7.0 Hz), 4.54 (0.5H, d, J = 7.6 Hz), 4.57 (0.5 H, d, J = 7.6 Hz), 7.34 (1 H, d, J = 9.3 Hz), 7.40 (1 H, d, J = 7.5 Hz), 8.00 (1 H, s) Compound 1-1627, m.p. 182.2 C
Compound 1-1638, 3.66 (2H, s), 7.31 (1 H, s), 7.34 (1 H, d, J = 9.3 Hz), 7.62 (1 H, d, J = 7.2 Hz), 8.08 (1 H, s) Compound 1-1639, m.p. 158.9 C (decomp.) Compound 1-1641, 1.55 (3H, d, J = 7.2 Hz), 3.88 (IH, q, J = 7.2 Hz), 7.32 (1 H, s), 7.37 (1 H, d, J = 9.2 Hz), 7.69 (1 H, d, J = 7.1 Hz), 8.03 (1 H, s) Compound 1-1650, 1.1 1(3H, t, J = 7.5 Hz), 2.03-2.12 (2H, m), 2.43 (3H, q, J 1.8 Hz), 3.75 (3H, s), 4.58 (1 H, t, J 7.5 Hz), 6.92 0 H, d, J 8.2 Hz), 7.32 (1H, d, J 9.3 Hz), 8.00 (1 H, s) Compound 1-1655, m.p. 119.7 C, 1.29 (3H, t, J 7.1 Hz), 2.43 (3H, q, J = 1.8 Hz), 4.26 (2H, q, J = 7.1 Hz), 4.68 (2H, s), 6.91 (1 H, s), 7.99 (1H, s) Compound 1-1663, m.p. 136.2 C, 2.44 (3H, q, J = 1.8 Hz), 2.58 (1H, t, J = 2.3 Hz), 4.78 (2H, d, J = 2.3 Hz), 7.12 (1H, s), 7.59 (1H, s), 8.01 (1 H, s) Compound 1-1665, m.p. 1.23 (3H, t, J = 6.9 Hz), 1.68 (3H, d, J = 6.8 Hz), 2.42 (3H, q, J = 1.8 Hz), 4.1-4.3 (2H,m),4.72(1H,q,J=6.8Hz),6.90(1H,s),7.58.
(1 H, s), 7.97 (1 H, s) Compound 1-1670, m.p. 118.1 C
Compound 1-1673, m.p. 107.2 C
Compound 1-1678, m.p. 164.7 C
Compound 1-1679, m.p. 1.73 (3H, d, J = 6.9 Hz), 2.54 (1H, d, J = 2.1 Hz), 4.73-4.90 (1H, m), 7.20 (1H, d, J = 6.3 Hz), 7.30 (1H, s), 7.49 (1H, d, J =
8.7 Hz), 8.00 (1H, s).
Compound 1-1680, m.p. 90.1 C
Compound 1-1681, m.p. 148.1 C
Compound 1-1682, m.p. 107.0 C
Compound 1-1683, m.p. 1.73 (3H, d, J = 6.9 Hz), 2.54 (111, d, J = 6.8 Hz), 2.42 (3H, q, J = 1.5 Hz), 4.13-4.26 (2H, m), 4.70 (1H, q, J = 6.8 Hz), 6.96 (1H, d, J = 6.3 Hz), 7.48 (1 H, d, J = 9.0 Hz), 7.97 (1 H, s) Compound 1-1687, m.p. 200.1 C
Compound 1-1689, m.p. 76.3 C
Compound 1-1690, m.p. 196.1 C
Compound 1-1691, 3.06 (3H, s), 7.10-7.30 (1H, b), 7.30 (1H, s), 7.64 (1H, s), 7.74 (1 H, s), 8.06 (1 H, q, J = 2.1 Hz) Compound 1-1701, 1.39 (3H, t, J = 7.1 Hz), 4.40 (2H, q, J = 7.1 Hz), 7.33 (1 H, q, J 1.1 Hz), 7.69 (1 H, s), 7.97 (1 H, s), 8.06 (1 H, q, J 2.2 Hz) Compound 1-1718, rn.p. 63.9 C
Compound 1-1719, m.p. 189.5 C
Compound 1-1720, in.p. 117.3 C
Compound 1-1721, in.p. 156.1 C
Compound 1-1722, 2.47 (3H, q, J = 1.8 Hz), 3.05 (3H, s), 7.15-7.30 (1H, b), 7.66 (1 H, s), 7.78 (1 H, s), 8.03 (I H, s) Compound 1-1732, 1.38 (3H, t, J = 7.1 Hz), 2.44 (3H, q, J = 1.8 Hz), 4.39 (2H, q, J = 7.1 Hz), 7.68 (IH, s), 7.96 (1H, s), 8.02 ( I H, s) Compound 1-1748, 1.38 (6H, d, J = 6.0 Hz), 2.44 (3H, q, J = 1.9 Hz), 4.40-4.59 (1 H, m), 6.95 (1 H, s), 7.55 (1 H, s), 8.00 (1 H, s) Compound 1-1780, m.p. 76.4 C
Compound 1-1781. 3.51 (3H, s), 3.51 (3H, s), 7.30 (IH, q, J = 1.2 Hz), 7.59 (1 H, d, J = 6.7 Hz), 7.65 (1 H, d, J = 9.0 Hz), 8.06 (1 H, d, J = 2.1 Hz) Compound 1-1782, 3.03 (3H, s), 7.09 (1 H, s), 7.32 (1 H, q, J = 1.0 Hz), 7.53 (1 H, d, J = 8.7 Hz), 7.77 (1 H, d, J = 6.8 Hz), 8.07 (1 H, q, J = 2.2 Hz) Compound 1-1783, 1.38 (6H, d, J = 6.1 Hz), 2.43 (3H, q, J = 1.7 Hz), 4.4-4.6 (1 H, m), 6.95 (1 H, d, J = 6.4 Hz), 7.47 (1 H, d, J = 8.9 Hz), 8.00 (1 H, s) Compound 1-1785, 2.43 (3H, q, J = 1.9 Hz), 3.03 (3H, s), 7.03 (1 H, s), 7.52 (1 H, d, J = 8.8 Hz), 7.76 (1 H, d, J = 6.9 Hz), 8.02 (1 H, s) Compound 1-1789, m.p. 78.3'C
Compound 1-1790, m.p. 63.2 C
Compound 1-1879, 2.42 (3H, q, J = 1.8 Hz), 5.38 (2H, s), 7.28-7.47 (5H, m), 7.56 (1 H, d, J = 8.7 Hz), 7.72-7.79 (1 H, m), 8.00 (1 H, s), 8.18 (1 H, d, J = 2.5 Hz) Compound 1-1881, 2.20 (0.75H, s), 2.24 (2.25H, s), 2.42 (3H, q, J = 1.9 Hz), 3.82 (0.75H, s), 3.98 (2.25H, s), 7.47-7.68 (3H, m), 8.00 (IH, s) Compound 1-1901, rn.p. 99.2 C
Compound 1-1908, rn.p. 77.6 C
Compound 1-1910, rn.p. 75.3 C
Compound 1-1930, m.p. 139.7 C
Compound 1-2051, 1.25 (3H, t, J= 7.2 Hz), 2.42 (3H, q, J = 1.9 Hz), 4.17 (2H, q, J = 7.2 Hz), 4.71 (2H, s), 4.82 (2H, s), 7.10 (1 H, d, J= 6.3 Hz), 7.33 (I H, d, J = 9.1 Hz), 7.99 (1 H, s) Compound 1-2054, 1.24 (3H, t, J = 7.1 Hz), 1.51 (3H, d, J = 7.2 Hz), 2.42 (3H, q, J = 1.8 Hz), 4.15 (2H, q, J = 7.1 Hz), 4.78 (2H, s), 5.19 (1H, q, J= 7.2 Hz), 7.08 (1 H, d, J = 6.3 Hz), 7.32 (1 H, d, J = 9.1 Hz), 7.98 (1 H, s) Compound 2-203, 2.3-2.4 (1 H, m), 2.35 (3H, q, J= 1.9 Hz), 4.5-4.7 (4H, m), 7.00 ( I H, d, J = 6.5 Hz), 7.19 (1 H, m), 7.39 (IH, d, J= 2.5 Hz), 7.95 (1 H, s) Compound 2-251, m.p. 168.3 C
Compound 2-328, 0.90 (3H, t, J = 7.3 Hz), 1.54 (3H, d, J = 7.0 Hz), 1.70-1.90 (2H, m), 2.46 (3H, m), 4.50 (1 H, m), 7.18 (1 H, d, J = 5.75 Hz), 7.35 (1 H, d, J
= 8.8 Hz), 8.04 (1 H, s) Compound 2-583, m.p. 149.1 C
Compound 2-631, m.p. 168.3 C
Compound 2-708, 0.90 (3H, t, J 7.3 Hz), 1.55 (3H, d, J = 7.0 Hz), 1.75-1.95 (2H, m), 4.50 (IH, m), 7.22 (1 H, d, J 5.8 Hz), 7.30-7.40 (2H, m), 8.08 (1 H, q, J = 2.2 Hz) Compound 2-821, m.p. 162.7 C
Compound 3-139, m.p. 88.2 C
Compound 4-434, 1.67 (3H, s), 2.35 (3H, q, J = 1.7 Hz), 3.0-3.2 (IH, m), 3.4-3.7 (1 H, m), 3.71 (3H, s), 7.03 (1 H, d, J = 5.0 Hz), 7.97 (1 H, q, J =
3.3 Hz) Compound 4-451, 1.53 (6H, s), 2.43 (3H, q, J = 1.9 Hz), 2.96 (IH, d, J
16.2Hz),3.08(1H,d,J=16.2Hz),7.07(1H,d,J=9.9Hz),7.99(IH,s) Compound 4-452, 1.4-1.5 (3H, m), 2.43 (3H, q, J = 2.0 Hz), 2.7-3.0 (IH, m), 3.1-3.5 (1 H, m), 3.5-3.8 (2H, m), 7.07 (1 H, d, J = 10.0 Hz), 8.00 (1 H, q, J = 2.5 Hz) The following will describe formulation examples, in which the present compounds are designated by their compound numbers shown in Tables I to 5 and parts are by weight.
Formulation Example I
Fifty parts of each of compounds 1-1 to 1-2157, 2-1 to 2-950, 3-1 to 3-582, 4-1 to 4-936, and 5-1 to 5-87, 3 parts of calcium ligninsulfonate, 2 parts of sodium laurylsulfate, and 45 parts of synthetic hydrated silicon oxide are well pulverized and mixed to give a wettable powder for each compound.
Formulation Example 2 Ten parts of each of compounds 1-1 to 1-2157, 2-1 to 2-950, 3-1 to 3-582, 4-1 to 4-936, and 5-1 to 5-87, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 35 parts of xylene, and 35 parts of cyclohexanone are well mixed to give an emulsifiable concentrate for each compound.
Formulation Example 3 Two parts of each of compounds 1-1 to 1-2157, 2-1 to 2-950, 3-1 to 3-582, 4-1 to 4-936, and 5-1 to 5-87, 2 parts of synthetic hydrated silicon oxide, 2 parts of calcium ligninsulfonate, 30 parts of bentonite, and 64 parts of kaoline clay are well pulverized and mixed, to which water is added, and the mixture is well kneaded, granulated, and dried to give granules for each compound.
Formulation Example 4 Twenty-five parts of each of compounds 1-1 to 1-2157, 2-1 to 2-950, 3-1 to 3-582, 4-1 to 4-936, and 5-1 to 5-87, 50 parts of 10% aqueous polyvinyl alcohol solution, and 25 parts of water are mixed, and the mixture is pulverized until the average particle size becomes 5 m or less to give a flowable for each compound.
Formulation Example 5 Five parts of compound 1-1650 is added to 40 parts of 10% aqueous polyvinyl alcohol solution and dispersed by emulsion wifh a homogenizer until the mean particle size becomes 10 m or less, to which 55 parts of water is added to give a concentrated emulsion.
The following test examples will demonstrate that the present compounds are useful as active ingredients of herbicides. The present compounds are designated by their compound numbers shown in Tables I to 5.
The herbicidal activity and phytotoxicity were evaluated at 6 levels with indices of 0 to 5, i.e., designated by the numeral "0", "1", "2", "3", "4" or "5", wherein "0" means that there was no or little difference in the degree of germination or growth between the treated and the untreated test plants at the time of examination, and "5" means that the test plants died or their germination or growth was completely inhibited. The herbicidal activity is excellent when rated at "4" or "5" but insufficient when rated at "3" or lower. The phytotoxicity is not problematic for practical use when rated at "0"
or "1" but not allowed when rated at "2" or higher.
Test Example 1: Foliar treatment on upland fields Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with soil, in which the seeds of entireleaf morningglory (Ipofitoea hederacea var.
ijitegriuscitla) and velvetleaf (Abutilon theophrasti) were sown, and the test plants were grown in a greenhouse for 19 days. Each of the test compounds listed below was formulated into an emulsifiable concentrate according to Formulation Example 2, which was diluted with water containing a spreading agent to a prescribed concentration. The dilution was uniformly sprayed over the foliage of the test plants with a sprayer at a volume of 1000 liters per hectare. After the application, the test plants were grown in the greenhouse for 19 days, and the herbicidal activity was examined. The results are shown in Table 6.
Application amount of Herbicidal activity Test activeinb edient compound ~bma~ Entireleaf Velvetleaf morningglory 1-335 500 { 5 5 TABLE 6 (contn'd) Application amount of Herbicidal activity Test active ingredient compound ~gma) Entireleaf Velvetleaf morningglory 1-987 500 5 5 1-1670 500 5 5 =
TABLE 6 (contn'd) Application amount of Herbicidal activity Test active ingredient compound ~gma~ Entireleaf Velvetleaf morningglory 1-1691 500 5 5 Test Example 2: Foliar treatment on upland fields Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with soil, in which the seeds of barnyardgrass (Echinochloa crus-galli), entireleaf mom-ingglory (Ipornoea hedei-acea var. iritegriarscula), and velvetleaf (Abutilor2 theophr-asti) were sown, , and the test plants were grown in a greenhouse for 19 days. Each of the test compounds listed below was formulated into an emulsifiable concentrate according to Formulation Example 2, which was diluted with water containing a spreading agent to a prescribed concentration. The dilution was uniformly sprayed over the foliage of the test plants with a sprayer at a volume of 10001iters per hectare. After the application, the test plants were grown in the greenhouse for 19 days, apd the herbicidal activity was examined. The results are shown in Table 7.
Application amount of Herbicidal activity Test active ingredient compound (gnla) Barnyardgrass Entireleaf Velvetleaf morningglory 1-369 32 5 5 5 1-576 32 5 _5 5 1-1665 32 5 5 5, TABLE 7 (contn'd) Test Application amount of Herbicidal activity compound active ingredient Entireleaf (g/ha) Branyardgrass morningglory Velvetleaf Test Example 3: Soil surface treatment on upland fields Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with soil, in which the seeds of entireleaf morningglory (Ipanoea hederacea var.
integr=iuscula) and velvetleaf (Abutilon theophrcisti) were sown. Each of the test compounds listed below was formulated into an emulsifiable concentrate according to Formulation Example 2, which was diluted with water to a prescribed concentration. The dilution was uniformly sprayed over the soil surface in the pots with a sprayer at a volume of 10001iters per hectare. After the application, the test plants were grown in a greenhouse for 19 days, and the herbicidal activity was examined. The results are shown in Table 8.
Application amount of Herbicidal activity Test active ingredient compound (gma) Entireleaf Velvetleaf morningglory 1-347 500 5 ~ 5 TABLE 8 (contn'd) Application amount of Herbicidal activity Test active ingredient compound ~gma~ Entireleaf Velvetleaf morningglory 1-398 .500 5 5 1-4,49 500 5 5 TAB E 8 (contn'd) Application amount of Herbicidal activity Test active ingredient compound (bma) Entireleaf Velvetleaf morningglory = 326 Test Example 4: Flooding treatment on paddy fields Cylindrical plastic pots of 9 cm in diameter and 11 cm in depth were filled with soil, in which the seeds of barnyardgrass (Echinochloa oryzicola) were sown.
These pots were flooded to form a paddy field, and the test plants were grown in a green-house for 7 days. Each of the test compounds listed below was formulated into an emulsifiable concentrate according to Formulation Example 2, which was diluted with water to a prescribed concentration. The dilution was applied to the water surface in the pots at a volume of 501iters per hectare. After the application, the test plants were grown in the greenhouse for 19 days, and the herbicidal activity was examined. The results are shown in Table 9.
Test Application amount of Herbicidal activity com ound active ingredient p (giha) Barnyardgrass 1-482 250 . 5 TABLE 9 (contn'dl Test Application amount of Herbicidal activity compound active ingredient (g/ha) I Barnyardgrass TABLE 9 (contn'd) Test Application amount of Herbicidal activity compound active ingredient (g/ha) Bamyardgrass 1-1638 250 5 1-1721 500 5 "
Test Example 5: Foliar treatment on upland fields Plastic pots of 25 x 18 cm2 in area and 7 cm in depth were filled with soil, in which the seeds of soybean (Glvcine max). corn (Zea mays), entireleaf morningglory (Ipomoea hederacea var. integriuscula), common cocklebur (Xanthium pensylvanictcm), comtnon ragweed (Ambrosia artemisiifolia), and common lambsquarters (Chenopodiurn album) were sown, and the test plants were grown for 16 days. Each of the test compounds listed below was formulated into an emulsifiable concentrate according to Formulation Example 2, which was diluted with water to a prescribed concentration. The dilution was uniformly sprayed over the foliage of the test plants with a sprayer at a volume of 1000 liters per hectare. At this time, the unfavorable weeds and crop plants, although their growth state was different depending upon the weed species, were at the 1- to 4-leaf stage, and the plant height was 5 to 20 cm. After 18 days from the applica-tion, the herbicidal activity and phytotoxicity were examined. The results are shown in Table 10. This test was made in a greenhouse over the entire period.
Application Herbicidal activity and phytotoxicity Test amount of active Entireleaf Common compound ingredient Corn Soy- Common mornin Common lamb-~g~a) bean cocklebur glory g ragweed squarters Test Example 6; Foliar treatment on upland fields Plastic pots of 16 x 1 1 cm2 in area and 7 cm in depth were filled with soil, in which the seeds of wheat (Ti-itictcfia aestivuna), pale smartweed (Polygonum lapatlzi-folli[f17), catchweed bedstraw (Galium apariiie), and coinmon chickweed (Stellaria media) were sown, and the test plants were grown for 29 days. Each of the test compounds listed below was formulated into an emulsifiable concentrate according to Formulation Example 2, which was diluted with water to a prescribed concentration. The dilution was uniformly sprayed over the foliage of the test plants with a sprayer at a volume of 1000 liters per hectare. At this time, the unfavorable weeds and crop plants, although their growth state was different depending upon the weed species, were at the 1- to 4-leaf stage, and the plant height was 5 to 15 cm. After 25 days from the applica-tion, the herbicidal activity and phytotoxicity were examined. The results are shown in Table 11. This test was made in a greenhouse over the entire period.
Application Herbicidal activity and phytotoxicity Test amount of compound active Pale Catch- Common ingredient Wheat smart- weed chick-(glha) weed bedstraw weed Test Example 7: Soil surface treatment on upland fields Plastic pots of 25 x 18 cm2 in area and 7 cm in depth were filled with soil, in which the seeds of soybean (Glycine rnax), corn (Zea mays), common lambsquarters (Chenopodium album), slender amaranth (Amaranthus gracilis), and pale smartweed (Polygonum lapathifolium) were sown. Each of the test compounds listed below was formulated into an emulsifiable concentrate according to Formulation Example 2, which was diluted with water to a prescribed concentration. The dilution was uniformly sprayed over the soil surface in the pots with a sprayer at a volume of 1000 liters per hectare. After the application, the test plants were grown in a greenhouse for 19 days, and the herbicidal activity and phytotoxicity were examined. The results are shown in Table 12.
= Application Herbicidal activity and phytotoxicity Test ~"-ount of compound active Common Slender Pale ingredient Soybean Corn lamb- ~~~~ smart-(g/ha) squarters weed a
Claims (58)
1. A compound of the formula:
wherein R1 is C1-C3 haloalkyl; R2 and R3 are the same or different and are hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, or C1-C3 alkoxy C1-C3 alkyl; and Q is [Q-1], [Q-2], [Q-3] or [Q-4] of the formula:
wherein X is hydrogen or halogen;
Y is halogen, nitro, cyano, or trifluoromethyl;
Z1 is oxygen, sulfur, or NH;
Z2 is oxygen or sulfur;
n is 0 or 1;
B is hydrogen, halogen, nitro, cyano, chlorosulfonyl, OR10, SR10, SO2-OR10, N(R11)R12, SO2N(R11)R12, NR11(COR13), NR11(SO2R14), N(SO2R14)-(SO2R15), N(SO2R14)(COR13), NHCOOR13, COOR10, CON(R11)R12, CSN(R11)R12, COR16, CR17=CR18COR16, CR17=CR18COOR13, CR17=CR18CON(R11)R12, CH2CH-WCOOR13, CH2CHWCON(R11)R12, CR17=NOR33, CR17=NN(R11)R12, CR17(Z2-R34)2, OCO2R19, or OCOR19;
R4 is hydrogen or C1-C3 alkyl;
R5 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkylalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, cyano C1-C6 alkyl, C2-C8 alkoxyalkyl, C3-C8 alkoxyalkoxyalkyl, carboxy C1-C6 alkyl, (C1-C6 alkoxy)-carbonyl C1-C6 alkyl, {(C1-C4 alkoxy) C1-C4 alkoxy}carbonyl C1-C6 alkyl, (C3-cycloalkoxy)carbonyl C1-C6 alkyl, CH2CON(R11)R12, CH2COON(R11)R12, CH(C1-C4 alkyl)CON(R11)R12, CH(C1-C4 alkyl)COON(R11)R12, C2-C8 alkylthioalkyl, or hydroxy C1-C6 alkyl, R6 is C1-C6 alkyl, C1-C6 haloalkyl, formyl, cyano, carboxyl, hydroxy C1-C6 alkyl, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkoxy C1-C6 alkoxy C1-C6 alkyl, (C1-C6 alkyl)carbonyloxy C1-C6 alkyl, (C1-C6 haloalkyl)carbonyloxy C1-C6 alkyl, (C1-C6 alkoxy)carbonyl, or (C1-C6 alkyl)carbonyl;
R7 is hydrogen or C1-C6 alkyl, and R8 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, hydroxy C1-C6 alkyl, C2-C8 alkoxyalkyl, C3-C10 alkoxyalkoxyalkyl, (C1-C5 alkyl)carbonyloxy C1-C6 alkyl, (C1-C6 haloalkyl)carbonyloxy C1-C6 alkyl, carboxyl, carboxy C1-C6 alkyl, (C1-C8 alkoxy)-carbonyl, (C1-C6 haloalkoxy)carbonyl, (C3-C10 cycloalkoxy)carbonyl, (C3-C8 alkenyl-oxy)carbonyl, (C3-C8 alkynyloxy)carbonyl, aminocarbonyl, (C1-C6 alkyl)amino-carbonyl, di(C1-C6 alkyl)aminocarbonyl, (C1-C6 alkyl)aminocarbonyloxy C1-C6 alkyl, or di(C1-C6 alkyl)aminocarbonyloxy C1-C6 alkyl;
wherein R10 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, benzyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, cyano C1-C6 alkyl, C2-C8 alkoxyalkyl, C2-C8 alkylthioalkyl, carboxy C1-C6 alkyl, (C1-alkoxy)carbonyl C1-C6 alkyl, (C1-C6 haloalkoxy)carbonyl C1-C6 alkyl, {(C1-C4 alkoxy) C1-C4 alkoxy}carbonyl C1-C6 alkyl, (C3-C8 cycloalkoxy)carbonyl C1-C6 alkyl, (C1-C6 alkyl)carbonyl C1-C6 alkyl, (C1-C6 haloalkyl)carbonyl C1-C6 alkyl, {(C1-C4 alkoxy) C1-C4 alkyl)carbonyl C1-C6 alkyl, (C3-C8 cycloalkyl)carbonyl C1-C6 alkyl, (R11)R12, CH2COON(R11)R12, CH(C1-C4 alkyl)CON(R11)R12, CH(C1-C4 alkyl)-COON(R11)R12, {(C1-C6 alkoxy)carbonyl C1-C6 alkyl}oxycarbonyl C1-C6 alkyl, or hydroxy C1-C6 alkyl;
R11 and R12 are independently hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 alkenyl, C3-C6 alkynyl, cyano C1-C6 alkyl, C2-C8 alkoxyalkyl, C2-C8 alkylthio-alkyl, carboxy C1-C6 alkyl, (C1-C6 alkoxy)carbonyl C1-C6 alkyl, (C3-C8 cycloalkoxy)-carbonyl C1-C6 alkyl, {(C1-C4 alkoxy) C1-C4 alkoxy}carbonyl C1-C6 alkyl, or R11 and R12 are combined together to form tetramethylene, pentamethylene, or ethyleneoxy-ethylene;
R13 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, or C3-C6 alkenyl;
R14 and R15 are independently C1-C6 alkyl, C1-C6 haloalkyl, or phenyl unsubstituted or substituted with methyl or nitro;
R16 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C8 alkoxyalkyl, or hydroxy alkyl, R17 and R18 are independently hydrogen or C1-C6 alkyl, R19 is C1-C6 alkyl;
R33 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, cyano C1-C6 alkyl, or (C1-C6 alkoxy)carbonyl C1-C6 alkyl, R34 is C1-C6 alkyl, or two R34's are combined together to form (CH2)2 or (CH2)3; and W is hydrogen, chlorine, or bromine.
wherein R1 is C1-C3 haloalkyl; R2 and R3 are the same or different and are hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, or C1-C3 alkoxy C1-C3 alkyl; and Q is [Q-1], [Q-2], [Q-3] or [Q-4] of the formula:
wherein X is hydrogen or halogen;
Y is halogen, nitro, cyano, or trifluoromethyl;
Z1 is oxygen, sulfur, or NH;
Z2 is oxygen or sulfur;
n is 0 or 1;
B is hydrogen, halogen, nitro, cyano, chlorosulfonyl, OR10, SR10, SO2-OR10, N(R11)R12, SO2N(R11)R12, NR11(COR13), NR11(SO2R14), N(SO2R14)-(SO2R15), N(SO2R14)(COR13), NHCOOR13, COOR10, CON(R11)R12, CSN(R11)R12, COR16, CR17=CR18COR16, CR17=CR18COOR13, CR17=CR18CON(R11)R12, CH2CH-WCOOR13, CH2CHWCON(R11)R12, CR17=NOR33, CR17=NN(R11)R12, CR17(Z2-R34)2, OCO2R19, or OCOR19;
R4 is hydrogen or C1-C3 alkyl;
R5 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkylalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, cyano C1-C6 alkyl, C2-C8 alkoxyalkyl, C3-C8 alkoxyalkoxyalkyl, carboxy C1-C6 alkyl, (C1-C6 alkoxy)-carbonyl C1-C6 alkyl, {(C1-C4 alkoxy) C1-C4 alkoxy}carbonyl C1-C6 alkyl, (C3-cycloalkoxy)carbonyl C1-C6 alkyl, CH2CON(R11)R12, CH2COON(R11)R12, CH(C1-C4 alkyl)CON(R11)R12, CH(C1-C4 alkyl)COON(R11)R12, C2-C8 alkylthioalkyl, or hydroxy C1-C6 alkyl, R6 is C1-C6 alkyl, C1-C6 haloalkyl, formyl, cyano, carboxyl, hydroxy C1-C6 alkyl, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkoxy C1-C6 alkoxy C1-C6 alkyl, (C1-C6 alkyl)carbonyloxy C1-C6 alkyl, (C1-C6 haloalkyl)carbonyloxy C1-C6 alkyl, (C1-C6 alkoxy)carbonyl, or (C1-C6 alkyl)carbonyl;
R7 is hydrogen or C1-C6 alkyl, and R8 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, hydroxy C1-C6 alkyl, C2-C8 alkoxyalkyl, C3-C10 alkoxyalkoxyalkyl, (C1-C5 alkyl)carbonyloxy C1-C6 alkyl, (C1-C6 haloalkyl)carbonyloxy C1-C6 alkyl, carboxyl, carboxy C1-C6 alkyl, (C1-C8 alkoxy)-carbonyl, (C1-C6 haloalkoxy)carbonyl, (C3-C10 cycloalkoxy)carbonyl, (C3-C8 alkenyl-oxy)carbonyl, (C3-C8 alkynyloxy)carbonyl, aminocarbonyl, (C1-C6 alkyl)amino-carbonyl, di(C1-C6 alkyl)aminocarbonyl, (C1-C6 alkyl)aminocarbonyloxy C1-C6 alkyl, or di(C1-C6 alkyl)aminocarbonyloxy C1-C6 alkyl;
wherein R10 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, benzyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, cyano C1-C6 alkyl, C2-C8 alkoxyalkyl, C2-C8 alkylthioalkyl, carboxy C1-C6 alkyl, (C1-alkoxy)carbonyl C1-C6 alkyl, (C1-C6 haloalkoxy)carbonyl C1-C6 alkyl, {(C1-C4 alkoxy) C1-C4 alkoxy}carbonyl C1-C6 alkyl, (C3-C8 cycloalkoxy)carbonyl C1-C6 alkyl, (C1-C6 alkyl)carbonyl C1-C6 alkyl, (C1-C6 haloalkyl)carbonyl C1-C6 alkyl, {(C1-C4 alkoxy) C1-C4 alkyl)carbonyl C1-C6 alkyl, (C3-C8 cycloalkyl)carbonyl C1-C6 alkyl, (R11)R12, CH2COON(R11)R12, CH(C1-C4 alkyl)CON(R11)R12, CH(C1-C4 alkyl)-COON(R11)R12, {(C1-C6 alkoxy)carbonyl C1-C6 alkyl}oxycarbonyl C1-C6 alkyl, or hydroxy C1-C6 alkyl;
R11 and R12 are independently hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 alkenyl, C3-C6 alkynyl, cyano C1-C6 alkyl, C2-C8 alkoxyalkyl, C2-C8 alkylthio-alkyl, carboxy C1-C6 alkyl, (C1-C6 alkoxy)carbonyl C1-C6 alkyl, (C3-C8 cycloalkoxy)-carbonyl C1-C6 alkyl, {(C1-C4 alkoxy) C1-C4 alkoxy}carbonyl C1-C6 alkyl, or R11 and R12 are combined together to form tetramethylene, pentamethylene, or ethyleneoxy-ethylene;
R13 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, or C3-C6 alkenyl;
R14 and R15 are independently C1-C6 alkyl, C1-C6 haloalkyl, or phenyl unsubstituted or substituted with methyl or nitro;
R16 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C8 alkoxyalkyl, or hydroxy alkyl, R17 and R18 are independently hydrogen or C1-C6 alkyl, R19 is C1-C6 alkyl;
R33 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, cyano C1-C6 alkyl, or (C1-C6 alkoxy)carbonyl C1-C6 alkyl, R34 is C1-C6 alkyl, or two R34's are combined together to form (CH2)2 or (CH2)3; and W is hydrogen, chlorine, or bromine.
2. A compound according to claim 1, wherein R1 is trifluoromethyl.
3. A compound according to claim 1, wherein R2 is hydrogen or C1-C3 alkyl, and R3 is hydrogen or C1-C3 alkyl.
4. A compound according to claim 1, wherein R1 is trifluoromethyl, R2 is hydrogen or C1-C3 alkyl, and R3 is hydrogen or C1-C3 alkyl.
5. A compound according to claim 1, 2, 3, or 4, wherein Q is [Q-1].
6. A compound according to claim 1, 2, 3, or 4, wherein Q is [Q-2].
7. A compound according to claim 1, 2, 3, or 4, wherein Q is [Q-3].
8. A compound according to claim 1, 2, 3, or 4, wherein Q is [Q-4].
9. A compound according to claim 5, wherein B is OR10.
10. A compound according to claim 5, wherein B is SR10.
11. A compound according to claim 5, wherein B is N(R11)R12.
12. A compound according to claim 5, wherein B is NR11(SO2R14).
13. A compound according to claim 5, wherein B is COOR10.
14. A compound according to claim 5, wherein X is fluorine and Y is chlorine.
15. A compound according to claim 5, wherein X is fluorine, Y is chlorine, and B is OR10.
16. A compound according to claim 6, wherein Z1 is oxygen and n is 1.
17. A compound according to claim 1, which is 7-fluoro-6-(5-trifluoro-methyl-3-pyridazinon-2-yl)-4-propargyl-2H-1,4-benzoxazin-3-one (compound 2-631).
18. A compound according to claim 1, which is 7-fluoro-6-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)-4-propargyl-2H-1,4-benzoxazin-3-one (compound 2-251).
19. A compound according to claim 1, which is 6-(5-trifluoromethyl-3-pyridazinon-2-yl)-4-propargyl-2H-1,4-benzoxazin-3-one (compound 2-583).
20. A compound according to claim 1, which is 6-(4-methyl-5-trifluoro-methyl-3-pyridazinon-2-yl)-4-propargyl-2H-1,4-benzoxazin-3-one (compound 2-203).
21. A compound according to claim 1, which is 2-(4-chloro-2-fluoro-5-isopropoxyphenyl)-4-methyl-5-trifluoromethylpyridazin-3-one (compound 1-476).
22. A compound according to claim 1, which is 2-(4-chloro-2-fluoro-5-methoxyphenyl)-4-methyl-5-trifluoromethylpyridazin-3-one (compound 1-474).
23. A compound according to claim 1, which is 2-(4-chloro-2-fluoro-5-ethoxyphenyl)-4-methyl-5-trifluoromethylpyridazin-3-one (compound 1-475).
24. A compound according to claim 1, which is 2-(4-chloro-2-fluoro-5-propargyloxyphenyl)-4-methyl-5-trifluoromethylpyridazin-3-one (compound 1-486).
25. A compound according to claim 1, which is methyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxyacetate (compound 1-495).
26. A compound according to claim 1, which is ethyl2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxyacetate (compound 1-496).
27. A compound according to claim 1, which is propyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxyacetate (compound 1-497).
28. A compound according to claim 1, which is isopropyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxyacetate (compound 1-500).
29. A compound according to claim 1, which is butyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxyacetate (compound 1-498).
30. A compound according to claim 1, which is pentyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxyacetate (compound 1-499).
31. A compound according to claim 1, which is cyclopentyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxyacetate (compound 1-501).
32. A compound according to claim 1, which is ethyl 2-{2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxy}propionate (compound 1-504).
33. A compound according to claim 1, which is methyl 2-{2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxy}propionate (compound 1-503).
34. A compound according to claim 1, which is ethyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenylthioacetate (compound 1-577).
35. A compound according to claim 1, which is methyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenylthioacetate (compound 1-576).
36. A compound according to claim 1, which is ethyl 2-{2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenylthio}propionate (compound 1-585).
37. A compound according to claim 1, which is methyl 2-{2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenylthio}propionate (compound 1-584).
38. A compound according to claim 1, which is methyl 2-{2-chloro-4-fluoro-5-(5-trifluoromethyl-3-pyridazinon-2-yl)phenoxy}propionate (compound 1-1140).
39. A compound according to claim 1, which is ethyl 2-(2-chloro-4-fluoro-5-(5-trifluoromethyl-3-pyridazinon-2-yl)phenoxy)propionate (compound 1-1141).
40. A compound according to claim 1, which is ethyl 2-chloro-4-fluoro-5-(5-trifluoromethyl-3-pyridazinon-2-yl)phenylthioacetate (compound 1-1214).
41. A compound according to claim 1, which is methyl 2-chloro-4-fluoro-5-(5-trifluoromethyl-3-pyridazinon-2-yl)phenylthioacetate (compound 1-1213).
42. A compound according to claim 1, which is ethyl2-{2-chloro-4-fluoro-5-(5-trifluoromethyl-3-pyridazinon-2-yl)phenylthio}propionate (compound 1-1222).
43. A compound according to claim 1, which is methyl 2-12-chloro-4-fluoro-5-(5-trifluoromethyl-3-pyridazinon-2-yl)phenylthio}propionate (compound 1-1221).
44. A compound according to claim 1, which is isopropyl 2-{2-chloro-4-fluoro-5-(5-trifluoromethyl-3-pyridazinon-2-yl)phenylthio}propionate (compound 1-1226).
45. A compound according to claim 1, which is ethyl 2-(2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenylamino)propionate (compound 1-420).
46. A compound according to claim 1, which is ethyl 2-{2-chloro-4-fluoro-5-(5-trifluoromethyl-3-pyridazinon-2-yl)phenylamino}propionate (compound 1-1057).
47. A compound according to claim 1, which is N-{2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenyl}methanesulfonamide (compound 1-367).
48. A compound according to claim 1, which is N-{2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenyl}chloromethanesulfonamide (compound 1-369).
49. A compound according to claim 1, which is N-{2-chloro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenyl}methanesulfonamide (compound 1-398).
50. A compound according to claim 1, which is methyl 2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)benzoate (compound 1-641).
51. A compound according to claim 1, which is ethyl2-chloro-4-fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)benzoate (compound 1-642).
52. A compound according to claim 1, which is ethyl 2-chloro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)benzoate (compound 1-621).
53. A compound according to claim 1, which is isopropyl 2-chloro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)benzoate (compound 1-625).
54. A compound according to claim 1, which is 2-(4-chloro-2-fluoro-5-propargyloxyphenyl)-6-methyl-5-trifluoromethylpyridazin-3-one (compound 1-1441).
55. A herbicidal composition comprising a herbicidally effective amount of a compound of formula (1) as defined in claim 1, and an inert carrier or diluent.
56. A method for controlling unfavorable weeds, which comprises applying a herbicidally effective amount of a compound of formula (1) as defined in claim 1 to an area where the unfavorable weeds grow or will grow.
57. Use of the compound according to claim 1 as a herbicide.
58. A compound of the formula:
wherein R3 is as defined in claim 1, and Q1 is [Q1-1], [Q-2], [Q1-3] or [Q-4]
of the formula:
wherein X, Y, Z1, Z2, n, R4, R5, R7, and R8 are as defined in claim 1;
B1 is hydrogen, halogen, nitro, cyano, OR27, SR27, SO2OR27, NR11(R12) SO2NR11(R12), NR11(COR13), NR11(SO2R14), N(SO2R14)(SO2R15), N(SO2R14)-(COR13), NHCOOR13, COOR27, CONR11(R12), CSNR11(R12), CR17=CR18COOR13, CR17=CR18CONR11(R12), CH2CHWCOOR13, CH2CHWCONR11(R12), CR17=N-OR33, CR17=NNR11(R12), CR17(Z2R34)2, OCO2R19, or OCOR19; and R9 is C1-C6 alkyl, C1-C6 haloalkyl, cyano, carboxyl, hydroxy C1-C6 alkyl, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkoxy C1-C6 alkoxy C1-C6 alkyl, (C1-C6 alkyl) carbonyloxy C1-C6 alkyl, (C1-C6 haloalkyl)carbonyloxy C1-C6 alkyl, (C1-C6 alkoxy) carbonyl, or (C1-C6 alkyl)carbonyl;
wherein R27 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, benzyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, cyano C1-C6 alkyl, C2-C8 alkoxyalkyl, C2-C8 alkylthioalkyl, carboxy C1-C6 alkyl, (C1-alkoxy)carbonyl C1-C6 alkyl, (C1-C6 haloalkoxy)carbonyl C1-C6 alkyl, {(C1-C4 alkoxy) C1-C4 alkoxy)carbonyl C1-C6 alkyl, (C3-C8 cycloalkoxy)carbonyl C1-C6 alkyl, N(R11)R12, CH2COON(R11)R12, CH(C1-C4 alkyl)CON(R11)R12, CH(C1-C4 alkyl) COON(R11)R12, {(C1-C6 alkoxy)carbonyl C1-C6 alkyl}oxycarbonyl C1-C6 alkyl, or hydroxy C1-C6 alkyl; and R11, R12, R13, R14, R15, R17, R18, R19, R33, R34, and W
are as defined in claim 1
wherein R3 is as defined in claim 1, and Q1 is [Q1-1], [Q-2], [Q1-3] or [Q-4]
of the formula:
wherein X, Y, Z1, Z2, n, R4, R5, R7, and R8 are as defined in claim 1;
B1 is hydrogen, halogen, nitro, cyano, OR27, SR27, SO2OR27, NR11(R12) SO2NR11(R12), NR11(COR13), NR11(SO2R14), N(SO2R14)(SO2R15), N(SO2R14)-(COR13), NHCOOR13, COOR27, CONR11(R12), CSNR11(R12), CR17=CR18COOR13, CR17=CR18CONR11(R12), CH2CHWCOOR13, CH2CHWCONR11(R12), CR17=N-OR33, CR17=NNR11(R12), CR17(Z2R34)2, OCO2R19, or OCOR19; and R9 is C1-C6 alkyl, C1-C6 haloalkyl, cyano, carboxyl, hydroxy C1-C6 alkyl, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkoxy C1-C6 alkoxy C1-C6 alkyl, (C1-C6 alkyl) carbonyloxy C1-C6 alkyl, (C1-C6 haloalkyl)carbonyloxy C1-C6 alkyl, (C1-C6 alkoxy) carbonyl, or (C1-C6 alkyl)carbonyl;
wherein R27 is hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl, benzyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, cyano C1-C6 alkyl, C2-C8 alkoxyalkyl, C2-C8 alkylthioalkyl, carboxy C1-C6 alkyl, (C1-alkoxy)carbonyl C1-C6 alkyl, (C1-C6 haloalkoxy)carbonyl C1-C6 alkyl, {(C1-C4 alkoxy) C1-C4 alkoxy)carbonyl C1-C6 alkyl, (C3-C8 cycloalkoxy)carbonyl C1-C6 alkyl, N(R11)R12, CH2COON(R11)R12, CH(C1-C4 alkyl)CON(R11)R12, CH(C1-C4 alkyl) COON(R11)R12, {(C1-C6 alkoxy)carbonyl C1-C6 alkyl}oxycarbonyl C1-C6 alkyl, or hydroxy C1-C6 alkyl; and R11, R12, R13, R14, R15, R17, R18, R19, R33, R34, and W
are as defined in claim 1
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP236098/1995 | 1995-08-21 | ||
| JP23609895 | 1995-08-21 | ||
| JP60232/1996 | 1996-02-21 | ||
| JP6023296 | 1996-02-21 | ||
| JP10461896 | 1996-04-01 | ||
| JP104618/1996 | 1996-04-01 | ||
| PCT/JP1996/002311 WO1997007104A1 (en) | 1995-08-21 | 1996-08-19 | Pyridazin-3-one derivatives, their use, and intermediates for their production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2230199A1 CA2230199A1 (en) | 1997-02-27 |
| CA2230199C true CA2230199C (en) | 2007-09-25 |
Family
ID=27297120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002230199A Expired - Lifetime CA2230199C (en) | 1995-08-21 | 1996-08-19 | Pyridazin-3-one derivatives, their use as a herbicide, and intermediates for their production |
Country Status (26)
| Country | Link |
|---|---|
| US (4) | US6090753A (en) |
| EP (1) | EP0850227B1 (en) |
| KR (1) | KR100510028B1 (en) |
| CN (2) | CN1117083C (en) |
| AR (1) | AR003325A1 (en) |
| AT (1) | ATE383344T1 (en) |
| BG (1) | BG102326A (en) |
| BR (1) | BR9609908A (en) |
| CA (1) | CA2230199C (en) |
| CO (1) | CO4750760A1 (en) |
| CZ (1) | CZ25698A3 (en) |
| DE (1) | DE69637405T2 (en) |
| EA (1) | EA000868B1 (en) |
| ES (1) | ES2300107T3 (en) |
| HU (1) | HUP9802304A3 (en) |
| IL (1) | IL123162A (en) |
| MX (1) | MX9801353A (en) |
| NO (1) | NO980720L (en) |
| NZ (1) | NZ315400A (en) |
| PL (1) | PL325062A1 (en) |
| RO (1) | RO117915B1 (en) |
| SK (1) | SK22198A3 (en) |
| TR (2) | TR199800290T2 (en) |
| TW (1) | TW332202B (en) |
| UA (1) | UA49844C2 (en) |
| WO (1) | WO1997007104A1 (en) |
Families Citing this family (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19520613A1 (en) * | 1995-06-06 | 1996-12-12 | Bayer Ag | Phenylpyridazinones |
| AR009380A1 (en) * | 1996-10-21 | 2000-04-12 | Sumitomo Chemical Co | PROCESS OF PREPARATION OF A DERIVATIVE OF PIRIDAZIN-3-ONA, USEFUL AS A HERBICIDE, CARBOXYLIC ACID FOR USE THEREOF, SALE OF THIS LAST AND PROCESS TO PREPARE SUCH CARBOXYLIC ACID |
| JP4788698B2 (en) * | 1996-10-21 | 2011-10-05 | 住友化学株式会社 | CARBOXYLIC ACID DERIVATIVE, PROCESS FOR PRODUCING THE SAME AND PROCESS FOR PRODUCING PYRIZAZN-3-ONE DERIVATIVE USING THE SAME |
| ZA978995B (en) | 1996-10-21 | 1998-08-25 | Sumitomo Chemical Co | Production of pyridazine herbicide |
| CN1165231C (en) * | 1997-02-17 | 2004-09-08 | 住友化学工业株式会社 | Herbicidal composition |
| US6022829A (en) * | 1997-02-17 | 2000-02-08 | Sumitomo Chemical Company, Limited | Herbicidal composition |
| EP0967872A1 (en) * | 1997-02-17 | 2000-01-05 | Sumitomo Chemical Company Limited | Herbicidal composition |
| EP0967871A1 (en) * | 1997-02-17 | 2000-01-05 | Sumitomo Chemical Company Limited | Herbicidal composition |
| BR9807396A (en) * | 1997-02-18 | 2000-03-14 | Sumitomo Chemical Co | Herbicidal composition |
| IL123339A0 (en) * | 1997-02-19 | 1998-09-24 | Sumitomo Chemical Co | Pyridazin-3-one derivatives and their use |
| IL123340A0 (en) * | 1997-02-20 | 1998-09-24 | Sumitomo Chemical Co | Pyridazin-3-one derivatives and their use |
| HUP0003462A3 (en) | 1997-09-17 | 2001-03-28 | Basf Ag | Herbicidal substituted 2-phenyl-3(2h)-pyridazinones and use thereof |
| CA2307815A1 (en) * | 1997-10-27 | 1999-05-06 | Isk Americas Incorporated | Substituted benzene compounds, process for their preparation, and herbicidal and defoliant compositions containing them |
| JP4211081B2 (en) * | 1998-03-19 | 2009-01-21 | 住友化学株式会社 | 4-cyanopyridazin-3-one derivatives |
| US6187920B1 (en) | 1998-03-26 | 2001-02-13 | Sumitomo Chemical Co., Ltd. | Pyridazinone derivatives |
| BR9909548A (en) * | 1998-04-09 | 2000-12-12 | Bayer Ag | Substituted phenylpyridazinones |
| US6077953A (en) * | 1998-06-11 | 2000-06-20 | Sumitomo Chemical Co., Ltd. | 6-alkoxycarbonylpyridazin-3-one compounds |
| JP4154760B2 (en) * | 1998-08-05 | 2008-09-24 | 住友化学株式会社 | Herbicidal composition |
| JP2000063216A (en) * | 1998-08-12 | 2000-02-29 | Sumitomo Chem Co Ltd | Herbicide composition |
| JP2000063215A (en) * | 1998-08-12 | 2000-02-29 | Sumitomo Chem Co Ltd | Herbicide composition |
| JP4200559B2 (en) | 1998-10-23 | 2008-12-24 | 住友化学株式会社 | Herbicidal composition |
| DE19937500A1 (en) * | 1999-08-09 | 2001-02-15 | Bayer Ag | Substituted heterocyclylbenzofurans |
| US20030130123A1 (en) * | 2000-04-14 | 2003-07-10 | Michael Puhl | 2-Phenyl-2h-pyridazine-3-ones |
| EP1272475A1 (en) * | 2000-04-14 | 2003-01-08 | Basf Aktiengesellschaft | 2-phenyl-2h-pyridazine-3-ones |
| EP2052612A1 (en) | 2007-10-24 | 2009-04-29 | Bayer CropScience AG | Herbicide combination |
| DE102008037629A1 (en) * | 2008-08-14 | 2010-02-18 | Bayer Cropscience Ag | Herbicide combination with dimethoxytriazinyl-substituted difluoromethanesulfonylanilides |
| CA2763938C (en) | 2009-06-19 | 2017-07-11 | Basf Se | Herbicidal benzoxazinones |
| FR2949643B1 (en) * | 2009-09-08 | 2012-09-28 | Fonds De Dev Des Filieres Des Oleagineux Et Proteagineux Fidop | USE OF GLYCEROL ETHERS AS ACTIVATORS OF HERBICIDE EFFECTS OF A HERBICIDE SUBSTANCE |
| US8669208B2 (en) | 2010-10-01 | 2014-03-11 | Basf Se | Herbicidal benzoxazinones |
| WO2012080239A1 (en) | 2010-12-15 | 2012-06-21 | Basf Se | Herbicidal compositions |
| EP3281524A1 (en) | 2016-08-09 | 2018-02-14 | Basf Se | Method for controlling ppo resistant weeds |
| TWI785022B (en) * | 2017-03-28 | 2022-12-01 | 美商富曼西公司 | Novel pyridazinone herbicides |
| US20200392103A1 (en) | 2017-11-23 | 2020-12-17 | Basf Se | Herbicidal pyridylethers |
| CN110050794A (en) * | 2019-04-29 | 2019-07-26 | 广西化工研究院有限公司 | A kind of herbicidal composition and its preparation method and application |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE29123C (en) | FARBWERKE VORM. Meister, Lucius & Brüning in Höchst a. M | Process for the preparation of alkylated hydroderivatives of oxymethylquinolines and their methyl resp. Ethyl ether | ||
| CH373919A (en) * | 1959-02-02 | 1963-12-15 | Ciba Geigy | Method of controlling weeds |
| BE627826A (en) * | 1960-09-09 | |||
| US3641098A (en) * | 1967-09-26 | 1972-02-08 | Bayer Ag | Cyano substituted phenylhydrazones of 1 2-dicarbonyl compounds |
| DE2706700A1 (en) * | 1977-02-17 | 1978-08-24 | Consortium Elektrochem Ind | METHOD FOR PREPARING PYRIDAZINE-3-ON COMPOUNDS, NEW PYRIDAZINE-3-ONE AND THEIR USE |
| DE2808193A1 (en) * | 1978-02-25 | 1979-09-06 | Basf Ag | PYRIDAZONE CONNECTIONS |
| DE3013267A1 (en) * | 1980-04-05 | 1981-10-15 | Basf Ag, 6700 Ludwigshafen | SUBSTITUTED PYRIDAZONE, METHOD FOR THE PRODUCTION THEREOF, THE HERBICIDES CONTAINING IT AND THEIR USE AS HERBICIDES |
| IL61273A (en) * | 1979-10-24 | 1984-02-29 | Basf Ag | Preparation of anilines and certain novel anilines |
| DE4343528A1 (en) * | 1993-12-16 | 1995-06-22 | Schering Ag | New di-heterocyclyl-benzene or pyridine derivs. |
| DE19520613A1 (en) * | 1995-06-06 | 1996-12-12 | Bayer Ag | Phenylpyridazinones |
| AR009380A1 (en) * | 1996-10-21 | 2000-04-12 | Sumitomo Chemical Co | PROCESS OF PREPARATION OF A DERIVATIVE OF PIRIDAZIN-3-ONA, USEFUL AS A HERBICIDE, CARBOXYLIC ACID FOR USE THEREOF, SALE OF THIS LAST AND PROCESS TO PREPARE SUCH CARBOXYLIC ACID |
| DE19754348A1 (en) * | 1996-12-11 | 1998-06-18 | Ciba Geigy Ag | New 2-(hetero)aryl-2(3H)-pyridazinone derivatives |
| US6294503B1 (en) * | 1998-12-03 | 2001-09-25 | Ishihara Sangyo Kaisha, Ltd. | Fused heterocycle compounds, process for their preparation, and herbicidal compositions containing them |
-
1996
- 1996-08-19 NZ NZ315400A patent/NZ315400A/en unknown
- 1996-08-19 AT AT96927192T patent/ATE383344T1/en not_active IP Right Cessation
- 1996-08-19 SK SK221-98A patent/SK22198A3/en unknown
- 1996-08-19 DE DE69637405T patent/DE69637405T2/en not_active Expired - Lifetime
- 1996-08-19 TR TR1998/00290T patent/TR199800290T2/en unknown
- 1996-08-19 PL PL96325062A patent/PL325062A1/en unknown
- 1996-08-19 HU HU9802304A patent/HUP9802304A3/en unknown
- 1996-08-19 EP EP96927192A patent/EP0850227B1/en not_active Expired - Lifetime
- 1996-08-19 ES ES96927192T patent/ES2300107T3/en not_active Expired - Lifetime
- 1996-08-19 CN CN96197700A patent/CN1117083C/en not_active Expired - Lifetime
- 1996-08-19 CA CA002230199A patent/CA2230199C/en not_active Expired - Lifetime
- 1996-08-19 WO PCT/JP1996/002311 patent/WO1997007104A1/en active IP Right Grant
- 1996-08-19 KR KR10-1998-0701256A patent/KR100510028B1/en not_active IP Right Cessation
- 1996-08-19 US US09/011,269 patent/US6090753A/en not_active Expired - Lifetime
- 1996-08-19 TR TR2001/02127T patent/TR200102127T2/xx unknown
- 1996-08-19 BR BR9609908A patent/BR9609908A/en not_active IP Right Cessation
- 1996-08-19 CZ CZ98256A patent/CZ25698A3/en unknown
- 1996-08-19 EA EA199800219A patent/EA000868B1/en not_active IP Right Cessation
- 1996-08-19 CN CNB031425011A patent/CN1252066C/en not_active Expired - Lifetime
- 1996-08-19 UA UA98031420A patent/UA49844C2/en unknown
- 1996-08-19 RO RO98-00298A patent/RO117915B1/en unknown
- 1996-08-19 IL IL12316296A patent/IL123162A/en not_active IP Right Cessation
- 1996-08-20 TW TW085110140A patent/TW332202B/en not_active IP Right Cessation
- 1996-08-21 AR ARP960104072A patent/AR003325A1/en active IP Right Grant
- 1996-08-21 CO CO96044163A patent/CO4750760A1/en unknown
-
1998
- 1998-02-18 MX MX9801353A patent/MX9801353A/en unknown
- 1998-02-20 NO NO980720A patent/NO980720L/en not_active Application Discontinuation
- 1998-03-13 BG BG102326A patent/BG102326A/en unknown
-
2000
- 2000-03-07 US US09/521,200 patent/US6348628B1/en not_active Expired - Lifetime
-
2002
- 2002-01-07 US US10/036,528 patent/US6482773B1/en not_active Expired - Fee Related
- 2002-10-03 US US10/263,168 patent/US6703503B2/en not_active Expired - Fee Related
Also Published As
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2230199C (en) | Pyridazin-3-one derivatives, their use as a herbicide, and intermediates for their production | |
| US9029552B2 (en) | Tetrazoyloxime derivative and plant disease control agent | |
| US6013663A (en) | Dithiolan derivatives, their preparation and their therapeutic effect | |
| US20170096402A1 (en) | 5-(hetero)arylpyridazinones and their use as herbicides | |
| CA2500225C (en) | Pyrazole compounds | |
| US20070031514A1 (en) | Use of isoindolinone derivatives as insecticides | |
| JP2000169371A (en) | Medicament containing dithiolane derivative | |
| US20050032858A1 (en) | Novel heterocyclic compound and anti-inflamatory agent | |
| TW200409757A (en) | 1-aralkyl-N-(3-quinolyl)-1-cyclohexancarboxamide derivatives | |
| US6100257A (en) | Pyrimidin-4-one derivatives, their intermediates for their production and processes for producing these compounds | |
| US6869913B1 (en) | Pyridazin-3-one derivatives, their use and intermediates for their production | |
| EP3145918B1 (en) | 2-(hetero)aryl pyridazinones and their use as herbicides | |
| JPH06247933A (en) | Pyridyloxy derivative | |
| JP2002128762A (en) | New phenanthridinone derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKEX | Expiry |
Effective date: 20160819 |