CA1314546C - Ureas - Google Patents
UreasInfo
- Publication number
- CA1314546C CA1314546C CA000596184A CA596184A CA1314546C CA 1314546 C CA1314546 C CA 1314546C CA 000596184 A CA000596184 A CA 000596184A CA 596184 A CA596184 A CA 596184A CA 1314546 C CA1314546 C CA 1314546C
- Authority
- CA
- Canada
- Prior art keywords
- urea
- methyl
- trifluoromethyl
- pyrimidin
- phenyl
- 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 - Fee Related
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/42—One nitrogen atom
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
-
- 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing heterocyclic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
-
- 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
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur 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
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6509—Six-membered rings
- C07F9/6512—Six-membered rings having the nitrogen atoms in positions 1 and 3
Abstract
Novel Ureas Abstract The present invention relates to novel N-phenyl-N-pyrimidin-2-ylureas having a herbicidal and plant growth-regulating activity, to agrochemical compositions containing those substances as active ingredients, to the use of the novel ureas for controlling weeds or for regulating plant growth, and to processes for the preparation of the novel compounds. The invention also relates to novel intermediates and to processes for the preparation thereof.
The novel compounds correspond to formula I
(I), in which R1, R2 and R3 are each, independently of the others, hydrogen; halogen;
C1-C4alkyl; C1-C4alkoxy; C1-C4haloalkyl; C1-C4haloalkoxy; C1-C4alkyl-S(O)n-; nitro; cyano; C1-C4alkoxycarbonyl; C1-C4alkylcarbonyl; di-(C1-C4alkylamino)-carbonyl; mono-(C1-C4alkylamino)carbonyl; carbamoyl;
C1-C4haioalkyl-S(O)n-; or -PO[O-(C1-C4)-alkyl]2;
R4 is C1-C6alkyl; C1-C4alkoxy; C1-C4alkyl-S(O)n-; C1-C4haloalkyl;
C1-C4haloalkoxy; phenyl that is unsubstitutsd or is substituted by up to three identical or different substituents from halogen, C1-C4alkyl, C1-C4haloalkyl and C1-C4alkoxy; 2-furanyl; 2-thienyl; 3-thienyl; C3-C6-cycloalkyl that is unsubstituted or ls substituted by up to three ideneical or different C1-C4alkyl radicals; cyano; C2-C4haloalkenyl;
C1-C4alkoxy-C1-C4alkyl; C1-C4alkoxy-C1-C4alkoxy; or halogen-C1-C4alkyl-thio;
R5 is hydrogen; C1-C3alkyl; C1-C3haloalkyl; halogen; or C1-C3haloalkoxy;
and n is 0, 1 or 2, with the proviso that when one of the radicals R1, R2 and R3 is nitro, that substituent may not be bonded in tho 2- or 6-position of the phenyl ring.
The novel compounds correspond to formula I
(I), in which R1, R2 and R3 are each, independently of the others, hydrogen; halogen;
C1-C4alkyl; C1-C4alkoxy; C1-C4haloalkyl; C1-C4haloalkoxy; C1-C4alkyl-S(O)n-; nitro; cyano; C1-C4alkoxycarbonyl; C1-C4alkylcarbonyl; di-(C1-C4alkylamino)-carbonyl; mono-(C1-C4alkylamino)carbonyl; carbamoyl;
C1-C4haioalkyl-S(O)n-; or -PO[O-(C1-C4)-alkyl]2;
R4 is C1-C6alkyl; C1-C4alkoxy; C1-C4alkyl-S(O)n-; C1-C4haloalkyl;
C1-C4haloalkoxy; phenyl that is unsubstitutsd or is substituted by up to three identical or different substituents from halogen, C1-C4alkyl, C1-C4haloalkyl and C1-C4alkoxy; 2-furanyl; 2-thienyl; 3-thienyl; C3-C6-cycloalkyl that is unsubstituted or ls substituted by up to three ideneical or different C1-C4alkyl radicals; cyano; C2-C4haloalkenyl;
C1-C4alkoxy-C1-C4alkyl; C1-C4alkoxy-C1-C4alkoxy; or halogen-C1-C4alkyl-thio;
R5 is hydrogen; C1-C3alkyl; C1-C3haloalkyl; halogen; or C1-C3haloalkoxy;
and n is 0, 1 or 2, with the proviso that when one of the radicals R1, R2 and R3 is nitro, that substituent may not be bonded in tho 2- or 6-position of the phenyl ring.
Description
1314~46 Novel Ureas The present invention relates to novel N-phenyl-N-pyrimidin-2-ylureas having a herbicidal and plant growth-regulating activity, to agrochemical compositions containing those substances as active ingredients, to the use of the novel ureas for co~trolling weeds or for regulating plant growth, and to processes for the preparation of the novel compounds. The invention also relates to novel intermediates and to processes fo} the preparation thereof.
(Pyrimidin-2-yl)-2-nitroanilines are known from Patent Specification DD-151 404 and from European Patent Application EP-A-O 172 786. These compounds are fungicidally active. In contrast, it has surprisingly been found that N-phenyl-N-pyrimidin-2-ylureas have a herbicidal and plant growth-regulating activity.
The invention relates to ureas of formula I
s R~
llZ
in which R1, R2 and R3 are each, independently of the o~hers, hydrogen; halogen;
Cl-C4alkyl; Cl-C4alkoxy; Cl-C4haloalkyl; Cl-C4haloalkoxy; Cl-C4alkyl-S(O) -; nitro; cyano; C1-C4alkoxycarbonyl; di-(C1-C4alkylamino)-carbonyl; mono-(C1~C4alXylamino)carbonyl, carbamoyl; C1-C4haloalkyl-S(O) -; C1-C4alkylcarbonyl; or -PO[O-(C1-C4)-alkyl]2;
R4 is C1-C6alkyl; C1-C4alkoxy; C1-C4alkyl-S(O) -; C1-C4haloalkyl;
C1-C4haloalkoxy; phenyl that is unsubstituted or is substituted by up to three identical or different substi~uents from halogen, C1-C4alkyl,
(Pyrimidin-2-yl)-2-nitroanilines are known from Patent Specification DD-151 404 and from European Patent Application EP-A-O 172 786. These compounds are fungicidally active. In contrast, it has surprisingly been found that N-phenyl-N-pyrimidin-2-ylureas have a herbicidal and plant growth-regulating activity.
The invention relates to ureas of formula I
s R~
llZ
in which R1, R2 and R3 are each, independently of the o~hers, hydrogen; halogen;
Cl-C4alkyl; Cl-C4alkoxy; Cl-C4haloalkyl; Cl-C4haloalkoxy; Cl-C4alkyl-S(O) -; nitro; cyano; C1-C4alkoxycarbonyl; di-(C1-C4alkylamino)-carbonyl; mono-(C1~C4alXylamino)carbonyl, carbamoyl; C1-C4haloalkyl-S(O) -; C1-C4alkylcarbonyl; or -PO[O-(C1-C4)-alkyl]2;
R4 is C1-C6alkyl; C1-C4alkoxy; C1-C4alkyl-S(O) -; C1-C4haloalkyl;
C1-C4haloalkoxy; phenyl that is unsubstituted or is substituted by up to three identical or different substi~uents from halogen, C1-C4alkyl,
2- 13~4~4~
Cl-C4haloalkyl and Cl-C4alkoxy; 2-furanyl; 2-thienyl; 3-thienyl; C3-C6-cycloalkyl that is unsubstituted or is substituted by up to three identical or different Cl-C4alkyl radicals; cyano; Cz-C~haloalkenyl;
Cl-C4alkoxy-Cl-C4alkyl; Cl-C4alkoxy-C1-G4alkoxy; or halo-Cl-C4alkylthio;
Rs is hydrogen; C1-C3alkyl; Cl-C3haloalkyl; halogen; or Cl-C3haloalkoxy;
and n is 0, 1 or 2, with the proviso that when one of the radicals Rl, R2 and R3 is nitro, that substituent may not be bonded in the 2- or 6-position of the phenyl ring, and to salts and addition compounds of the compounds of formula I
with acids, bases and complex formers.
~ithin the scope of the invention disclosed herein, the generic terms mentioned include, for example, the following specific individual substituents, witho~t this list implying any limitation of the invention:
Alkyl includes straight-chained or branched Cl-C6alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl, isobutyl, the isomeric pentyl radicals, such as, for example, n-pentyl, tert.-pentyl (l,l-dimethylpropyl), isopentyl (l-ethylpropyl), and the isomeric hexyl radicals. Cl-Csalkyl radicals are preferred.
Halogen is fluorine, chlorine, bromine or iodine. Fluorine, chlorine and bromine are preferred.
Haloalkyl indicates alkyl radicals, according to the respective scope of definition given, that are completely or partially substituted by identical or different halogen atoms, such as, for example, trifluoro-methyl 7 difluoromethyl, 1,1,2,2-tetrafluoroethyl, 2-chloroethyl, penta-fluoroethyl, chlorodifluoromethyl, dichloromethyl, chlorofluoromethyl, 1,1-dichloro-2,2,2-trifluoroethyl, l,l-dichloroethyl or heptafluoro-propyl.
There may be mentioned as Cl-C4alkoxycarbonyl radicals, inter alia, methoxycarbonyl, ethoxycarbonyl and the isomeric propoxycarbonyls and busoxycarbonyls.
_ 3 _ 1 3 1 ~ ~ ~ 6 Alkoxy within the scope of the respective definition of the isomeric alkoxy radicals is especially methoxy, ethoxy, (i)-propoxy, (n)-propoxy, (i)-butoxy, (t)-butoxy, (n)-butoxy and (sec.)-butoxy.
Haloalkoxy and haloalkylthio within the scope of the respective defini-tion are isomeric alkyl radicals that are mono- or poly-substituted by identical or differenc halogen atoms, such as, for example, trifluoro-methoxy, 2,2,2-trifluoroethoxy, trifluoromethylthio, 2,2,3,3,3-penta-fluoropropoxy or 1,1,2,2-tetrafluoroethoxy, difluoromethoxy or 2-chloro-ethoxy.
There may be mentioned as alkoxyalkyl radicals, inter alia: 2-ethoxy-ethyl, 2-methoxyethyl, 3-methoxypropyl, 2-methoxy-1-methylethyl and methoxymethyl.
The group C1-C4alkyl-S(O) - represents the respective alkylthio, alkyl-sulfinyl and alkylsulfonyl radicals. Methylthio, methylsulfinyl and methylsulfonyl may be mentioned as being especially preferred.
Of the groups PO~O(C1-C4)-alkyl]2, PO(OCH3)2 and PO(OC2Hs)2 are pre-ferred.
Di-(C1-C~alkylamino)carbonyl includes radicals substituted either by identical or different C1-C4alkyl radicals.
Haloalkylthio is especially fluoromethylthio, difluoromethylthio, trifluoromethylthio, 1,1,2,2-tetrafluoroethylthio, chlorodifluoromethyl-thio and dichlorofluoromethylthio.
In the further substituents that are composed of several base elements,the sub-elements may be freely selected within the scope of the definition and have the above meaning.
Attention is drawn to compounds of formula I unsubstituted in the 4-position of the phenyl ring _ 4 _ 13~4~4~
R ~0_.~ ~N--~
R2 ~R3 ~ ~4 (I), in which Rl is halogen; cyano; C1-C~alkoxy; Cl-C4haloalkoxy; C1-C4alkyl-S(O) -;
Cl-C4alkyl; Cl-C4haloalkyl; Cl-C4alkoxycarbonyl; di-(Cl-C4alkylamino)-carbonyl; mono-(Cl-C4alkylamino)carbonyl; carbamoyl; Cl-C4haloalkyl-S(O)n~; or -PO[O-(Cl-C4)alkyl]z;
R2 is hydrogen; halogen, cyano; nitro; Cl-C4alkyl; Cl-C4alkoxy; Cl-C4-haloalkyl; Cl-C4alkoxycarbonyl; or Cl-C4alkylcarbonyl;
R3 is hydrogen; halogen; or Cl-C4alkyl, and n and the radicals R4 and Rs are as defined hereinbefore.
Preferred sub-groups are formed by those compounds of formula I in which a) the radical Rl is bonded at the 2-position of the phenyl ring, b) the radical R2 is bonded at the 3-position of the phenyl ring, c) the radical R; is bonded at the 5-position of the phenyl ring, d) the radical R2 is bonded at the ~-position of the phenyl ring, e) the radical Rl is bonded at the 3-position of the phenyl ring, f) the radical R3 is bonded at the 3-position of the phenyl ring, g) the radical R2 is bonded at the 5-position of the phenyl ring.
Attention is drawn to the following combinations of sub-groups: a+b, a+g, a~d, e+g, e+d, atb+c, a+f+d, a+c+d and e+c+d, the radical R3 being hydrogen in combinations of only two sub-groups.
Attention is drawn especially to compounds of formula I in which Rl is halogen; cyano; Cl-C3alkoxy; Cl-C2haloalkoxy; methyl-S(O) -;
Cl-C3alkyl; Cl-C2haloalkyl; C1-C4alkoxycarbonyl; carbamoyl; difluoro-methylthio or -PO[O-(Cl-C2)-alkyl]2;
R2 is hydrogen; fluorine; chlorine; bromine; cyano; nitro; C~-C3alkyl;
Cl-C2haloalkyl; or C1-C3alkoxycarbonyl;
R3 is hydrogen; chlorine; fluorine; or Cl-C3alkyl;
~ s - -R4 is C1-Csalkyl C1-C4alkoxy, C1-C4alkylthio; cyclopropyl: phenyl;
furan-2-yl; thiophen-2-yl; cyano; C1-C3haloalkoxy; C1-C2alkoxy-C1-C~-alkyl; C1-C2alkoxy-C1-C2alkoxy; methylsulfinyl; methy~sulfonyl; or C2-C3haloalkenyl;
Rs is C1-C3alkyl; fluorine; chlorine; bromine; C1-C3haloalkyl; or C1-C3haloalkoxy; and n is 0, 1 or 2.
Especially preferred are compounds of formula I in which Rl is halogen; methyl; trifluoromethyl; trifluoromethoxy; difluoro-methoxy; C1-C3alkoxy; methyl~hio; methylsulfinyl; methylsulfonyl; cyano;
C1-C4alkoxycarbonyl; carbamoyl; difluoromethylthio; or -PO(O-CzHs)2;
R2 is hydrogen; fluorine; chlorine; bromine; nitro; ethyl; methyl;
trifluoromethyl; methoxy; or C1-C3alkoxycarbonyl;
R3 is hydrogen; chlorine; or methyl;
R4 is C1-Csalkyl; C1-C4alkoxy; C1-C4alkylthio; cyclopropyl; phenyl;
furan-2-yl; thiophen-2-yl; cyano; 1,1,2,2-tetrafluoroethoxy; 2-chloro-ethoxy; methoxymethyl; 2-methoxy-ethoxy; methylsulfinyl; methylsulfonyl;
or 2,2-dichlorovinyl;
Rs is C1-C3alkyl; fluorine; chlorine; bromine; difluoromethoxy; tri-fluoromethyl; pentafluoroethyl; chlorodifluoromethyl; difluoromethyl;
dichloromethyl; chlorofluoromethyl; l,l-dichloro-2,2,2-trifluoroethyl;
l,l-dichloroethyl; or heptafluoropropyl.
The invention relates especially to compounds of formula I in which R1 is fluorine; chlorine; bromine; iodine; trifluoromethyl; methyl;
difluoromethoxy; methoxy; methylthio; PO(OC2Hs)z; methoxycarbonyl;
methylsulfonyl; or cyano;
R2 is hydrogen; fluorine; chlorine; bromine; nitro; methyl; ethyl;
trifluoromethyl; or methoxycarbonyl;
R3 is hydrogen; or methyl;
R4 is C~-Csalkyl; butylthio; thiophen-2-yl; furan 2-yl; C1-C4alkoxy;
methylthio; methylsulfinyl; methylsulfonyl; or cyclopropyl; and Rs is methyl; chlorine; dichloromethyl; pentafluoroethyl; difluoromethyl;
chlorofluoromethyl; trifluoromethyl; or chlorodifluoromethyl.
131~4~
Attention is drawn furthermore to compounds of formula I in which a) Rl is fluorine, chlorine, bromine, trifluoromethyl, cyano, difluoro-methoxy, trifluoromethoxy, methyl or methoxy. each bonded in the 2-position of the phenyl ring, R2 and R3 are each hydrogen, R4 is methyl, furan-2-yl or cyclopropyl, and Rs is chlorine, methyl, trifluoromethyl or chlorodifluoromethyl, or b) Rl is fluorine, chlorine, bromine, trifluoromethyl, difluoromethoxy, trifluoromethoxy, cyano or methoxy, each bonded in the 2-position of the phenyl ring, R2 is fluorine or chlorine, each bonded in the 3-, 5- or 6-position of the phenyl ring, R4 is methyl, furan-2-yl or cyclopropyl, and Rs is chlorine, methyl, trifluoromethyl or chlorodifluoromethyl, or c) R~ is chlorine bonded in the 3-position of the phenyl ring, R2 is chlorine bonded in the 5-position of the phenyl ring, R4 is methyl, furan-2-yl or cyclopropyl, and Rs is chlorine, methyl, trifluoromethyl or chlorodifluoromethyl.
The following compounds may be mentioned specifically on account of their herbicidal activity:
N-(2-bromophenyl)-N-~4-chloro-6-methyl-pyrimidin-2-yl)-urea, N-(4-methyl-6-trifluoromethyl-pyrimidin~2-yl)-N-(2-trifluoromethyl-phenyl)-urea, N-(2,3-dichlorophenyl)-N-(4-methyl-6-trifluoromethylpyrimidin-2-yl)-urea, N-(2,5-dichlorophenyl)-N-(4,6-dimethyl-pyrimidin-2-yl)-urea, N-(4-chloro-6-methyl-pyrimidin-2-yl)-N-(2,5-dichlorophenyl)-urea, N-(2,5-dichlorophenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-[4-(chlorodifluoromethyl)-6-methyl-pyrimidin-2-yl]-N-(2,5-dichloro-phenyl)-urea, N-(4-chloro-6-methyl-pyrimidin-2-yl)-N-(2,6-dichlorophenyl)-urea, N-(2,6-dichlorophenyl~-N-(4-methyl-6-trifiuoromethyl-pyrimidin-2-yl)-urea, _ 7 _ ~ 3 ~
N-(4-cyclopropyl-6-trifluoromethyl-pyrimidin-2-yl)-N-(2,6-dichloro-phenyl)-uren, N-(3,5-dichlorophenyl)-N-(4-me~hyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(5-chloro-2-methyl-pllenyl)-N-(4-chloro-6-methyl-pyrimidin-2-yl)-urea, N-(5-chloro-2-methoxyphenyl)-N-~4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2-iodophenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2-chloro-6-methylphenyl)-N-(4-chloro-6-methyl-pyrimidin-2-yl)-urea, N-(3-chloro-2-methoxypilenyl)-N-(4-metllyl-6-trifluoromethylpyrimidin-2--yl)-urea, N-(2,6-difluorophenyl)-N-(4-methyl-6-trif`l~oromethylpyrimidin-2-yl)-urea, N-(2,5-difluorophenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2-cyanophenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-Z-yl)-urea N-(2-bromophenyl)-N-(4-cyclopropyl-6-trifluoromethyl-pyrimidin-2-yl~-urea, N-(4-isopropyl-6-trifluoromethyl-pyrimidin-2-yl)~N~~2-trifluoromethyl-phenyl)-urea, N-(2-fluorophenyl)-N-(4-methyl-6-trifluorom~thyl-pyrimid~n-2-yl)-urea, N-(2-fluorophenyl)-N-(4-isopropyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2,5-dlchlorophenyl)-N-(4-ethyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2,6-dichlorophenyl)-N-(4-difluoromethyl-6-methyl-pyrimidin-2-yl)-urea, N-(2,6-dichlorophenyl)-N-(4-methylthio-6-trifluoromethyl-pyrimidin-2-yl~-urea, N-(2,6-dichloro-3-methyl)-N-(4-methyl-6-trifluorornethyl-pyrimidin-2-yl)-urea, N-(2,6-dichloro-3-methylphenyl)-N-(4-isopropyl-6-.tri~luoromethylpyrimidin--2-yl)-urea, N-(2-chloro-6-trifluoromethyl-phenyl)-N-(4-methyl--6-trifluororr~ethyl-pyrlmidin-2-yl)-urea, N-(2-chloro-6-methyl-pllenyl)-N-(4-mcthyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2-methyl-6-trifluoromethyl-phenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(5-chloro-2-difluoromethoxy-phenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, ~,~
13~4~
- 8 - 214~9-7698 N-(2-methylthio-phenyl)-N-(4-me~hyl-6-trifluoromethyl-pyrimidln-2-yl)-urea, N-(4-cyclopropyl-6-trifluoromethyl-pyrimidin-2-yl)-N-(2,5-difluoro--phenyl)-urea, N-(2,6-difluorophenyl)-N-(4-ethyl-6-trifluoromethyl-pyrimidin-2-yl) urea, N-(6-chloro-2-fluoro-phenyl~-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)urea, N-(6-chloro-2-fluoro-phenyl)-N-(4-cyclopropyl-6-trifluoromethyl-pyrimi-din--2-yl )-urea, N-(2-difluoromethoxyphenyl)-N-(4-mathyl-6-tr1fluoromethyl-pyrlmidin-2-yl)urea, N-(6-chloro-2-methoxycarbonyl-phenyl)-N-(4-methyl-6-trlfluoromathyl-pyrimidin-2-yl)-urea, N-(2-bromophenyl)-N-~4-(furan-2-yl)-6-trlfluoromethyl-pyrimldin-2-yl]-urea, N-(2-chloro-6-methyl-phenyl)-N-(4-methoxymethyl-6-trifluoromethyl-pyrimidin-2-yl)-urea and N-(2-difluoromethoxy-6 methyl-phenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea.
The compounds of formula I can be prepared by a) reacting an aniline of formula II with phosgene to form a carbamoyl chloride of formula III and reacting this wlth N}13 ln a second step NII~ / COClz (II) (III) - ~ICl III + NH3 ~ I
to form a urea of formula I, or g b) r0acting an aniline of formula II with a halosulfonyl isocyanate IX to form a halosulfonylurea of formula IV
~ ~ (IX) ~ l3 ~ ~s (II) (IV) oz_y - HY
IV + 2HzO
- sO4H2 and hydrolysing this in a second step, or directly, to a compound of formula I, Y being a group that can be removed under the reaction conditions, such as halogen, preferably chlorine.
The reactions II --~ III, III ) I and IV ) I, which proceed with the remGval of hydrogen halide or the elimination of HY, are preferably carried out using acid-binding agents (bases).
Suitable acid-binding agents are organic or inorganic bases, for sxample tertiary amines, such as trialkylamines (trimethylamine, triethylamine, tripropylamine etc.), pyridines (pyridine, 4-dimethylaminopyridine, 4-pyrrolidylaminopyridine etc.), and alcoholates, such as, for example, potassium-tert.-butoxide, sodium methoxide or sodium ethoxide. The afore-mentioned reactions, including also the reaction VII ) II (which will be described hereinafter), can also be carried out with bases under phase transfer conditions according to processes that are known per se.
(Lit. Dehmlow & Dehmlow, Phase Transfer Catalysis Verlag Chemie, Wein-heim, 1983).
It is possible, in principle, for one or more solvents or diluents thatare inert towards the reaction to be present in process variants a) and b), should there be no specific details given. Suitable solvents or diluents are, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, ~31~6 carbon tetrachloride, tetrachloroethylene; ethers and ethereal compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert.-butyl-methyl ether etc.), anisole, dioxan, tetrahydrofuran; nitriles, such as acetonitrile, propionitrile; N,N-dialkylated amides, such as dimethyl-formamide; dimethyl sulfoxide; ketones, such as acetone, diethyl ketone, methyl ethyl ketone; and mixtures of such solvents with each other.
The anilines of formula II, like the carbamoyl chlorides of formula IIIand the ureas of formula IV, are valuable intermediates. The carbamoyl chlorides III and the ureas IV are novel, whereas some of the compounds of formula II are already known from DD-B-151 404.
The invention accordingly relates also to the novel compounds of formula II
~1 ~Rs ~- N--H--~ ~--NH~-~
R~ ~3 ~4 in which R1 is ha.logen; cyano; C1-C4alkoxy; Cl-C4haloalkoxy; C1-C4alkyl-S(O) -;
Cl-C4alkyl; Cl-C4haloalkyl; Cl-C4-alkoxycarbonyl; di-(Cl-C4alkylamino)-carbonyl; mono-(C1-C4alkylamino)carbonyl; carbamoyl; Cl-C4haloalkyl-S(O) -; or -PO[O-(C1-C4)-alkyl]z;
R2 is hydrogen; halogen; cyano; nitro; Cl-C4alkyl; C1-C4alkoxy; C1-C4-haloalkyl; C1-C4alkoxycarbonyl; or C1-C4alkylcarbonyl;
R3 is hydrogen; halogen; or Cl-C4alkyl;
R4 is C1-C6alkyl; C1-C4alkoxy; Cl-C4alkyl-S(O) -; Cl-C4haloalkyl;
Cl-C4haloalkoxy; phenyl that is unsubstituted or is substituted by up to three identical or different substituents from halogen, Cl-C4alkyl, C1-C4haloalkyl and Cl-C4alkoxy; 2-furanyl; 2-thienyl; 3-thienyl; C3-C6-cycloalkyl that is unsubstituted or is substituted by up to three identical or different C1-C4alkyl radicals; cyano; C2-C4haloalkenyl;
Cl-C4alkoxy-Cl-C4alkyl; Cl-C4alkoxy-Cl-C4alkoxy; or halo-Cl-C4alkylthio;
Rs is hydrogen; Cl-C3alkyl; Cl-C3haloalkyl; halogen; or Cl-C3haloalkoxy;
and n is 0, 1 or 2, 1314~4~
with the proviso that a) when one of the radicals R2 and R3 is nitro, that substituent may not be bonded in the 2- or 6-position of the phenyl ring and, when the radicals R4 and Rs are methyl, Rl is not chlorine, methoxy, ethoxy, fluorine, iodine, methyl or bromine and that, further-more, the following individual compounds are not included: N-[(4,6-bis-trifluoromethyl)-pyrimidin-2-yl]-2,6-dichloroaniline and N-(4-chloro-6-methylpyrimidin-2-yl)-3-chloroaniline.
The invention also relates to novel N,N-disubstituted carbamoyl chlorides of formula III
~ ~ ~N_-/RS
R2 ~R; ~ ~4 (III), in which the radicals Rl to Rs are as defined for formula I, and to novel ureas of formula IV
~ ~N--/Rs (IV), H
in which the radicals Rl to Rs are as defined for formula I, and Y is halogen, Cl-C4alkoxy or phenoxy.
The compounds of formulae III and IV are intermediates of processes a) and b) and can be prepared, as described, from the corresponding anilines of formula II.
The novel anilines of formula II can be prepared analogously to processes known from the literature, for example by aa) reacting guanidines of formula V with 1,3-dicarbonyl compounds of formula VI
- 12 - 1 3~
/ /R4 ) H~ NH-~
2 ~.~. \NH2 O=C~ - 2H20 R2 ~R3 ~4 (V) (VI) (II) the condensation reaction if desired being carried out in the presence of water-binding agents (Lit.: D.J. Brown in "The Chemistry of Heterocyclic Compounds" Vol. VI 1962, Interscience Publ. New York; J. Am. Chem.
Soc. 69 18~9 (1947); J. Am. Chem. Soc. 72 2940 (1950); J. Org. Chem. 29 1439 (1964) or J. Org. Chem. 29 1883 (1964), Houben-Weyl "Methoden d.
org. Chemie" Vol. VIII p. 180 ff), or bb) reacting an aniline of formula VII with a pyrimidine of formula VIII
under the action of a base, H-~ ~--NH2 + X ~ / N \N- /
VII VIII II
in which formulae the radicals Rl to Rs are as defined hereinbefore and X
is a nucleofugal group, such as halogen, C1-C4alkylsulfonyl or phenyl-sulfonyl.
Suitable bases for carrying out this process are, inter alia, potassiumtert.-butoxide, NazCO3, KzCO3 or NaH.
These processes are generally available for the synthesis of compounds of formula II and are applicable to all educts of formulae V, VI, VII
and VIII (in which the radicals Rl to Rs are as defined within the scope of the formula of compounds I).
The invention furthermore relates to herbicidal and plant growth-regulat-ing compositions containing a compound of formula I together with suitable adjuvan~s and/or carriers.
- 13 - 1 3 1 ~ 5 4 6 The active ingredients of the formula I are in general used successfully at application rates of from 0.005 to 5 kg/ha, especially from 0.1 to
Cl-C4haloalkyl and Cl-C4alkoxy; 2-furanyl; 2-thienyl; 3-thienyl; C3-C6-cycloalkyl that is unsubstituted or is substituted by up to three identical or different Cl-C4alkyl radicals; cyano; Cz-C~haloalkenyl;
Cl-C4alkoxy-Cl-C4alkyl; Cl-C4alkoxy-C1-G4alkoxy; or halo-Cl-C4alkylthio;
Rs is hydrogen; C1-C3alkyl; Cl-C3haloalkyl; halogen; or Cl-C3haloalkoxy;
and n is 0, 1 or 2, with the proviso that when one of the radicals Rl, R2 and R3 is nitro, that substituent may not be bonded in the 2- or 6-position of the phenyl ring, and to salts and addition compounds of the compounds of formula I
with acids, bases and complex formers.
~ithin the scope of the invention disclosed herein, the generic terms mentioned include, for example, the following specific individual substituents, witho~t this list implying any limitation of the invention:
Alkyl includes straight-chained or branched Cl-C6alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl, isobutyl, the isomeric pentyl radicals, such as, for example, n-pentyl, tert.-pentyl (l,l-dimethylpropyl), isopentyl (l-ethylpropyl), and the isomeric hexyl radicals. Cl-Csalkyl radicals are preferred.
Halogen is fluorine, chlorine, bromine or iodine. Fluorine, chlorine and bromine are preferred.
Haloalkyl indicates alkyl radicals, according to the respective scope of definition given, that are completely or partially substituted by identical or different halogen atoms, such as, for example, trifluoro-methyl 7 difluoromethyl, 1,1,2,2-tetrafluoroethyl, 2-chloroethyl, penta-fluoroethyl, chlorodifluoromethyl, dichloromethyl, chlorofluoromethyl, 1,1-dichloro-2,2,2-trifluoroethyl, l,l-dichloroethyl or heptafluoro-propyl.
There may be mentioned as Cl-C4alkoxycarbonyl radicals, inter alia, methoxycarbonyl, ethoxycarbonyl and the isomeric propoxycarbonyls and busoxycarbonyls.
_ 3 _ 1 3 1 ~ ~ ~ 6 Alkoxy within the scope of the respective definition of the isomeric alkoxy radicals is especially methoxy, ethoxy, (i)-propoxy, (n)-propoxy, (i)-butoxy, (t)-butoxy, (n)-butoxy and (sec.)-butoxy.
Haloalkoxy and haloalkylthio within the scope of the respective defini-tion are isomeric alkyl radicals that are mono- or poly-substituted by identical or differenc halogen atoms, such as, for example, trifluoro-methoxy, 2,2,2-trifluoroethoxy, trifluoromethylthio, 2,2,3,3,3-penta-fluoropropoxy or 1,1,2,2-tetrafluoroethoxy, difluoromethoxy or 2-chloro-ethoxy.
There may be mentioned as alkoxyalkyl radicals, inter alia: 2-ethoxy-ethyl, 2-methoxyethyl, 3-methoxypropyl, 2-methoxy-1-methylethyl and methoxymethyl.
The group C1-C4alkyl-S(O) - represents the respective alkylthio, alkyl-sulfinyl and alkylsulfonyl radicals. Methylthio, methylsulfinyl and methylsulfonyl may be mentioned as being especially preferred.
Of the groups PO~O(C1-C4)-alkyl]2, PO(OCH3)2 and PO(OC2Hs)2 are pre-ferred.
Di-(C1-C~alkylamino)carbonyl includes radicals substituted either by identical or different C1-C4alkyl radicals.
Haloalkylthio is especially fluoromethylthio, difluoromethylthio, trifluoromethylthio, 1,1,2,2-tetrafluoroethylthio, chlorodifluoromethyl-thio and dichlorofluoromethylthio.
In the further substituents that are composed of several base elements,the sub-elements may be freely selected within the scope of the definition and have the above meaning.
Attention is drawn to compounds of formula I unsubstituted in the 4-position of the phenyl ring _ 4 _ 13~4~4~
R ~0_.~ ~N--~
R2 ~R3 ~ ~4 (I), in which Rl is halogen; cyano; C1-C~alkoxy; Cl-C4haloalkoxy; C1-C4alkyl-S(O) -;
Cl-C4alkyl; Cl-C4haloalkyl; Cl-C4alkoxycarbonyl; di-(Cl-C4alkylamino)-carbonyl; mono-(Cl-C4alkylamino)carbonyl; carbamoyl; Cl-C4haloalkyl-S(O)n~; or -PO[O-(Cl-C4)alkyl]z;
R2 is hydrogen; halogen, cyano; nitro; Cl-C4alkyl; Cl-C4alkoxy; Cl-C4-haloalkyl; Cl-C4alkoxycarbonyl; or Cl-C4alkylcarbonyl;
R3 is hydrogen; halogen; or Cl-C4alkyl, and n and the radicals R4 and Rs are as defined hereinbefore.
Preferred sub-groups are formed by those compounds of formula I in which a) the radical Rl is bonded at the 2-position of the phenyl ring, b) the radical R2 is bonded at the 3-position of the phenyl ring, c) the radical R; is bonded at the 5-position of the phenyl ring, d) the radical R2 is bonded at the ~-position of the phenyl ring, e) the radical Rl is bonded at the 3-position of the phenyl ring, f) the radical R3 is bonded at the 3-position of the phenyl ring, g) the radical R2 is bonded at the 5-position of the phenyl ring.
Attention is drawn to the following combinations of sub-groups: a+b, a+g, a~d, e+g, e+d, atb+c, a+f+d, a+c+d and e+c+d, the radical R3 being hydrogen in combinations of only two sub-groups.
Attention is drawn especially to compounds of formula I in which Rl is halogen; cyano; Cl-C3alkoxy; Cl-C2haloalkoxy; methyl-S(O) -;
Cl-C3alkyl; Cl-C2haloalkyl; C1-C4alkoxycarbonyl; carbamoyl; difluoro-methylthio or -PO[O-(Cl-C2)-alkyl]2;
R2 is hydrogen; fluorine; chlorine; bromine; cyano; nitro; C~-C3alkyl;
Cl-C2haloalkyl; or C1-C3alkoxycarbonyl;
R3 is hydrogen; chlorine; fluorine; or Cl-C3alkyl;
~ s - -R4 is C1-Csalkyl C1-C4alkoxy, C1-C4alkylthio; cyclopropyl: phenyl;
furan-2-yl; thiophen-2-yl; cyano; C1-C3haloalkoxy; C1-C2alkoxy-C1-C~-alkyl; C1-C2alkoxy-C1-C2alkoxy; methylsulfinyl; methy~sulfonyl; or C2-C3haloalkenyl;
Rs is C1-C3alkyl; fluorine; chlorine; bromine; C1-C3haloalkyl; or C1-C3haloalkoxy; and n is 0, 1 or 2.
Especially preferred are compounds of formula I in which Rl is halogen; methyl; trifluoromethyl; trifluoromethoxy; difluoro-methoxy; C1-C3alkoxy; methyl~hio; methylsulfinyl; methylsulfonyl; cyano;
C1-C4alkoxycarbonyl; carbamoyl; difluoromethylthio; or -PO(O-CzHs)2;
R2 is hydrogen; fluorine; chlorine; bromine; nitro; ethyl; methyl;
trifluoromethyl; methoxy; or C1-C3alkoxycarbonyl;
R3 is hydrogen; chlorine; or methyl;
R4 is C1-Csalkyl; C1-C4alkoxy; C1-C4alkylthio; cyclopropyl; phenyl;
furan-2-yl; thiophen-2-yl; cyano; 1,1,2,2-tetrafluoroethoxy; 2-chloro-ethoxy; methoxymethyl; 2-methoxy-ethoxy; methylsulfinyl; methylsulfonyl;
or 2,2-dichlorovinyl;
Rs is C1-C3alkyl; fluorine; chlorine; bromine; difluoromethoxy; tri-fluoromethyl; pentafluoroethyl; chlorodifluoromethyl; difluoromethyl;
dichloromethyl; chlorofluoromethyl; l,l-dichloro-2,2,2-trifluoroethyl;
l,l-dichloroethyl; or heptafluoropropyl.
The invention relates especially to compounds of formula I in which R1 is fluorine; chlorine; bromine; iodine; trifluoromethyl; methyl;
difluoromethoxy; methoxy; methylthio; PO(OC2Hs)z; methoxycarbonyl;
methylsulfonyl; or cyano;
R2 is hydrogen; fluorine; chlorine; bromine; nitro; methyl; ethyl;
trifluoromethyl; or methoxycarbonyl;
R3 is hydrogen; or methyl;
R4 is C~-Csalkyl; butylthio; thiophen-2-yl; furan 2-yl; C1-C4alkoxy;
methylthio; methylsulfinyl; methylsulfonyl; or cyclopropyl; and Rs is methyl; chlorine; dichloromethyl; pentafluoroethyl; difluoromethyl;
chlorofluoromethyl; trifluoromethyl; or chlorodifluoromethyl.
131~4~
Attention is drawn furthermore to compounds of formula I in which a) Rl is fluorine, chlorine, bromine, trifluoromethyl, cyano, difluoro-methoxy, trifluoromethoxy, methyl or methoxy. each bonded in the 2-position of the phenyl ring, R2 and R3 are each hydrogen, R4 is methyl, furan-2-yl or cyclopropyl, and Rs is chlorine, methyl, trifluoromethyl or chlorodifluoromethyl, or b) Rl is fluorine, chlorine, bromine, trifluoromethyl, difluoromethoxy, trifluoromethoxy, cyano or methoxy, each bonded in the 2-position of the phenyl ring, R2 is fluorine or chlorine, each bonded in the 3-, 5- or 6-position of the phenyl ring, R4 is methyl, furan-2-yl or cyclopropyl, and Rs is chlorine, methyl, trifluoromethyl or chlorodifluoromethyl, or c) R~ is chlorine bonded in the 3-position of the phenyl ring, R2 is chlorine bonded in the 5-position of the phenyl ring, R4 is methyl, furan-2-yl or cyclopropyl, and Rs is chlorine, methyl, trifluoromethyl or chlorodifluoromethyl.
The following compounds may be mentioned specifically on account of their herbicidal activity:
N-(2-bromophenyl)-N-~4-chloro-6-methyl-pyrimidin-2-yl)-urea, N-(4-methyl-6-trifluoromethyl-pyrimidin~2-yl)-N-(2-trifluoromethyl-phenyl)-urea, N-(2,3-dichlorophenyl)-N-(4-methyl-6-trifluoromethylpyrimidin-2-yl)-urea, N-(2,5-dichlorophenyl)-N-(4,6-dimethyl-pyrimidin-2-yl)-urea, N-(4-chloro-6-methyl-pyrimidin-2-yl)-N-(2,5-dichlorophenyl)-urea, N-(2,5-dichlorophenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-[4-(chlorodifluoromethyl)-6-methyl-pyrimidin-2-yl]-N-(2,5-dichloro-phenyl)-urea, N-(4-chloro-6-methyl-pyrimidin-2-yl)-N-(2,6-dichlorophenyl)-urea, N-(2,6-dichlorophenyl~-N-(4-methyl-6-trifiuoromethyl-pyrimidin-2-yl)-urea, _ 7 _ ~ 3 ~
N-(4-cyclopropyl-6-trifluoromethyl-pyrimidin-2-yl)-N-(2,6-dichloro-phenyl)-uren, N-(3,5-dichlorophenyl)-N-(4-me~hyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(5-chloro-2-methyl-pllenyl)-N-(4-chloro-6-methyl-pyrimidin-2-yl)-urea, N-(5-chloro-2-methoxyphenyl)-N-~4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2-iodophenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2-chloro-6-methylphenyl)-N-(4-chloro-6-methyl-pyrimidin-2-yl)-urea, N-(3-chloro-2-methoxypilenyl)-N-(4-metllyl-6-trifluoromethylpyrimidin-2--yl)-urea, N-(2,6-difluorophenyl)-N-(4-methyl-6-trif`l~oromethylpyrimidin-2-yl)-urea, N-(2,5-difluorophenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2-cyanophenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-Z-yl)-urea N-(2-bromophenyl)-N-(4-cyclopropyl-6-trifluoromethyl-pyrimidin-2-yl~-urea, N-(4-isopropyl-6-trifluoromethyl-pyrimidin-2-yl)~N~~2-trifluoromethyl-phenyl)-urea, N-(2-fluorophenyl)-N-(4-methyl-6-trifluorom~thyl-pyrimid~n-2-yl)-urea, N-(2-fluorophenyl)-N-(4-isopropyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2,5-dlchlorophenyl)-N-(4-ethyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2,6-dichlorophenyl)-N-(4-difluoromethyl-6-methyl-pyrimidin-2-yl)-urea, N-(2,6-dichlorophenyl)-N-(4-methylthio-6-trifluoromethyl-pyrimidin-2-yl~-urea, N-(2,6-dichloro-3-methyl)-N-(4-methyl-6-trifluorornethyl-pyrimidin-2-yl)-urea, N-(2,6-dichloro-3-methylphenyl)-N-(4-isopropyl-6-.tri~luoromethylpyrimidin--2-yl)-urea, N-(2-chloro-6-trifluoromethyl-phenyl)-N-(4-methyl--6-trifluororr~ethyl-pyrlmidin-2-yl)-urea, N-(2-chloro-6-methyl-pllenyl)-N-(4-mcthyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2-methyl-6-trifluoromethyl-phenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(5-chloro-2-difluoromethoxy-phenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, ~,~
13~4~
- 8 - 214~9-7698 N-(2-methylthio-phenyl)-N-(4-me~hyl-6-trifluoromethyl-pyrimidln-2-yl)-urea, N-(4-cyclopropyl-6-trifluoromethyl-pyrimidin-2-yl)-N-(2,5-difluoro--phenyl)-urea, N-(2,6-difluorophenyl)-N-(4-ethyl-6-trifluoromethyl-pyrimidin-2-yl) urea, N-(6-chloro-2-fluoro-phenyl~-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)urea, N-(6-chloro-2-fluoro-phenyl)-N-(4-cyclopropyl-6-trifluoromethyl-pyrimi-din--2-yl )-urea, N-(2-difluoromethoxyphenyl)-N-(4-mathyl-6-tr1fluoromethyl-pyrlmidin-2-yl)urea, N-(6-chloro-2-methoxycarbonyl-phenyl)-N-(4-methyl-6-trlfluoromathyl-pyrimidin-2-yl)-urea, N-(2-bromophenyl)-N-~4-(furan-2-yl)-6-trlfluoromethyl-pyrimldin-2-yl]-urea, N-(2-chloro-6-methyl-phenyl)-N-(4-methoxymethyl-6-trifluoromethyl-pyrimidin-2-yl)-urea and N-(2-difluoromethoxy-6 methyl-phenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea.
The compounds of formula I can be prepared by a) reacting an aniline of formula II with phosgene to form a carbamoyl chloride of formula III and reacting this wlth N}13 ln a second step NII~ / COClz (II) (III) - ~ICl III + NH3 ~ I
to form a urea of formula I, or g b) r0acting an aniline of formula II with a halosulfonyl isocyanate IX to form a halosulfonylurea of formula IV
~ ~ (IX) ~ l3 ~ ~s (II) (IV) oz_y - HY
IV + 2HzO
- sO4H2 and hydrolysing this in a second step, or directly, to a compound of formula I, Y being a group that can be removed under the reaction conditions, such as halogen, preferably chlorine.
The reactions II --~ III, III ) I and IV ) I, which proceed with the remGval of hydrogen halide or the elimination of HY, are preferably carried out using acid-binding agents (bases).
Suitable acid-binding agents are organic or inorganic bases, for sxample tertiary amines, such as trialkylamines (trimethylamine, triethylamine, tripropylamine etc.), pyridines (pyridine, 4-dimethylaminopyridine, 4-pyrrolidylaminopyridine etc.), and alcoholates, such as, for example, potassium-tert.-butoxide, sodium methoxide or sodium ethoxide. The afore-mentioned reactions, including also the reaction VII ) II (which will be described hereinafter), can also be carried out with bases under phase transfer conditions according to processes that are known per se.
(Lit. Dehmlow & Dehmlow, Phase Transfer Catalysis Verlag Chemie, Wein-heim, 1983).
It is possible, in principle, for one or more solvents or diluents thatare inert towards the reaction to be present in process variants a) and b), should there be no specific details given. Suitable solvents or diluents are, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, ~31~6 carbon tetrachloride, tetrachloroethylene; ethers and ethereal compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert.-butyl-methyl ether etc.), anisole, dioxan, tetrahydrofuran; nitriles, such as acetonitrile, propionitrile; N,N-dialkylated amides, such as dimethyl-formamide; dimethyl sulfoxide; ketones, such as acetone, diethyl ketone, methyl ethyl ketone; and mixtures of such solvents with each other.
The anilines of formula II, like the carbamoyl chlorides of formula IIIand the ureas of formula IV, are valuable intermediates. The carbamoyl chlorides III and the ureas IV are novel, whereas some of the compounds of formula II are already known from DD-B-151 404.
The invention accordingly relates also to the novel compounds of formula II
~1 ~Rs ~- N--H--~ ~--NH~-~
R~ ~3 ~4 in which R1 is ha.logen; cyano; C1-C4alkoxy; Cl-C4haloalkoxy; C1-C4alkyl-S(O) -;
Cl-C4alkyl; Cl-C4haloalkyl; Cl-C4-alkoxycarbonyl; di-(Cl-C4alkylamino)-carbonyl; mono-(C1-C4alkylamino)carbonyl; carbamoyl; Cl-C4haloalkyl-S(O) -; or -PO[O-(C1-C4)-alkyl]z;
R2 is hydrogen; halogen; cyano; nitro; Cl-C4alkyl; C1-C4alkoxy; C1-C4-haloalkyl; C1-C4alkoxycarbonyl; or C1-C4alkylcarbonyl;
R3 is hydrogen; halogen; or Cl-C4alkyl;
R4 is C1-C6alkyl; C1-C4alkoxy; Cl-C4alkyl-S(O) -; Cl-C4haloalkyl;
Cl-C4haloalkoxy; phenyl that is unsubstituted or is substituted by up to three identical or different substituents from halogen, Cl-C4alkyl, C1-C4haloalkyl and Cl-C4alkoxy; 2-furanyl; 2-thienyl; 3-thienyl; C3-C6-cycloalkyl that is unsubstituted or is substituted by up to three identical or different C1-C4alkyl radicals; cyano; C2-C4haloalkenyl;
Cl-C4alkoxy-Cl-C4alkyl; Cl-C4alkoxy-Cl-C4alkoxy; or halo-Cl-C4alkylthio;
Rs is hydrogen; Cl-C3alkyl; Cl-C3haloalkyl; halogen; or Cl-C3haloalkoxy;
and n is 0, 1 or 2, 1314~4~
with the proviso that a) when one of the radicals R2 and R3 is nitro, that substituent may not be bonded in the 2- or 6-position of the phenyl ring and, when the radicals R4 and Rs are methyl, Rl is not chlorine, methoxy, ethoxy, fluorine, iodine, methyl or bromine and that, further-more, the following individual compounds are not included: N-[(4,6-bis-trifluoromethyl)-pyrimidin-2-yl]-2,6-dichloroaniline and N-(4-chloro-6-methylpyrimidin-2-yl)-3-chloroaniline.
The invention also relates to novel N,N-disubstituted carbamoyl chlorides of formula III
~ ~ ~N_-/RS
R2 ~R; ~ ~4 (III), in which the radicals Rl to Rs are as defined for formula I, and to novel ureas of formula IV
~ ~N--/Rs (IV), H
in which the radicals Rl to Rs are as defined for formula I, and Y is halogen, Cl-C4alkoxy or phenoxy.
The compounds of formulae III and IV are intermediates of processes a) and b) and can be prepared, as described, from the corresponding anilines of formula II.
The novel anilines of formula II can be prepared analogously to processes known from the literature, for example by aa) reacting guanidines of formula V with 1,3-dicarbonyl compounds of formula VI
- 12 - 1 3~
/ /R4 ) H~ NH-~
2 ~.~. \NH2 O=C~ - 2H20 R2 ~R3 ~4 (V) (VI) (II) the condensation reaction if desired being carried out in the presence of water-binding agents (Lit.: D.J. Brown in "The Chemistry of Heterocyclic Compounds" Vol. VI 1962, Interscience Publ. New York; J. Am. Chem.
Soc. 69 18~9 (1947); J. Am. Chem. Soc. 72 2940 (1950); J. Org. Chem. 29 1439 (1964) or J. Org. Chem. 29 1883 (1964), Houben-Weyl "Methoden d.
org. Chemie" Vol. VIII p. 180 ff), or bb) reacting an aniline of formula VII with a pyrimidine of formula VIII
under the action of a base, H-~ ~--NH2 + X ~ / N \N- /
VII VIII II
in which formulae the radicals Rl to Rs are as defined hereinbefore and X
is a nucleofugal group, such as halogen, C1-C4alkylsulfonyl or phenyl-sulfonyl.
Suitable bases for carrying out this process are, inter alia, potassiumtert.-butoxide, NazCO3, KzCO3 or NaH.
These processes are generally available for the synthesis of compounds of formula II and are applicable to all educts of formulae V, VI, VII
and VIII (in which the radicals Rl to Rs are as defined within the scope of the formula of compounds I).
The invention furthermore relates to herbicidal and plant growth-regulat-ing compositions containing a compound of formula I together with suitable adjuvan~s and/or carriers.
- 13 - 1 3 1 ~ 5 4 6 The active ingredients of the formula I are in general used successfully at application rates of from 0.005 to 5 kg/ha, especially from 0.1 to
3 kg/ha. The dosage necessary to achieve the desired effect can be ascertained by tests. It is dependent upon the nature of the action, the stage of development of the crop plants and of the weed and on the application (locus, time, method), and may vary within wide ranges, subject to these parameters.
At lower rates of application the compounds of formula I are distin-guished by growth-inhibiting and herbicidal properties, which make them excellent for use in crops of useful plants, especially cereals, cotton, soybeans, sunflowers, rape, maize and rice.
The compounds of formula I also have plant growth-regulating properties.
The growth of both monocotyledons and dicotyledons is affected. Inhibi-tion of the vegetative growth makes it possible with many crop plants for the crop to be more densely planted, so that it is possible to achieve a higher yield per unit area of soil. Another mechanism of the increase in yield when using growth regulators is based on the fact that the nutrients are used to the greater advantage of the formation of the flowers and fruit whilst the vegetative growth is restricted. At higher rates of application, weeds and grasses are damaged in their development to such an extent that they die.
In an especially advantageous manner, the growth-regulating compounds of formula I can be used for regulating the growth of intersown plants in maize crops.
Plants that are suitable in principle for intersowing in maize crops are those that cover the soil between the individual maize plants and thus, especially, counteract soil erosion in maize crops. Suitable plants for intersowing are, inter alia, rape, trefoil, grasses or leguminosae.
At suitable rates of application, the compounds of formula I inhibit the new growth of grasses. This makes it possible to reduce the number of cuts necessary, or to increase the intervals between cutting, in grassed areas (parks, gardens, etc.). In an especially advantageous manner, it is - 14 - ~ 6 possible to use granulate formulations of the active ingredients of formula I for this purpose. ~ither the granulate may contain the active ingredient on its own together with the customary ~djuvants and carriers, or the active ingredient is formulated as a granulate together with a mineral fertiliser and/or, if desired, other active ingredients for controlling moss or other plant growth that is undesirable in grassed areas. Application in the form of a strewing granulate (for direct soil application) makes it possible, using equipment customary for maintaining grassed areas, to inhibit the new growth of grasses for a relatively long period. The granulate can be prepared in a manner known per se, and it preferably has a granule size of 0.1 to 2.0 mm, especially 0.25 to 1.0 mm.
The invention relates also to herbicidal and plant growth-regulating compositions that contain an active ingredient of formula I, and to methods of controlling weeds pre-emergence and post-emergence and of influencing the growth of monocotyledonous and dicotyledonous plants, especially grasses, tropical cover crops and suckers.
The compounds of formula I are used in unmodified form or, preferably, in the form of compositions together with the adjuvants conventionally employed in the art of formulation, and are therefore advantageously formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g.
polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The active substances of formula I can thus also be applied to mineral fertilisers (dressing). The composition so obtainable is advantageously suitable as a growth regulator for grasses.
The formulations, i.e. the compositions, preparations or mixtures containing the compound (active ingredient) of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, 131~6 e.g. by homogeneously mixing andlor grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclo-hexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil;
or water.
The solid carriers used e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
Depending on the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties.
The term "surfactants" will also be understood as comprising mixtures of surfactants.
Both so-called water-soluble soaps and also water-soluble synthetic surface-active compounds are suitable anionic surfactants.
- 16 - 1 ~ ~4 5 ~
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids ~Clo-C2z)~ e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C8-C22alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphtha-lenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.
Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide, or phospholipids.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 10 glycol ether groups and 8 to 20 carbon atoms in the (aliphaticS hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
- 17 13~4~6 Further suitable non-ionic surfactants are the water-soluble adducts ofpolyethylene oxide with polypropylene glycol, ethylenediaminopoly-propylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 e~chylene glycol units per propylene glycol unit.
Examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylenetpolyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxy-polyethoxyethanol.
Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one Cg-C22alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-~ower alkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
Agglutinants are especially those adjuvants that in the case of granula-tion cause the carrier material, the adjuvants and the active ingredients to stick together, such as gum arabic or carboxymethylcellulose.
Surfactants customary in the art of formulation are described, inter alia, in the following publications:
"1907 International Mc Cutcheon's Emulsifiers and Detergents", Glen Rock, N.J., USA.
Dr. Helmut Stache "Tensid Taschenbuch"
Carl Hanser Varlag, Munich/Vienna 1981.
The preparations usually contain 0.1 to 95 %, preferably 0.1 to 80 %, of a compound of formula I, 1 to 99.9 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 25 %, of a surfactant.
131~46 Preferred formulations are composed especially as follows (% = percent by weight).
Emulsifiable concentrates:
a compound of formula I:1 to 20 %, preferably 5 to 10 ~/0 surfactant:5 to 30 %, preferably 10 to 20 %
liquid carrier:50 to 94 %, preferably 70 to 85 %.
Dustc:
a compound of formula I:0.1 to 10 %, preferably 0.1 to 1 %
solid carrier:99.9 to 90 %, preferably 99.9 to 99 %.
Suspension concentrates:
a compound of formula I:5 to 75 %, preferably 10 to 50 %
water: 94 to 25 %, preferably 90 to 30 %
surfactant:1 to 40 %, preferably 2 to 30 %.
~ettable powders:
a compound of formula I:0.5 to 90 %, preferably 1 to 80 %
surfactant:0.5 to 20 %, preferably 1 to 15 %
solid carrier:5 to 95 %, preferably 15 to 90 %.
Granulates:
a compound of formula I:0.5 to 30 %, preferably 3 to 15 %
solid carrier:99.5 to 70 %, preferably 97 to ô5 %.
Strewing granulate:
a compound of formula I:0.01 to 30 %, preferably 0.05 to 15 %
agglutinant: 0.05 to 5 %, preferably 0.1 to 2 %
- 19 - 1 31 ~ ~ 6 surfactant: 0.5 to 20 %, preferably 1 to 15 %
solid carrier: 99.44 to 45 %, preferably 95 to 65 %
Whereas commercial products will preferably be formulated as concen-trates, the end user will normally employ dilute formulations. The formulations can be diluted to a concentration of as low as 0.001 %
active ingredient. The rates of application are normally from 0.005 to 5 kg active ingredient/ha.
The compositions may also contain further additives such as stabilisers, antifoams, viscosity regulators, binders, tackifiers and also ferti-lisers, or other active ingredients for obtaining special effects.
Preparation Examples:
The (uncorrected) melting points in the following Preparation Examples are in C.
P. 1. Compounds of formula I
P. 1.1. N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-N-(2-trifluoro-methylphenyl)-urea At 3C, 3.6 g (0.026 mole) of chlorosulfonyl isocyanate are added to a solution of 6.4 g (0.02 mole) of N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-2-trifluoromethylaniline in 100 ml of ethyl acetate. After stirring the batch for 2 hours at 3C, 100 ml of ethyl acetate and 50 ml of ice-water are added. The aqueous phase is separated off, and the organic phase is washed with sodium chloride solution, dried with sodium sulfate and concentrated by evaporation in a rotary evaporator. The crystals remaining are triturated with hexane, filtered off and dried in vacuo at 40C.
131~5~6 6.1 g (83.8 %) of the title compound of formula N--~
are isolated in the form of crystals having a melting point of 150-153DC
(Comp. No. 1.020).
P. 1.2. N-(2,5-dichlorophenyl)-N-(4,6-dimethylpyrimidin-2-yl)-urea
At lower rates of application the compounds of formula I are distin-guished by growth-inhibiting and herbicidal properties, which make them excellent for use in crops of useful plants, especially cereals, cotton, soybeans, sunflowers, rape, maize and rice.
The compounds of formula I also have plant growth-regulating properties.
The growth of both monocotyledons and dicotyledons is affected. Inhibi-tion of the vegetative growth makes it possible with many crop plants for the crop to be more densely planted, so that it is possible to achieve a higher yield per unit area of soil. Another mechanism of the increase in yield when using growth regulators is based on the fact that the nutrients are used to the greater advantage of the formation of the flowers and fruit whilst the vegetative growth is restricted. At higher rates of application, weeds and grasses are damaged in their development to such an extent that they die.
In an especially advantageous manner, the growth-regulating compounds of formula I can be used for regulating the growth of intersown plants in maize crops.
Plants that are suitable in principle for intersowing in maize crops are those that cover the soil between the individual maize plants and thus, especially, counteract soil erosion in maize crops. Suitable plants for intersowing are, inter alia, rape, trefoil, grasses or leguminosae.
At suitable rates of application, the compounds of formula I inhibit the new growth of grasses. This makes it possible to reduce the number of cuts necessary, or to increase the intervals between cutting, in grassed areas (parks, gardens, etc.). In an especially advantageous manner, it is - 14 - ~ 6 possible to use granulate formulations of the active ingredients of formula I for this purpose. ~ither the granulate may contain the active ingredient on its own together with the customary ~djuvants and carriers, or the active ingredient is formulated as a granulate together with a mineral fertiliser and/or, if desired, other active ingredients for controlling moss or other plant growth that is undesirable in grassed areas. Application in the form of a strewing granulate (for direct soil application) makes it possible, using equipment customary for maintaining grassed areas, to inhibit the new growth of grasses for a relatively long period. The granulate can be prepared in a manner known per se, and it preferably has a granule size of 0.1 to 2.0 mm, especially 0.25 to 1.0 mm.
The invention relates also to herbicidal and plant growth-regulating compositions that contain an active ingredient of formula I, and to methods of controlling weeds pre-emergence and post-emergence and of influencing the growth of monocotyledonous and dicotyledonous plants, especially grasses, tropical cover crops and suckers.
The compounds of formula I are used in unmodified form or, preferably, in the form of compositions together with the adjuvants conventionally employed in the art of formulation, and are therefore advantageously formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g.
polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The active substances of formula I can thus also be applied to mineral fertilisers (dressing). The composition so obtainable is advantageously suitable as a growth regulator for grasses.
The formulations, i.e. the compositions, preparations or mixtures containing the compound (active ingredient) of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, 131~6 e.g. by homogeneously mixing andlor grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclo-hexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil;
or water.
The solid carriers used e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
Depending on the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties.
The term "surfactants" will also be understood as comprising mixtures of surfactants.
Both so-called water-soluble soaps and also water-soluble synthetic surface-active compounds are suitable anionic surfactants.
- 16 - 1 ~ ~4 5 ~
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids ~Clo-C2z)~ e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C8-C22alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphtha-lenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.
Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide, or phospholipids.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 10 glycol ether groups and 8 to 20 carbon atoms in the (aliphaticS hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
- 17 13~4~6 Further suitable non-ionic surfactants are the water-soluble adducts ofpolyethylene oxide with polypropylene glycol, ethylenediaminopoly-propylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 e~chylene glycol units per propylene glycol unit.
Examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylenetpolyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxy-polyethoxyethanol.
Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one Cg-C22alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-~ower alkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
Agglutinants are especially those adjuvants that in the case of granula-tion cause the carrier material, the adjuvants and the active ingredients to stick together, such as gum arabic or carboxymethylcellulose.
Surfactants customary in the art of formulation are described, inter alia, in the following publications:
"1907 International Mc Cutcheon's Emulsifiers and Detergents", Glen Rock, N.J., USA.
Dr. Helmut Stache "Tensid Taschenbuch"
Carl Hanser Varlag, Munich/Vienna 1981.
The preparations usually contain 0.1 to 95 %, preferably 0.1 to 80 %, of a compound of formula I, 1 to 99.9 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 25 %, of a surfactant.
131~46 Preferred formulations are composed especially as follows (% = percent by weight).
Emulsifiable concentrates:
a compound of formula I:1 to 20 %, preferably 5 to 10 ~/0 surfactant:5 to 30 %, preferably 10 to 20 %
liquid carrier:50 to 94 %, preferably 70 to 85 %.
Dustc:
a compound of formula I:0.1 to 10 %, preferably 0.1 to 1 %
solid carrier:99.9 to 90 %, preferably 99.9 to 99 %.
Suspension concentrates:
a compound of formula I:5 to 75 %, preferably 10 to 50 %
water: 94 to 25 %, preferably 90 to 30 %
surfactant:1 to 40 %, preferably 2 to 30 %.
~ettable powders:
a compound of formula I:0.5 to 90 %, preferably 1 to 80 %
surfactant:0.5 to 20 %, preferably 1 to 15 %
solid carrier:5 to 95 %, preferably 15 to 90 %.
Granulates:
a compound of formula I:0.5 to 30 %, preferably 3 to 15 %
solid carrier:99.5 to 70 %, preferably 97 to ô5 %.
Strewing granulate:
a compound of formula I:0.01 to 30 %, preferably 0.05 to 15 %
agglutinant: 0.05 to 5 %, preferably 0.1 to 2 %
- 19 - 1 31 ~ ~ 6 surfactant: 0.5 to 20 %, preferably 1 to 15 %
solid carrier: 99.44 to 45 %, preferably 95 to 65 %
Whereas commercial products will preferably be formulated as concen-trates, the end user will normally employ dilute formulations. The formulations can be diluted to a concentration of as low as 0.001 %
active ingredient. The rates of application are normally from 0.005 to 5 kg active ingredient/ha.
The compositions may also contain further additives such as stabilisers, antifoams, viscosity regulators, binders, tackifiers and also ferti-lisers, or other active ingredients for obtaining special effects.
Preparation Examples:
The (uncorrected) melting points in the following Preparation Examples are in C.
P. 1. Compounds of formula I
P. 1.1. N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-N-(2-trifluoro-methylphenyl)-urea At 3C, 3.6 g (0.026 mole) of chlorosulfonyl isocyanate are added to a solution of 6.4 g (0.02 mole) of N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-2-trifluoromethylaniline in 100 ml of ethyl acetate. After stirring the batch for 2 hours at 3C, 100 ml of ethyl acetate and 50 ml of ice-water are added. The aqueous phase is separated off, and the organic phase is washed with sodium chloride solution, dried with sodium sulfate and concentrated by evaporation in a rotary evaporator. The crystals remaining are triturated with hexane, filtered off and dried in vacuo at 40C.
131~5~6 6.1 g (83.8 %) of the title compound of formula N--~
are isolated in the form of crystals having a melting point of 150-153DC
(Comp. No. 1.020).
P. 1.2. N-(2,5-dichlorophenyl)-N-(4,6-dimethylpyrimidin-2-yl)-urea
4.0 g (0.012 mole) of N-chlorocarbonyl-N-(4,6-dimethylpyrimidin-2-yl)-2,5-dichloroaniline are dissolved in 50 ml of chloroform. An excess of ammonia gas is introduced into the solution. When the exothermic reaction has subsided, the reaction mixture is washed twice with water, dried with magnesium sulfate and concentrated by evaporation.
Recrystallisation from ethanol yields 2.4 g (64.9 %) of the title compound of formula /Cl N- / 3 \.=./ ~ ~=./
C~ ICO CH3 ~H2 in the form of crystals having a melting point of 153C (decomp.) (Comp.
No. 1.050).
The compounds of Table I can be obtained analogously to the P.1 Prepara-tion Examples.
~l- 1314~S
Table I
Compounds of formula ~1 N_./R5 H- ~ /- ~ \N-./ I
R2 ~R3 ~= \R4 Hz Comp.No. Rl R2 R3 R4 Rs Physical data 1.001 2-Cl H H CH3 CH3 from 147C decomp.
1.002 2-Cl H H CH3 OCHFz 1.003 2-Cl H H CH3 Cl 1.004 2-Cl H H CH3 CF3 1.005 2-Cl H H CH3 CFzCF3 1.006 2-Cl H H CHzGH3 CF3 1.007 2-Cl H H CH3 CF2Cl 1.008 2-Cl H H CH3 CHF2 1.009 2-Br H H CH3 Cl m.p. 149-150C
1.010 2-Br H H OCH3 CF3 1.011 2-Br H H CH3 CF3 1.012 2-Br H H SCH3 CF3 1.013 2-Br H H CHzCH3 CF3 1.014 2-Br H H CH3 CHCl2 1.015 2-Br H H CH3 CHFCl 1.016 2-Br H H Cyclo- CF3 m.p. 183-184C
propyl 1.017 2-CF3 H H Phenyl CF3 1.018 2-CF3 H H 2-Furyl CF3 1.019 2-CF3 H H CH3 Cl 1.020 2-CF3 H H CH3 CF3 m.p. 150-153C
1.021 2-CF3 H H CH3 CH3 m.p. 145-146DC.
1.022 2-CF3 H H CH2CH3 CF3 1.023 2-CF3 H H CH(CH3)2 CF3 m.p. 137-138C
1.024 2-CF3 H H (n)C3H7 CF3 m.p. 153-154C
1.025 2-CF3 H H OCH3 CF3 1.026 2-CF3 H H OCzHs CF3 1.027 2-CF3 H H _ SCH3 CF3 1.028 2-CF3 H H ~CH(CH3)z CF3 1.029 2-CF3 H H ¦CH3 CF2CF3 - 22 - ~ 3 1 ~ ~ ~ 6 Table 1 (continued) -Comp.No. Rl R2 R3 R4 l Rs Physical data 1.030 2-CF3 H H CH3 CHFCl 1.031 2-J H H CH3 Cl 1.032 2-J H H CH3 CF3 m.p. 168-160C
1.033 2-J H H CH2CH3 CF3 1.034 2-J H H CH3 CF2Cl 1.035 2-F H H CH3 CH3 from 159C decomp.
1.036 2-F H H CH3 Cl 1.037 2-F }I H CH3 CF3 from 169C decomp.
1.038 2-F H H CH(CH3)z CF3 m.p. 144-146C
1.039 2-F H H Cl CF3 1.040 2-F H H OC2Hs CF3 1.041 2-Cl 3-Cl H CH3 Cl m.p. 143-144C
1.042 2-Cl 3-Cl H CH3 CF3 m.p. 139-140C
1.043 2-Cl 3-Cl H OCH3 CF3 1.044 2-Cl 3-Cl H OC4Hg(n) CF3 1.045 2-Cl 3-Cl H SCzHs CF3 1.046 2-Cl 3-Cl H Phenyl CF3 1.047 2-Cl 3-Cl H CH3 CFzCl 1.048 2-Cl 3-Cl H CH3 CHFCl 1.049 2-Cl 3-Cl H CH3 CH3 from 163C decomp.
1.050 2-Cl 5-Cl H CH3 CH3 from 153C decomp.
1.051 2-Cl 5-Cl H CH3 oCHF2 1.052 2-Cl 5-Cl H CH3 Cl m.p. 123-125C
1.053 2-Cl 5-Cl H OCH3 CH3 1.054 2-Cl 5-Cl H CH3 Br 1.055 2-Cl 5-Cl H CH3 CF3 m.p. 150-151C
1.056 2-Cl 5-Cl H CH2CH3 CF3 m.p. 149-150C
1.057 2-Cl 5-Cl H C3H7(n) CF3 m.p. 148-149C
1.058 2-Cl 5-Cl H C3H7(i) CF3 m.p. 156-157C
1.059 2-Cl 5-Cl H Cyclo- CF3 m.p. 174-175C
propyl 1.060 2-Cl 5-Cl H Phenyl CF3 1.061 2-Cl 5-Cl H ¦, ~-Thienyl CF3 m.p. 177-178C
1.062 2-Cl 5-Cl H 2-Furyl CF3 m.p. 168-169C
1.063 2-Cl 5-Cl H CH3 CF2CF3 m.p. 157-158C
1.064 2-Cl 5-Cl H CH3 CFzCl m.p. 178-179C
1.065 2-Cl 5-Cl H CH3 CHF2 m.p. 159-160C
1.066 2-Cl 5-Cl H CH3 CHClF m.p. 153-154C
1.067 2-Cl 5-Cl H CH2CH3 CF2Cl 1.068 2-Cl 5-Cl H C3H7(i) CF2Cl m.p. 161-162C
1.069 2-Cl 5-Cl H OCH3 CF3 1.070 2-Cl 5-Cl H OC2Hs CF3 1.071 2-Cl 5-Cl H OC3H7 CF3 1.072 2-Cl 5-Cl H OC3H7(i) CF3 1.073 2-Cl 5-Cl H OC4Hg(n) CF3 1.074 2-Cl 5-Cl H OC4Hg(i) CF3 1.075 2-Cl 5-Cl H SCH3 CF3 1.076 2-Cl 5-Cl H SC2Hs CF3 1.077 2-Cl 5-Cl H SC3H7(n) CF3 1.078 2-Cl 5-Cl H SC3H7(i) CF3 - 23 ~ 4 ~ ~ ~
Table 1 (continued) No. - - R2 R3 R~ Rs Physical data 1.079 2-Cl 5-Cl H SC4Hg(n) CF3 1.080 2-Cl 5-Cl H C4Hg(n) CF3 m.p. 123-124C
1.081 2-Cl 5-Cl H C4Hg(i) CF3 1.082 2-Cl 5-Cl H C4Hg(t) CF3 m.p. 159-160C
1.083 2-Cl 5-Cl H C2Hs CF2CF3 m.p. 157-158C
1.084 2-Cl 5-Cl H C3H7(i) CFzCF3 m.p. 161-162C
1.085 2-Cl 5-Cl H C3H7(n) CF2CF3 1.086 2-Cl 5-Cl H OCF2CHFz CF3 1.087 2-Cl 5-Cl H CH3 CCl2CF3 1.088 2-Cl 5-Cl H C2Hs CCl2CF3 1.089 2-Cl 5-Cl H CH3 CHClz m.p. 157-159C
1.090 2-Cl 5-Cl H C2Hs CHCl2 1.091 2-Cl 5-Cl H CH3 CClzCH3 1.092 2-Cl 5-Cl H CZHs CCl2CH3 1.093 2-Cl 6-Cl H CH3 CH3 m.p. 173-174C
1.094 2-Cl 6-Cl H CH3 CzHs 1.095 2-Cl 6-Cl H CH3 C3H7(i) 1.096 2-Cl 6-Cl H CH3 Cl m.p. 184-185C
1.097 2-Cl 6-Cl H CH3 CCl2CH3 1.098 2-Cl 6-Cl H CzHs CClzCH3 1.099 2-Cl 6-Cl H CH3 CHC12 1.100 2-Cl 6-Cl H CZHs CHCl2 1.101 2-Cl 6-Cl H CH3 CCl2CF3 1.102 2-Cl 6-Cl H C3H7(i) CClzCF3 1.103 2-Cl 6-Cl H CH3 CHClF
1.104 2-Cl 6-Cl H C2Hs CHClF
1.105 2-Cl 6-Cl H CH3 CF2Cl 1.106 2-Cl 6-Cl H C2Hs CF2Cl 1.107 2-Cl 6-Cl H C3H7(i) CFzCl 1.108 2-Cl 6-Cl H C3H7(n) CF2Cl 1.109 2-Cl 6-Cl H CH3 CF3 m.p. 156-157C
1.110 2-Cl 6-Cl H CzHs CF3 1.111 2-Cl 6-Cl H C3H7(n) CF3 1.112 2-Cl 6-Cl H C3H7(i~ CF3 1.113 2-Cl 6-Cl H Cyclo- CF3 m.p. 187-188C
propyl 1.114 2-Cl 6-Cl H Phenyl CF3 1.115 2-Cl 6-Cl H ~ -Thienyl CF3 m.p. 201-202C
1.116 2-Cl 6-Cl H 2-Furyl CF3 1.117 2-Cl 6-Cl H CH3 CFzCF3 1.118 2-Cl 6-Cl H CZHs CF2CF3 m.p. 168-169~C
1.119 2-Cl 6-Cl H C3H7(i) CF2CF3 m.p. 154-155C
1.120 2-Cl 6-Cl H C3H7(n) CF2CF3 1.121 2-Cl 6-Cl H Cyclo- CF2CF3 propyl 1.122 2-Cl 6-Cl H CH3 OCHF2 1.123 2-Cl 6-Cl H C4Hg(n) CF3 1.124 2-Cl 6-Cl H C4Hg(i) CF3 1.125 2-Cl 6-Cl H C4Hg(t) CF3 m.p. 174-175C
- 24 - 1 31 ~6 Table 1 (continued) Comp.No. R' R2 R3 R4 Rs Physical data 1.126 2-C1 6-Cl H OCH3 CF3 1.127 2-Cl 6-C1 H OC2Hs CF3 1.128 2-C1 6-Cl H OC3H7(n) CF3 1.129 2-Cl 6-Cl H OC3H7(i) CF3 1.130 2-C1 6-Cl H OC4Hg(n) CF3 1.131 2-C1 6-C1 H OC4Hg(i) CF3 1.132 2-Cl 6-Cl H SCH3 CF3 m.p. 158-159C
1.133 2-Cl 6-Cl H SC2Hs CF3 1.134 2-C1 6-Cl H SC3H7(n) CF3 1.135 2-Cl 6-Cl H SC3H7(i) CF3 1.136 2-Cl 6-Cl H SC4Hg(n) CF3 1.137 2-Cl 6-Cl H OCH3 CH3 1.138 2-Cl 6-Cl H C2Hs Cl 1.139 2-Cl 6-Cl H OCH3 CZHs 1.140 2-Cl 6-Cl H - '2Hs OCHFz 1.141 2-Cl 6-Cl 3-CH3 CH3 CF3 m.p. 182C decomp.
1.142 2-Cl 6-Cl 3-CH3 CzHs CF3 1.143 2-Cl 6-Cl 3-CH3 C3H7(n) CF3 1.144 2-Cl 6-Cl 3-CH3 C3H7(i) CF3 m.p. 160-162C
1.145 2-Cl 6-Cl 3-CH3 CH3 CF2CF3 m.p. 164-166C
1.146 2-Cl 6-Cl 3-CH3 CZHs CFzCF3 1.147 2-Cl 6-Cl 3-CH3 Cl CF3 1.148 2-Cl 6-Cl 3-CH3 OCH3 CF3 1.149 2-C1 6-Cl 3-CH3 OC2Hs CF3 1.150 2-C1 6-C1 3-CH3 SCH3 CF3 1.151 2-C1 6-Cl 3-CH3 SC4Hg(n ~CF3 1.152 2-Cl 6-Cl 3-CH3 CH3 CF2Cl 1.153 2-Cl 6-Cl 3-CH3 CH3 CHFz 1.154 2-Cl 6-Cl 3-CH _ CH3 CHC12 1.155 2-Cl 3-CF3 H H3 Cl 1.156 2-Cl 3-CF3 H CH 3 CH3 1.157 2-Cl 3-CF3 H CH3 CF3 1.158 2-Cl 3-CF3 H CzHs CF3 1.159 2-Cl 3-CF3 H C3N7(n) CF3 1.160 2-Cl 3-CF3 H CH3 CFzCF3 1.161 2-Cl 3-CF3 H CH3 CClF2 1.162 2-Cl 3-CF3 H CH~ CHClF
1.163 2-Cl 5-CF3 H CH3 Cl m.p. 148-149C
1.164 2-Cl 5-CF3 H CH3 CF3 m.p. 144-145C
1.165 2-Cl 5-CF3 H CH3 CClFz 1.166 2-Cl 5-CF3 H C2Hs CF3 1.167 2-Cl 5-CF3 H OCH3 CF3 1.168 2-Cl 6-CF3 H CH3 Cl 1.169 2-Cl 6-CF3 H CH3 CH3 1.170 2-Cl 6-CF3 H CH3 CF3 m.p. 155-156C
1.171 2-Cl 6-CF3 H CzHs CF3 1.172 2-Cl 6-CF3 H C3H7(n) CF3 1.173 2-Cl 6-CF3 H C3H7(i) CF3 - 25 - 1 3 1 ~ ~ 4 ~
Table 1 (continucd) Comp.No. Rl R2 R3 R~ Rs Physical data 1.174 2-Cl 6-CF3 H Cyclo- CF3 propyl 1.175 2-Cl 6-CF3 H C4H9~n~ CF3 1.176 2-Cl 6-CF3 H Cl,H9(i) CF3 1.177 2-Cl 6-CF3 H C4H9(t) CF3 1.178 2-Cl 6-CF3 H CH3 CF2CF3 1.179 2-Cl 6-CF3 H C2Hs CF2CF3 1.180 2-Cl 6-CF3 H CH3 CHCl2 1.181 2-Cl 6-CF3 H CH3 CClF2 1.182 2-Cl 6-CF3 H C2Hs CClF2 1.183 2-Cl 6-CF3 H CH3 CHF2 1.184 2-C1 6-CF3 H CH3 OCHF2 1.185 2-Cl 6-CF3 H OCH3 CF3 1.186 2-Cl 6-CF3 H OC2Hs CF3 1.187 2-Cl 6-CF3 H SC2Hs CF3 1.188 2-Cl 6-CF3 H CH3 CClzCF3 1.189 2-Cl 6-CF3 H CH3 CCl2CH3 1.190 2-Cl 6-CF3 H Phenyl CF3 1.191 2-Cl 3-CH3 H CH3 CF3 1.192 2-Cl 3-CH3 H CH3 CF2CF3 1.193 2-Cl 3-CH3 H C2Hs CF3 1.194 2-Cl 3-CH3 H C3H7(n~ CF3 1.195 2-Cl 3-CH3 H C3H7(i) CF3 1.196 2-Cl 3-CH3 H CH3 C1 1.197 2-Cl 3-CH3 H CH3 CFzCl 1.198 2-Cl 3-CH3 H CH3 CHClz 1.199 2-Cl 3-CH3 H CH3 CHClF
1.200 2-Cl 3-CH3 H OCH3 CF3 1.201 2-Cl 5-CH3 H CH3 Cl m.p. 140-141C
1.202 2-Cl 5-CH3 H CH3 CHC12 1.203 2-Cl 5-CH3 H CH3 CClzCF3 1.204 2-Cl 5-CH3 H CH3 CHClF
1.205 2-Cl 5-CH3 H CH3 CF2Cl 1.206 2-Cl 5-CH3 H C2Hs CF2Cl 1.207 2-Cl 5-CH3 H CH3 CF3 1.208 2-Cl 5-CH3 H C2Hs CF3 1.209 2-Cl 5-CH3 H C3H7(n) CF3 1.210 2-Cl 5-CH3 H C3H7(i) CF3 1.211 2-Cl 5-CH3 H C4Hg(n) CF3 1.212 2-Cl 5-CH3 H C4Hg(t) CF3 1.213 2-Cl 5-CH3 H 2-Furyl CF3 1.214 2-Cl 5-CH3 H CH 3 CF2CF3 1.215 2-Cl 5-CH3 H C2Hs CFzCF3 1.216 2-Cl 5-CH3 H OCH3 CF3 1.217 2-Cl 5-CH3 H OC2Hs CF3 1.218 2-Cl 5-CH3 H SCH3 CF3 1.219 2-Cl 6-CH3 H CH3 Cl m.p. 167-168C
1.220 2-Cl 6-CH3 H CN CH3 1.221 2-Cl 6-CH3 H CH3 CF3 m.p. 192-193C
- 26 - 1 31 ~ ~ 4 6 Table 1 (continued) Comp.No. R~ R2 R3 R4 Rs Physical data 1.222 2-Cl 6-CH3 H CH3 CFzCl m.p. 185-187C
1.223 2-Cl 6-CH3 H CH3 CFzCF3 1.224 2-Cl 6-CH3 H CH3 CClzCF3 1.225 2-Cl 6-CH3 H CH3 CHFz 1.226 2-Cl 6-CH3 H CH3 CHcl2 1.227 2-Cl 6-CH3 H CzHs CF3 m.p. 155-157C
1.228 2-Cl 6-CH3 H C3H7(i) CF3 m.p. 146-148C
1.229 2-Cl 6-CH3 H Cyclo- CF3 m.p. 177-178C
propyl 1.230 2-Cl 6-CH3 H C4Hg(i) CF3 1.231 2-Cl 6-CH3 H CzHs CF2CF3 1.232 2-Cl 6-CH3 H _ OCH3 CF3 1.233 2-Cl 6-CH3 H ( )CH2CHzCl CF3 1.234 2-Cl 6-CH3 H )CH2CH2OCI ~ CF3 1.235 2-Cl 6-CH3 H OC2Hs CF3 1.236 2-Cl 6-CH3 H SCH3 CF3 1.237 2-Cl 6-CH3 H SC2Hs CF3 1.238 2-Cl 6-CH3 H SC3H7(i) CF3 1.239 2-Cl 6-CH3 H SC4Hg(i) CF3 1.240 2-Cl 5-OCH3 H CH3 CF3 1.241 2-Cl 5-OCH3 H C2Hs CF3 1.242 ~-Cl 5-OCH3 H CH3 Cl 1.243 2-Cl 5-OCH3 H OCH3 CF3 1.244 2-Cl 5-OCH3 H CH3 CHFz 1.245 2-Cl 5-OCH3 H CH3 CFzCF3 1.246 2-Cl 5-OCH3 H CH3 CF2Cl 1.247 2-Cl 5-COOCH3 H CH3 CF3 m.p. 152-153C
1.248 2-Cl 5-COOCH3 H CzHs CF3 1.249 2-Cl 5-COOCzHs H CH3 CF3 1.250 2-Cl 5-COOCzHs H CH3 CFzCF3 1.251 2-Cl 5-COOC3H7(i) H CH3 CF3 1.252 2-Cl 5-COOC3H7(i) H C3H7(i) CF3 1.253 2-Cl 5-COOC3H7(i) H CH3 CF2Cl 1.254 2-Cl 5-COOC 3 H7(i) H Phenyl CF3 1.255 2-Cl 5-COOC3H7(i) H Cyclo- CF3 propyl 1.256 2-Cl 5-COOC3H7(i, _ H CH3 CHFCl 1.257 3-Cl 5-Cl H CH3 Cl m.p. 117-118C
1.258 3-Cl 5-Cl H CH3 CF3 m.p. 129-130C
1.259 3-Cl 5-Cl H CZHs CF3 1.260 3-Cl 5-Cl H C3H7(n) CF3 1.261 3-Cl 5-Cl H C3H7(i) CF3 1.262 3-Cl 5-Cl H Cyclo- CF3 propyl 1.263 3-Cl 5-Cl H Phenyl CF3 1.264 3-Cl 5-Cl H CH3 CHF2 1.265 3-Cl 5-Cl H CH3 CF2Cl 1.266 3-Cl 5-Cl H C2Hs CFzCl 1.267 3-Cl 5-Cl H OCH3 CF3 - 27 - ~ 31~5~ ~
Table_l (continued) Comp.No. R~ R2 R3 R4 Rs Physical data 1.268 3-Cl 5-Cl H OC2Hs CF3 1.269 3-Cl 5-Cl H SCH3 CF3 1.270 3-Cl 5-Cl H SC3H7(i) CF3 1.271 2-CH3 5-Cl H CH3 Cl m.p. 141-142C
1.272 2-CH3 5-Cl H CH3 CF3 1.273 2-CH3 5-Cl H CN CF3 1.274 2-CH3 5-Cl H C2Hs Cl 1.275 2-CH3 5-Cl H CH3 OCHFz 1.276 2-CH3 5-Cl H CH3 Br 1.277 2-CH3 5-Cl H CH3 F
1.278 2-CH3 5-Cl H CH3 CH3 m.p. 150-151C
1.279 2-CH3 5-Cl H OCH3 CH3 1.280 2-CH3 5-Cl H C2Hs CF3 1.281 2-CH3 5-Cl H C3H7(n) CF3 1.282 2-CH3 5-Cl H C3H7(i) CF3 1.283 2-CH3 5-Cl H Cyclo- CF3 propyl 1.284 2-CH3 5-Cl H Phenyl CF3 1.285 2-CH3 5-Cl H C4Hg(n) CF3 1.286 2-CH3 5-Cl H C4Hg(i) CF3 1.287 2-CH3 5-Cl H C4Hg(t) CF3 1.288 2-CH3 5-Cl H CH3 CF2CF3 1.289 2-CH3 5-Cl H C2Hs CF2CF3 1.290 2-CH3 5-Cl H C3H7(i) CFzCF3 1.291 2-CH3 5-C1 H CH3 CF2Cl 1.292 2-CH3 5-Cl H C2Hs CF2Cl 1.293 2-CH3 5-Cl H CH3 CHFz 1.294 2-CH3 5-Cl H C2Hs CHFz 1.295 2-CH3 5-Cl H CH3 CHFCl 1.296 2-CH3 5-Cl H C2Hs CHFCl 1.297 2-CH3 5-Cl H CH3 CHCl2 1.298 2-CH3 5-Cl H C2Hs CHCl2 1.299 2-CH3 5-Cl H CH3 CCl2CF3 1.300 2-CH3 5-Cl H CH3 CCl2CH3 1.301 2-CH3 5-Cl H OCH3 CF3 1.302 2-CH3 5-Cl H OC2Hs CF3 1.303 2-CH3 5-Cl H SCH3 CF3 1.304 2-CH3 5-Cl H SC2Hs CF3 1.305 2--CH3 5-Cl H SC4Hg(i) CF3 1.306 2-CH3 3-Cl H CH3 Cl m.p. 155-156C
1.307 2-CH3 3-Cl H CH3 CF3 1.308 2-CH3 3-Cl H CzHs CF3 1.309 2-CH3 3-Cl H C3H7(i) CF3 1.310 2-CH3 3-Cl H Cyclo- CF3 propyl 1.311 2-CH3 3-Cl H CH3 CF2Cl 1.312 2-CH3 3-Cl H CH3 CF2CF3 1.313 2-CH3 3-Cl H C2Hs CFzCF3 1.314 2-CH3 3-Cl H OCH3 CF3 131~46 Table I (continued) Com~.No. Rl R2 R3 R4 Rs Physical data 1.315 2-CH3 3-Cl H SCH3 CF3 1.316 2-CH3 5-NO2 H CH3 Cl m.p. 142-143C
1.317 2-CH3 5-NO2 H CH3 CF3 1.318 2-CH3 5-NO2 H CH3 CF2Cl 1.319 2-CH3 5-NOz H CH3 CHFz 1.320 2-CH3 5-NO2 H C2Hs CF3 1.321 2-CH3 5-NO2 H C3H7(n) CF3 1.322 2-CH3 5-NO2 H C3H7(i) CF3 1.323 2-CH3 5-NOz H C4Hg(t) CF3 1.324 2-CH3 3-NO2 H CH3 Cl m.p. 158-159C
1.325 2-CH3 3-NO2 H CH3 CF3 1.326 2-CH3 3-NOz H CH3 CF2CF3 1.327 2-CH3 3-NO2 H C2Hs CF2CF3 1.328 2~CH3 3-NOz H Phenyl CF3 1.329 2-CH3 3-NO2 H CzHs CF3 1.330 2-CH3 3-NO2 H C3H7(i) CF3 1.331 2-CH3 6-CF3 H CH3 Cl 1.332 2-CH3 6-CF3 H CH3 CF3 m.p. 164-165C
1.333 2-CH3 6-CF3 H CH3 CHF2 1.334 2-CH3 6-CF3 H CH3 CF2Clz 1.335 2-CH3 6-CF3 H CH3 CHC12 1.336 2-CH3 6-CF3 H OCH3 CF3 1.337 2-CH3 6-CF3 H OC2Hs CF3 1.338 2-CH3 6-CF3 H SCH3 CF3 1.339 2-CH3 6-CF3 H SC2Hs CF3 1.340 2-CH3 6-CF3 H C2Hs CF3 1.341 2-CH3 6-CF3 H CH3 CF2CF3 1.342 2-CH3 6-CF3 H C2Hs CF2CF3 1.343 2-CH3 6-CF3 H C3H7(i) CF3 1.344 2-CH3 6-CF3 H C3H7(n) CF3 1.345 2-CH3 6-CF3 H Cyclo- CF3 propyl 1.346 2-OCHF2 5-Cl H CH3 Cl m.p. 138-139C
1.347 2-OCHFz 5-Cl H CH3 CH3 1.348 2-OCHF2 5-Cl H CH3 CHCl2 1.349 2-OCHF2 5-Cl H CH3 CHFCl 1.350 2-oCHFz 5-Cl H CH3 CHF2 1.351 2-OCHF2 5-Cl H CH3 CFzCl 1.352 2-OCHF2 5-Cl H CH3 CF3 m.p. 142-143C
1.353 2-OCHF2 5-Cl H CH3 CFzCF3 1.354 2-OCHFz 5-Cl H CH3 CClzCF3 1.355 2-oCHFz 5-Cl H CH3 CCl2CH3 1.356 2-OCHF2 5-Cl H C2Hs C~3 1.357 2-OCHF2 5-Cl H C3H7(n) CF3 1.358 2-OCHF2 5-Cl H C3H7(i) CF3 1.359 2-CH3 6-Cl H Cyclo- CF3 propyl 1.360 2-CH3 6-Cl H C4Hg(n) CF3 1.361 2-CH3 6-Cl H C4Hg(i) CF3 - 29 - 1 ~ 145 ~ ~
Table 1 (continued) Comp.No. R~ R2 R3 R4 R5 Physical data 1.362 2-CH3 6-Cl H C~Hg(t) CF3 1.363 2-CH3 6-Cl H Phenyl CF3 1.364 2-CH3 6-Cl H 2-Furyl CF3 1.365 2-CH3 6-Cl H L -Thienyl CF3 1.366 2-CH3 6-Cl H CzHs CF2CF3 1.367 2-CH3 6-C] H C2Hs CCl2CH3 1.368 2-CH3 6-Cl H OCH3 CF3 1.369 2-CH3 6-Cl H OCzHs CF3 1.370 2-CH3 6-Cl H SCH3 CF3 1.371 2-Cl 6-Cl 3-Cl CH3 Cl 1.372 2-Cl 6-Cl 3-Cl CH3 CF3 1.373 2-Cl 6-Cl 3-Cl C2Hs CF3 1.374 2-Cl 6-Cl 3-Cl C3H7(i) CF3 1.375 2-Cl 6-Cl 3-Cl CH3 CFzCF3 1.376 2-Cl 6-Cl 3-Cl Phenyl CF3 1.377 2-Cl 6-Cl 3-Cl OCH3 CF3 1.378 2-Cl 6-Cl 3-Cl OC2Hs CF3 1.379 2-Cl 6-Cl 3-Cl SCzHs CF3 1.380 2-OCH3 3-Cl H CH3 CF3 m.p. 179-180C
1.381 2-OCH3 3-Cl H C2Hs CF3 1.382 2-OCH3 3-Cl H C3H7(n) CF3 1.383 2-OCH3 3-Cl H Cyclo- CF3 propyl 1.384 2-OCH3 3-Cl H CH3 Cl 1.385 2-OCH3 3-Cl H CH3 CF2CF3 1.386 2-OCH3 3-Cl H OCH3 CF3 1.387 2-OCH3 3-Cl H SCH3 CF3 1.388 2-OCH3 3-Cl H CH3 CFzCl 1.389 2-oCH3 3-Cl H CH3 CHF2 1.390 2-OCH3 5-Cl H CH3 Cl 1.391 2-OCH3 5-Cl H CH3 CH3 m.p. 157-158C
1.392 2-OCH3 5-Cl H CH3 CF3 m.p. 158-159C
1.393 2-OCH3 5-Cl H CH3 Br 1.394 2-OCH3 5-Cl H CN CH3 1.395 2-oCH3 5-Cl H CH3 CFzC
1.396 2-OCH3 5-Cl H CH3 CHF2 1.397 2-OCH3 5-Cl H CH3 CHCl2 1.398 2-oCH3 5-Cl H CH3 CF2CF3 m.p. 125-126C
1.399 2-OCH3 5-Cl H CH3 CCl2CF3 1.400 2-OCH3 5-Cl H CH3 CHClF
1.401 2-OCH3 5-Cl H CH3 CCl2CH3 1.402 2-OCH3 5-Cl H C2Hs CF3 1.403 2-OCH3 5-Cl H C2Hs CF2CF3 m.p. 148-150C
1.404 2-OCH3 5-Cl H C2Hs CF2Cl 1.405 2-OCH3 5-Cl H C3H7(n> CF3 m.p. 168-169C
1.406 2-oCH3 5-Cl H C3H7(i) CF3 m.p. 167-168C
1.407 2-OCH3 5-Cl H C3H7~i) CF2CF3 1.408 2-OCH3 5-Cl H Cyclo- CF3 propyl 1~14~6 Table 1 (continued) Comp.No. Rl R2 R3 R4 Rs Physical da~a 1.409 2-OCH3 5-Cl H C4Hg(n) CF3 1.410 2-OCH3 5-Cl H C2Hs(i) CF3 1.411 2-OCH3 5-Cl H C4Hg(t) CF3 m.p. 156-157~C
1.412 2-OCH3 5-Cl H OCH3 CF3 1.413 2-OCH3 5-Cl H OC4Hg(n) CF3 1.414 2-OCH3 5-Cl H SCH3 CF3 1.415 2-OCH3 5-Cl H SCzHs CF3 1.416 2-OCH3 5-Cl H SC3H7(n) CF3 1.417 2-OCH3 5-Cl H SC3H7(i) CF3 1.418 2-OC2Hs 5-Cl H CH3 Cl 1.419 2-OCZHs 5-Cl H CH3 CF3 1.420 2-OC2Hs 5-Cl H CZHs CF3 1.421 2-OC2Hs 5-Cl H C3H7(i) CF3 1.422 2-OCzHs 5-Cl H Cyclo- CF3 propyl 1.423 2-OC2Hs 5-Cl H Phenyl CF3 1.424 2-OC2Hs 5-Cl H OCH3 CF3 1.425 2-OCzHs 5- -Cl H CH3 CFzCF3 1.426 2-OC3H7(i) 5-Cl H CH3 Cl 1.427 2-OC3H7(i) 5-Cl H CH3 CF3 1.428 2-OC3H7(i) 5-Cl H CH3 CF2Cl 1.429 2-OC3H7(i) 5-Cl H C2Hs CF3 1.430 2-OC3H7(i) 5-Cl H C3H7(n) CF3 1.431 2-OC3H7(i) 5-Cl H CH3 CHF3 1.432 2-OC3H7(i) 5-Cl H OCH3 CF3 1.433 2-OC3H7~ i) 5-Cl H SCH3 CF3 1.434 2-OCF3 H H CH3 Cl 1.435 2-OCF3 H H CH3 CF3 1.436 2-OCF3 H H CH3 CFzCl 1.437 2-oCF3 H H CH3 CHF2 1.438 2-OCF3 H H CH3 CHFCl 1.439 2-OCF3 H H C2Hs CF3 1.440 2-OCF3 H H C3H7(i) CF3 1.441 2-OCF3 H H C4Hg(n) CF3 i.442 2-OCF3 H H C4Hg(t) CF3 1.443 2-OCF3 5-Cl H CH3 CF3 1.444 2-OCF3 5-Cl H CH3 Cl 1.445 2-OCF3 5-Cl H CH3 CF3 1.446 2-OCF3 5-Cl H CH3 CF2Cl 1.447 2-OCF3 5-Cl H CH3 CHF2 1.448 2-OCF3 5-Cl H CH3 CHCl2 1.449 2-OCF3 5-Cl H CH3 CHFCl 1.450 2-OCF3 5-Cl H CH3 CF2CF3 1.451 2-OCF3 5-Cl H C2Hs CF2CF3 1.452 2-OCF3 5-Cl H C2Hs CF3 1.453 2-OCF3 5-Cl H C3H7(i) CF3 1.454 2-oCF3 5-Cl H Cyclo- CF3 propyl 1.455 2-OCF3 5-Cl H Phenyl CF3 1314~4~
Table 1 (continued) Comp.No. Rl _ R3 R4 Rs Physical data _ 1.456 2-OCF3 5-Cl H OCzHs CF3 1.457 2-OCF3 5-Cl H SCzHs CF3 1.458 2-SCH3 H H CH3 Cl 1.459 2-SCH3 H H CH3 CF3 m.p. 156-157C
1.460 2-SCH3 H H CH3 CHFz 1.461 2-SCH3 H H CH3 CFzCF3 1.462 2-SCH3 H H CZHs CF3 1.463 2-SCH3 H H C3H7(i) CF3 m.p. 170-171C
1.464 2-SCH3 H H C4Hg(n) CF3 1.465 2-SCH3 H H C4Hg(t) CF3 1.466 2-SCH3 5-Cl H CH3 Cl 1.467 2-SCH3 5-Cl H CH3 CF3 m.p. 162-163C
1.468 2-SCH3 5-Cl H CH3 CFzCF3 1.469 2-SCH3 5-Cl H CH3 CFzCl 1.470 2-SCH3 5-Cl H CZHs CF3 1.471 2-SOCH3 H H CH3 Cl 1.472 2-SOCH3 H H CH3 CF3 m.p. 80-82C
1.473 2-SOCH3 H H CH3 CHFz 1.474 2-SOCH3 H H CH3 CF2CF3 1.475 2-SOCH3 H H C2Hs CF3 1.476 2-SOCH3 H H C3H7(i) CF3 1.477 2-SOCH3 H H C4H9(n) CF3 1.478 2-SOCH3 H H C4Hg(t) CF3 1.479 2-SOzCH _ H H CH3 Cl m.p. 164-165~C
1.480 2-SOzCH3 H H CH3 CF3 m.p. 166-167C
1.481 2-SOzCH3 H H CzHs CF3 1.482 2-SOzCH3 H H C3H7(n) CF3 1.483 2-So2CH3 H H C3H7(i) CF3 1.484 2-SOzCH3 H H Cyclo- CF3 propyl 1.485 2-SOzCH3 H H C4Hs(i) CF3 1.486 2-SOzCH3 H H CH3 CFzCF3 1.487 2-SozCH3 H H CzHs CFzCF3 1.488 2-SO2CH ! H H C3H7(i) CFzCF3 1.489 2-SOCH3 5-Cl H CH3 Cl 1.490 2-SOCH3 5-Cl H CH3 CF3 m.p. 132-133C
1.491 2-SOCH3 5 Cl H CzHs CF3 1.492 2-SOCH3 5-Cl H CH3 CF2CF3 1.493 2-SOCH3 _5-Cl H C3H7(i) CF3 1.494 2-SOzCH 5-Cl H CH3 Cl 1.495 2-SOzCH3 5-Cl H CH3 CF3 m.p. 154-155C
1.496 2-So2CH3 5-Cl H CzHs CF3 1.497 2-SOzCH3 5-Cl H CH3 CFzCF3 1.498 2-SO2CH l 5-Cl H C3H7(i) CF3 1.499 2-F 5-F H CH3 OCHF2 1.500 2-F 5-F H CH3 Cl 1.501 2-F 5-F H CH3 CF3 m.p. 152-153C
1.502 2-F 5-F H CzHs CF3 - 32 - ~ 31~
Table 1 (continued) Comp.No. Rl R2 R3 R4 RS Physical data 1.503 2-F 5-F H C3H7(n) CF3 1.504 2-F 5-F H C3H7(i) CF3 1.505 2-F 5-F H Cyclo- CF3 m.p. 174-175C
propyl 1.506 2-F 5-F H CH3 CF2CF3 1.507 2-F 5-F H CH3 CF2CF2C]
1.508 2-F 5-F H CH3 CFzCl 1.509 2-F 5-F H CH3 CHFz 1.510 2-F 5-F H CH3 CHClF
1.511 2-F 5-F H C2Hs CF2Cl 1.512 2-F 5-F H C3H7~i) CF2Cl m.p. 161-162C
1.513 2-F 5-F H C4Hg(n) CF3 1.514 2-F 5-F H C4Hg(t) CF3 m.p. 156-157C
1.515 2-F 5-F H C2Hs CFzCF3 1.516 2-F 5-F H C3H7(i) CFzCF3 m.p. 150-151C
1.517 2-F 5-F H C3H7(n) CFzCF3 1.518 2-F 5-F H CH3 CCl2CF3 1.519 2-F 5-F H CH3 CHCl2 1.520 2-F 5-F H C2Hs CHC12 m.p. 144-145C
1.521 2-F 5-F H CH3 CCl2Ch3 1.522 2-F 5-F H OCH3 CF3 1.523 2-F 5-F H OC3H7(i~ CF3 1.524 2-F 5-F H SCH3 CF3 1.525 2-F 5-F H SC3H7(i) CF3 1.526 2-F 6-F H CH3 Cl 1.527 2-F 6-F H CH3 CF3 m.p. 177-178C
1.528 2-F 6-F H CZHs CF3 m.p. 151-153C
1.529 2-F 6-F H C3H7(n) CF3 1.530 2-F 6-F H C3H7(i) CF3 m.p. 158-159C
1.531 2-F 6-F H CH3 CF2CF3 1.532 2-F 6-F H C2Hs CFzCF3 m.p. 137-139C
1.533 2-F 6-F H CH3 CF2Cl m.p. 178-179C
1.534 2-F S-F H CH3 CHFz 1.535 2-F 6-F H CH3 CHClF
1.536 2-F 6-F H OCH3 CF3 1.537 2-F 6-F H SCH3 CF3 1.538 2-F 6-Cl H CH3 Cl 1.539 2-F 6-Cl H CH3 CH3 1.540 2-F 6-Cl H CH3 CF3 m.p. 184-185C
1.541 2-F 6-Cl H C2Hs CF3 1.542 2-F 6-Cl H C3H7(i) CF3 m.p. 146-147C
1.543 2-F 6-Cl H Cyclo- CF3 m.p. 172-173C
propyl 1.544 2-F 6-Cl H CH3 CF2CF3 1.545 2-F 6-Cl H C3H7~i) CF2CF3 1.546 2-F 6-Cl H CH3 CCl2CF3 1.547 2-F 6-Cl H CH3 CHClz 1.548 2-F 6-Cl H CH3 CHFz 1.549 2-F 6-Cl H CH3 CHFCl - 33 - 1 31~
Table 1 (continued) Comp.No. R2 R3 R4 Rs Physical data _ _ _ 1.550 2-F 6-Cl H CH3 CFzCl 1.551 2-F 6-Cl H C3H7(i) CF2Cl 1.552 2-F 6-Cl H OCH3 CF3 1.553 2-CN H H CH3 CF3 m~p. 142-143C
1.554 2-CN H H CZHs CF3 1.555 2-CN H H C3H7(i) CF3 1.556 2-CN H H CH3 CFzCF3 1.557 2-CN H H CzHs CFzCF3 1.558 2-CN H H C3H7(i) CF2CF3 1.559 2-CN H H CH3 CHF2 1.560 2-CN H H CH3 CF2Cl 1.561 2-CN H H OCH3 CF3 1.562 2-CN H H OCzHs CF3 1.563 2-PO~OC Hs)z H H CH3 CF3 m.p. 144-145C
1.564 2-PO(OCzHs)2 H H C2Hs CF3 1.565 2-PO(OCzHs)2 H H C3H7(i) CF3 1.566 2-Cl 5-C: ~ H SOCH3 CF3 1.567 2-Cl 5-Cl H SOzCH3 CF3 1.568 2-Cl 6-Cl H SOCH3 CF3 1.569 2-Cl 6-Cl H SO2CH3 CF3 1.570 2-Cl 6-Cl H SOCH3 CH3 1.571 2-Cl 6-Cl H SOzCH3 CH3 1.572 2-Cl 6-Cl H CN CH3 1.573 2-Cl 6-Cl H CN CF3 1.574 2-Cl 6-Cl H CH=CClz Cl 1.575 2-Cl 5-Cl H CH=CClz Cl 1.576 2-CF3 H H CH=CClz Cl 1.577 2-Cl 6-Cl H CH20CH3 CF3 1.578 2-Cl 6-Cl H CHzOCH3 C2Fs 1.579 2-Cl 5-Cl H CHzOCH3 CF3 1.580 2-Cl 5-Cl H CH20CH3 CFzCl 1.581 2-OCH3 5-Cl H CHzOCH3 CF3 1.582 2-OCH3 5-Cl H CHzOCH3 CFzCF3 1.583 2-F 5-F H CHzOCH3 CF3 1.584 2-OCHFz 5-Cl H CHzOCH3 CF3 1.585 2-OCHFz 5-Cl H CHzOCH3 CFzCl 1.586 3-Br H H CH3 Cl m.p. 133-134C
1.587 3-Br H H CH3 CF3 1.588 2-Br 5-Br H CH3 Cl 1.589 2-Br 5-Br H CH3 CF3 m.p. 155-156C
1.590 2-Br 5-Br H OCH3 CF3 1.591 2-Br 5-Br H CzHs CF3 1.592 2-Br 5-Br H CH3 CFzC
1.593 2-Br 5-Br H CH3 CHFz 1.594 2-CF3 5-Cl H CH3 CF3 m.p. 152-153C
1.595 2-CF3 5-Cl H CH3 Cl m.p. 142-143C
1.596 2-CF3 5-Cl H CzHs CF3 1.597 2-CF3 5-Cl H C3H7(i) CF3 - 34 - 1 3 1 ~ ~4 ~
Table 1 (continued) Comp.No. R~ R3 R4 ~ Physical data 1.598 2-CF 3 5-Cl H Cyclo- CF3 propyl 1.599 2-CF3 5-Cl H CH3 CH2Cl 1.600 2-CF3 5-Cl H CH3 CHFz 1.601 2-CF3 5-Cl H C2Hs CF2Cl 1.602 2-CF3 5-Cl H C3H7ti) CF2Cl 1.603 2-CF3 5-Cl H CH3 CF2CF3 1.604 2-CF 3 5-Cl H OCH3 CF 3 1.605 2-CF3 5-Cl H SCH3 CF3 1.606 2-CF3 5-Cl H SOCH3 CF3 1.607 2-CF3 5-Cl H SO2CH3 CH3 1.608 2-CH3 3-CH3 H CH3 Cl 1.609 2-CH3 3-CH3 H CH3 CF3 1.610 2-CH3 5-CH3 H CH3 Cl 1.611 2-CH3 5-CH3 H CH3 CF3 1.612 2-CH3 6-CH3 H CH3 Cl 1.613 2-CH3 6-CH3 H CH3 CF3 m.p. 160-161C
1.614 2-CH3 6-CH3 H CH3 CF2Cl m.p. 169-i70C
1.615 2-CH3 6-CH3 H CH3 CHzCF3 1.616 2-CH3 6-CH3 H OCH3 CF3 1.617 2-CH3 6-CH3 H SCH3 CF3 1.618 2-CH3 6-CzHs H CH3 Cl 1.619 2-CH3 6-C2Hs H CH3 CF3 m.p. 140-144C
1.620 2-CH3 6-C2Hs H OCH3 CF3 1.621 2-CH3 5-F H CH3 Cl 1.622 2-CH3 5-F H CH3 CF3 m.p. 170-172C
1.623 2-CH3 5-F H CH3 CHF2 1.624 2-CH3 5-F H CH3 CF2Cl 1.625 2-CH3 5-F H CZHs CF3 1.626 2-CH3 5-F H C3H7(i) CF3 1.627 2-CH3 5-F H OCH3 CF3 1.628 2-CH3 5-F H OC2Hs CF3 1.629 2-Br 6-Br H CH3 Cl 1.630 2-Br 6-Br H CH3 CF3 1.631 2-Br 6-Br H CZHs CF3 m.p. 157-158C
1.632 2-Br 6~Br H C3H7(i) CF3 1.633 2-Br 6-Br H Cyclo- CF3 propyl 1.634 2-Br 6-Br H CH3 CHC12 1.635 2-Br 6-Br H CH3 CFzCF3 1.636 2-Br H H C3H7(i) CF2CF3 m.p. 149-150C
1.637 2-CF3 H CH3 CHC12 m.p. 161-162C
1 3 ~ 6 Table 1 (contin~ed) Comp.No. ~ RZ R3 R4 Rs Physical data 1.638 2-OCHF2 }I H CH3 CF3 m.p. 145-146C
1.639 2-OCHF2 H H C3H7(i) CF3 1.640 2-OCHF2 H H Cyclo- CF3 m.p. 137-138C
propyl 1.641 2-OCHFz H H CH3 CHF2 1.642 2-OCHF2 H H CH3 CHFCl 1.643 2-CF3 H H CH3 CHFz 1.644 2-CF3 H H CH3 CF2Cl 1.645 2-CF3 H H C3H7(i) CFzCl m.p. 140-141C
1.646 2-CF3 H H Cyclo- CF3 m.p. 169-170C
propyl 1.647 2-CF3 H H 2-Thienyl CF3 m.p. 170-171~C
1.648 2-Br H H C4Hg(n) CF3 m.p. 144-145C
1.649 2-Br H H C3H7(i) CF3 m.p. 169-170C
1.650 2-Br H H CH3 CHF2 1.651 2-Br H H CH3 CFzCl 1.652 2-Br H H Cyclo- CFzCl propyl 1.653 2-Br H H C2Hs CHF2 1.654 2-Cl 6-CH3 H CH3 CH3 m.p. 165-167C
1.655 2-Cl 6-Cl H CH3 CHF2 m.p. 182-183C
1.656 2-Cl 6-Cl H C2Hs CHFz 1.657 2-Cl 5-Cl H CsH1l(n) CF3 m.p. 118-119C
1.658 2-COOCH3 H H CH3 CF3 m.p. 138-139C
1.659 2-COOCH3 H H C2Hs CF3 1.660 2-COOCH3 H H C3H7~i) CF3 1.661 2-COOCH3 H H Cyclo- CF3 propyl 1.662 2-COOCH3 H H CH3 CFzCl 1.663 2-COOCH3 H H CH3 CHF2 1.664 2-COOC2Hs H H CH3 CF3 1.665 2-COOC3H7~n) H H CH3 CF3 1.666 2-COOC3H7(i) H H CH3 CF3 1.667 2-COOC4Hg(n) H H CH3 CF3 1.668 2-OCH3 5-F H CH3 CF3 ~ P 141-142C
1.669 2-OCH3 5-F H CH3 CHF2 1.670 2-OCH3 5-F H CzHs CHF2 1.671 2-OCH3 5-F H C3H7(i) CF3 1.672 2-OCH3 5-F H Cyclo- CF3 propyl 1.673 2-OCH3 5-F H Cycl~- CF3Cl propyl - 36 - 13~4 ~ 4 ~
Table 1 (continued) Comp.No. R~ R2 R3 R4 Rs Physical data _.
1.674 2-OCHFz 5-F H CH3 CF3 1.675 2-OCHFz 5-F H CH3 CHF2 1.676 2-OCHF2 5-F H CH3 CF2Cl 1.677 2-COOCH3 6-CH3 H CH3 CF3 m.p. 161-162C
1.678 2-COoCH3 6-CH3 H CH3 CHF2 1.679 2-COOCH3 6-CH3 H C3H7(i) CF3 1.680 2-COOCH3 6-CH3 H Cyclo- CF3 propyl 1.681 2-COOCH3 6-Cl H CH3 CF3 m.p. 144-145C
1.682 2-COOCH3 6-Cl H CH3 CHFz 1.683 2-Br 11 H 2-Furyl CF3 m.p. 176-177C
1.684 2-Cl 6-Cl 3-CH ¦CH3 Cl 1.685 2-CF3 H H CzHs CHC12 m.p. 155-156C
1.686 2-Cl 5-Cl H Cl CF3 1.687 2-CONH2 H H CH3 CF3 ÇH3 1.688 2-Cl 6-Cl H CHCH2CH3 CF3 m.p. 124-125C
1.689 2-F H H C2Hs CF3 m.p. 136-137C
1.690 2-F H H CH20CH3 CF3 m.p. 122-124C
1 o91 2-F H H CHzOCH3 CF2Cl m.p. 145-147C
1.692 2-OCH3 6-Cl H CH3 CF3 m.p. 191-192C
1.693 2-OCH3 6-Cl H CzHs CF3 m.p 147-149C
1.694 2-OCH3 6-Cl H C3H7(i) CF3 m.p. 143-146C
1.695 2-CH3 6-CH3 H CzHs CF3 m.p. 158-160C
1.696 2-CH3 6-CH3 H C3H7(i) CF3 m.p. 143-146C
1.697 2-F 6-F H C4Hg(i) CF3 m.p. 135-137C
1.698 2-F 6-F H - ~¦ CF3 m.p. 158-159C
1.699 2-F 6-F H CH20CH3 CF3 m.p. 138-139C
1.700 2-F 6-F H C2Hs CHC12 m.p. 169-171C
1.701 2-F 6-F H 2-Furyl CF3 m.p. 152-153C
1.702 2-CH3 5-F H C2Hs CHC12 1.703 2-Cl 6-CH3 H CH20CH3 CF3 m.p. 137-138C
1.704 2-Cl 6-CH3 H CHzOCH3 CF2Cl m.p. 133-134C
1.705 2-Cl 6-CH3 H C3H7(i) CF2Cl m.p. 142-144C
1.706 2-Cl 6-CH3 H Cl CF3 1.707 2-Cl 6-CH3 H CH20CH3 CHF2 m.p. 142-144C
1.708 2-F H H CH20CH3 CHF2 m.p. 116-118C
1.709 2-OCH3 6-CH3 H CH3 CP3 m.p. 180-181C
1.710 2 Cl 6-Cl H Cl CF3 m.p. 189-190C
1.711 2-SCHF2 H H CH3 CF3 1.712 2-OCHF2 6-CH3 H CH3 CF3 1.713 2-OCHF2 6-CH3 H CZHs CF3 1.714 2-F 6-Cl H 2-Furyl CF3 1.715 2-CH3 6-F H C2Hs CHC12 m.p. 141-142C
- 37 - 13 1 4 ~ 4~
P.2. Compounds of formula II
P. 2.1. N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-2-trifluoro-methylaniline A suspension of 24 g (0.1 mole) of 2-trifluoromethylphenyl-guanidinium hydrochloride in 80 ml of tetrahydrofuran is added to a solution of 12 g (0.1 mole) of potassium tert.-butoxide in 100 ml of tetrahydrofuran. When the exothermic reaction has subsided, 15.4 g (0.1 mole) of ~ -tri-fluoroacetylacetone in 20 ml of tetrahydrofuran are added. The reaction mixture is stirred for 2 hours at 60C, then concentrated by evaporation in a rotary evaporator. The residue is chromatographed on silica gel with a mixture of ethyl acetate and hexane (ratio 1:2)~ 18.7 g (58 2 % of the theoretical amount) of the title compound of formula ~--NH--~ ~-\.=./ \N=-/
\CF3 are obtained in the form of crystals having a melting point of 65-66C
(Comp. No. 2.020).
The compounds of Table II can be obtained analogously to Example P. 2:
- 38 - 1 3~ ~ ~ 4 6 Table II
Compounds of formula ~ N- /
H- ~ /--NH \N- / II
2 .~ --\R4 Comp.No. Rl - R2 R3 R4 Rs Physical data _ 2.001 2-Cl H H CH3 CH3 2.002 2-Cl H H CH3 OCHF2 2.003 2-Cl H H CH3 Cl 2.004 2-Cl H H CH3 CF3 2.005 2-Cl H H CH3 CF2CF3 2.006 2-Cl H H CH2CH3 CF3 2.007 2-Cl H H CH3 CF2Cl 2.008 2-Cl H H CH3 CHF2 2.009 2-Br H H CH3 Cl m.p. 109-110C
2.010 2-Br H H OCH3 CF3 2.011 2-Br H H CH3 CF 3 2.012 2-~Br H H SCH 3 CF3 2.013 2-Br H H CH2CH3 CF3 2.014 2-Br H H CH3 CHClz 2.015 2-Br H H CH3 CHFCl 2.016 2-Br H H Cyclo- CF3 m.p. 85-86C
propyl 2.017 2-CF3 H H Phenyl CF3 2.018 2-CF3 H H 2-Furyl CF3 2.019 2-CF3 H H CH3 Cl 2.020 2-CF3 H H CH3 CF3 m.p. 65-66C
2.021 2-CF3 H H CH3 CH3 m.p. 70-72C
2.022 2-CF3 H H CHzCH3 CF3 2.023 2-CF3 H H CH(CH3)z CF3 nD5: i,4960 2.024 2-CF3 H H (n)C3H7 CF3 n~5: 1,4970 2.025 2-CF3 H H OCH3 CF3 2.026 2-CF3 H H oC2Hs CF3 2.027 2-CF3 H H SCH3 CF3 2.028 2-CF3 H H ~ iCH(CH3)2 CF3 2.029 2-CF3 H H ¦CH3 CF2CF3 _ 39 - 1 ~ ~ 4~ ~
Table II (continued) Comp.No. ---- R2 R3 R4 Rs Physical data 2.030 2-CF3 H H CH3 CHFCl 2.Q31 2-J H H CH3 Cl 2.032 2-J H H CH3 CF3 m.p. 109-110C
2.033 2-J H H CH2CH3 CF3 2.034 2-J H H CH3 CF2Cl 2.035 2-F H H CH3 CH3 2.036 2-F H H CH3 Cl 2.037 2-F H H CH3 CF3 m.p. 64-66C
2.038 2-F H H CH(CH3)2 CF3 nDS: 1.5240 2.039 2-F H H Cl CF3 2.040 2-F H H OCzHs CF3 2.041 2-Cl 3-Cl H CH3 Cl m.p. 123-124C
2.042 2 Cl 3-Cl H CH3 CF3 m.p. 109-110C
2.043 2-Cl 3-Cl H OCH3 CF3 2.044 2-Cl 3-Cl H OC4Hg(n) CF3 2.045 2-Cl 3-Cl H SC2Hs CF3 2.046 2-Cl 3-Cl H Phenyl CF3 2.047 2-Cl 3-Cl H CH3 CF2Cl 2.048 2-Cl 3-Cl H CH3 CHFCl 2.049 2-Cl 3-Cl H CH3 CH3 2.050 2-Cl 5-Cl H CH3 CH3 2.051 2-Cl 5-Cl H CH3 OCHF2 2.052 2-Cl 5-Cl H CH3 Cl m.p. 99-100C
2.053 2-Cl 5-Cl H OCH3 CH3 2.054 2-Cl 5-Cl H CH3 Br 2.055 2-Cl 5-Cl H CH3 CF3 m.p. 79-80C
2.056 2-Cl 5-Cl H CHzCH3 CF3 m.p. 62-63 C
2.057 2-Cl 5-Cl H C3H7(n) CF3 nD5: 1,5490 2.058 2-Cl 5-Cl H C3H7(i) CF3 m.p. 60-61C
2.059 2-Cl 5-Cl H Cyclo- CF3 m.p. 106-107C
propyl 2.060 2-Cl 5-Cl H Phenyl CF3 2.061 2-Cl 5-Cl H [ -Thienyl CF3 m.p. 112-113C
2.062 2-Cl 5-Cl H 2-Furyl CF3 m.p. 102-103C
2.063 2-Cl 5-Cl H CH3 CF2CF3 m.p. 99-100C
2.064 2-Cl 5-Cl H CH3 CF2Cl m.p. 67C
2.065 2-Cl 5-Cl H CH3 CHF2 m.p. 72-74C
2.066 2-Cl 5-Cl H CH3 CHClF m.p. 66-67C
2.067 2-Cl 5-Cl H CH2CH3 CF2Cl 2.068 2-Cl 5-Cl H C3H7(i) CF2Cl nD5: 1,5682 2.069 2-Cl 5-Cl H OCH3 CF3 2.070 2-Cl 5-Cl H OCzHs CF3 2.071 2-Cl 5-Cl H OC3H7 CF3 2.072 2-Cl 5-Cl H OC3H7(i) CF3 2.073 2-Cl 5-Cl H OC4Hg(n) CF3 2.074 2-Cl 5-Cl H OC4Hg(i) CF3 _ 40 _ 1 3 1 4 ~ ~ 6 Table II (continued) Comp.No. R1 R2 R3 R4 Rs Physical data .
2.075 2-Cl 5-Cl H SCH3 CF3 2.076 2-Cl 5-Cl H SCzHs CF3 2.077 2-Cl 5-Cl H SC3H7(n) CF3 2.078 2-Cl 5-Cl H SC3H7(i) CF3 2.079 2-Cl 5-C~ H SC4Hg(n) CF3 2.080 2-Cl 5-Cl H C4Hg(n) CF3 nD5: 1,5475 2.081 2-Cl 5-Cl H C4Hg(i) CF3 2.082 2-Cl 5-Cl H C4Hg(t) CF3 m.p. 106-107C
2.083 2-Cl 5-Cl H C2Hs CF2CF3 m.p. 70-72C
2.084 2-Cl 5-Cl H C3H7(i) CF2CF3 m.p. 39-41C
2.085 2-Cl 5-Cl H C3H7(n) CFzCF3 2.086 2-Cl 5-Cl H OCF2CHF2 CF3 2.087 2-Cl 5-Cl H CH3 CCl2CF3 2.088 2-Cl 5-Cl H C2Hs CCl2CF3 2.089 2-Cl 5-Cl H CH3 CHCl2 m.p. 80-82C
2.090 2-Cl 5-Cl H CZHs CHCl2 nD5: 1,6115 2.091 2-Cl 5-Cl H CH3 CCl2CH3 2.092 2-Cl 5-Cl H CZHs CClzCH3 2.093 2-Cl 6-Cl H CH3 CH3 m.p. 185-186C
2.094 2-Cl 6-Cl H CH3 C2Hs 2.095 2-Cl 6-Cl H CH3 C3H7(i) 2.096 2-Cl 6-Cl H CH3 Cl m.p. 190-191C
2.097 2-Cl 6-Cl H CH 3 CCl2CH3 2.0S8 2-Cl 6-Cl H CZHs CCl2CH3 2.099 2-Cl 6-Cl H CH3 CHCl2 2.100 2-Cl 6-Cl H C2Hs CHCl2 2.101 2-Cl 6-Cl H CH3 CCl 2 CF3 2.102 2-Cl 6-Cl H C3H7(i) CClzCF3 2.103 2-Cl 6-Cl H CH3 CHClF
2.104 2-Cl 6-Cl H C2Hs CHClF
2.105 2-Cl 6-Cl H CH3 CF2Cl 2.106 2-Cl 6-Cl H C2Hs CF2Cl 2.107 2-Cl 6-Cl H C3H7(i) CF2Cl 2.108 2-Cl 6-Cl H C3H7(n) CFzCl 2.109 2-Cl 6-Cl H CH3 CF3 m.p. 138-139C
2.110 2-Cl 6-Cl H CZHs CF3 2.111 2-Cl 6-Cl H C3H7(n) CF3 2.112 2-Cl 6-Cl H C3H7~i) CF3 2.113 2-Cl 6-Cl H Cyclo- CF3 m.p. 70-73C
propyl 2.114 2-Cl 6-Cl H Phenyl CF3 2.115 2-Cl 6-Cl H ~ -Thienyl CF3 m.p. 119-120C
2.116 2-Cl 6-Cl H 2-Furyl CF3 2.117 2-Cl 6-Cl H CH3 CF2CF3 2.118 2-Cl 6-Cl H CzHs CF2CF3 m.p. 96-98C
2.119 2-Cl 6-Cl H C3H7(i) CFzCF3 m.p. 88-90C
2.120 2-Cl 6-Cl H C3H7(n) CF2CF3 ~ 41 - 1 3 1 ~ ~ 4 6 Table II (continued) Comp.No. R1 R2 R3 R4 Rs Physical data 2.121 2-Cl 6-Cl H propyl CFzCF3 2.122 2-Cl 6-Cl H CH3 OCHF2 2.123 2-Cl 6-Cl H C4Hg(n) CF3 2.124 2-Cl 6-Cl H C4Hs(i) CF3 2.125 2-Cl 6-Cl H C4Hg(t) CF3 m.p. 79-81C
2.126 2-Cl 6-Cl H OCH3 CF3 2.127 2-Cl 6-Cl H OCzHs CF3 2.128 2-Cl 6-Cl H OC3H7(n) CF3 2.129 2-Cl 6-Cl H OC3H7(i) CF3 2.130 2-Cl 6-Cl H OC4Hg(n) CF3 2.131 2-Cl 6-Cl H OC4Hg(i) CF3 2.132 2-Cl 6-Cl H SCH3 CF3 m.p. 70-71C
2.133 2-Cl 6-Cl H SC2Hs CF3 2.134 2-Cl 6-Cl H SC3H7(n) CF3 2.135 2-Cl 6-Cl H SC3H7(i~ CF3 2.136 2-Cl 6-Cl H SC4Hg(n) CF3 2.137 2-Cl 6-Cl H OCH3 CH3 2.138 2-Cl 6-Cl H C2Hs Cl 2.139 2-Cl 6-Cl H OCH3 C2Hs 2.140 2-Cl 6-Cl H C2Hs OCHF2 2.141 2-Cl 6-Cl 3-CH _ CH3 CF3 m.p. 124-125C
2.142 2-Cl 6-Cl 3-CH3 C2Hs CF3 m.p. 90-91C
2.143 2-Cl 6-Cl 3-CH3 C3H7(n) CF3 2.144 2-Cl 6-Cl 3-CH3 C3H7(i) CF3 m.p. 74-75C
2.145 2-Cl 6-Cl 3-CH3 CH3 CF2CF3 m.p. 119-121C
2.146 2-Cl 6-Cl 3-CH3 C2Hs CF2CF3 2.147 2-Cl 6-Cl 3-CH3 Cl CF3 2.148 2-Cl 6-C1 3-CH3 OCH3 CF3 2.149 2-Cl 6-Cl 3-CH3 OCZHs CF3 2.150 2-Cl 6-Cl 3-CH3 SCH3 CF3 2.151 2-Cl 6-Cl 3-CH3 SC4Hg(n, ~CF3 2.152 2-Cl 6-Cl 3-CH3 CH3 CFzCl 2.153 2-Cl 6-Cl 3-CH3 CH3 CHF2 2.154 2-Cl 6-Cl 3-CH l CH3 CHCl2 2.155 2-Cl 3-CF3 H CH3 Cl 2.156 2-Cl 3-CF3 H CH3 CH3 2.157 2-Cl 3-CF3 H CH3 CF3 2.158 2-Cl 3-CF3 H C2Hs CF3 2.159 2-Cl 3-CF3 H C3H7(n) CF3 2.160 2 Cl 3-CF3 H CH3 CF2CF3 2.161 2-Cl 3-CF3 H CH3 CClF2 2.162 2-Cl 3-CF3 H CH3 CHClF
2.163 2-Cl 5-CF3 H CH3 Cl m.p. 101-103C
2.164 2-Cl 5-CF3 H CH3 CF3 m.p. 84-85C
2.165 2-Cl 5-CF3 H CH3 CClF2 2.166 2-Cl 5-CF3 H C2Hs CF3 2.167 2-Cl 5-CF3 H OCH3 CF3 -- 42 - 1 3 1 4 ~ 4 6 Table II (continued) Comp.No. R1 R2 R3 R4 Rs Physical data ..... __ 2.168 2-Cl 6-CF3 H CH3 Cl 2.169 2-Cl 6-CF3 H CH3 CH3 2.170 2-Cl 6-CF3 H CH3 CF3 m.p. 117-119C
2.171 2-Cl 6-CF3 H CzHs CF3 2.172 2-Cl 6-CF3 H C3H7(n) CF3 2.173 2-Cl 6-CF3 H C3H7(i) CF3 2.174 2-Cl 6-CF3 H Cyclo- CF3 propyl 2.175 2-Cl 6-CF3 H C4Hg(n) CF3 2.176 2-Cl 6-CF3 H C4Hg(i) CF3 2.177 2-Cl 6-CF3 H C4Hg(t) CF3 2.178 2-Cl 6-CF3 H CH3 CF2CF3 2.179 2-Cl 6-CF3 H C2Hs CFzCF3 2.180 2-Cl 6-CF3 H CH3 CHClz 2.181 2-Cl 6-CF3 H CH3 CClF 2 2.182 2-Cl 6-CF3 H CzHs CClF2 2.183 2-Cl 6-CF3 H CH3 CHF2 2.184 2-Cl 6-CF3 H CH3 OCHFz 2.185 2-Cl 6-CF3 H OCH3 CF3 2.186 2-Cl 6-CF3 H OC2Hs CF3 2.187 2-Cl 6-CF3 H SC2Hs CF3 2.188 2-Cl 6-CF3 H CH3 CClzCF3 2.189 2-Cl 6-CF3 H CH3 CClzCH3 2.190 2-Cl 6-CF3 H Phenyl CF3 2.191 2-Cl 3-CH3 H CH3 CF3 2.192 2-Cl 3-CH3 H CH3 CF2CF3 2.193 2-Cl 3-CH3 H CzHs CF3 2.194 2-Cl 3-CH3 H C3H7(n) CF3 2.195 2-Cl 3-CH3 H C3H7(i) CF3 2.196 2-Cl 3-CH3 H CH3 Cl 2.197 2-Cl 3-CH3 H CH3 CFzCl 2.198 2-Cl 3-CH3 H CH3 CHCl2 2.199 2-Cl 3-CIi3 H CH3 CHClF
2.200 2-Cl 3-CH3 H OCH3 CF3 2.201 2-Cl 5-CH3 H CH3 Cl m.p. 77-78C
2.202 2-Cl 5-CH3 H CH3 CHClz 2.203 2-Cl 5-CH3 H CH3 CCl2CF3 2.204 2-Cl 5-CH3 H CH3 CHClF
2.205 2-Cl 5-C}i3 H CH3 CFzCl 2.206 2-Cl 5-CH3 H C2Hs CF2Cl 2.207 2-Cl 5-CH3 H CH3 CF3 2.208 2-Cl 5-CH3 H C2Hs CF3 2.209 2-Cl 5-CH3 li C3H7(n) CF3 2.210 2-Cl 5-CH3 H C3H7~i) CF3 2.211 2-Cl 5-CH3 H C4Hg(n) CF3 2.212 2-Cl 5-CH3 H C4Hg(t) CF3 2.213 2-Cl 5-CH3 H 2-Furyl CF3 2.214 2-Cl 5-CH3 H CH3 CFzCF3 2.215 2-Cl 5-CH3 H CzHs CFzCF3 ~ 43 - 1314 5 ~ 6 Table II (continued) Comp.No. Rl R-2 R3 R4 ~s Physical data 2.216 2-Cl 5-CH3 H OCH3 C~3 2.217 2-Cl 5-CH3 H OCzHs CF3 2.218 2-Cl 5-CH3 H SCH3 CF3 2.219 2-Cl 6-CH3 H CH3 Cl m.p. 142-143C
2.220 2-Cl 6-CH 3 H CN CH3 2.221 2-Cl 6-CH3 H CH3 CF3 m.p. 143-144C
2.222 2-Cl 6-CH3 H CH3 CF2Cl m.p. 158-162C
2.223 2-Cl 6-CH3 H CH3 CF2CF3 2.224 2-Cl 6-CH3 H CH3 CCl2CF3 2.225 2-Cl 6-CH3 H CH3 CHF2 2.226 2-Cl 6-CH3 H CH3 CHClz 2.227 2-Cl 6-CH3 H C2Hs CF3 m.p. 99-102C
2.228 2-Cl 6-CH3 H C3H7(i) CF3 m.p. 56-59C
2.229 2-Cl 6-CH3 H Cyclo- CF3 m.p. 75-77C
propyl 2.230 2-Cl 6-CH3 H C4Hg(i) CF3 2.231 2-Cl 6-CH3 H C2Hs CF2CF3 m.p. 89-91C
2.232 2-Cl 6-CH3 H OCH3 CF3 2.233 2-Cl 6-CH3 H IOCH2CH2Cl CF3 2.234 2-Cl 6-CH3 H ~ )CH2CH20C1 ~ CF3 2.235 2-Cl 6-CH3 H OCzHs CF3 2.236 2-Cl 6-CH3 H SCH3 CF3 2.237 2-Cl 6-CH3 H SCzHs CF3 2.238 2-Cl 6-CH3 H SC3H7(i) CF3 2.239 2-Cl 6-CH3 H SC4Hg(i) CF3 2.240 2-Cl 5-OCH3 H CH3 CF3 2.241 2-Cl 5-OCH3 H C2Hs CF3 2.242 2-Cl 5-OCH3 H CH3 Cl 2.243 2-Cl 5-OCH3 H OCH3 CF3 2.244 2-Cl 5-OCH3 H CH3 CHF2 2.245 2-Cl 5-OCH3 H CH3 CF2CF3 2.246 2-Cl 5-OCH3 H CH3 CF2Cl 2.247 2-Cl 5-COOCH3 H CH3 CF3 m.p. 88-89C
2.248 2-Cl 5-COOCH3 H C2Hs CF3 2.249 2-Cl 5~COOC2Hs }I CH3 CF3 2.250 2-Cl 5-COOC2Hs _H CH3 CFzCF3 2.251 2-Cl 5-COOC3H7(i l H CH3 CF3 2.252 2-Cl 5-COOC3H7(i) H C3H7(i) CF3 2.253 2-Cl 5-COOC3H7(i) H CH3 CF2Cl 2.254 2-Cl 5-COOC3H7(i) H Phenyl CF3 2.255 2-Cl 5-COOC3H7(i) H Cyclo- CF3 p~opyl 2.256 2-Cl 5-COOC3H7(i, _ H CH3 CHFCl 2.257 3-Cl 5-Cl H CH3 Cl m.p. 152-153C
2.258 3-Cl 5-Cl H CH3 CF3 m.p. 93-94C
2.259 3-Cl 5-Cl H C2Hs CF3 2.260 3-Cl 5-Cl H C3H7~n) CF3 2.261 3-Cl 5-Cl H C3H7(i) CF3 Table II (continued) Co~p.No. Rl _ R2 R3 R~ Rs Physical data 2.262 3-Cl 5-Cl H Cyclo- CF3 propyl 2.263 3-Cl 5-Cl H Phenyl CF3 2.264 3-Cl 5-Cl H CH3 CHF2 2.265 3-Cl 5-Cl H CH3 CF2Cl 2.266 3-Cl 5-Cl H CZHs CF2Cl 2.267 3-Cl 5-Cl H OCH3 CF3 2.268 3-Cl 5-Cl H OC2Hs CF3 2.269 3-Cl 5-Cl H SCH3 CF3 2.270 3-Cl 5-Cl H SC3H7(i) CF3 2.271 2-CH3 5-Cl H CH3 Cl m.p. 118-119C
2.272 2-CH3 5-Cl H CH3 CF3 2.273 2-CH3 5-Cl H CN CF3 2.274 2-CH3 5-Cl H C2Hs Cl 2.275 2-CH3 5-Cl H CH3 OCHFz 2.276 2-CH3 5-Cl H CH3 Br 2.277 2-CH3 5-Cl H CH3 F
2.278 2-CH3 5-Cl H CH3 CH3 m.p. 121-122C
2.279 2-CH3 5-Cl H OCH3 CH3 2.280 2-CH3 5-Cl H CzHs CF3 2.281 2-CH3 5-Cl H C3H7(n) CF3 2.282 2-CH3 5-Cl H C3H7(i) CF3 2.283 2-CH3 5-Cl H Cyclo- CF3 propyl 2.284 2-CH 3 5-Cl H Phenyl CF 3 2.285 2-CH3 5-Cl H C4Hg(n) CF3 2.286 2-CH3 5-Cl H C4Hg(i) CF3 2.287 2-CH3 5-Cl H C4Hg(t) CF3 2.288 2-CH3 5-Cl H CH3 CF2CF3 2.289 2-CH3 5-Cl H CzHs CF2CF3 2.290 2-CH3 5-Cl H C3H7(i) CF2CF3 2.291 2-CH3 5-Cl H CH3 CF2Cl 2.292 2-CH3 5-Cl H C2Hs CF2Cl 2.293 2-CH3 5-Cl H CH3 CHF2 2.294 2-CH3 5-Cl H CZHs CHF2 2.295 2-CH 3 5-Cl H CH3 CHFCl 2.296 2-CH3 5-Cl H C2Hs CHFCl 2.297 2-CH3 5-Cl H CH3 CHCl2 2.298 2-CH3 5-Cl H C2Hs CHC12 2.299 2-CH3 5-Cl H CH3 CClzCF3 2.300 2-CH3 5-Cl H CH3 CCl2CH3 2.301 2-CH3 5-Cl H OCH3 CF3 2.302 2-CH3 5-Cl H OCzHs CF3 2.303 2-CH3 5-Cl H SCH3 CF3 2.304 2-CH3 5-Cl H SC2Hs CF3 2.305 2-CH3 5-Cl H SC4Hg(i) CF3 2.306 2-CH3 3-Cl H CH3 Cl m.p. 116-117C
2.307 2-CH3 3-Cl H CH3 CF3 2.308 2-CH3 3-Cl H C2Hs CF3 - 45 - 1 3 1 4 ~ ~ 6 Table II (continued) Comp.No. R1 R2 R3 R4 Rs Physical data 2.309 2-CH3 3-Cl H C3H7(i) CF3 2.310 2-CH3 3-Cl H Cyclo- CF3 propyl 2.311 2-CH3 3-Cl H CH3 CFzCl 2.312 2-CH3 3-Cl H CH3 CFzCF3 2.313 2-CH3 3-Cl H C2Hs CF2CF3 2.314 2-CH3 3-Cl H OCH3 CF3 2.315 2-CH3 3-Cl H SCH3 CF3 2.316 2-CH3 5-NOz H CH3 Cl m.p. 178-179C
2.317 2-CH3 5-NOz H CH3 CF3 2.318 2-CH3 5-NOz H CH3 CFzCl 2.319 2-CH3 5-NOz H CH3 CHFz 2.320 2-CH3 5-NOz H CZHs CF3 2.321 2-CH3 5-NOz H C3H7(n) CP3 2.322 2-CH3 5-NO2 H C3H7(i) CF3 2.323 2-CH3 5-NO2 H C4Hg(t) CF3 2.324 2-CH3 3-NO2 H CH3 Cl m.p. 160-161C
2.325 2-CH3 3-NOz H CH3 CF3 2.326 2-CH3 3-NO2 H CH3 CF2CF3 2.327 2-CH3 3-NO2 H CzHs CFzCF3 2.328 2-CH3 3-NOz H Phenyl CF3 2.329 2-CH3 3-NO2 H CZHs CF3 2.330 2-CH3 3-NO2 H C3H7(i) CF3 2.331 2-CH3 6-CF3 H CH3 Cl 2.332 2-CH3 6-CF3 H CH3 CF3 m.p. 100-101C
2.333 2-CH3 6-CF3 H CH3 CHF2 2.334 2-CH3 6-CF3 H CH3 CF2C12 2.335 2-CH3 6-CF3 H CH3 CHCl2 2.336 2-CH3 6-CF3 H OCH3 CF3 2.337 2-CH3 6-CF3 H OC2Hs CF3 2.338 2-CH3 6-CF3 H SCH3 CF3 2.339 2-CH3 6-CF3 H SC2Hs CF3 2.340 2-CH3 6-CF3 H C2Hs CF3 2.341 2-CH3 6-CF3 H CH3 CF2CF3 2.342 2-CH3 6-CF3 H C2Hs CF2CF3 2.343 2-CH3 6-CF3 H C3H7(i) CF3 2.344 2-CH3 6-CF3 H C3H7(n) CF3 2.345 2-CH3 6-CF3 H Cyclo- CF3 propyl 2.346 2-OCHF2 5-Cl H CH3 Cl m.p. 61-62C
2.347 2-OCHF2 5-Cl H CH3 CH3 2.348 2-OCHF2 5-Cl H CH3 CHCl2 2.349 2-OCHF2 5-Cl H CH3 CHFCl 2.350 2-oCHFz 5-Cl H CH3 CHF2 2.351 2-OCHF2 5-Cl H CH3 CF2Cl 2.352 2-OCHF2 5-Cl H CH3 CF3 m.p. 66-67C
2.353 2-OCHF2 5-Cl H CH3 CF2CF3 2.354 2-OCHF2 5-Cl H CH3 CClzCF3 2.355 2-OCHF2 5-Cl H CH3 CCl2CH3 131~6 Table II (continued) _ Comp.No. R1 RZ R3 R4 Rs Physical data 2.356 2-OCHF2 5-Cl H CzHs CF3 2.357 2-OCHF2 5-Cl H C3H7(n) CF3 2.358 2-OCHF2 5-Cl H C3H7(i) CF3 2.359 2-CH3 6-Cl H Cyclo- CF3 2.360 2-CH3 6-Cl H C4Hg(n) CF3 2.361 2-CH3 6-Cl H C4Hg(i) CF3 2.362 2-CH3 6-Cl H C4Hg(t) CF3 2.363 2-CH3 6-Cl H Phenyl CF3 2.364 2-CH3 6-Cl H 2-Furyl CF
2.365 2-CH3 6-Cl H L ~ -Thienyl CF3 2.366 2-CH3 6-Cl H CzHs CF2CF3 2.367 2-CH3 6-Cl H C2Hs CCl2CH3 2.368 2-CH3 6-Cl H OCH3 CF3 2.369 2-CH3 6-Cl H OCZHs CF3 2.370 2-CH3 6-Cl H SCH3 CF3 2.371 2-Cl 6~Cl 3-Cl CH3 Cl 2.372 2-Cl 6-Cl 3-Cl CH3 CF3 2.373 2-Cl 6-Cl 3-Cl C2Hs CF3 2.374 2-Cl 6-Cl 3-Cl C3H7(i) CF3 2.375 2-Cl 6-Cl 3-Cl CH3 CF2CF3 2.376 2-Cl 6-Cl 3-Cl Phenyl CF3 2.377 2-Cl 6-Cl 3-Cl OCH3 CF3 2.378 2-Cl 6-Cl 3-Cl OC2Hs CF3 2.379 2-Cl 6-Cl 3-Cl SC2Hs CF3 2.380 2-OCH3 3-Cl H CH3 CF3 m.p. 41-42C
2.381 2-OCH3 3-Cl H C2Hs CF3 2.382 2-OCH3 3-Cl H C3H7(n) CF3 2.383 2-OCH3 3-Cl H Cyclo- CF3 propyl 2.384 2-OCH3 3-Cl H CH3 Cl 2.385 2-OCH3 3-Cl H CH3 CF2CF3 2.386 2-OCH3 3-Cl H OCH3 CF3 2.387 2-OCH3 3-Cl H SCH3 CF3 2.388 2-OCH3 3-C:L H CH3 CF2Cl 2.389 2-OCH3 3-C:L H CH3 CHFz 2.390 2-OCH3 5-Cl H CH3 Cl 2.391 2-OCH3 5-Cl H CH3 CH3 m.p. 106-107C
2.392 2-oCH3 5-Cl H CH3 CF3 m.p. 65-66C
2.393 2-OCH3 5-Cl H CH3 Br 2.394 2-oCH3 5-Cl H CN CH3 2.395 2-OCH3 5-Cl H CH3 CF2Cl 2.396 2-OCH3 5-Cl H CH3 CHFz 2.397 2-oCH3 5-Cl H CH3 CHCl2 2.398 2-OCH3 5-Cl H CH3 CF2CF3 m.p. 75-76C
2.399 2-OCH3 5-Cl H CH3 CCl2CF3 2.400 2-oCH3 5-Cl H CH3 CHClF
2.401 2-oCH3 5-Cl H CH3 CCl2CH3 2.402 2-OCH3 5-Cl H C2Hs CF3 131~5~
Table II (continued) Comp.No. R2- R3 R4 l Rs Physical data _ _ 2.403 2-OCH3 5-Cl H C2Hs CFzCF3 m.p. 64-65C
2.404 2-OCH3 5-Cl H C2Hs CF2Cl 2.405 2-oCH3 5-Cl H C3H7(n) CF3 nD5: 1,5463 2.406 2-OCH3 5-Cl H C3H7(i) CF3 nD5: 1,5455 2.407 2-OCH3 5-Cl H C3H7(i) CFzCF 3 2.408 2-OCH3 5-Cl H Cyclo- CF3 propyl 2.409 2-OCH3 5-Cl H C4Hg(n) CF3 2.410 2-oCH3 5-Cl H C2Hs(i) CF3 2.411 2-OCH3 5-Cl H C4Hg(t) CF3 m.p. 55-56C
2.412 2-oCH3 5-Cl H OCH3 CF3 2.413 2-oCH3 5-Cl H OC4Hg(n) CF3 2.414 2-OCH3 5-Cl H SCH1 CF3 2.415 2-OCH3 5-Cl }I SC2Hs CF3 2.416 2-OCH3 5-Cl H SC3H7(n) CF3 2.417 2-OCH3 5-Cl H SC3H7(i) CF3 2.418 2-oC2Hs 5-Cl H CH3 Cl 2.419 2-oC2Hs 5-Cl H CH3 CF3 2.420 2-OCzHs 5-Cl H CzHs CF3 2.421 2-OC2Hs 5-Cl H C3H7(i) CF3 2.422 2-OCzHs 5-Cl H Cyclo- CP3 propyl 2.423 2-OCzHs 5-Cl H Phenyl CF3 2.424 2-OC2Hs 5-Cl H OCH3 CF3 2.425 2-OC2Hs 5-Cl H CH3 CFzCF3 2.426 2-OC3H7 i) 5-Cl H CH3 Cl 2.427 2-OC3H7(i) 5-Cl H CH3 CF3 2.428 2-OC3H7(i~ 5-Cl H CH3 CF2Cl 2.429 2-OC3H7(i) 5-Cl H C2Hs CF3 2.430 2-OC3H7(i) 5-Cl H C3H7(n) CF3 2.431 2-OC3H7(i) 5-Cl H CH3 CHF3 2.432 2-OC3H7(i) 5-Cl H OCH3 CF3 2.433 2-OC3H7~ i) 5-Cl H SCH3 CF3 2.434 2-OCF3 H H CH3 Cl 2.435 2-OCF3 H H CH3 CF3 nD3: 1,4943 2.436 2-OCF3 H H CH3 CF2Cl 2.437 2-OCF3 H H CH3 CHF2 2.438 2-OCF3 H H CH3 CHFCl 2.439 2-OCF3 H H C2}1s CF3 2.440 2-OCF3 H H C3H7(i) CF3 2.441 2-OCF3 H H C4Hg(n) CF3 2.442 2-OCF3 H H C4Hg(t) CF3 2.443 2-oCF3 5-Cl H CH3 CF3 2.444 2-OCF3 5-Cl H CH3 Cl 2.445 2-OCF3 5-Cl H CH3 CF3 2.446 2-OCF3 5-Cl H CH3 CF2Cl 2.447 2-OCF3 5-Cl H CH3 CHF2 2.448 2-OCF3 5-Cl H CH3 CHC12 - 48 - 1 31~5 4 6 Table II (continued) Comp.~~ R~ R2 R3 R4 Rs Physical data 2.449 2-OCF3 5-Cl H CH3 CHFCl 2.450 2-OCF3 5-Cl H CH3 CF 2 CF3 2.451 2-OCF3 5-Cl H CZHs CF2CF3 2.452 2-OCF3 5-Cl H C2Hs CF3 2.453 2-OCF3 5-Cl H C3H7(i) CF3 2.454 2-OCF3 5-Cl H Cyclo- CF3 propyl 2.455 2-OCF3 5-Cl H Phenyl CF3 2.456 2-OCF3 5-Cl H OCZHs CF3 2.457 2-OCF3 5-Cl H SC 2 Hs CF3 2.458 2-SCH3 H H CH3 Cl 2.459 2-SCH3 H H CH3 CF3 m.p. 74-75C
2.460 2-SCH3 H H CH3 CHFz 2.461 2-SCH3 H H CH3 CF2CF3 2.462 2-SCH3 H H C2Hs CF3 2.463 2-SCH3 H H C3H7(i) CF3 nDS: 1,5575 2.464 2-SCH3 H H C4Hg(n) CF3 2.465 2-SCH3 H H C4Hg(t) CF3 2.466 2-SCH3 5-Cl H CH3 Cl 2.467 2-SCH3 5-Cl H CH3 CF3 m.p. 144-145C
2.468 2-SCH3 5-Cl H CH3 CF2CF3 2.469 2-SCH3 5-Cl H CH3 CFzCl 2.470 2-SCH3 5-Cl H C2Hs CF3 2.471 2-SOCH3 H H CH3 Cl 2.472 2-SOCH3 H H CH3 CF3 2.473 2-SOCH3 H H CH3 CHFz 2.474 2-SOCH3 H H CH3 CFzCF3 2.475 2-SOCH3 H H C2Hs CF3 2.476 2-SOCH3 H H C3H7(i) CF3 2.477 2-SOCH3 H H C4Hg(n) CF3 2.478 2-SOCH3 H H C4Hg(t) CF3 2.479 2-SO2CH _ H H CH3 Cl m.p. 168C
2.480 2-SO2CH3 H H CH3 CF3 m.p. 149C
2.481 2-SO2CH3 H H C2Hs CF3 2.482 2-SO2CH3 H H C3H7(n) CF3 2.483 2-SO2CH3 H H C3H7(i) CF3 2.484 2-SO2CH3 H H Cyclo- CF3 propyl 2.485 2-So2CH3 H H C4Hg(i) CF3 2.486 2-SO2CH3 H H CH3 CFzCF3 2.487 2-SOzCH3 H H CzHs CF2CF3 2.488 2-SOzCH3 H H C3H7(i) CF2CF3 2.489 2-SOCH3 _ 5-Cl H CH3 Cl 2.490 2-SOCH3 5-Cl H CH3 CF3 m.p. 194-195C
2.491 2-SOCH3 5-Cl H CzHs CF3 2.492 2-SOCH3 5-Cl H CH3 CFzCF3 2.493 2-SOCH3 _5-Cl H C3H7(i) CF3 2.494 2-SO2CH l¦5-Cl H CH3 Cl - 49 - 1 31~ ~4 6 Table II (continued) Comp.No. R2 R3 R4 Rs Physical data 2.495 2-502CH3 5-Cl H CH3 CF3 m.p. 183-184C
2.496 2-SO2CH3 5-Cl H C2Hs CF3 2.497 2-SO2CH3 5-Cl H CH3 CF2CF3 2.498 2-SOzCH _ 5-Cl H C3H7(i) CF3 2.499 2-F 5-F H CH3 OCHF2 2.500 2-F 5-F H CH3 Cl 2.501 2-F 5-F H CH3 CF3 m.p. 68-69C
2.502 2-F 5-F H CzHs CF3 2.503 2-F 5-F H C3H7(n) CF3 2.504 2-F 5-F H C3H7(i) CF3 2.505 2-F 5-F H Cyclo- CF3 m.p. 103-104C
propyl 2.506 2-F 5-F H CH3 CF2CF3 _ 2.507 2-F 5-F H CH3 CF2CF2C]
2.508 2-F 5-F H CH3 CF2Cl 2.509 2-F 5-F H CH3 CHFz 2.510 2-F 5-F H CH3 CHClF
2.511 2-F 5-F H C2Hs CF2Cl O 2.512 2-F 5-F H C3H7(i) CF2Cl nD5: 1,5358 2.513 2-F 5-F H C4Hg(n) CF3 2.514 2-F 5-F H C4Hg(t) CF3 m.p. 37-38C
2.515 2-F 5-F H C2Hs CFzCF3 2.516 2-F 5-F H C3H7(i) CFzCF3 m.p. 53-54C
2.517 2-F 5-F H C3H7(n) CF2CF3 2.518 2-F 5-F H CH3 CClzCF3 2.519 2-F 5-F H CH3 CHCl2 2.520 2-F 5-F H CzHs CHC12 nD5: 1,5324 2.521 2-F 5-F H CH3 CClzCH3 2.522 2-F 5-F H OCH3 CF3 2.523 2-F 5-F H OC3H7(i) CF3 2.524 2-F 5-F H SCH3 CF3 2.525 2-F 5-F H SC3H7(i) CF3 2.526 2-F 6-F H CH3 Cl 2.527 2-F 6-F H CH3 CF3 m.p. 164C
2.528 2-F 6-F H C2Hs CF3 m.p. 120-121C
2.529 2-F 6-F H C3H7(n) CF3 2.530 2-F 6-F H C3H7(i) CF3 m.p. 92-94C
2.531 2-F 6-F H CH3 CF2CF3 2.532 2-F 6-F H C2Hs CF2CF3 m.p. 85-87C
2.533 2-F 6-F H CH3 CF2Cl m.p. 92-95C
2.534 2-F 6-F H CH3 CHFz 2.535 2-F 6-F H CH3 CHClF
2.536 2-F 6-F H OCH3 CF3 2.537 2-F 6-F H SCH3 CF3 2.538 2-F 6-Cl H CH3 Cl 2.539 2-F 6-Cl H CH3 CH3 2.540 2-F 6-Cl H CH3 CF3 m.p. 160-161C
2.541 2-F 6-Cl H CZHs CF3 2.542 2-F 6-Cl H C3H7(i) CF3 m.p. 108-109C
~ 50 - 1 3145~ 6 Table II (continued) Comp.No. Rl R2 R3 - R5 Physical data 2.543 2-F 6-Cl H propyl CF3 m.p. 95-96C
2.544 2-F 6-Cl H CH3 CF2CF3 2.545 2-F 6-Cl H C3H7(i) CF2CF3 2.546 2-F 6-Cl H CH3 CCl2CF3 2.547 2-F 6-Cl H CH3 CHCl2 2.548 2-F 6-Cl H CH3 CHFz 2.549 2-F 6-Cl H CH3 CHFCl 2.550 2-F 6-Cl H CH3 CFzCl 2.551 2-F 6-Cl H C3H7(i) CF2Cl 2.552 2-F 6-Cl H OCH3 CF3 2.553 2-CN H H CH3 CF3 m.p. 117~118C
2.554 2-CN H H C2Hs CF3 2.555 2-CN H H C3H7(i) CF3 2.556 2-CN H H CH3 CF2CF3 2.557 2-CN H H CZHs CFzCF3 2.558 2-CN H H C3H7(i) CFzCF3 2.559 2-CN H H CH3 CHF2 2.560 2-CN H H CH3 CFzCl 2.561 2-CN H H OCH3 CF3 2.562 2-CN H H OCZHs CF3 2.563 2-Po(oC, !Hs)2 H H CH3 CF3 m.p. 60-61C
2.564 2-PO(OCzHs~2 H H C2Hs CF3 2.565 2-Po(oC ~Hs)z H H C3H7(i) CF3 2.566 2-Cl 5-Cl H SOCH3 CF3 2.567 2-Cl 5-Cl H SO2CH3 CF3 2.568 2-Cl 6-Cl H SOCH3 CF3 m.p. 144-148C
2.569 2-Cl 6-Cl H SOzCH3 CF3 m.p. 144-146C
2.570 2-Cl 6-Cl H SOCH3 CH3 2.571 2-Cl 6-Cl H SO2CH3 CH3 2.572 2-Cl 6-Cl H CN CH3 2.573 2-Cl 6-Cl H CN CF3 2.574 2-Cl 6-Cl H CH=CCl2 Cl 2.575 2-Cl 5-Cl H CH=CCl2 Cl 2.576 2-CF3 H H CH=CCl2 Cl 2.577 2-Cl 6-Cl H CHzOCH3 CF3 2.578 2-Cl 6-C:L H CH20CH3 C2Fs 2.579 2-Cl 5-Cl H CH20CH3 CF3 2.580 2-Cl 5-Cl H CH20CH3 CF2Cl 2.581 2-OCH3 5-Cl H CH20CH3 CF3 2.582 2-OCH3 5-Cl H CH20CH3 CF2CF3 2.583 2-F 5-F H CH20CH3 CF3 2.584 2-OCHF2 5-Cl H CH20CH3 CF3 2.585 2-OCHF2 5-Cl H CH20CH3 CF2Cl 2.586 3-Br H H CH3 Cl m.p. 101-102C
2.587 3-Br H H CH3 CF3 2.588 2-Br 5-8r H CH3 Cl 2.589 2-Br 5-Br H CH3 CF3 m.p. 95-97C
2.590 2-Br 5-Br H OCH3 CF3 - 51 - 1314~ 46 Table II (continued) Comp.No. R1 R2 R3 R4 Rs Physical da~a _ 2.591 2-Br 5-Br H CZHs CF3 2.592 2-Br 5-Br H CH3 CF2Cl 2.593 2-Br 5-Br H CH3 CHF2 2.594 2-CF3 5-Cl H CH3 CF3 m.p. 65-67C
2.595 2-CF3 5-Cl H CH3 Cl m.p. 117-118C
2.596 2-CF3 5-Cl H C2Hs CF3 2.597 2-CF3 5-Cl H C3H7(i) CF3 2.598 2-CF3 5-Cl H Cyclo- CF3 propyl 2.599 2-CF3 5-Cl H CH3 CH2Cl 2.600 2-CF3 5-Cl H CH3 CHFz 2.601 2-CF3 5-Cl H C2Hs CF2Cl 2.602 2-CF3 5-Cl H C3H7(i) CF2Cl 2.603 2-CF3 5-Cl H CH3 CF2CF3 2.604 2-CF3 5-Cl H OCH3 CF3 2.605 2-CF3 5-Cl H SCH3 CF3 2.606 2-CF3 5-Cl H SOCH3 CF3 2.607 2-CF3 5-Cl H 5OzCH3 CH3 2.608 2-CH3 3-CH3 H CH3 Cl 2.609 2-CH3 3-CH3 H CH3 CF3 2.610 2-CH3 5-CH3 H CH3 Cl 2.$11 2-CH3 5-CH3 H CH3 CF3 2.612 2-CH3 6-CH3 H CH3 Cl 2.613 2-CH3 6-CH3 H CH3 CF3 m.p. 145-146C
2.614 2-CH3 6-CH3 H CH3 CF2Cl m.p. 147-148C
2.615 2-CH3 6-CH3 H CH3 CH2CF3 2.616 2-CH3 6-CH3 H OCH3 CF3 2.617 2-CH3 6-CH3 H SCH3 CF3 2.618 2-CH3 6-C2Hs H CH3 Cl 2.619 2-CH3 6-CZHs H CH3 CF3 m.p. 90-93C
2.620 2-CH3 6-C2Hs H OCH3 CF3 2.621 2-CH3 5-F H CH3 Cl 2.622 2-CH3 5-F H CH3 CF3 m.p. 78-79C
2.623 2-CH3 5-F H CH3 CHFz 2.624 2-CH3 5-F H CH3 CF2Cl 2.625 2-CH3 5-F H C2Hs CF3 2.626 2-CH3 5-F H C3H7(i) CF3 2.627 2-CH3 5-F H OCH3 CF3 2.628 2-CH3 5-F H OC2Hs CF3 2.629 2-Br 6-Br H CH3 Cl 2.630 2-Br 6-Br H CH3 CF3 2.631 2-Br 6-Br H C2Hs CF3 m.p. 104-105C
2.632 2 Br 6-Br H C3H7(i) CF3 2.633 2-Br 6-Br H Cyclo- CF3 propyl 2.634 2-Br 6-Br H CH3 CHCl2 2.635 2-Br 6-Br H CH3 CF2CF3 2.636 2-Br H H C3H7(i) CF2CF3 nD5: 1,5307 2.637 2-CF3 H H CH3 CHC12 m.p. 72-74C
- 52 - 1 3 1 4 a Table II (continued~
Comp.No. R1 R2 R3 R4 ~s Physical data 2.638 2-OCHFz H H CH3 CF3 m.p. 71-72C
2.639 2-OCHFz H H C3H7(i) CF3 2.640 2-OCHF2 H H Cyclo- CF3 nD5: 1,5242 propyl 2.641 2-OCHF2 H H CH3 CHFz 2.642 2-OCHFz H H CH3 CHFCl 2.643 2-CF3 H H CH3 CHF2 2.644 2-CF3 H H CH3 CF2Cl 2.645 2-CF3 H H C3H7(i) CF2Cl nD5: 1,5184 2.646 2-CF3 H H Cyclo- CF3 m.p. 63-64C
propyl 2.647 2-CF3 H H 2-Thienyl CF3 m.p. 97-98C
2.648 2-Br H H C4Hg(n) CF3 m.p. 65-66C
2.649 2-Br H H C3H7(i) CF3 nD5: 1,5583 2.650 2-Br H H CH3 CHF2 2.651 2-Br H H CH3 CF2Cl 2.652 2-Br H H Cyclo- CF2Cl propyl 2.653 2-Br H H C2Hs CHFz 2.654 2-Cl 6-CH3 H CH3 CH3 m.p. 141-142C
2.655 2-Cl 6-Cl H CH3 CHF2 m.p. 99-101C
2.656 2-Cl 6-Cl H C2Hs CHFz 2.657 2-Cl 5-Cl H CsH1l(n) CF3 m.p. 56-57C
2.658 2-COoCH3 H H CH3 CF3 m.p. 143-145C
2.659 2-COOCH3 H H CzHs CF3 2.660 2-COOCH3 H H C3H7(i) CF3 2.661 2-COOCH3 H H Cyclo- CF3 propyl 2.662 2-COOCH3 H H CH3 CF2Cl 2.663 2-CooCH3 H H CH3 CHF2 2.664 2-COOC2Hs H H CH3 CF3 2.665 2-COOC3H7(n) H H CH3 CF3 2.666 2-COOC3H7(i) H H CH3 CF3 2.667 2-COOC4Hg(n) H H CH3 CF3 2.668 2-OCH3 5-F H CH3 CF3 m.p. 89-93C
2.669 2-OCH3 5-F H CH3 CHF2 2.670 2-OCH3 5-F H C2Hs CHF2 2.671 2-OCH3 5-F H C3H7(i) CF3 2.672 2-OCH3 5-F H Cyclo- CF3 propyl 2.673 2-OCH3 5-F H Cyclo- CF3Cl - 53 - 13~4~
Table II (continued) Comp.No. Ri R~ R3 R4 _ _ Physical data 2.674 2-OCHF2 S-F H CH3 CF3 2.675 2-OCHF2 5-F H CH3 CHF2 2.676 2-OCHF2 5-F H CH3 CFzCl 2.677 2-COOCH3 6-CH3 H CH 3 CF3 m.p. 90- 91C
2.678 2-COOCH3 6-CH3 H CH3 CHFz 2.679 2-COOCH3 6-CH3 H C3H7(i) CF3 2.680 2-COOCH3 6-CH3 H Cyclo- CF3 propyl 2.681 2-COOCH3 6-Cl H CH3 CF3 m .p. 86-87C
2.682 2-COOCH3 6-Cl H CH3 CHFz 2.683 2-Br H H 2-Furyl CF3 m.p. 108-109C
2.684 2-Cl 6-Cl 3-CH ~CH3 Cl m.p. 158-164C
2.685 2-CF3 H H CzHs CHC12 nD5: 1,5462 2.686 2-Cl S-Cl H Cl CF3 m.p. 66-67C
2.687 2-CONHz H H CHH3 CF3 m.p. 187-190C
2.688 2-Cl 6-Cl H CHCHzCH3 CF3 m.p. 91-92C
2.689 2-F H H CzHs CF3 nDS: 1,5332 2.690 2-F H H CH20CH3 CF3 m.p. 48-50C
2.691 2-F H H CH20CH3 CF2Cl nDS: 1,5525 2.692 2-OCH3 6-Cl H CH3 CF3 m.p. 113-114C
2.693 2-OCH3 6-Cl H CzHs CF3 m.p. 68-70 C
2.694 2-OCH3 6-Cl H C3H7(i) CF3 m.p. 80-81C
2.695 2-CH3 6-CH3 H CzHs CF3 m.p. 88-89C
2.696 2-CH3 6-CH3 H C3H7(i) CF3 m.p. 64-65C
2.697 2-F 6-F H C4Hg(i) CF3 m.p. 97-99C
2.698 2-F 6-F H _ /¦ CF3 m.p. 111-113C
2.699 2-F 6-F H CH20CH3 CF3 m.p. 62-65C
2.700 2-F 6-F H C2Hs CHClz m.p. 123-125C
2.701 2-F 6-F H 2-Furyl CF3 m.p. 122-123C
2.702 2-CH3 5-F H C2Hs CHC12 Oel 2.703 2-Cl 6-CH3 H CHzOCH3 CF3 m.p. 95-96C
2.704 2-Cl 6-CH3 H CH20CH3 CF2Cl m.p. 103-105C
2.705 2-Cl 6-CH3 H C3H7(i) CF2Cl m.p. 60-61C
2.706 2-Cl 6-CH3 H Cl CF3 m.p. 102C
2.707 2-Cl 6-CH3 H CH20CH3 CHFz nDS: 1,5375 2.708 2-F H H CH20CH3 CHFz m.p. 44-45C
2.709 2-OCH3 6-CH3 H CH3 CF3 m.p. 94-95C
2.710 2-Cl 6-Cl H Cl CF3 m.p. 124-125C
2.711 2-SCHF2 H H CH3 CF3 m.p. 78-79C
2.712 2-OCHF2 6-CH3 H CH3 CF3 nD3: 1,5050 2.713 2-OCHFz 6-CH3 H CZHs CF3 nD3: 1,4910 2.714 2-F 6-Cl H 2-Furyl CF3 m.p. 119-120C
2.715 2-CH3 6-F H CzHs CHClz _ 54 _ 1 31~5 4~
P. 3. Compounds of formula III
P. 3.1. N-chlorocarbonyl-N-(4,6-dimethyl-pyrimidin-2-yl)-2,5-dichloro-aniline
Recrystallisation from ethanol yields 2.4 g (64.9 %) of the title compound of formula /Cl N- / 3 \.=./ ~ ~=./
C~ ICO CH3 ~H2 in the form of crystals having a melting point of 153C (decomp.) (Comp.
No. 1.050).
The compounds of Table I can be obtained analogously to the P.1 Prepara-tion Examples.
~l- 1314~S
Table I
Compounds of formula ~1 N_./R5 H- ~ /- ~ \N-./ I
R2 ~R3 ~= \R4 Hz Comp.No. Rl R2 R3 R4 Rs Physical data 1.001 2-Cl H H CH3 CH3 from 147C decomp.
1.002 2-Cl H H CH3 OCHFz 1.003 2-Cl H H CH3 Cl 1.004 2-Cl H H CH3 CF3 1.005 2-Cl H H CH3 CFzCF3 1.006 2-Cl H H CHzGH3 CF3 1.007 2-Cl H H CH3 CF2Cl 1.008 2-Cl H H CH3 CHF2 1.009 2-Br H H CH3 Cl m.p. 149-150C
1.010 2-Br H H OCH3 CF3 1.011 2-Br H H CH3 CF3 1.012 2-Br H H SCH3 CF3 1.013 2-Br H H CHzCH3 CF3 1.014 2-Br H H CH3 CHCl2 1.015 2-Br H H CH3 CHFCl 1.016 2-Br H H Cyclo- CF3 m.p. 183-184C
propyl 1.017 2-CF3 H H Phenyl CF3 1.018 2-CF3 H H 2-Furyl CF3 1.019 2-CF3 H H CH3 Cl 1.020 2-CF3 H H CH3 CF3 m.p. 150-153C
1.021 2-CF3 H H CH3 CH3 m.p. 145-146DC.
1.022 2-CF3 H H CH2CH3 CF3 1.023 2-CF3 H H CH(CH3)2 CF3 m.p. 137-138C
1.024 2-CF3 H H (n)C3H7 CF3 m.p. 153-154C
1.025 2-CF3 H H OCH3 CF3 1.026 2-CF3 H H OCzHs CF3 1.027 2-CF3 H H _ SCH3 CF3 1.028 2-CF3 H H ~CH(CH3)z CF3 1.029 2-CF3 H H ¦CH3 CF2CF3 - 22 - ~ 3 1 ~ ~ ~ 6 Table 1 (continued) -Comp.No. Rl R2 R3 R4 l Rs Physical data 1.030 2-CF3 H H CH3 CHFCl 1.031 2-J H H CH3 Cl 1.032 2-J H H CH3 CF3 m.p. 168-160C
1.033 2-J H H CH2CH3 CF3 1.034 2-J H H CH3 CF2Cl 1.035 2-F H H CH3 CH3 from 159C decomp.
1.036 2-F H H CH3 Cl 1.037 2-F }I H CH3 CF3 from 169C decomp.
1.038 2-F H H CH(CH3)z CF3 m.p. 144-146C
1.039 2-F H H Cl CF3 1.040 2-F H H OC2Hs CF3 1.041 2-Cl 3-Cl H CH3 Cl m.p. 143-144C
1.042 2-Cl 3-Cl H CH3 CF3 m.p. 139-140C
1.043 2-Cl 3-Cl H OCH3 CF3 1.044 2-Cl 3-Cl H OC4Hg(n) CF3 1.045 2-Cl 3-Cl H SCzHs CF3 1.046 2-Cl 3-Cl H Phenyl CF3 1.047 2-Cl 3-Cl H CH3 CFzCl 1.048 2-Cl 3-Cl H CH3 CHFCl 1.049 2-Cl 3-Cl H CH3 CH3 from 163C decomp.
1.050 2-Cl 5-Cl H CH3 CH3 from 153C decomp.
1.051 2-Cl 5-Cl H CH3 oCHF2 1.052 2-Cl 5-Cl H CH3 Cl m.p. 123-125C
1.053 2-Cl 5-Cl H OCH3 CH3 1.054 2-Cl 5-Cl H CH3 Br 1.055 2-Cl 5-Cl H CH3 CF3 m.p. 150-151C
1.056 2-Cl 5-Cl H CH2CH3 CF3 m.p. 149-150C
1.057 2-Cl 5-Cl H C3H7(n) CF3 m.p. 148-149C
1.058 2-Cl 5-Cl H C3H7(i) CF3 m.p. 156-157C
1.059 2-Cl 5-Cl H Cyclo- CF3 m.p. 174-175C
propyl 1.060 2-Cl 5-Cl H Phenyl CF3 1.061 2-Cl 5-Cl H ¦, ~-Thienyl CF3 m.p. 177-178C
1.062 2-Cl 5-Cl H 2-Furyl CF3 m.p. 168-169C
1.063 2-Cl 5-Cl H CH3 CF2CF3 m.p. 157-158C
1.064 2-Cl 5-Cl H CH3 CFzCl m.p. 178-179C
1.065 2-Cl 5-Cl H CH3 CHF2 m.p. 159-160C
1.066 2-Cl 5-Cl H CH3 CHClF m.p. 153-154C
1.067 2-Cl 5-Cl H CH2CH3 CF2Cl 1.068 2-Cl 5-Cl H C3H7(i) CF2Cl m.p. 161-162C
1.069 2-Cl 5-Cl H OCH3 CF3 1.070 2-Cl 5-Cl H OC2Hs CF3 1.071 2-Cl 5-Cl H OC3H7 CF3 1.072 2-Cl 5-Cl H OC3H7(i) CF3 1.073 2-Cl 5-Cl H OC4Hg(n) CF3 1.074 2-Cl 5-Cl H OC4Hg(i) CF3 1.075 2-Cl 5-Cl H SCH3 CF3 1.076 2-Cl 5-Cl H SC2Hs CF3 1.077 2-Cl 5-Cl H SC3H7(n) CF3 1.078 2-Cl 5-Cl H SC3H7(i) CF3 - 23 ~ 4 ~ ~ ~
Table 1 (continued) No. - - R2 R3 R~ Rs Physical data 1.079 2-Cl 5-Cl H SC4Hg(n) CF3 1.080 2-Cl 5-Cl H C4Hg(n) CF3 m.p. 123-124C
1.081 2-Cl 5-Cl H C4Hg(i) CF3 1.082 2-Cl 5-Cl H C4Hg(t) CF3 m.p. 159-160C
1.083 2-Cl 5-Cl H C2Hs CF2CF3 m.p. 157-158C
1.084 2-Cl 5-Cl H C3H7(i) CFzCF3 m.p. 161-162C
1.085 2-Cl 5-Cl H C3H7(n) CF2CF3 1.086 2-Cl 5-Cl H OCF2CHFz CF3 1.087 2-Cl 5-Cl H CH3 CCl2CF3 1.088 2-Cl 5-Cl H C2Hs CCl2CF3 1.089 2-Cl 5-Cl H CH3 CHClz m.p. 157-159C
1.090 2-Cl 5-Cl H C2Hs CHCl2 1.091 2-Cl 5-Cl H CH3 CClzCH3 1.092 2-Cl 5-Cl H CZHs CCl2CH3 1.093 2-Cl 6-Cl H CH3 CH3 m.p. 173-174C
1.094 2-Cl 6-Cl H CH3 CzHs 1.095 2-Cl 6-Cl H CH3 C3H7(i) 1.096 2-Cl 6-Cl H CH3 Cl m.p. 184-185C
1.097 2-Cl 6-Cl H CH3 CCl2CH3 1.098 2-Cl 6-Cl H CzHs CClzCH3 1.099 2-Cl 6-Cl H CH3 CHC12 1.100 2-Cl 6-Cl H CZHs CHCl2 1.101 2-Cl 6-Cl H CH3 CCl2CF3 1.102 2-Cl 6-Cl H C3H7(i) CClzCF3 1.103 2-Cl 6-Cl H CH3 CHClF
1.104 2-Cl 6-Cl H C2Hs CHClF
1.105 2-Cl 6-Cl H CH3 CF2Cl 1.106 2-Cl 6-Cl H C2Hs CF2Cl 1.107 2-Cl 6-Cl H C3H7(i) CFzCl 1.108 2-Cl 6-Cl H C3H7(n) CF2Cl 1.109 2-Cl 6-Cl H CH3 CF3 m.p. 156-157C
1.110 2-Cl 6-Cl H CzHs CF3 1.111 2-Cl 6-Cl H C3H7(n) CF3 1.112 2-Cl 6-Cl H C3H7(i~ CF3 1.113 2-Cl 6-Cl H Cyclo- CF3 m.p. 187-188C
propyl 1.114 2-Cl 6-Cl H Phenyl CF3 1.115 2-Cl 6-Cl H ~ -Thienyl CF3 m.p. 201-202C
1.116 2-Cl 6-Cl H 2-Furyl CF3 1.117 2-Cl 6-Cl H CH3 CFzCF3 1.118 2-Cl 6-Cl H CZHs CF2CF3 m.p. 168-169~C
1.119 2-Cl 6-Cl H C3H7(i) CF2CF3 m.p. 154-155C
1.120 2-Cl 6-Cl H C3H7(n) CF2CF3 1.121 2-Cl 6-Cl H Cyclo- CF2CF3 propyl 1.122 2-Cl 6-Cl H CH3 OCHF2 1.123 2-Cl 6-Cl H C4Hg(n) CF3 1.124 2-Cl 6-Cl H C4Hg(i) CF3 1.125 2-Cl 6-Cl H C4Hg(t) CF3 m.p. 174-175C
- 24 - 1 31 ~6 Table 1 (continued) Comp.No. R' R2 R3 R4 Rs Physical data 1.126 2-C1 6-Cl H OCH3 CF3 1.127 2-Cl 6-C1 H OC2Hs CF3 1.128 2-C1 6-Cl H OC3H7(n) CF3 1.129 2-Cl 6-Cl H OC3H7(i) CF3 1.130 2-C1 6-Cl H OC4Hg(n) CF3 1.131 2-C1 6-C1 H OC4Hg(i) CF3 1.132 2-Cl 6-Cl H SCH3 CF3 m.p. 158-159C
1.133 2-Cl 6-Cl H SC2Hs CF3 1.134 2-C1 6-Cl H SC3H7(n) CF3 1.135 2-Cl 6-Cl H SC3H7(i) CF3 1.136 2-Cl 6-Cl H SC4Hg(n) CF3 1.137 2-Cl 6-Cl H OCH3 CH3 1.138 2-Cl 6-Cl H C2Hs Cl 1.139 2-Cl 6-Cl H OCH3 CZHs 1.140 2-Cl 6-Cl H - '2Hs OCHFz 1.141 2-Cl 6-Cl 3-CH3 CH3 CF3 m.p. 182C decomp.
1.142 2-Cl 6-Cl 3-CH3 CzHs CF3 1.143 2-Cl 6-Cl 3-CH3 C3H7(n) CF3 1.144 2-Cl 6-Cl 3-CH3 C3H7(i) CF3 m.p. 160-162C
1.145 2-Cl 6-Cl 3-CH3 CH3 CF2CF3 m.p. 164-166C
1.146 2-Cl 6-Cl 3-CH3 CZHs CFzCF3 1.147 2-Cl 6-Cl 3-CH3 Cl CF3 1.148 2-Cl 6-Cl 3-CH3 OCH3 CF3 1.149 2-C1 6-Cl 3-CH3 OC2Hs CF3 1.150 2-C1 6-C1 3-CH3 SCH3 CF3 1.151 2-C1 6-Cl 3-CH3 SC4Hg(n ~CF3 1.152 2-Cl 6-Cl 3-CH3 CH3 CF2Cl 1.153 2-Cl 6-Cl 3-CH3 CH3 CHFz 1.154 2-Cl 6-Cl 3-CH _ CH3 CHC12 1.155 2-Cl 3-CF3 H H3 Cl 1.156 2-Cl 3-CF3 H CH 3 CH3 1.157 2-Cl 3-CF3 H CH3 CF3 1.158 2-Cl 3-CF3 H CzHs CF3 1.159 2-Cl 3-CF3 H C3N7(n) CF3 1.160 2-Cl 3-CF3 H CH3 CFzCF3 1.161 2-Cl 3-CF3 H CH3 CClF2 1.162 2-Cl 3-CF3 H CH~ CHClF
1.163 2-Cl 5-CF3 H CH3 Cl m.p. 148-149C
1.164 2-Cl 5-CF3 H CH3 CF3 m.p. 144-145C
1.165 2-Cl 5-CF3 H CH3 CClFz 1.166 2-Cl 5-CF3 H C2Hs CF3 1.167 2-Cl 5-CF3 H OCH3 CF3 1.168 2-Cl 6-CF3 H CH3 Cl 1.169 2-Cl 6-CF3 H CH3 CH3 1.170 2-Cl 6-CF3 H CH3 CF3 m.p. 155-156C
1.171 2-Cl 6-CF3 H CzHs CF3 1.172 2-Cl 6-CF3 H C3H7(n) CF3 1.173 2-Cl 6-CF3 H C3H7(i) CF3 - 25 - 1 3 1 ~ ~ 4 ~
Table 1 (continucd) Comp.No. Rl R2 R3 R~ Rs Physical data 1.174 2-Cl 6-CF3 H Cyclo- CF3 propyl 1.175 2-Cl 6-CF3 H C4H9~n~ CF3 1.176 2-Cl 6-CF3 H Cl,H9(i) CF3 1.177 2-Cl 6-CF3 H C4H9(t) CF3 1.178 2-Cl 6-CF3 H CH3 CF2CF3 1.179 2-Cl 6-CF3 H C2Hs CF2CF3 1.180 2-Cl 6-CF3 H CH3 CHCl2 1.181 2-Cl 6-CF3 H CH3 CClF2 1.182 2-Cl 6-CF3 H C2Hs CClF2 1.183 2-Cl 6-CF3 H CH3 CHF2 1.184 2-C1 6-CF3 H CH3 OCHF2 1.185 2-Cl 6-CF3 H OCH3 CF3 1.186 2-Cl 6-CF3 H OC2Hs CF3 1.187 2-Cl 6-CF3 H SC2Hs CF3 1.188 2-Cl 6-CF3 H CH3 CClzCF3 1.189 2-Cl 6-CF3 H CH3 CCl2CH3 1.190 2-Cl 6-CF3 H Phenyl CF3 1.191 2-Cl 3-CH3 H CH3 CF3 1.192 2-Cl 3-CH3 H CH3 CF2CF3 1.193 2-Cl 3-CH3 H C2Hs CF3 1.194 2-Cl 3-CH3 H C3H7(n~ CF3 1.195 2-Cl 3-CH3 H C3H7(i) CF3 1.196 2-Cl 3-CH3 H CH3 C1 1.197 2-Cl 3-CH3 H CH3 CFzCl 1.198 2-Cl 3-CH3 H CH3 CHClz 1.199 2-Cl 3-CH3 H CH3 CHClF
1.200 2-Cl 3-CH3 H OCH3 CF3 1.201 2-Cl 5-CH3 H CH3 Cl m.p. 140-141C
1.202 2-Cl 5-CH3 H CH3 CHC12 1.203 2-Cl 5-CH3 H CH3 CClzCF3 1.204 2-Cl 5-CH3 H CH3 CHClF
1.205 2-Cl 5-CH3 H CH3 CF2Cl 1.206 2-Cl 5-CH3 H C2Hs CF2Cl 1.207 2-Cl 5-CH3 H CH3 CF3 1.208 2-Cl 5-CH3 H C2Hs CF3 1.209 2-Cl 5-CH3 H C3H7(n) CF3 1.210 2-Cl 5-CH3 H C3H7(i) CF3 1.211 2-Cl 5-CH3 H C4Hg(n) CF3 1.212 2-Cl 5-CH3 H C4Hg(t) CF3 1.213 2-Cl 5-CH3 H 2-Furyl CF3 1.214 2-Cl 5-CH3 H CH 3 CF2CF3 1.215 2-Cl 5-CH3 H C2Hs CFzCF3 1.216 2-Cl 5-CH3 H OCH3 CF3 1.217 2-Cl 5-CH3 H OC2Hs CF3 1.218 2-Cl 5-CH3 H SCH3 CF3 1.219 2-Cl 6-CH3 H CH3 Cl m.p. 167-168C
1.220 2-Cl 6-CH3 H CN CH3 1.221 2-Cl 6-CH3 H CH3 CF3 m.p. 192-193C
- 26 - 1 31 ~ ~ 4 6 Table 1 (continued) Comp.No. R~ R2 R3 R4 Rs Physical data 1.222 2-Cl 6-CH3 H CH3 CFzCl m.p. 185-187C
1.223 2-Cl 6-CH3 H CH3 CFzCF3 1.224 2-Cl 6-CH3 H CH3 CClzCF3 1.225 2-Cl 6-CH3 H CH3 CHFz 1.226 2-Cl 6-CH3 H CH3 CHcl2 1.227 2-Cl 6-CH3 H CzHs CF3 m.p. 155-157C
1.228 2-Cl 6-CH3 H C3H7(i) CF3 m.p. 146-148C
1.229 2-Cl 6-CH3 H Cyclo- CF3 m.p. 177-178C
propyl 1.230 2-Cl 6-CH3 H C4Hg(i) CF3 1.231 2-Cl 6-CH3 H CzHs CF2CF3 1.232 2-Cl 6-CH3 H _ OCH3 CF3 1.233 2-Cl 6-CH3 H ( )CH2CHzCl CF3 1.234 2-Cl 6-CH3 H )CH2CH2OCI ~ CF3 1.235 2-Cl 6-CH3 H OC2Hs CF3 1.236 2-Cl 6-CH3 H SCH3 CF3 1.237 2-Cl 6-CH3 H SC2Hs CF3 1.238 2-Cl 6-CH3 H SC3H7(i) CF3 1.239 2-Cl 6-CH3 H SC4Hg(i) CF3 1.240 2-Cl 5-OCH3 H CH3 CF3 1.241 2-Cl 5-OCH3 H C2Hs CF3 1.242 ~-Cl 5-OCH3 H CH3 Cl 1.243 2-Cl 5-OCH3 H OCH3 CF3 1.244 2-Cl 5-OCH3 H CH3 CHFz 1.245 2-Cl 5-OCH3 H CH3 CFzCF3 1.246 2-Cl 5-OCH3 H CH3 CF2Cl 1.247 2-Cl 5-COOCH3 H CH3 CF3 m.p. 152-153C
1.248 2-Cl 5-COOCH3 H CzHs CF3 1.249 2-Cl 5-COOCzHs H CH3 CF3 1.250 2-Cl 5-COOCzHs H CH3 CFzCF3 1.251 2-Cl 5-COOC3H7(i) H CH3 CF3 1.252 2-Cl 5-COOC3H7(i) H C3H7(i) CF3 1.253 2-Cl 5-COOC3H7(i) H CH3 CF2Cl 1.254 2-Cl 5-COOC 3 H7(i) H Phenyl CF3 1.255 2-Cl 5-COOC3H7(i) H Cyclo- CF3 propyl 1.256 2-Cl 5-COOC3H7(i, _ H CH3 CHFCl 1.257 3-Cl 5-Cl H CH3 Cl m.p. 117-118C
1.258 3-Cl 5-Cl H CH3 CF3 m.p. 129-130C
1.259 3-Cl 5-Cl H CZHs CF3 1.260 3-Cl 5-Cl H C3H7(n) CF3 1.261 3-Cl 5-Cl H C3H7(i) CF3 1.262 3-Cl 5-Cl H Cyclo- CF3 propyl 1.263 3-Cl 5-Cl H Phenyl CF3 1.264 3-Cl 5-Cl H CH3 CHF2 1.265 3-Cl 5-Cl H CH3 CF2Cl 1.266 3-Cl 5-Cl H C2Hs CFzCl 1.267 3-Cl 5-Cl H OCH3 CF3 - 27 - ~ 31~5~ ~
Table_l (continued) Comp.No. R~ R2 R3 R4 Rs Physical data 1.268 3-Cl 5-Cl H OC2Hs CF3 1.269 3-Cl 5-Cl H SCH3 CF3 1.270 3-Cl 5-Cl H SC3H7(i) CF3 1.271 2-CH3 5-Cl H CH3 Cl m.p. 141-142C
1.272 2-CH3 5-Cl H CH3 CF3 1.273 2-CH3 5-Cl H CN CF3 1.274 2-CH3 5-Cl H C2Hs Cl 1.275 2-CH3 5-Cl H CH3 OCHFz 1.276 2-CH3 5-Cl H CH3 Br 1.277 2-CH3 5-Cl H CH3 F
1.278 2-CH3 5-Cl H CH3 CH3 m.p. 150-151C
1.279 2-CH3 5-Cl H OCH3 CH3 1.280 2-CH3 5-Cl H C2Hs CF3 1.281 2-CH3 5-Cl H C3H7(n) CF3 1.282 2-CH3 5-Cl H C3H7(i) CF3 1.283 2-CH3 5-Cl H Cyclo- CF3 propyl 1.284 2-CH3 5-Cl H Phenyl CF3 1.285 2-CH3 5-Cl H C4Hg(n) CF3 1.286 2-CH3 5-Cl H C4Hg(i) CF3 1.287 2-CH3 5-Cl H C4Hg(t) CF3 1.288 2-CH3 5-Cl H CH3 CF2CF3 1.289 2-CH3 5-Cl H C2Hs CF2CF3 1.290 2-CH3 5-Cl H C3H7(i) CFzCF3 1.291 2-CH3 5-C1 H CH3 CF2Cl 1.292 2-CH3 5-Cl H C2Hs CF2Cl 1.293 2-CH3 5-Cl H CH3 CHFz 1.294 2-CH3 5-Cl H C2Hs CHFz 1.295 2-CH3 5-Cl H CH3 CHFCl 1.296 2-CH3 5-Cl H C2Hs CHFCl 1.297 2-CH3 5-Cl H CH3 CHCl2 1.298 2-CH3 5-Cl H C2Hs CHCl2 1.299 2-CH3 5-Cl H CH3 CCl2CF3 1.300 2-CH3 5-Cl H CH3 CCl2CH3 1.301 2-CH3 5-Cl H OCH3 CF3 1.302 2-CH3 5-Cl H OC2Hs CF3 1.303 2-CH3 5-Cl H SCH3 CF3 1.304 2-CH3 5-Cl H SC2Hs CF3 1.305 2--CH3 5-Cl H SC4Hg(i) CF3 1.306 2-CH3 3-Cl H CH3 Cl m.p. 155-156C
1.307 2-CH3 3-Cl H CH3 CF3 1.308 2-CH3 3-Cl H CzHs CF3 1.309 2-CH3 3-Cl H C3H7(i) CF3 1.310 2-CH3 3-Cl H Cyclo- CF3 propyl 1.311 2-CH3 3-Cl H CH3 CF2Cl 1.312 2-CH3 3-Cl H CH3 CF2CF3 1.313 2-CH3 3-Cl H C2Hs CFzCF3 1.314 2-CH3 3-Cl H OCH3 CF3 131~46 Table I (continued) Com~.No. Rl R2 R3 R4 Rs Physical data 1.315 2-CH3 3-Cl H SCH3 CF3 1.316 2-CH3 5-NO2 H CH3 Cl m.p. 142-143C
1.317 2-CH3 5-NO2 H CH3 CF3 1.318 2-CH3 5-NO2 H CH3 CF2Cl 1.319 2-CH3 5-NOz H CH3 CHFz 1.320 2-CH3 5-NO2 H C2Hs CF3 1.321 2-CH3 5-NO2 H C3H7(n) CF3 1.322 2-CH3 5-NO2 H C3H7(i) CF3 1.323 2-CH3 5-NOz H C4Hg(t) CF3 1.324 2-CH3 3-NO2 H CH3 Cl m.p. 158-159C
1.325 2-CH3 3-NO2 H CH3 CF3 1.326 2-CH3 3-NOz H CH3 CF2CF3 1.327 2-CH3 3-NO2 H C2Hs CF2CF3 1.328 2~CH3 3-NOz H Phenyl CF3 1.329 2-CH3 3-NO2 H CzHs CF3 1.330 2-CH3 3-NO2 H C3H7(i) CF3 1.331 2-CH3 6-CF3 H CH3 Cl 1.332 2-CH3 6-CF3 H CH3 CF3 m.p. 164-165C
1.333 2-CH3 6-CF3 H CH3 CHF2 1.334 2-CH3 6-CF3 H CH3 CF2Clz 1.335 2-CH3 6-CF3 H CH3 CHC12 1.336 2-CH3 6-CF3 H OCH3 CF3 1.337 2-CH3 6-CF3 H OC2Hs CF3 1.338 2-CH3 6-CF3 H SCH3 CF3 1.339 2-CH3 6-CF3 H SC2Hs CF3 1.340 2-CH3 6-CF3 H C2Hs CF3 1.341 2-CH3 6-CF3 H CH3 CF2CF3 1.342 2-CH3 6-CF3 H C2Hs CF2CF3 1.343 2-CH3 6-CF3 H C3H7(i) CF3 1.344 2-CH3 6-CF3 H C3H7(n) CF3 1.345 2-CH3 6-CF3 H Cyclo- CF3 propyl 1.346 2-OCHF2 5-Cl H CH3 Cl m.p. 138-139C
1.347 2-OCHFz 5-Cl H CH3 CH3 1.348 2-OCHF2 5-Cl H CH3 CHCl2 1.349 2-OCHF2 5-Cl H CH3 CHFCl 1.350 2-oCHFz 5-Cl H CH3 CHF2 1.351 2-OCHF2 5-Cl H CH3 CFzCl 1.352 2-OCHF2 5-Cl H CH3 CF3 m.p. 142-143C
1.353 2-OCHF2 5-Cl H CH3 CFzCF3 1.354 2-OCHFz 5-Cl H CH3 CClzCF3 1.355 2-oCHFz 5-Cl H CH3 CCl2CH3 1.356 2-OCHF2 5-Cl H C2Hs C~3 1.357 2-OCHF2 5-Cl H C3H7(n) CF3 1.358 2-OCHF2 5-Cl H C3H7(i) CF3 1.359 2-CH3 6-Cl H Cyclo- CF3 propyl 1.360 2-CH3 6-Cl H C4Hg(n) CF3 1.361 2-CH3 6-Cl H C4Hg(i) CF3 - 29 - 1 ~ 145 ~ ~
Table 1 (continued) Comp.No. R~ R2 R3 R4 R5 Physical data 1.362 2-CH3 6-Cl H C~Hg(t) CF3 1.363 2-CH3 6-Cl H Phenyl CF3 1.364 2-CH3 6-Cl H 2-Furyl CF3 1.365 2-CH3 6-Cl H L -Thienyl CF3 1.366 2-CH3 6-Cl H CzHs CF2CF3 1.367 2-CH3 6-C] H C2Hs CCl2CH3 1.368 2-CH3 6-Cl H OCH3 CF3 1.369 2-CH3 6-Cl H OCzHs CF3 1.370 2-CH3 6-Cl H SCH3 CF3 1.371 2-Cl 6-Cl 3-Cl CH3 Cl 1.372 2-Cl 6-Cl 3-Cl CH3 CF3 1.373 2-Cl 6-Cl 3-Cl C2Hs CF3 1.374 2-Cl 6-Cl 3-Cl C3H7(i) CF3 1.375 2-Cl 6-Cl 3-Cl CH3 CFzCF3 1.376 2-Cl 6-Cl 3-Cl Phenyl CF3 1.377 2-Cl 6-Cl 3-Cl OCH3 CF3 1.378 2-Cl 6-Cl 3-Cl OC2Hs CF3 1.379 2-Cl 6-Cl 3-Cl SCzHs CF3 1.380 2-OCH3 3-Cl H CH3 CF3 m.p. 179-180C
1.381 2-OCH3 3-Cl H C2Hs CF3 1.382 2-OCH3 3-Cl H C3H7(n) CF3 1.383 2-OCH3 3-Cl H Cyclo- CF3 propyl 1.384 2-OCH3 3-Cl H CH3 Cl 1.385 2-OCH3 3-Cl H CH3 CF2CF3 1.386 2-OCH3 3-Cl H OCH3 CF3 1.387 2-OCH3 3-Cl H SCH3 CF3 1.388 2-OCH3 3-Cl H CH3 CFzCl 1.389 2-oCH3 3-Cl H CH3 CHF2 1.390 2-OCH3 5-Cl H CH3 Cl 1.391 2-OCH3 5-Cl H CH3 CH3 m.p. 157-158C
1.392 2-OCH3 5-Cl H CH3 CF3 m.p. 158-159C
1.393 2-OCH3 5-Cl H CH3 Br 1.394 2-OCH3 5-Cl H CN CH3 1.395 2-oCH3 5-Cl H CH3 CFzC
1.396 2-OCH3 5-Cl H CH3 CHF2 1.397 2-OCH3 5-Cl H CH3 CHCl2 1.398 2-oCH3 5-Cl H CH3 CF2CF3 m.p. 125-126C
1.399 2-OCH3 5-Cl H CH3 CCl2CF3 1.400 2-OCH3 5-Cl H CH3 CHClF
1.401 2-OCH3 5-Cl H CH3 CCl2CH3 1.402 2-OCH3 5-Cl H C2Hs CF3 1.403 2-OCH3 5-Cl H C2Hs CF2CF3 m.p. 148-150C
1.404 2-OCH3 5-Cl H C2Hs CF2Cl 1.405 2-OCH3 5-Cl H C3H7(n> CF3 m.p. 168-169C
1.406 2-oCH3 5-Cl H C3H7(i) CF3 m.p. 167-168C
1.407 2-OCH3 5-Cl H C3H7~i) CF2CF3 1.408 2-OCH3 5-Cl H Cyclo- CF3 propyl 1~14~6 Table 1 (continued) Comp.No. Rl R2 R3 R4 Rs Physical da~a 1.409 2-OCH3 5-Cl H C4Hg(n) CF3 1.410 2-OCH3 5-Cl H C2Hs(i) CF3 1.411 2-OCH3 5-Cl H C4Hg(t) CF3 m.p. 156-157~C
1.412 2-OCH3 5-Cl H OCH3 CF3 1.413 2-OCH3 5-Cl H OC4Hg(n) CF3 1.414 2-OCH3 5-Cl H SCH3 CF3 1.415 2-OCH3 5-Cl H SCzHs CF3 1.416 2-OCH3 5-Cl H SC3H7(n) CF3 1.417 2-OCH3 5-Cl H SC3H7(i) CF3 1.418 2-OC2Hs 5-Cl H CH3 Cl 1.419 2-OCZHs 5-Cl H CH3 CF3 1.420 2-OC2Hs 5-Cl H CZHs CF3 1.421 2-OC2Hs 5-Cl H C3H7(i) CF3 1.422 2-OCzHs 5-Cl H Cyclo- CF3 propyl 1.423 2-OC2Hs 5-Cl H Phenyl CF3 1.424 2-OC2Hs 5-Cl H OCH3 CF3 1.425 2-OCzHs 5- -Cl H CH3 CFzCF3 1.426 2-OC3H7(i) 5-Cl H CH3 Cl 1.427 2-OC3H7(i) 5-Cl H CH3 CF3 1.428 2-OC3H7(i) 5-Cl H CH3 CF2Cl 1.429 2-OC3H7(i) 5-Cl H C2Hs CF3 1.430 2-OC3H7(i) 5-Cl H C3H7(n) CF3 1.431 2-OC3H7(i) 5-Cl H CH3 CHF3 1.432 2-OC3H7(i) 5-Cl H OCH3 CF3 1.433 2-OC3H7~ i) 5-Cl H SCH3 CF3 1.434 2-OCF3 H H CH3 Cl 1.435 2-OCF3 H H CH3 CF3 1.436 2-OCF3 H H CH3 CFzCl 1.437 2-oCF3 H H CH3 CHF2 1.438 2-OCF3 H H CH3 CHFCl 1.439 2-OCF3 H H C2Hs CF3 1.440 2-OCF3 H H C3H7(i) CF3 1.441 2-OCF3 H H C4Hg(n) CF3 i.442 2-OCF3 H H C4Hg(t) CF3 1.443 2-OCF3 5-Cl H CH3 CF3 1.444 2-OCF3 5-Cl H CH3 Cl 1.445 2-OCF3 5-Cl H CH3 CF3 1.446 2-OCF3 5-Cl H CH3 CF2Cl 1.447 2-OCF3 5-Cl H CH3 CHF2 1.448 2-OCF3 5-Cl H CH3 CHCl2 1.449 2-OCF3 5-Cl H CH3 CHFCl 1.450 2-OCF3 5-Cl H CH3 CF2CF3 1.451 2-OCF3 5-Cl H C2Hs CF2CF3 1.452 2-OCF3 5-Cl H C2Hs CF3 1.453 2-OCF3 5-Cl H C3H7(i) CF3 1.454 2-oCF3 5-Cl H Cyclo- CF3 propyl 1.455 2-OCF3 5-Cl H Phenyl CF3 1314~4~
Table 1 (continued) Comp.No. Rl _ R3 R4 Rs Physical data _ 1.456 2-OCF3 5-Cl H OCzHs CF3 1.457 2-OCF3 5-Cl H SCzHs CF3 1.458 2-SCH3 H H CH3 Cl 1.459 2-SCH3 H H CH3 CF3 m.p. 156-157C
1.460 2-SCH3 H H CH3 CHFz 1.461 2-SCH3 H H CH3 CFzCF3 1.462 2-SCH3 H H CZHs CF3 1.463 2-SCH3 H H C3H7(i) CF3 m.p. 170-171C
1.464 2-SCH3 H H C4Hg(n) CF3 1.465 2-SCH3 H H C4Hg(t) CF3 1.466 2-SCH3 5-Cl H CH3 Cl 1.467 2-SCH3 5-Cl H CH3 CF3 m.p. 162-163C
1.468 2-SCH3 5-Cl H CH3 CFzCF3 1.469 2-SCH3 5-Cl H CH3 CFzCl 1.470 2-SCH3 5-Cl H CZHs CF3 1.471 2-SOCH3 H H CH3 Cl 1.472 2-SOCH3 H H CH3 CF3 m.p. 80-82C
1.473 2-SOCH3 H H CH3 CHFz 1.474 2-SOCH3 H H CH3 CF2CF3 1.475 2-SOCH3 H H C2Hs CF3 1.476 2-SOCH3 H H C3H7(i) CF3 1.477 2-SOCH3 H H C4H9(n) CF3 1.478 2-SOCH3 H H C4Hg(t) CF3 1.479 2-SOzCH _ H H CH3 Cl m.p. 164-165~C
1.480 2-SOzCH3 H H CH3 CF3 m.p. 166-167C
1.481 2-SOzCH3 H H CzHs CF3 1.482 2-SOzCH3 H H C3H7(n) CF3 1.483 2-So2CH3 H H C3H7(i) CF3 1.484 2-SOzCH3 H H Cyclo- CF3 propyl 1.485 2-SOzCH3 H H C4Hs(i) CF3 1.486 2-SOzCH3 H H CH3 CFzCF3 1.487 2-SozCH3 H H CzHs CFzCF3 1.488 2-SO2CH ! H H C3H7(i) CFzCF3 1.489 2-SOCH3 5-Cl H CH3 Cl 1.490 2-SOCH3 5-Cl H CH3 CF3 m.p. 132-133C
1.491 2-SOCH3 5 Cl H CzHs CF3 1.492 2-SOCH3 5-Cl H CH3 CF2CF3 1.493 2-SOCH3 _5-Cl H C3H7(i) CF3 1.494 2-SOzCH 5-Cl H CH3 Cl 1.495 2-SOzCH3 5-Cl H CH3 CF3 m.p. 154-155C
1.496 2-So2CH3 5-Cl H CzHs CF3 1.497 2-SOzCH3 5-Cl H CH3 CFzCF3 1.498 2-SO2CH l 5-Cl H C3H7(i) CF3 1.499 2-F 5-F H CH3 OCHF2 1.500 2-F 5-F H CH3 Cl 1.501 2-F 5-F H CH3 CF3 m.p. 152-153C
1.502 2-F 5-F H CzHs CF3 - 32 - ~ 31~
Table 1 (continued) Comp.No. Rl R2 R3 R4 RS Physical data 1.503 2-F 5-F H C3H7(n) CF3 1.504 2-F 5-F H C3H7(i) CF3 1.505 2-F 5-F H Cyclo- CF3 m.p. 174-175C
propyl 1.506 2-F 5-F H CH3 CF2CF3 1.507 2-F 5-F H CH3 CF2CF2C]
1.508 2-F 5-F H CH3 CFzCl 1.509 2-F 5-F H CH3 CHFz 1.510 2-F 5-F H CH3 CHClF
1.511 2-F 5-F H C2Hs CF2Cl 1.512 2-F 5-F H C3H7~i) CF2Cl m.p. 161-162C
1.513 2-F 5-F H C4Hg(n) CF3 1.514 2-F 5-F H C4Hg(t) CF3 m.p. 156-157C
1.515 2-F 5-F H C2Hs CFzCF3 1.516 2-F 5-F H C3H7(i) CFzCF3 m.p. 150-151C
1.517 2-F 5-F H C3H7(n) CFzCF3 1.518 2-F 5-F H CH3 CCl2CF3 1.519 2-F 5-F H CH3 CHCl2 1.520 2-F 5-F H C2Hs CHC12 m.p. 144-145C
1.521 2-F 5-F H CH3 CCl2Ch3 1.522 2-F 5-F H OCH3 CF3 1.523 2-F 5-F H OC3H7(i~ CF3 1.524 2-F 5-F H SCH3 CF3 1.525 2-F 5-F H SC3H7(i) CF3 1.526 2-F 6-F H CH3 Cl 1.527 2-F 6-F H CH3 CF3 m.p. 177-178C
1.528 2-F 6-F H CZHs CF3 m.p. 151-153C
1.529 2-F 6-F H C3H7(n) CF3 1.530 2-F 6-F H C3H7(i) CF3 m.p. 158-159C
1.531 2-F 6-F H CH3 CF2CF3 1.532 2-F 6-F H C2Hs CFzCF3 m.p. 137-139C
1.533 2-F 6-F H CH3 CF2Cl m.p. 178-179C
1.534 2-F S-F H CH3 CHFz 1.535 2-F 6-F H CH3 CHClF
1.536 2-F 6-F H OCH3 CF3 1.537 2-F 6-F H SCH3 CF3 1.538 2-F 6-Cl H CH3 Cl 1.539 2-F 6-Cl H CH3 CH3 1.540 2-F 6-Cl H CH3 CF3 m.p. 184-185C
1.541 2-F 6-Cl H C2Hs CF3 1.542 2-F 6-Cl H C3H7(i) CF3 m.p. 146-147C
1.543 2-F 6-Cl H Cyclo- CF3 m.p. 172-173C
propyl 1.544 2-F 6-Cl H CH3 CF2CF3 1.545 2-F 6-Cl H C3H7~i) CF2CF3 1.546 2-F 6-Cl H CH3 CCl2CF3 1.547 2-F 6-Cl H CH3 CHClz 1.548 2-F 6-Cl H CH3 CHFz 1.549 2-F 6-Cl H CH3 CHFCl - 33 - 1 31~
Table 1 (continued) Comp.No. R2 R3 R4 Rs Physical data _ _ _ 1.550 2-F 6-Cl H CH3 CFzCl 1.551 2-F 6-Cl H C3H7(i) CF2Cl 1.552 2-F 6-Cl H OCH3 CF3 1.553 2-CN H H CH3 CF3 m~p. 142-143C
1.554 2-CN H H CZHs CF3 1.555 2-CN H H C3H7(i) CF3 1.556 2-CN H H CH3 CFzCF3 1.557 2-CN H H CzHs CFzCF3 1.558 2-CN H H C3H7(i) CF2CF3 1.559 2-CN H H CH3 CHF2 1.560 2-CN H H CH3 CF2Cl 1.561 2-CN H H OCH3 CF3 1.562 2-CN H H OCzHs CF3 1.563 2-PO~OC Hs)z H H CH3 CF3 m.p. 144-145C
1.564 2-PO(OCzHs)2 H H C2Hs CF3 1.565 2-PO(OCzHs)2 H H C3H7(i) CF3 1.566 2-Cl 5-C: ~ H SOCH3 CF3 1.567 2-Cl 5-Cl H SOzCH3 CF3 1.568 2-Cl 6-Cl H SOCH3 CF3 1.569 2-Cl 6-Cl H SO2CH3 CF3 1.570 2-Cl 6-Cl H SOCH3 CH3 1.571 2-Cl 6-Cl H SOzCH3 CH3 1.572 2-Cl 6-Cl H CN CH3 1.573 2-Cl 6-Cl H CN CF3 1.574 2-Cl 6-Cl H CH=CClz Cl 1.575 2-Cl 5-Cl H CH=CClz Cl 1.576 2-CF3 H H CH=CClz Cl 1.577 2-Cl 6-Cl H CH20CH3 CF3 1.578 2-Cl 6-Cl H CHzOCH3 C2Fs 1.579 2-Cl 5-Cl H CHzOCH3 CF3 1.580 2-Cl 5-Cl H CH20CH3 CFzCl 1.581 2-OCH3 5-Cl H CHzOCH3 CF3 1.582 2-OCH3 5-Cl H CHzOCH3 CFzCF3 1.583 2-F 5-F H CHzOCH3 CF3 1.584 2-OCHFz 5-Cl H CHzOCH3 CF3 1.585 2-OCHFz 5-Cl H CHzOCH3 CFzCl 1.586 3-Br H H CH3 Cl m.p. 133-134C
1.587 3-Br H H CH3 CF3 1.588 2-Br 5-Br H CH3 Cl 1.589 2-Br 5-Br H CH3 CF3 m.p. 155-156C
1.590 2-Br 5-Br H OCH3 CF3 1.591 2-Br 5-Br H CzHs CF3 1.592 2-Br 5-Br H CH3 CFzC
1.593 2-Br 5-Br H CH3 CHFz 1.594 2-CF3 5-Cl H CH3 CF3 m.p. 152-153C
1.595 2-CF3 5-Cl H CH3 Cl m.p. 142-143C
1.596 2-CF3 5-Cl H CzHs CF3 1.597 2-CF3 5-Cl H C3H7(i) CF3 - 34 - 1 3 1 ~ ~4 ~
Table 1 (continued) Comp.No. R~ R3 R4 ~ Physical data 1.598 2-CF 3 5-Cl H Cyclo- CF3 propyl 1.599 2-CF3 5-Cl H CH3 CH2Cl 1.600 2-CF3 5-Cl H CH3 CHFz 1.601 2-CF3 5-Cl H C2Hs CF2Cl 1.602 2-CF3 5-Cl H C3H7ti) CF2Cl 1.603 2-CF3 5-Cl H CH3 CF2CF3 1.604 2-CF 3 5-Cl H OCH3 CF 3 1.605 2-CF3 5-Cl H SCH3 CF3 1.606 2-CF3 5-Cl H SOCH3 CF3 1.607 2-CF3 5-Cl H SO2CH3 CH3 1.608 2-CH3 3-CH3 H CH3 Cl 1.609 2-CH3 3-CH3 H CH3 CF3 1.610 2-CH3 5-CH3 H CH3 Cl 1.611 2-CH3 5-CH3 H CH3 CF3 1.612 2-CH3 6-CH3 H CH3 Cl 1.613 2-CH3 6-CH3 H CH3 CF3 m.p. 160-161C
1.614 2-CH3 6-CH3 H CH3 CF2Cl m.p. 169-i70C
1.615 2-CH3 6-CH3 H CH3 CHzCF3 1.616 2-CH3 6-CH3 H OCH3 CF3 1.617 2-CH3 6-CH3 H SCH3 CF3 1.618 2-CH3 6-CzHs H CH3 Cl 1.619 2-CH3 6-C2Hs H CH3 CF3 m.p. 140-144C
1.620 2-CH3 6-C2Hs H OCH3 CF3 1.621 2-CH3 5-F H CH3 Cl 1.622 2-CH3 5-F H CH3 CF3 m.p. 170-172C
1.623 2-CH3 5-F H CH3 CHF2 1.624 2-CH3 5-F H CH3 CF2Cl 1.625 2-CH3 5-F H CZHs CF3 1.626 2-CH3 5-F H C3H7(i) CF3 1.627 2-CH3 5-F H OCH3 CF3 1.628 2-CH3 5-F H OC2Hs CF3 1.629 2-Br 6-Br H CH3 Cl 1.630 2-Br 6-Br H CH3 CF3 1.631 2-Br 6-Br H CZHs CF3 m.p. 157-158C
1.632 2-Br 6~Br H C3H7(i) CF3 1.633 2-Br 6-Br H Cyclo- CF3 propyl 1.634 2-Br 6-Br H CH3 CHC12 1.635 2-Br 6-Br H CH3 CFzCF3 1.636 2-Br H H C3H7(i) CF2CF3 m.p. 149-150C
1.637 2-CF3 H CH3 CHC12 m.p. 161-162C
1 3 ~ 6 Table 1 (contin~ed) Comp.No. ~ RZ R3 R4 Rs Physical data 1.638 2-OCHF2 }I H CH3 CF3 m.p. 145-146C
1.639 2-OCHF2 H H C3H7(i) CF3 1.640 2-OCHF2 H H Cyclo- CF3 m.p. 137-138C
propyl 1.641 2-OCHFz H H CH3 CHF2 1.642 2-OCHF2 H H CH3 CHFCl 1.643 2-CF3 H H CH3 CHFz 1.644 2-CF3 H H CH3 CF2Cl 1.645 2-CF3 H H C3H7(i) CFzCl m.p. 140-141C
1.646 2-CF3 H H Cyclo- CF3 m.p. 169-170C
propyl 1.647 2-CF3 H H 2-Thienyl CF3 m.p. 170-171~C
1.648 2-Br H H C4Hg(n) CF3 m.p. 144-145C
1.649 2-Br H H C3H7(i) CF3 m.p. 169-170C
1.650 2-Br H H CH3 CHF2 1.651 2-Br H H CH3 CFzCl 1.652 2-Br H H Cyclo- CFzCl propyl 1.653 2-Br H H C2Hs CHF2 1.654 2-Cl 6-CH3 H CH3 CH3 m.p. 165-167C
1.655 2-Cl 6-Cl H CH3 CHF2 m.p. 182-183C
1.656 2-Cl 6-Cl H C2Hs CHFz 1.657 2-Cl 5-Cl H CsH1l(n) CF3 m.p. 118-119C
1.658 2-COOCH3 H H CH3 CF3 m.p. 138-139C
1.659 2-COOCH3 H H C2Hs CF3 1.660 2-COOCH3 H H C3H7~i) CF3 1.661 2-COOCH3 H H Cyclo- CF3 propyl 1.662 2-COOCH3 H H CH3 CFzCl 1.663 2-COOCH3 H H CH3 CHF2 1.664 2-COOC2Hs H H CH3 CF3 1.665 2-COOC3H7~n) H H CH3 CF3 1.666 2-COOC3H7(i) H H CH3 CF3 1.667 2-COOC4Hg(n) H H CH3 CF3 1.668 2-OCH3 5-F H CH3 CF3 ~ P 141-142C
1.669 2-OCH3 5-F H CH3 CHF2 1.670 2-OCH3 5-F H CzHs CHF2 1.671 2-OCH3 5-F H C3H7(i) CF3 1.672 2-OCH3 5-F H Cyclo- CF3 propyl 1.673 2-OCH3 5-F H Cycl~- CF3Cl propyl - 36 - 13~4 ~ 4 ~
Table 1 (continued) Comp.No. R~ R2 R3 R4 Rs Physical data _.
1.674 2-OCHFz 5-F H CH3 CF3 1.675 2-OCHFz 5-F H CH3 CHF2 1.676 2-OCHF2 5-F H CH3 CF2Cl 1.677 2-COOCH3 6-CH3 H CH3 CF3 m.p. 161-162C
1.678 2-COoCH3 6-CH3 H CH3 CHF2 1.679 2-COOCH3 6-CH3 H C3H7(i) CF3 1.680 2-COOCH3 6-CH3 H Cyclo- CF3 propyl 1.681 2-COOCH3 6-Cl H CH3 CF3 m.p. 144-145C
1.682 2-COOCH3 6-Cl H CH3 CHFz 1.683 2-Br 11 H 2-Furyl CF3 m.p. 176-177C
1.684 2-Cl 6-Cl 3-CH ¦CH3 Cl 1.685 2-CF3 H H CzHs CHC12 m.p. 155-156C
1.686 2-Cl 5-Cl H Cl CF3 1.687 2-CONH2 H H CH3 CF3 ÇH3 1.688 2-Cl 6-Cl H CHCH2CH3 CF3 m.p. 124-125C
1.689 2-F H H C2Hs CF3 m.p. 136-137C
1.690 2-F H H CH20CH3 CF3 m.p. 122-124C
1 o91 2-F H H CHzOCH3 CF2Cl m.p. 145-147C
1.692 2-OCH3 6-Cl H CH3 CF3 m.p. 191-192C
1.693 2-OCH3 6-Cl H CzHs CF3 m.p 147-149C
1.694 2-OCH3 6-Cl H C3H7(i) CF3 m.p. 143-146C
1.695 2-CH3 6-CH3 H CzHs CF3 m.p. 158-160C
1.696 2-CH3 6-CH3 H C3H7(i) CF3 m.p. 143-146C
1.697 2-F 6-F H C4Hg(i) CF3 m.p. 135-137C
1.698 2-F 6-F H - ~¦ CF3 m.p. 158-159C
1.699 2-F 6-F H CH20CH3 CF3 m.p. 138-139C
1.700 2-F 6-F H C2Hs CHC12 m.p. 169-171C
1.701 2-F 6-F H 2-Furyl CF3 m.p. 152-153C
1.702 2-CH3 5-F H C2Hs CHC12 1.703 2-Cl 6-CH3 H CH20CH3 CF3 m.p. 137-138C
1.704 2-Cl 6-CH3 H CHzOCH3 CF2Cl m.p. 133-134C
1.705 2-Cl 6-CH3 H C3H7(i) CF2Cl m.p. 142-144C
1.706 2-Cl 6-CH3 H Cl CF3 1.707 2-Cl 6-CH3 H CH20CH3 CHF2 m.p. 142-144C
1.708 2-F H H CH20CH3 CHF2 m.p. 116-118C
1.709 2-OCH3 6-CH3 H CH3 CP3 m.p. 180-181C
1.710 2 Cl 6-Cl H Cl CF3 m.p. 189-190C
1.711 2-SCHF2 H H CH3 CF3 1.712 2-OCHF2 6-CH3 H CH3 CF3 1.713 2-OCHF2 6-CH3 H CZHs CF3 1.714 2-F 6-Cl H 2-Furyl CF3 1.715 2-CH3 6-F H C2Hs CHC12 m.p. 141-142C
- 37 - 13 1 4 ~ 4~
P.2. Compounds of formula II
P. 2.1. N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-2-trifluoro-methylaniline A suspension of 24 g (0.1 mole) of 2-trifluoromethylphenyl-guanidinium hydrochloride in 80 ml of tetrahydrofuran is added to a solution of 12 g (0.1 mole) of potassium tert.-butoxide in 100 ml of tetrahydrofuran. When the exothermic reaction has subsided, 15.4 g (0.1 mole) of ~ -tri-fluoroacetylacetone in 20 ml of tetrahydrofuran are added. The reaction mixture is stirred for 2 hours at 60C, then concentrated by evaporation in a rotary evaporator. The residue is chromatographed on silica gel with a mixture of ethyl acetate and hexane (ratio 1:2)~ 18.7 g (58 2 % of the theoretical amount) of the title compound of formula ~--NH--~ ~-\.=./ \N=-/
\CF3 are obtained in the form of crystals having a melting point of 65-66C
(Comp. No. 2.020).
The compounds of Table II can be obtained analogously to Example P. 2:
- 38 - 1 3~ ~ ~ 4 6 Table II
Compounds of formula ~ N- /
H- ~ /--NH \N- / II
2 .~ --\R4 Comp.No. Rl - R2 R3 R4 Rs Physical data _ 2.001 2-Cl H H CH3 CH3 2.002 2-Cl H H CH3 OCHF2 2.003 2-Cl H H CH3 Cl 2.004 2-Cl H H CH3 CF3 2.005 2-Cl H H CH3 CF2CF3 2.006 2-Cl H H CH2CH3 CF3 2.007 2-Cl H H CH3 CF2Cl 2.008 2-Cl H H CH3 CHF2 2.009 2-Br H H CH3 Cl m.p. 109-110C
2.010 2-Br H H OCH3 CF3 2.011 2-Br H H CH3 CF 3 2.012 2-~Br H H SCH 3 CF3 2.013 2-Br H H CH2CH3 CF3 2.014 2-Br H H CH3 CHClz 2.015 2-Br H H CH3 CHFCl 2.016 2-Br H H Cyclo- CF3 m.p. 85-86C
propyl 2.017 2-CF3 H H Phenyl CF3 2.018 2-CF3 H H 2-Furyl CF3 2.019 2-CF3 H H CH3 Cl 2.020 2-CF3 H H CH3 CF3 m.p. 65-66C
2.021 2-CF3 H H CH3 CH3 m.p. 70-72C
2.022 2-CF3 H H CHzCH3 CF3 2.023 2-CF3 H H CH(CH3)z CF3 nD5: i,4960 2.024 2-CF3 H H (n)C3H7 CF3 n~5: 1,4970 2.025 2-CF3 H H OCH3 CF3 2.026 2-CF3 H H oC2Hs CF3 2.027 2-CF3 H H SCH3 CF3 2.028 2-CF3 H H ~ iCH(CH3)2 CF3 2.029 2-CF3 H H ¦CH3 CF2CF3 _ 39 - 1 ~ ~ 4~ ~
Table II (continued) Comp.No. ---- R2 R3 R4 Rs Physical data 2.030 2-CF3 H H CH3 CHFCl 2.Q31 2-J H H CH3 Cl 2.032 2-J H H CH3 CF3 m.p. 109-110C
2.033 2-J H H CH2CH3 CF3 2.034 2-J H H CH3 CF2Cl 2.035 2-F H H CH3 CH3 2.036 2-F H H CH3 Cl 2.037 2-F H H CH3 CF3 m.p. 64-66C
2.038 2-F H H CH(CH3)2 CF3 nDS: 1.5240 2.039 2-F H H Cl CF3 2.040 2-F H H OCzHs CF3 2.041 2-Cl 3-Cl H CH3 Cl m.p. 123-124C
2.042 2 Cl 3-Cl H CH3 CF3 m.p. 109-110C
2.043 2-Cl 3-Cl H OCH3 CF3 2.044 2-Cl 3-Cl H OC4Hg(n) CF3 2.045 2-Cl 3-Cl H SC2Hs CF3 2.046 2-Cl 3-Cl H Phenyl CF3 2.047 2-Cl 3-Cl H CH3 CF2Cl 2.048 2-Cl 3-Cl H CH3 CHFCl 2.049 2-Cl 3-Cl H CH3 CH3 2.050 2-Cl 5-Cl H CH3 CH3 2.051 2-Cl 5-Cl H CH3 OCHF2 2.052 2-Cl 5-Cl H CH3 Cl m.p. 99-100C
2.053 2-Cl 5-Cl H OCH3 CH3 2.054 2-Cl 5-Cl H CH3 Br 2.055 2-Cl 5-Cl H CH3 CF3 m.p. 79-80C
2.056 2-Cl 5-Cl H CHzCH3 CF3 m.p. 62-63 C
2.057 2-Cl 5-Cl H C3H7(n) CF3 nD5: 1,5490 2.058 2-Cl 5-Cl H C3H7(i) CF3 m.p. 60-61C
2.059 2-Cl 5-Cl H Cyclo- CF3 m.p. 106-107C
propyl 2.060 2-Cl 5-Cl H Phenyl CF3 2.061 2-Cl 5-Cl H [ -Thienyl CF3 m.p. 112-113C
2.062 2-Cl 5-Cl H 2-Furyl CF3 m.p. 102-103C
2.063 2-Cl 5-Cl H CH3 CF2CF3 m.p. 99-100C
2.064 2-Cl 5-Cl H CH3 CF2Cl m.p. 67C
2.065 2-Cl 5-Cl H CH3 CHF2 m.p. 72-74C
2.066 2-Cl 5-Cl H CH3 CHClF m.p. 66-67C
2.067 2-Cl 5-Cl H CH2CH3 CF2Cl 2.068 2-Cl 5-Cl H C3H7(i) CF2Cl nD5: 1,5682 2.069 2-Cl 5-Cl H OCH3 CF3 2.070 2-Cl 5-Cl H OCzHs CF3 2.071 2-Cl 5-Cl H OC3H7 CF3 2.072 2-Cl 5-Cl H OC3H7(i) CF3 2.073 2-Cl 5-Cl H OC4Hg(n) CF3 2.074 2-Cl 5-Cl H OC4Hg(i) CF3 _ 40 _ 1 3 1 4 ~ ~ 6 Table II (continued) Comp.No. R1 R2 R3 R4 Rs Physical data .
2.075 2-Cl 5-Cl H SCH3 CF3 2.076 2-Cl 5-Cl H SCzHs CF3 2.077 2-Cl 5-Cl H SC3H7(n) CF3 2.078 2-Cl 5-Cl H SC3H7(i) CF3 2.079 2-Cl 5-C~ H SC4Hg(n) CF3 2.080 2-Cl 5-Cl H C4Hg(n) CF3 nD5: 1,5475 2.081 2-Cl 5-Cl H C4Hg(i) CF3 2.082 2-Cl 5-Cl H C4Hg(t) CF3 m.p. 106-107C
2.083 2-Cl 5-Cl H C2Hs CF2CF3 m.p. 70-72C
2.084 2-Cl 5-Cl H C3H7(i) CF2CF3 m.p. 39-41C
2.085 2-Cl 5-Cl H C3H7(n) CFzCF3 2.086 2-Cl 5-Cl H OCF2CHF2 CF3 2.087 2-Cl 5-Cl H CH3 CCl2CF3 2.088 2-Cl 5-Cl H C2Hs CCl2CF3 2.089 2-Cl 5-Cl H CH3 CHCl2 m.p. 80-82C
2.090 2-Cl 5-Cl H CZHs CHCl2 nD5: 1,6115 2.091 2-Cl 5-Cl H CH3 CCl2CH3 2.092 2-Cl 5-Cl H CZHs CClzCH3 2.093 2-Cl 6-Cl H CH3 CH3 m.p. 185-186C
2.094 2-Cl 6-Cl H CH3 C2Hs 2.095 2-Cl 6-Cl H CH3 C3H7(i) 2.096 2-Cl 6-Cl H CH3 Cl m.p. 190-191C
2.097 2-Cl 6-Cl H CH 3 CCl2CH3 2.0S8 2-Cl 6-Cl H CZHs CCl2CH3 2.099 2-Cl 6-Cl H CH3 CHCl2 2.100 2-Cl 6-Cl H C2Hs CHCl2 2.101 2-Cl 6-Cl H CH3 CCl 2 CF3 2.102 2-Cl 6-Cl H C3H7(i) CClzCF3 2.103 2-Cl 6-Cl H CH3 CHClF
2.104 2-Cl 6-Cl H C2Hs CHClF
2.105 2-Cl 6-Cl H CH3 CF2Cl 2.106 2-Cl 6-Cl H C2Hs CF2Cl 2.107 2-Cl 6-Cl H C3H7(i) CF2Cl 2.108 2-Cl 6-Cl H C3H7(n) CFzCl 2.109 2-Cl 6-Cl H CH3 CF3 m.p. 138-139C
2.110 2-Cl 6-Cl H CZHs CF3 2.111 2-Cl 6-Cl H C3H7(n) CF3 2.112 2-Cl 6-Cl H C3H7~i) CF3 2.113 2-Cl 6-Cl H Cyclo- CF3 m.p. 70-73C
propyl 2.114 2-Cl 6-Cl H Phenyl CF3 2.115 2-Cl 6-Cl H ~ -Thienyl CF3 m.p. 119-120C
2.116 2-Cl 6-Cl H 2-Furyl CF3 2.117 2-Cl 6-Cl H CH3 CF2CF3 2.118 2-Cl 6-Cl H CzHs CF2CF3 m.p. 96-98C
2.119 2-Cl 6-Cl H C3H7(i) CFzCF3 m.p. 88-90C
2.120 2-Cl 6-Cl H C3H7(n) CF2CF3 ~ 41 - 1 3 1 ~ ~ 4 6 Table II (continued) Comp.No. R1 R2 R3 R4 Rs Physical data 2.121 2-Cl 6-Cl H propyl CFzCF3 2.122 2-Cl 6-Cl H CH3 OCHF2 2.123 2-Cl 6-Cl H C4Hg(n) CF3 2.124 2-Cl 6-Cl H C4Hs(i) CF3 2.125 2-Cl 6-Cl H C4Hg(t) CF3 m.p. 79-81C
2.126 2-Cl 6-Cl H OCH3 CF3 2.127 2-Cl 6-Cl H OCzHs CF3 2.128 2-Cl 6-Cl H OC3H7(n) CF3 2.129 2-Cl 6-Cl H OC3H7(i) CF3 2.130 2-Cl 6-Cl H OC4Hg(n) CF3 2.131 2-Cl 6-Cl H OC4Hg(i) CF3 2.132 2-Cl 6-Cl H SCH3 CF3 m.p. 70-71C
2.133 2-Cl 6-Cl H SC2Hs CF3 2.134 2-Cl 6-Cl H SC3H7(n) CF3 2.135 2-Cl 6-Cl H SC3H7(i~ CF3 2.136 2-Cl 6-Cl H SC4Hg(n) CF3 2.137 2-Cl 6-Cl H OCH3 CH3 2.138 2-Cl 6-Cl H C2Hs Cl 2.139 2-Cl 6-Cl H OCH3 C2Hs 2.140 2-Cl 6-Cl H C2Hs OCHF2 2.141 2-Cl 6-Cl 3-CH _ CH3 CF3 m.p. 124-125C
2.142 2-Cl 6-Cl 3-CH3 C2Hs CF3 m.p. 90-91C
2.143 2-Cl 6-Cl 3-CH3 C3H7(n) CF3 2.144 2-Cl 6-Cl 3-CH3 C3H7(i) CF3 m.p. 74-75C
2.145 2-Cl 6-Cl 3-CH3 CH3 CF2CF3 m.p. 119-121C
2.146 2-Cl 6-Cl 3-CH3 C2Hs CF2CF3 2.147 2-Cl 6-Cl 3-CH3 Cl CF3 2.148 2-Cl 6-C1 3-CH3 OCH3 CF3 2.149 2-Cl 6-Cl 3-CH3 OCZHs CF3 2.150 2-Cl 6-Cl 3-CH3 SCH3 CF3 2.151 2-Cl 6-Cl 3-CH3 SC4Hg(n, ~CF3 2.152 2-Cl 6-Cl 3-CH3 CH3 CFzCl 2.153 2-Cl 6-Cl 3-CH3 CH3 CHF2 2.154 2-Cl 6-Cl 3-CH l CH3 CHCl2 2.155 2-Cl 3-CF3 H CH3 Cl 2.156 2-Cl 3-CF3 H CH3 CH3 2.157 2-Cl 3-CF3 H CH3 CF3 2.158 2-Cl 3-CF3 H C2Hs CF3 2.159 2-Cl 3-CF3 H C3H7(n) CF3 2.160 2 Cl 3-CF3 H CH3 CF2CF3 2.161 2-Cl 3-CF3 H CH3 CClF2 2.162 2-Cl 3-CF3 H CH3 CHClF
2.163 2-Cl 5-CF3 H CH3 Cl m.p. 101-103C
2.164 2-Cl 5-CF3 H CH3 CF3 m.p. 84-85C
2.165 2-Cl 5-CF3 H CH3 CClF2 2.166 2-Cl 5-CF3 H C2Hs CF3 2.167 2-Cl 5-CF3 H OCH3 CF3 -- 42 - 1 3 1 4 ~ 4 6 Table II (continued) Comp.No. R1 R2 R3 R4 Rs Physical data ..... __ 2.168 2-Cl 6-CF3 H CH3 Cl 2.169 2-Cl 6-CF3 H CH3 CH3 2.170 2-Cl 6-CF3 H CH3 CF3 m.p. 117-119C
2.171 2-Cl 6-CF3 H CzHs CF3 2.172 2-Cl 6-CF3 H C3H7(n) CF3 2.173 2-Cl 6-CF3 H C3H7(i) CF3 2.174 2-Cl 6-CF3 H Cyclo- CF3 propyl 2.175 2-Cl 6-CF3 H C4Hg(n) CF3 2.176 2-Cl 6-CF3 H C4Hg(i) CF3 2.177 2-Cl 6-CF3 H C4Hg(t) CF3 2.178 2-Cl 6-CF3 H CH3 CF2CF3 2.179 2-Cl 6-CF3 H C2Hs CFzCF3 2.180 2-Cl 6-CF3 H CH3 CHClz 2.181 2-Cl 6-CF3 H CH3 CClF 2 2.182 2-Cl 6-CF3 H CzHs CClF2 2.183 2-Cl 6-CF3 H CH3 CHF2 2.184 2-Cl 6-CF3 H CH3 OCHFz 2.185 2-Cl 6-CF3 H OCH3 CF3 2.186 2-Cl 6-CF3 H OC2Hs CF3 2.187 2-Cl 6-CF3 H SC2Hs CF3 2.188 2-Cl 6-CF3 H CH3 CClzCF3 2.189 2-Cl 6-CF3 H CH3 CClzCH3 2.190 2-Cl 6-CF3 H Phenyl CF3 2.191 2-Cl 3-CH3 H CH3 CF3 2.192 2-Cl 3-CH3 H CH3 CF2CF3 2.193 2-Cl 3-CH3 H CzHs CF3 2.194 2-Cl 3-CH3 H C3H7(n) CF3 2.195 2-Cl 3-CH3 H C3H7(i) CF3 2.196 2-Cl 3-CH3 H CH3 Cl 2.197 2-Cl 3-CH3 H CH3 CFzCl 2.198 2-Cl 3-CH3 H CH3 CHCl2 2.199 2-Cl 3-CIi3 H CH3 CHClF
2.200 2-Cl 3-CH3 H OCH3 CF3 2.201 2-Cl 5-CH3 H CH3 Cl m.p. 77-78C
2.202 2-Cl 5-CH3 H CH3 CHClz 2.203 2-Cl 5-CH3 H CH3 CCl2CF3 2.204 2-Cl 5-CH3 H CH3 CHClF
2.205 2-Cl 5-C}i3 H CH3 CFzCl 2.206 2-Cl 5-CH3 H C2Hs CF2Cl 2.207 2-Cl 5-CH3 H CH3 CF3 2.208 2-Cl 5-CH3 H C2Hs CF3 2.209 2-Cl 5-CH3 li C3H7(n) CF3 2.210 2-Cl 5-CH3 H C3H7~i) CF3 2.211 2-Cl 5-CH3 H C4Hg(n) CF3 2.212 2-Cl 5-CH3 H C4Hg(t) CF3 2.213 2-Cl 5-CH3 H 2-Furyl CF3 2.214 2-Cl 5-CH3 H CH3 CFzCF3 2.215 2-Cl 5-CH3 H CzHs CFzCF3 ~ 43 - 1314 5 ~ 6 Table II (continued) Comp.No. Rl R-2 R3 R4 ~s Physical data 2.216 2-Cl 5-CH3 H OCH3 C~3 2.217 2-Cl 5-CH3 H OCzHs CF3 2.218 2-Cl 5-CH3 H SCH3 CF3 2.219 2-Cl 6-CH3 H CH3 Cl m.p. 142-143C
2.220 2-Cl 6-CH 3 H CN CH3 2.221 2-Cl 6-CH3 H CH3 CF3 m.p. 143-144C
2.222 2-Cl 6-CH3 H CH3 CF2Cl m.p. 158-162C
2.223 2-Cl 6-CH3 H CH3 CF2CF3 2.224 2-Cl 6-CH3 H CH3 CCl2CF3 2.225 2-Cl 6-CH3 H CH3 CHF2 2.226 2-Cl 6-CH3 H CH3 CHClz 2.227 2-Cl 6-CH3 H C2Hs CF3 m.p. 99-102C
2.228 2-Cl 6-CH3 H C3H7(i) CF3 m.p. 56-59C
2.229 2-Cl 6-CH3 H Cyclo- CF3 m.p. 75-77C
propyl 2.230 2-Cl 6-CH3 H C4Hg(i) CF3 2.231 2-Cl 6-CH3 H C2Hs CF2CF3 m.p. 89-91C
2.232 2-Cl 6-CH3 H OCH3 CF3 2.233 2-Cl 6-CH3 H IOCH2CH2Cl CF3 2.234 2-Cl 6-CH3 H ~ )CH2CH20C1 ~ CF3 2.235 2-Cl 6-CH3 H OCzHs CF3 2.236 2-Cl 6-CH3 H SCH3 CF3 2.237 2-Cl 6-CH3 H SCzHs CF3 2.238 2-Cl 6-CH3 H SC3H7(i) CF3 2.239 2-Cl 6-CH3 H SC4Hg(i) CF3 2.240 2-Cl 5-OCH3 H CH3 CF3 2.241 2-Cl 5-OCH3 H C2Hs CF3 2.242 2-Cl 5-OCH3 H CH3 Cl 2.243 2-Cl 5-OCH3 H OCH3 CF3 2.244 2-Cl 5-OCH3 H CH3 CHF2 2.245 2-Cl 5-OCH3 H CH3 CF2CF3 2.246 2-Cl 5-OCH3 H CH3 CF2Cl 2.247 2-Cl 5-COOCH3 H CH3 CF3 m.p. 88-89C
2.248 2-Cl 5-COOCH3 H C2Hs CF3 2.249 2-Cl 5~COOC2Hs }I CH3 CF3 2.250 2-Cl 5-COOC2Hs _H CH3 CFzCF3 2.251 2-Cl 5-COOC3H7(i l H CH3 CF3 2.252 2-Cl 5-COOC3H7(i) H C3H7(i) CF3 2.253 2-Cl 5-COOC3H7(i) H CH3 CF2Cl 2.254 2-Cl 5-COOC3H7(i) H Phenyl CF3 2.255 2-Cl 5-COOC3H7(i) H Cyclo- CF3 p~opyl 2.256 2-Cl 5-COOC3H7(i, _ H CH3 CHFCl 2.257 3-Cl 5-Cl H CH3 Cl m.p. 152-153C
2.258 3-Cl 5-Cl H CH3 CF3 m.p. 93-94C
2.259 3-Cl 5-Cl H C2Hs CF3 2.260 3-Cl 5-Cl H C3H7~n) CF3 2.261 3-Cl 5-Cl H C3H7(i) CF3 Table II (continued) Co~p.No. Rl _ R2 R3 R~ Rs Physical data 2.262 3-Cl 5-Cl H Cyclo- CF3 propyl 2.263 3-Cl 5-Cl H Phenyl CF3 2.264 3-Cl 5-Cl H CH3 CHF2 2.265 3-Cl 5-Cl H CH3 CF2Cl 2.266 3-Cl 5-Cl H CZHs CF2Cl 2.267 3-Cl 5-Cl H OCH3 CF3 2.268 3-Cl 5-Cl H OC2Hs CF3 2.269 3-Cl 5-Cl H SCH3 CF3 2.270 3-Cl 5-Cl H SC3H7(i) CF3 2.271 2-CH3 5-Cl H CH3 Cl m.p. 118-119C
2.272 2-CH3 5-Cl H CH3 CF3 2.273 2-CH3 5-Cl H CN CF3 2.274 2-CH3 5-Cl H C2Hs Cl 2.275 2-CH3 5-Cl H CH3 OCHFz 2.276 2-CH3 5-Cl H CH3 Br 2.277 2-CH3 5-Cl H CH3 F
2.278 2-CH3 5-Cl H CH3 CH3 m.p. 121-122C
2.279 2-CH3 5-Cl H OCH3 CH3 2.280 2-CH3 5-Cl H CzHs CF3 2.281 2-CH3 5-Cl H C3H7(n) CF3 2.282 2-CH3 5-Cl H C3H7(i) CF3 2.283 2-CH3 5-Cl H Cyclo- CF3 propyl 2.284 2-CH 3 5-Cl H Phenyl CF 3 2.285 2-CH3 5-Cl H C4Hg(n) CF3 2.286 2-CH3 5-Cl H C4Hg(i) CF3 2.287 2-CH3 5-Cl H C4Hg(t) CF3 2.288 2-CH3 5-Cl H CH3 CF2CF3 2.289 2-CH3 5-Cl H CzHs CF2CF3 2.290 2-CH3 5-Cl H C3H7(i) CF2CF3 2.291 2-CH3 5-Cl H CH3 CF2Cl 2.292 2-CH3 5-Cl H C2Hs CF2Cl 2.293 2-CH3 5-Cl H CH3 CHF2 2.294 2-CH3 5-Cl H CZHs CHF2 2.295 2-CH 3 5-Cl H CH3 CHFCl 2.296 2-CH3 5-Cl H C2Hs CHFCl 2.297 2-CH3 5-Cl H CH3 CHCl2 2.298 2-CH3 5-Cl H C2Hs CHC12 2.299 2-CH3 5-Cl H CH3 CClzCF3 2.300 2-CH3 5-Cl H CH3 CCl2CH3 2.301 2-CH3 5-Cl H OCH3 CF3 2.302 2-CH3 5-Cl H OCzHs CF3 2.303 2-CH3 5-Cl H SCH3 CF3 2.304 2-CH3 5-Cl H SC2Hs CF3 2.305 2-CH3 5-Cl H SC4Hg(i) CF3 2.306 2-CH3 3-Cl H CH3 Cl m.p. 116-117C
2.307 2-CH3 3-Cl H CH3 CF3 2.308 2-CH3 3-Cl H C2Hs CF3 - 45 - 1 3 1 4 ~ ~ 6 Table II (continued) Comp.No. R1 R2 R3 R4 Rs Physical data 2.309 2-CH3 3-Cl H C3H7(i) CF3 2.310 2-CH3 3-Cl H Cyclo- CF3 propyl 2.311 2-CH3 3-Cl H CH3 CFzCl 2.312 2-CH3 3-Cl H CH3 CFzCF3 2.313 2-CH3 3-Cl H C2Hs CF2CF3 2.314 2-CH3 3-Cl H OCH3 CF3 2.315 2-CH3 3-Cl H SCH3 CF3 2.316 2-CH3 5-NOz H CH3 Cl m.p. 178-179C
2.317 2-CH3 5-NOz H CH3 CF3 2.318 2-CH3 5-NOz H CH3 CFzCl 2.319 2-CH3 5-NOz H CH3 CHFz 2.320 2-CH3 5-NOz H CZHs CF3 2.321 2-CH3 5-NOz H C3H7(n) CP3 2.322 2-CH3 5-NO2 H C3H7(i) CF3 2.323 2-CH3 5-NO2 H C4Hg(t) CF3 2.324 2-CH3 3-NO2 H CH3 Cl m.p. 160-161C
2.325 2-CH3 3-NOz H CH3 CF3 2.326 2-CH3 3-NO2 H CH3 CF2CF3 2.327 2-CH3 3-NO2 H CzHs CFzCF3 2.328 2-CH3 3-NOz H Phenyl CF3 2.329 2-CH3 3-NO2 H CZHs CF3 2.330 2-CH3 3-NO2 H C3H7(i) CF3 2.331 2-CH3 6-CF3 H CH3 Cl 2.332 2-CH3 6-CF3 H CH3 CF3 m.p. 100-101C
2.333 2-CH3 6-CF3 H CH3 CHF2 2.334 2-CH3 6-CF3 H CH3 CF2C12 2.335 2-CH3 6-CF3 H CH3 CHCl2 2.336 2-CH3 6-CF3 H OCH3 CF3 2.337 2-CH3 6-CF3 H OC2Hs CF3 2.338 2-CH3 6-CF3 H SCH3 CF3 2.339 2-CH3 6-CF3 H SC2Hs CF3 2.340 2-CH3 6-CF3 H C2Hs CF3 2.341 2-CH3 6-CF3 H CH3 CF2CF3 2.342 2-CH3 6-CF3 H C2Hs CF2CF3 2.343 2-CH3 6-CF3 H C3H7(i) CF3 2.344 2-CH3 6-CF3 H C3H7(n) CF3 2.345 2-CH3 6-CF3 H Cyclo- CF3 propyl 2.346 2-OCHF2 5-Cl H CH3 Cl m.p. 61-62C
2.347 2-OCHF2 5-Cl H CH3 CH3 2.348 2-OCHF2 5-Cl H CH3 CHCl2 2.349 2-OCHF2 5-Cl H CH3 CHFCl 2.350 2-oCHFz 5-Cl H CH3 CHF2 2.351 2-OCHF2 5-Cl H CH3 CF2Cl 2.352 2-OCHF2 5-Cl H CH3 CF3 m.p. 66-67C
2.353 2-OCHF2 5-Cl H CH3 CF2CF3 2.354 2-OCHF2 5-Cl H CH3 CClzCF3 2.355 2-OCHF2 5-Cl H CH3 CCl2CH3 131~6 Table II (continued) _ Comp.No. R1 RZ R3 R4 Rs Physical data 2.356 2-OCHF2 5-Cl H CzHs CF3 2.357 2-OCHF2 5-Cl H C3H7(n) CF3 2.358 2-OCHF2 5-Cl H C3H7(i) CF3 2.359 2-CH3 6-Cl H Cyclo- CF3 2.360 2-CH3 6-Cl H C4Hg(n) CF3 2.361 2-CH3 6-Cl H C4Hg(i) CF3 2.362 2-CH3 6-Cl H C4Hg(t) CF3 2.363 2-CH3 6-Cl H Phenyl CF3 2.364 2-CH3 6-Cl H 2-Furyl CF
2.365 2-CH3 6-Cl H L ~ -Thienyl CF3 2.366 2-CH3 6-Cl H CzHs CF2CF3 2.367 2-CH3 6-Cl H C2Hs CCl2CH3 2.368 2-CH3 6-Cl H OCH3 CF3 2.369 2-CH3 6-Cl H OCZHs CF3 2.370 2-CH3 6-Cl H SCH3 CF3 2.371 2-Cl 6~Cl 3-Cl CH3 Cl 2.372 2-Cl 6-Cl 3-Cl CH3 CF3 2.373 2-Cl 6-Cl 3-Cl C2Hs CF3 2.374 2-Cl 6-Cl 3-Cl C3H7(i) CF3 2.375 2-Cl 6-Cl 3-Cl CH3 CF2CF3 2.376 2-Cl 6-Cl 3-Cl Phenyl CF3 2.377 2-Cl 6-Cl 3-Cl OCH3 CF3 2.378 2-Cl 6-Cl 3-Cl OC2Hs CF3 2.379 2-Cl 6-Cl 3-Cl SC2Hs CF3 2.380 2-OCH3 3-Cl H CH3 CF3 m.p. 41-42C
2.381 2-OCH3 3-Cl H C2Hs CF3 2.382 2-OCH3 3-Cl H C3H7(n) CF3 2.383 2-OCH3 3-Cl H Cyclo- CF3 propyl 2.384 2-OCH3 3-Cl H CH3 Cl 2.385 2-OCH3 3-Cl H CH3 CF2CF3 2.386 2-OCH3 3-Cl H OCH3 CF3 2.387 2-OCH3 3-Cl H SCH3 CF3 2.388 2-OCH3 3-C:L H CH3 CF2Cl 2.389 2-OCH3 3-C:L H CH3 CHFz 2.390 2-OCH3 5-Cl H CH3 Cl 2.391 2-OCH3 5-Cl H CH3 CH3 m.p. 106-107C
2.392 2-oCH3 5-Cl H CH3 CF3 m.p. 65-66C
2.393 2-OCH3 5-Cl H CH3 Br 2.394 2-oCH3 5-Cl H CN CH3 2.395 2-OCH3 5-Cl H CH3 CF2Cl 2.396 2-OCH3 5-Cl H CH3 CHFz 2.397 2-oCH3 5-Cl H CH3 CHCl2 2.398 2-OCH3 5-Cl H CH3 CF2CF3 m.p. 75-76C
2.399 2-OCH3 5-Cl H CH3 CCl2CF3 2.400 2-oCH3 5-Cl H CH3 CHClF
2.401 2-oCH3 5-Cl H CH3 CCl2CH3 2.402 2-OCH3 5-Cl H C2Hs CF3 131~5~
Table II (continued) Comp.No. R2- R3 R4 l Rs Physical data _ _ 2.403 2-OCH3 5-Cl H C2Hs CFzCF3 m.p. 64-65C
2.404 2-OCH3 5-Cl H C2Hs CF2Cl 2.405 2-oCH3 5-Cl H C3H7(n) CF3 nD5: 1,5463 2.406 2-OCH3 5-Cl H C3H7(i) CF3 nD5: 1,5455 2.407 2-OCH3 5-Cl H C3H7(i) CFzCF 3 2.408 2-OCH3 5-Cl H Cyclo- CF3 propyl 2.409 2-OCH3 5-Cl H C4Hg(n) CF3 2.410 2-oCH3 5-Cl H C2Hs(i) CF3 2.411 2-OCH3 5-Cl H C4Hg(t) CF3 m.p. 55-56C
2.412 2-oCH3 5-Cl H OCH3 CF3 2.413 2-oCH3 5-Cl H OC4Hg(n) CF3 2.414 2-OCH3 5-Cl H SCH1 CF3 2.415 2-OCH3 5-Cl }I SC2Hs CF3 2.416 2-OCH3 5-Cl H SC3H7(n) CF3 2.417 2-OCH3 5-Cl H SC3H7(i) CF3 2.418 2-oC2Hs 5-Cl H CH3 Cl 2.419 2-oC2Hs 5-Cl H CH3 CF3 2.420 2-OCzHs 5-Cl H CzHs CF3 2.421 2-OC2Hs 5-Cl H C3H7(i) CF3 2.422 2-OCzHs 5-Cl H Cyclo- CP3 propyl 2.423 2-OCzHs 5-Cl H Phenyl CF3 2.424 2-OC2Hs 5-Cl H OCH3 CF3 2.425 2-OC2Hs 5-Cl H CH3 CFzCF3 2.426 2-OC3H7 i) 5-Cl H CH3 Cl 2.427 2-OC3H7(i) 5-Cl H CH3 CF3 2.428 2-OC3H7(i~ 5-Cl H CH3 CF2Cl 2.429 2-OC3H7(i) 5-Cl H C2Hs CF3 2.430 2-OC3H7(i) 5-Cl H C3H7(n) CF3 2.431 2-OC3H7(i) 5-Cl H CH3 CHF3 2.432 2-OC3H7(i) 5-Cl H OCH3 CF3 2.433 2-OC3H7~ i) 5-Cl H SCH3 CF3 2.434 2-OCF3 H H CH3 Cl 2.435 2-OCF3 H H CH3 CF3 nD3: 1,4943 2.436 2-OCF3 H H CH3 CF2Cl 2.437 2-OCF3 H H CH3 CHF2 2.438 2-OCF3 H H CH3 CHFCl 2.439 2-OCF3 H H C2}1s CF3 2.440 2-OCF3 H H C3H7(i) CF3 2.441 2-OCF3 H H C4Hg(n) CF3 2.442 2-OCF3 H H C4Hg(t) CF3 2.443 2-oCF3 5-Cl H CH3 CF3 2.444 2-OCF3 5-Cl H CH3 Cl 2.445 2-OCF3 5-Cl H CH3 CF3 2.446 2-OCF3 5-Cl H CH3 CF2Cl 2.447 2-OCF3 5-Cl H CH3 CHF2 2.448 2-OCF3 5-Cl H CH3 CHC12 - 48 - 1 31~5 4 6 Table II (continued) Comp.~~ R~ R2 R3 R4 Rs Physical data 2.449 2-OCF3 5-Cl H CH3 CHFCl 2.450 2-OCF3 5-Cl H CH3 CF 2 CF3 2.451 2-OCF3 5-Cl H CZHs CF2CF3 2.452 2-OCF3 5-Cl H C2Hs CF3 2.453 2-OCF3 5-Cl H C3H7(i) CF3 2.454 2-OCF3 5-Cl H Cyclo- CF3 propyl 2.455 2-OCF3 5-Cl H Phenyl CF3 2.456 2-OCF3 5-Cl H OCZHs CF3 2.457 2-OCF3 5-Cl H SC 2 Hs CF3 2.458 2-SCH3 H H CH3 Cl 2.459 2-SCH3 H H CH3 CF3 m.p. 74-75C
2.460 2-SCH3 H H CH3 CHFz 2.461 2-SCH3 H H CH3 CF2CF3 2.462 2-SCH3 H H C2Hs CF3 2.463 2-SCH3 H H C3H7(i) CF3 nDS: 1,5575 2.464 2-SCH3 H H C4Hg(n) CF3 2.465 2-SCH3 H H C4Hg(t) CF3 2.466 2-SCH3 5-Cl H CH3 Cl 2.467 2-SCH3 5-Cl H CH3 CF3 m.p. 144-145C
2.468 2-SCH3 5-Cl H CH3 CF2CF3 2.469 2-SCH3 5-Cl H CH3 CFzCl 2.470 2-SCH3 5-Cl H C2Hs CF3 2.471 2-SOCH3 H H CH3 Cl 2.472 2-SOCH3 H H CH3 CF3 2.473 2-SOCH3 H H CH3 CHFz 2.474 2-SOCH3 H H CH3 CFzCF3 2.475 2-SOCH3 H H C2Hs CF3 2.476 2-SOCH3 H H C3H7(i) CF3 2.477 2-SOCH3 H H C4Hg(n) CF3 2.478 2-SOCH3 H H C4Hg(t) CF3 2.479 2-SO2CH _ H H CH3 Cl m.p. 168C
2.480 2-SO2CH3 H H CH3 CF3 m.p. 149C
2.481 2-SO2CH3 H H C2Hs CF3 2.482 2-SO2CH3 H H C3H7(n) CF3 2.483 2-SO2CH3 H H C3H7(i) CF3 2.484 2-SO2CH3 H H Cyclo- CF3 propyl 2.485 2-So2CH3 H H C4Hg(i) CF3 2.486 2-SO2CH3 H H CH3 CFzCF3 2.487 2-SOzCH3 H H CzHs CF2CF3 2.488 2-SOzCH3 H H C3H7(i) CF2CF3 2.489 2-SOCH3 _ 5-Cl H CH3 Cl 2.490 2-SOCH3 5-Cl H CH3 CF3 m.p. 194-195C
2.491 2-SOCH3 5-Cl H CzHs CF3 2.492 2-SOCH3 5-Cl H CH3 CFzCF3 2.493 2-SOCH3 _5-Cl H C3H7(i) CF3 2.494 2-SO2CH l¦5-Cl H CH3 Cl - 49 - 1 31~ ~4 6 Table II (continued) Comp.No. R2 R3 R4 Rs Physical data 2.495 2-502CH3 5-Cl H CH3 CF3 m.p. 183-184C
2.496 2-SO2CH3 5-Cl H C2Hs CF3 2.497 2-SO2CH3 5-Cl H CH3 CF2CF3 2.498 2-SOzCH _ 5-Cl H C3H7(i) CF3 2.499 2-F 5-F H CH3 OCHF2 2.500 2-F 5-F H CH3 Cl 2.501 2-F 5-F H CH3 CF3 m.p. 68-69C
2.502 2-F 5-F H CzHs CF3 2.503 2-F 5-F H C3H7(n) CF3 2.504 2-F 5-F H C3H7(i) CF3 2.505 2-F 5-F H Cyclo- CF3 m.p. 103-104C
propyl 2.506 2-F 5-F H CH3 CF2CF3 _ 2.507 2-F 5-F H CH3 CF2CF2C]
2.508 2-F 5-F H CH3 CF2Cl 2.509 2-F 5-F H CH3 CHFz 2.510 2-F 5-F H CH3 CHClF
2.511 2-F 5-F H C2Hs CF2Cl O 2.512 2-F 5-F H C3H7(i) CF2Cl nD5: 1,5358 2.513 2-F 5-F H C4Hg(n) CF3 2.514 2-F 5-F H C4Hg(t) CF3 m.p. 37-38C
2.515 2-F 5-F H C2Hs CFzCF3 2.516 2-F 5-F H C3H7(i) CFzCF3 m.p. 53-54C
2.517 2-F 5-F H C3H7(n) CF2CF3 2.518 2-F 5-F H CH3 CClzCF3 2.519 2-F 5-F H CH3 CHCl2 2.520 2-F 5-F H CzHs CHC12 nD5: 1,5324 2.521 2-F 5-F H CH3 CClzCH3 2.522 2-F 5-F H OCH3 CF3 2.523 2-F 5-F H OC3H7(i) CF3 2.524 2-F 5-F H SCH3 CF3 2.525 2-F 5-F H SC3H7(i) CF3 2.526 2-F 6-F H CH3 Cl 2.527 2-F 6-F H CH3 CF3 m.p. 164C
2.528 2-F 6-F H C2Hs CF3 m.p. 120-121C
2.529 2-F 6-F H C3H7(n) CF3 2.530 2-F 6-F H C3H7(i) CF3 m.p. 92-94C
2.531 2-F 6-F H CH3 CF2CF3 2.532 2-F 6-F H C2Hs CF2CF3 m.p. 85-87C
2.533 2-F 6-F H CH3 CF2Cl m.p. 92-95C
2.534 2-F 6-F H CH3 CHFz 2.535 2-F 6-F H CH3 CHClF
2.536 2-F 6-F H OCH3 CF3 2.537 2-F 6-F H SCH3 CF3 2.538 2-F 6-Cl H CH3 Cl 2.539 2-F 6-Cl H CH3 CH3 2.540 2-F 6-Cl H CH3 CF3 m.p. 160-161C
2.541 2-F 6-Cl H CZHs CF3 2.542 2-F 6-Cl H C3H7(i) CF3 m.p. 108-109C
~ 50 - 1 3145~ 6 Table II (continued) Comp.No. Rl R2 R3 - R5 Physical data 2.543 2-F 6-Cl H propyl CF3 m.p. 95-96C
2.544 2-F 6-Cl H CH3 CF2CF3 2.545 2-F 6-Cl H C3H7(i) CF2CF3 2.546 2-F 6-Cl H CH3 CCl2CF3 2.547 2-F 6-Cl H CH3 CHCl2 2.548 2-F 6-Cl H CH3 CHFz 2.549 2-F 6-Cl H CH3 CHFCl 2.550 2-F 6-Cl H CH3 CFzCl 2.551 2-F 6-Cl H C3H7(i) CF2Cl 2.552 2-F 6-Cl H OCH3 CF3 2.553 2-CN H H CH3 CF3 m.p. 117~118C
2.554 2-CN H H C2Hs CF3 2.555 2-CN H H C3H7(i) CF3 2.556 2-CN H H CH3 CF2CF3 2.557 2-CN H H CZHs CFzCF3 2.558 2-CN H H C3H7(i) CFzCF3 2.559 2-CN H H CH3 CHF2 2.560 2-CN H H CH3 CFzCl 2.561 2-CN H H OCH3 CF3 2.562 2-CN H H OCZHs CF3 2.563 2-Po(oC, !Hs)2 H H CH3 CF3 m.p. 60-61C
2.564 2-PO(OCzHs~2 H H C2Hs CF3 2.565 2-Po(oC ~Hs)z H H C3H7(i) CF3 2.566 2-Cl 5-Cl H SOCH3 CF3 2.567 2-Cl 5-Cl H SO2CH3 CF3 2.568 2-Cl 6-Cl H SOCH3 CF3 m.p. 144-148C
2.569 2-Cl 6-Cl H SOzCH3 CF3 m.p. 144-146C
2.570 2-Cl 6-Cl H SOCH3 CH3 2.571 2-Cl 6-Cl H SO2CH3 CH3 2.572 2-Cl 6-Cl H CN CH3 2.573 2-Cl 6-Cl H CN CF3 2.574 2-Cl 6-Cl H CH=CCl2 Cl 2.575 2-Cl 5-Cl H CH=CCl2 Cl 2.576 2-CF3 H H CH=CCl2 Cl 2.577 2-Cl 6-Cl H CHzOCH3 CF3 2.578 2-Cl 6-C:L H CH20CH3 C2Fs 2.579 2-Cl 5-Cl H CH20CH3 CF3 2.580 2-Cl 5-Cl H CH20CH3 CF2Cl 2.581 2-OCH3 5-Cl H CH20CH3 CF3 2.582 2-OCH3 5-Cl H CH20CH3 CF2CF3 2.583 2-F 5-F H CH20CH3 CF3 2.584 2-OCHF2 5-Cl H CH20CH3 CF3 2.585 2-OCHF2 5-Cl H CH20CH3 CF2Cl 2.586 3-Br H H CH3 Cl m.p. 101-102C
2.587 3-Br H H CH3 CF3 2.588 2-Br 5-8r H CH3 Cl 2.589 2-Br 5-Br H CH3 CF3 m.p. 95-97C
2.590 2-Br 5-Br H OCH3 CF3 - 51 - 1314~ 46 Table II (continued) Comp.No. R1 R2 R3 R4 Rs Physical da~a _ 2.591 2-Br 5-Br H CZHs CF3 2.592 2-Br 5-Br H CH3 CF2Cl 2.593 2-Br 5-Br H CH3 CHF2 2.594 2-CF3 5-Cl H CH3 CF3 m.p. 65-67C
2.595 2-CF3 5-Cl H CH3 Cl m.p. 117-118C
2.596 2-CF3 5-Cl H C2Hs CF3 2.597 2-CF3 5-Cl H C3H7(i) CF3 2.598 2-CF3 5-Cl H Cyclo- CF3 propyl 2.599 2-CF3 5-Cl H CH3 CH2Cl 2.600 2-CF3 5-Cl H CH3 CHFz 2.601 2-CF3 5-Cl H C2Hs CF2Cl 2.602 2-CF3 5-Cl H C3H7(i) CF2Cl 2.603 2-CF3 5-Cl H CH3 CF2CF3 2.604 2-CF3 5-Cl H OCH3 CF3 2.605 2-CF3 5-Cl H SCH3 CF3 2.606 2-CF3 5-Cl H SOCH3 CF3 2.607 2-CF3 5-Cl H 5OzCH3 CH3 2.608 2-CH3 3-CH3 H CH3 Cl 2.609 2-CH3 3-CH3 H CH3 CF3 2.610 2-CH3 5-CH3 H CH3 Cl 2.$11 2-CH3 5-CH3 H CH3 CF3 2.612 2-CH3 6-CH3 H CH3 Cl 2.613 2-CH3 6-CH3 H CH3 CF3 m.p. 145-146C
2.614 2-CH3 6-CH3 H CH3 CF2Cl m.p. 147-148C
2.615 2-CH3 6-CH3 H CH3 CH2CF3 2.616 2-CH3 6-CH3 H OCH3 CF3 2.617 2-CH3 6-CH3 H SCH3 CF3 2.618 2-CH3 6-C2Hs H CH3 Cl 2.619 2-CH3 6-CZHs H CH3 CF3 m.p. 90-93C
2.620 2-CH3 6-C2Hs H OCH3 CF3 2.621 2-CH3 5-F H CH3 Cl 2.622 2-CH3 5-F H CH3 CF3 m.p. 78-79C
2.623 2-CH3 5-F H CH3 CHFz 2.624 2-CH3 5-F H CH3 CF2Cl 2.625 2-CH3 5-F H C2Hs CF3 2.626 2-CH3 5-F H C3H7(i) CF3 2.627 2-CH3 5-F H OCH3 CF3 2.628 2-CH3 5-F H OC2Hs CF3 2.629 2-Br 6-Br H CH3 Cl 2.630 2-Br 6-Br H CH3 CF3 2.631 2-Br 6-Br H C2Hs CF3 m.p. 104-105C
2.632 2 Br 6-Br H C3H7(i) CF3 2.633 2-Br 6-Br H Cyclo- CF3 propyl 2.634 2-Br 6-Br H CH3 CHCl2 2.635 2-Br 6-Br H CH3 CF2CF3 2.636 2-Br H H C3H7(i) CF2CF3 nD5: 1,5307 2.637 2-CF3 H H CH3 CHC12 m.p. 72-74C
- 52 - 1 3 1 4 a Table II (continued~
Comp.No. R1 R2 R3 R4 ~s Physical data 2.638 2-OCHFz H H CH3 CF3 m.p. 71-72C
2.639 2-OCHFz H H C3H7(i) CF3 2.640 2-OCHF2 H H Cyclo- CF3 nD5: 1,5242 propyl 2.641 2-OCHF2 H H CH3 CHFz 2.642 2-OCHFz H H CH3 CHFCl 2.643 2-CF3 H H CH3 CHF2 2.644 2-CF3 H H CH3 CF2Cl 2.645 2-CF3 H H C3H7(i) CF2Cl nD5: 1,5184 2.646 2-CF3 H H Cyclo- CF3 m.p. 63-64C
propyl 2.647 2-CF3 H H 2-Thienyl CF3 m.p. 97-98C
2.648 2-Br H H C4Hg(n) CF3 m.p. 65-66C
2.649 2-Br H H C3H7(i) CF3 nD5: 1,5583 2.650 2-Br H H CH3 CHF2 2.651 2-Br H H CH3 CF2Cl 2.652 2-Br H H Cyclo- CF2Cl propyl 2.653 2-Br H H C2Hs CHFz 2.654 2-Cl 6-CH3 H CH3 CH3 m.p. 141-142C
2.655 2-Cl 6-Cl H CH3 CHF2 m.p. 99-101C
2.656 2-Cl 6-Cl H C2Hs CHFz 2.657 2-Cl 5-Cl H CsH1l(n) CF3 m.p. 56-57C
2.658 2-COoCH3 H H CH3 CF3 m.p. 143-145C
2.659 2-COOCH3 H H CzHs CF3 2.660 2-COOCH3 H H C3H7(i) CF3 2.661 2-COOCH3 H H Cyclo- CF3 propyl 2.662 2-COOCH3 H H CH3 CF2Cl 2.663 2-CooCH3 H H CH3 CHF2 2.664 2-COOC2Hs H H CH3 CF3 2.665 2-COOC3H7(n) H H CH3 CF3 2.666 2-COOC3H7(i) H H CH3 CF3 2.667 2-COOC4Hg(n) H H CH3 CF3 2.668 2-OCH3 5-F H CH3 CF3 m.p. 89-93C
2.669 2-OCH3 5-F H CH3 CHF2 2.670 2-OCH3 5-F H C2Hs CHF2 2.671 2-OCH3 5-F H C3H7(i) CF3 2.672 2-OCH3 5-F H Cyclo- CF3 propyl 2.673 2-OCH3 5-F H Cyclo- CF3Cl - 53 - 13~4~
Table II (continued) Comp.No. Ri R~ R3 R4 _ _ Physical data 2.674 2-OCHF2 S-F H CH3 CF3 2.675 2-OCHF2 5-F H CH3 CHF2 2.676 2-OCHF2 5-F H CH3 CFzCl 2.677 2-COOCH3 6-CH3 H CH 3 CF3 m.p. 90- 91C
2.678 2-COOCH3 6-CH3 H CH3 CHFz 2.679 2-COOCH3 6-CH3 H C3H7(i) CF3 2.680 2-COOCH3 6-CH3 H Cyclo- CF3 propyl 2.681 2-COOCH3 6-Cl H CH3 CF3 m .p. 86-87C
2.682 2-COOCH3 6-Cl H CH3 CHFz 2.683 2-Br H H 2-Furyl CF3 m.p. 108-109C
2.684 2-Cl 6-Cl 3-CH ~CH3 Cl m.p. 158-164C
2.685 2-CF3 H H CzHs CHC12 nD5: 1,5462 2.686 2-Cl S-Cl H Cl CF3 m.p. 66-67C
2.687 2-CONHz H H CHH3 CF3 m.p. 187-190C
2.688 2-Cl 6-Cl H CHCHzCH3 CF3 m.p. 91-92C
2.689 2-F H H CzHs CF3 nDS: 1,5332 2.690 2-F H H CH20CH3 CF3 m.p. 48-50C
2.691 2-F H H CH20CH3 CF2Cl nDS: 1,5525 2.692 2-OCH3 6-Cl H CH3 CF3 m.p. 113-114C
2.693 2-OCH3 6-Cl H CzHs CF3 m.p. 68-70 C
2.694 2-OCH3 6-Cl H C3H7(i) CF3 m.p. 80-81C
2.695 2-CH3 6-CH3 H CzHs CF3 m.p. 88-89C
2.696 2-CH3 6-CH3 H C3H7(i) CF3 m.p. 64-65C
2.697 2-F 6-F H C4Hg(i) CF3 m.p. 97-99C
2.698 2-F 6-F H _ /¦ CF3 m.p. 111-113C
2.699 2-F 6-F H CH20CH3 CF3 m.p. 62-65C
2.700 2-F 6-F H C2Hs CHClz m.p. 123-125C
2.701 2-F 6-F H 2-Furyl CF3 m.p. 122-123C
2.702 2-CH3 5-F H C2Hs CHC12 Oel 2.703 2-Cl 6-CH3 H CHzOCH3 CF3 m.p. 95-96C
2.704 2-Cl 6-CH3 H CH20CH3 CF2Cl m.p. 103-105C
2.705 2-Cl 6-CH3 H C3H7(i) CF2Cl m.p. 60-61C
2.706 2-Cl 6-CH3 H Cl CF3 m.p. 102C
2.707 2-Cl 6-CH3 H CH20CH3 CHFz nDS: 1,5375 2.708 2-F H H CH20CH3 CHFz m.p. 44-45C
2.709 2-OCH3 6-CH3 H CH3 CF3 m.p. 94-95C
2.710 2-Cl 6-Cl H Cl CF3 m.p. 124-125C
2.711 2-SCHF2 H H CH3 CF3 m.p. 78-79C
2.712 2-OCHF2 6-CH3 H CH3 CF3 nD3: 1,5050 2.713 2-OCHFz 6-CH3 H CZHs CF3 nD3: 1,4910 2.714 2-F 6-Cl H 2-Furyl CF3 m.p. 119-120C
2.715 2-CH3 6-F H CzHs CHClz _ 54 _ 1 31~5 4~
P. 3. Compounds of formula III
P. 3.1. N-chlorocarbonyl-N-(4,6-dimethyl-pyrimidin-2-yl)-2,5-dichloro-aniline
5.0 g (0.018 mole) of N-(4,6-dimethyl-pyrimidin-2-yl)-2,5-dichloroaniline are dissolved in 100 ml of toluene and heated to reflux. A gentle stream of phosgene is then introduced for a period of 4 hours. The excess phosgene is blown out with nitrogen, and the toluene solution is washed cold with water, dried with magnesium sulfate and then concentrated by evaporation. 5.8 g (95.1 %) of the title compound of formula ~Cl /CH3 N--~
~1 are isolated in the form of crystals having a melting point of 121-123C.
Biological Examples Example B1: Pre-emergence herbicidal action In a greenhouse, immediately after sowing the test plants in seed trays the surface of the soil is treated with an aqueous spray mixture corre-sponding to a rate of application of 4 kg of active ingredient/hectare.
The seed trays are kept in a greenhouse at 22-25C and 50-70 ~/0 relative humidity.
After 3 weeks the herbicidal action is assessed in comparison with an untreated control group using a nine-stage evaluation scale (1 = total damage, 9 = no effect).
Ratings of 1 to 4 (especially 1 to 3) indicate a good to very good herbicidal action. Ratings of 6 to 9 (especially 7 to 9) indicate a good tolerance (especially in the case of crop plants).
- 55 - i3~45 ~ ~
In this test the following compounds of formula I show good to very good herbicidal action against Setaria italica and Stellaria media: Compound Nos. 1.009, 1.016, 1.020, 1.021, 1.023, 1.032, 1.037, 1.038, 1.042, 1.050, 1.052, 1.055, 1.056, 1.064, 1.065, 1.096, 1.109, 1.113, 1.132, 1.141, 1.144, 1.170, 1.219, 1.221, 1.258, 1.271, 1.332, 1.346, 1.380, 1.392, 1.459, 1.501, 1.505, 1.527, 1.528, 1.540, 1.543, 1.553, 1.638, 1.691, 1.703 and 1.712.
Example B2: Pre-emerRence herbicidal action (selective herbicidal action Immediately after the test plants have been sawn into beakers with 12 to 15 cm diameter the covering soil was treated with an aqueous formulation containing the active ingredient according to an application rate of 1000 and 500 [g] AS/[ha].
The beakers were kept in a greenhouse at temperature between 22 and 25C
and a rel. humidity of 50 to 70 %.
After 3 weeks the herbicidal action is assessed in comparison with an untreated control group using a nine-stage evaluation scale (1 = total damage, 9 = no effect).
Ratings of 1 to 4 (especially 1 to 3) indicate a good to very good herbicidal action. Ratings of 6 to 9 (especially 7 to 9) indicate a good tolerance (especially in case of crop plants).
The results of this experiment are compiled in table III. In this tale T
denotes good to very good tolerance (to the crop) and H denotes a good to very good herbicidal action (against ~he crop).
- 56 - ~3 14 ~ 4~
Table III
Compound No.
Plants tested 1.020 1.0551.0561.1411.219 1.528 1.540 barley T T T T T T
wheat T T T T T
maize T T T T T T T
soybeans T T T T T T T
cotton T T T T T T T
sunflower T T T T T T T
rape T
Lolium perenne H H H
Alopecurus Myos. H H
Digitaria sang. H H H H H H
Echinochloa crus galli H H H H H
Sorghum halep. H H H H
Chenopodium Sp. H H H H H H
Solanum nigrum H H H
Stellaria H H H H H H
Viola tricolor H H H H
Galuim aparine H H H
Veronica Sp. H H H H H H H
Example B3: Selective herbicidal action in paddy (transplanted ri Water weeds are sown in plastic beakers (425 cm2 surface area, 5 1 volume). To this rice which is transplanted at the three foliar stage.
After sowing and transplantation the beakers are filled to the soil surface with water. 3 days after sowing and transplantation the water level is raised slightly above (3-5 mm) the surface of the soil. The application of the test substance is done three days after sowing and transplantation at an application rate of 1000 and 500 [g/ha] by inject-ing an aqueous emulsion into the water (the application volume corre-sponds to 1400 l/ha~. l`he plant beakers are then place in a greenhouseunder optimum growth conditions for the rice and the weeds~ i.e. 25-30C
and high humidity.
The test is evaluated three weeks after application in comparison with an untreated control using a nine-stage evaluation scale.
Ratings of 1 to 4 (especially 1 to 3~ indicate good to very good herbici-dal action. Ratings of 6 to 9 (especially 7 to ~) indicate a good tolerance (especially in rice~.
1314~4~
In this test compounds nos. 1.009, 1.096 and 1.141 exhibit very good herbicidal action against Echinochloa crus galli and show a very good tolerance in rice. Moreover compound 1.141 shows very good herbicidal action against Monocharia.
Example B4: Growth inhibition in cereals The plants (for example summer barley of the Iban variety) are sown in 15 cm plastics pots containing sterilised soil and cultivated in a climatic chamber at a daytime temperature of 10-15C and a night time temperature of 5-10C. The illumination time is 13.5 hours per day at an intensity of approximately 25000 Lux.
Approximately 34 days after sowing and after thinning out to 4 plants per pot, 0.3 to 3 kg of active ingredient/ha, generally as a 25 % strength formulation in an aqueous spray mixture, are applied. The amount of water applied is approximately 500 l/ha. After the application the plants are placed in a greenhouse at a daytime temperature of at least 10C. The illumination time is at least 13.5 hours/day.
The evaluation is carried out approximately 28 days after the treatment.
At this point the height of the new growth is measured.
The compounds of formula I tested cause a reduction in new growth compared with the untreated control.
Example B5: Growth inh:ibition in grasses with trefoil A mixture of grasses (for example Poa, Festuca, Lolium, Bromus, Cyno-surus) and trefoil (Trifolium pratenselrepens) is sown in 15 cm plastics pots containing sterile soil and cultivated in a greenhouse at a daytime temperature of 21C and a night time temperature of 17C. The illumina-tion time is 13.5 hours/day at a light intensity of at least 7000 Lux.
After emergence, the plants are cut back weekly to a height of approxi-mately 6 cm. Approximately 42 days after sowing and 1 day after the last cut, 0.3 to 3 kg of active ingredientlhectare are applied, generally in a 25 % strength formulation in an aqueous spray mixture. The amount of water applied is approximately 500 llha.
Evaluation is carried out approximately 3 weeks after the treatment. Atthis point the height of the new growth is measured.
The compounds of formula I tested cause a reduction in new growth compared with the untreated control.
Formulation Examples Example Fl: Formulation Examples for active ingredients of formula I, (throughout, percentages are by weight) a) Fmulsifiable concentrates a) b) c) -a compound according to Preparation Example 1 20 %40 % 50 %
calcium dodecylbenzenesulfonate 5 % 8 % 5.8 %
castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5 % - -tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) - 12 % 4.2 %
cyclohexanone - 15 % 20 %
xylene mixture 70 % 25 % 20 %
Emulsions of any desired concentration can be produced from such concentrates by dilution with water.
b) Solutions a) b) c~
a compound according to ~reparation Example 1 80 % 10 % 5 %
ethylene glycol monomethyl ether 20 %
polyethylene glycol MW 400 - 70 %
N-methyl-2-pyrrolidone - 20 % 5 %
epoxidised coconut oil - - 90 %
These solutions are suitable for application in the form of micro-drops.
c) Granulates a) b) a compound according to Preparation Example 1 5 %10 %
kaolin 94 %
highly dispersed silicic acid 1 %
attapulgite - 90 %
.
A solution of the active ingredient is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.
d) Dusts a) b) a compound according to Preparation Example 1 2 % 5 %
highly dispersed silicic acid 1 % 5 %
talcum 97 %
kaolin - 90 %
Ready-for-use dusts are obtained by homogeneously mixing the carriers with the active ingredient.
e) Wettable powders a) b) a compound according to Preparation Example 1 20 % 60 %
sodium lignosulfonate5 % 5 %
sodium lauryl sulfate - 6 %
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 %
highly dispersed silicic acid 5 % 27 %
kaolin 70 %
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
- 60 - ~ 31 4 5~6 f) Extruder granulate a compound according to Preparation Example I 10 %
sodium lignosulfonate 2 %
carboxymethylcellulose 1 %
kaolin 87 %
The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
g) Coated granulate a compound according to Preparation Example 1 3 %
polyethylene glycol (MW 200) 3 %
kaolin 94 %
The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-tusty coated granulates are obtained in this manner.
h) Suspension concentrate a compound according to Preparation Example 1 40 %
ethylene glycol 10 %
nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6 %
sodium lignosulfonate 10 %
carboxymethylcellulose 1 %
37 % aqueous formaldehyde solution 0.2 %
silicone oil in the form of a 75 %
aqueous emulsion 0.8 %
water ad 100 %
The active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentra-tion can be obtained by dilution with water.
~1 are isolated in the form of crystals having a melting point of 121-123C.
Biological Examples Example B1: Pre-emergence herbicidal action In a greenhouse, immediately after sowing the test plants in seed trays the surface of the soil is treated with an aqueous spray mixture corre-sponding to a rate of application of 4 kg of active ingredient/hectare.
The seed trays are kept in a greenhouse at 22-25C and 50-70 ~/0 relative humidity.
After 3 weeks the herbicidal action is assessed in comparison with an untreated control group using a nine-stage evaluation scale (1 = total damage, 9 = no effect).
Ratings of 1 to 4 (especially 1 to 3) indicate a good to very good herbicidal action. Ratings of 6 to 9 (especially 7 to 9) indicate a good tolerance (especially in the case of crop plants).
- 55 - i3~45 ~ ~
In this test the following compounds of formula I show good to very good herbicidal action against Setaria italica and Stellaria media: Compound Nos. 1.009, 1.016, 1.020, 1.021, 1.023, 1.032, 1.037, 1.038, 1.042, 1.050, 1.052, 1.055, 1.056, 1.064, 1.065, 1.096, 1.109, 1.113, 1.132, 1.141, 1.144, 1.170, 1.219, 1.221, 1.258, 1.271, 1.332, 1.346, 1.380, 1.392, 1.459, 1.501, 1.505, 1.527, 1.528, 1.540, 1.543, 1.553, 1.638, 1.691, 1.703 and 1.712.
Example B2: Pre-emerRence herbicidal action (selective herbicidal action Immediately after the test plants have been sawn into beakers with 12 to 15 cm diameter the covering soil was treated with an aqueous formulation containing the active ingredient according to an application rate of 1000 and 500 [g] AS/[ha].
The beakers were kept in a greenhouse at temperature between 22 and 25C
and a rel. humidity of 50 to 70 %.
After 3 weeks the herbicidal action is assessed in comparison with an untreated control group using a nine-stage evaluation scale (1 = total damage, 9 = no effect).
Ratings of 1 to 4 (especially 1 to 3) indicate a good to very good herbicidal action. Ratings of 6 to 9 (especially 7 to 9) indicate a good tolerance (especially in case of crop plants).
The results of this experiment are compiled in table III. In this tale T
denotes good to very good tolerance (to the crop) and H denotes a good to very good herbicidal action (against ~he crop).
- 56 - ~3 14 ~ 4~
Table III
Compound No.
Plants tested 1.020 1.0551.0561.1411.219 1.528 1.540 barley T T T T T T
wheat T T T T T
maize T T T T T T T
soybeans T T T T T T T
cotton T T T T T T T
sunflower T T T T T T T
rape T
Lolium perenne H H H
Alopecurus Myos. H H
Digitaria sang. H H H H H H
Echinochloa crus galli H H H H H
Sorghum halep. H H H H
Chenopodium Sp. H H H H H H
Solanum nigrum H H H
Stellaria H H H H H H
Viola tricolor H H H H
Galuim aparine H H H
Veronica Sp. H H H H H H H
Example B3: Selective herbicidal action in paddy (transplanted ri Water weeds are sown in plastic beakers (425 cm2 surface area, 5 1 volume). To this rice which is transplanted at the three foliar stage.
After sowing and transplantation the beakers are filled to the soil surface with water. 3 days after sowing and transplantation the water level is raised slightly above (3-5 mm) the surface of the soil. The application of the test substance is done three days after sowing and transplantation at an application rate of 1000 and 500 [g/ha] by inject-ing an aqueous emulsion into the water (the application volume corre-sponds to 1400 l/ha~. l`he plant beakers are then place in a greenhouseunder optimum growth conditions for the rice and the weeds~ i.e. 25-30C
and high humidity.
The test is evaluated three weeks after application in comparison with an untreated control using a nine-stage evaluation scale.
Ratings of 1 to 4 (especially 1 to 3~ indicate good to very good herbici-dal action. Ratings of 6 to 9 (especially 7 to ~) indicate a good tolerance (especially in rice~.
1314~4~
In this test compounds nos. 1.009, 1.096 and 1.141 exhibit very good herbicidal action against Echinochloa crus galli and show a very good tolerance in rice. Moreover compound 1.141 shows very good herbicidal action against Monocharia.
Example B4: Growth inhibition in cereals The plants (for example summer barley of the Iban variety) are sown in 15 cm plastics pots containing sterilised soil and cultivated in a climatic chamber at a daytime temperature of 10-15C and a night time temperature of 5-10C. The illumination time is 13.5 hours per day at an intensity of approximately 25000 Lux.
Approximately 34 days after sowing and after thinning out to 4 plants per pot, 0.3 to 3 kg of active ingredient/ha, generally as a 25 % strength formulation in an aqueous spray mixture, are applied. The amount of water applied is approximately 500 l/ha. After the application the plants are placed in a greenhouse at a daytime temperature of at least 10C. The illumination time is at least 13.5 hours/day.
The evaluation is carried out approximately 28 days after the treatment.
At this point the height of the new growth is measured.
The compounds of formula I tested cause a reduction in new growth compared with the untreated control.
Example B5: Growth inh:ibition in grasses with trefoil A mixture of grasses (for example Poa, Festuca, Lolium, Bromus, Cyno-surus) and trefoil (Trifolium pratenselrepens) is sown in 15 cm plastics pots containing sterile soil and cultivated in a greenhouse at a daytime temperature of 21C and a night time temperature of 17C. The illumina-tion time is 13.5 hours/day at a light intensity of at least 7000 Lux.
After emergence, the plants are cut back weekly to a height of approxi-mately 6 cm. Approximately 42 days after sowing and 1 day after the last cut, 0.3 to 3 kg of active ingredientlhectare are applied, generally in a 25 % strength formulation in an aqueous spray mixture. The amount of water applied is approximately 500 llha.
Evaluation is carried out approximately 3 weeks after the treatment. Atthis point the height of the new growth is measured.
The compounds of formula I tested cause a reduction in new growth compared with the untreated control.
Formulation Examples Example Fl: Formulation Examples for active ingredients of formula I, (throughout, percentages are by weight) a) Fmulsifiable concentrates a) b) c) -a compound according to Preparation Example 1 20 %40 % 50 %
calcium dodecylbenzenesulfonate 5 % 8 % 5.8 %
castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5 % - -tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) - 12 % 4.2 %
cyclohexanone - 15 % 20 %
xylene mixture 70 % 25 % 20 %
Emulsions of any desired concentration can be produced from such concentrates by dilution with water.
b) Solutions a) b) c~
a compound according to ~reparation Example 1 80 % 10 % 5 %
ethylene glycol monomethyl ether 20 %
polyethylene glycol MW 400 - 70 %
N-methyl-2-pyrrolidone - 20 % 5 %
epoxidised coconut oil - - 90 %
These solutions are suitable for application in the form of micro-drops.
c) Granulates a) b) a compound according to Preparation Example 1 5 %10 %
kaolin 94 %
highly dispersed silicic acid 1 %
attapulgite - 90 %
.
A solution of the active ingredient is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.
d) Dusts a) b) a compound according to Preparation Example 1 2 % 5 %
highly dispersed silicic acid 1 % 5 %
talcum 97 %
kaolin - 90 %
Ready-for-use dusts are obtained by homogeneously mixing the carriers with the active ingredient.
e) Wettable powders a) b) a compound according to Preparation Example 1 20 % 60 %
sodium lignosulfonate5 % 5 %
sodium lauryl sulfate - 6 %
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2 %
highly dispersed silicic acid 5 % 27 %
kaolin 70 %
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
- 60 - ~ 31 4 5~6 f) Extruder granulate a compound according to Preparation Example I 10 %
sodium lignosulfonate 2 %
carboxymethylcellulose 1 %
kaolin 87 %
The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
g) Coated granulate a compound according to Preparation Example 1 3 %
polyethylene glycol (MW 200) 3 %
kaolin 94 %
The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-tusty coated granulates are obtained in this manner.
h) Suspension concentrate a compound according to Preparation Example 1 40 %
ethylene glycol 10 %
nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6 %
sodium lignosulfonate 10 %
carboxymethylcellulose 1 %
37 % aqueous formaldehyde solution 0.2 %
silicone oil in the form of a 75 %
aqueous emulsion 0.8 %
water ad 100 %
The active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentra-tion can be obtained by dilution with water.
Claims (27)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A urea of formula I
(I), in which R1, R2 and R3 are each, independently of the others, hydrogen; halogen C1-C4alkyl; C1-C4alkoxy; C1-C4haloalkyl; C1-C4haloalkoxy; C1-C4alkyl-S(0)n-; nitro; cyano; C1-C4alkoxyrarbonyl; di-(C1-C4alkylamino)-carbonyl;
mono-(C1-C4alkylamino)carbonyl; carbamoyl; C1-C4haloalkyl-S(O)n-;
C1-C4alkylcarbonyl; or -PO[O-(C1-C4)-alkyl]2;
R4 is C1-C6alkyl; C1-C4alkoxy; C1-C4alkyl-S(O)n-; C1-C4haloalkyl;
C1-C4haloalkoxy; phenyl that is unsubstituted or is substituted by up to three identical or different substituents from halogen, C1-C4alkyl, C1-C4haloalkyl and C1-C4alkoxy; 2-furanyl; 2-thienyl; 3-thienyl; C3-C6-cycloalkyl that is unsubstituted or is substituted by up to three identical or different C1-C4alkyl radicals; cyano; C2-C4haloalkenyl;
C1-C4alkoxy-C1-C4alkyl; C1-C4alkoxy-C1-C4alkoxy; or halo-C1-C4alkylthio;
R5 is hydrogen; C1-C3alkyl; C1-C3haloalkyl; halogen; or C1-C3haloalkoxy;
and n is 0, 1 or 2, with the proviso that when one of the radicals R1, R2 and R3 is nitro, that substituent may not be bonded in the 2- or 6-position of the phenyl ring, or a salt or addition compound of the compound of formula I with an acid, base or complex former.
(I), in which R1, R2 and R3 are each, independently of the others, hydrogen; halogen C1-C4alkyl; C1-C4alkoxy; C1-C4haloalkyl; C1-C4haloalkoxy; C1-C4alkyl-S(0)n-; nitro; cyano; C1-C4alkoxyrarbonyl; di-(C1-C4alkylamino)-carbonyl;
mono-(C1-C4alkylamino)carbonyl; carbamoyl; C1-C4haloalkyl-S(O)n-;
C1-C4alkylcarbonyl; or -PO[O-(C1-C4)-alkyl]2;
R4 is C1-C6alkyl; C1-C4alkoxy; C1-C4alkyl-S(O)n-; C1-C4haloalkyl;
C1-C4haloalkoxy; phenyl that is unsubstituted or is substituted by up to three identical or different substituents from halogen, C1-C4alkyl, C1-C4haloalkyl and C1-C4alkoxy; 2-furanyl; 2-thienyl; 3-thienyl; C3-C6-cycloalkyl that is unsubstituted or is substituted by up to three identical or different C1-C4alkyl radicals; cyano; C2-C4haloalkenyl;
C1-C4alkoxy-C1-C4alkyl; C1-C4alkoxy-C1-C4alkoxy; or halo-C1-C4alkylthio;
R5 is hydrogen; C1-C3alkyl; C1-C3haloalkyl; halogen; or C1-C3haloalkoxy;
and n is 0, 1 or 2, with the proviso that when one of the radicals R1, R2 and R3 is nitro, that substituent may not be bonded in the 2- or 6-position of the phenyl ring, or a salt or addition compound of the compound of formula I with an acid, base or complex former.
2. A urea according to claim 1 of formula (I), in which R1 is halogen; cyano; C1-C4alkoxy; C1-C4haloalkoxy; C1-C4alkyl-S(O)n-;
Cl-C4alkyl; C1-C4haloalkyl; C1-C4alkoxycarbonyl; di-(C1-C4alkylamino)-carbonyl; mono (C1-C4alkylamino)carbonyl; carbamoyl; C1-C4haloalkyl-S(O)n-; or -PO[O-(C1-C4)alkyl]2;
R2 is hydrogen; halogen; cyano; nitro; C1-C4alkyl;
C1-C4alkoxy; C1-C4haloalkyl; C1-C4alkoxycarbonyl; or C1-C4alkylcarbonyl;
R3 is hydrogen; halogen; or C1-C4alkyl, and n and the radicals R4 and R5 are as defined in claim 1.
Cl-C4alkyl; C1-C4haloalkyl; C1-C4alkoxycarbonyl; di-(C1-C4alkylamino)-carbonyl; mono (C1-C4alkylamino)carbonyl; carbamoyl; C1-C4haloalkyl-S(O)n-; or -PO[O-(C1-C4)alkyl]2;
R2 is hydrogen; halogen; cyano; nitro; C1-C4alkyl;
C1-C4alkoxy; C1-C4haloalkyl; C1-C4alkoxycarbonyl; or C1-C4alkylcarbonyl;
R3 is hydrogen; halogen; or C1-C4alkyl, and n and the radicals R4 and R5 are as defined in claim 1.
3. A urea according to claim 1 in which the radical R1 is bonded at the 2-position, and the radical R2 at the 3-position, of the phenyl ring.
4. A urea according to claim 1 in which the radical R1 is bonded at the 2-position, and the radical R2 at the 5-position, of the phenyl ring.
5. A urea according to claim 1 in which the radical R1 is bonded at the 2-position, and the radicnl R2 at the 6-position, of the phenyl ring.
6. A urea according to claim 1 in which the radical R1 is bonded at the 3-position, and the radical R2 at the 5-position, of the phenyl ring.
7. A urea according to claim 1 in which the radical R1 is bonded at the 3-position, and the radical R2 at the 6-position, of the phenyl ring.
8. A urea according to claim 1 in which the radical R1 is bonded at the 2-position, the radical R2 is bonded at the 3-position, and the radical R3 ls bonded at the 5-position, of the phenyl rlng.
9. A urea according to claim 1 in which the radical R1 is bonded at the 2-position, the radical R3 is bonded at the 3-position, and the radical R2 is bonded at the 6-position, of the phenyl ring.
10. A urea according to claim 1 in which the radical R1 is bonded at the 2-position, the radical R3 is bonded at the 5-position, snd the radical R2 is bonded at the 6-position, of the phenyl ring.
Il. A urea according to claim 1 in which the radical R1 is bonded at the 3-position, the radical R3 is bonded At the 5-position, and the radical R2 is bonded at the 6-position, of the phenyl ring.
12. A urea according to claim 1 in which R1 is halogen: cyano: C1-C3a1koxy1 C1-C2haloalkoxy; methyl-S(0)n-;
C1-C3alkyl; C1-C2haloalkyl; C1-C4alkoxycarbonyl; carbamoyl; difluoro-methylthio or -PO[O-(CI-C2)-alkyl]2;
R2 is hydrogen; fluorine; chlorine; bromine; cyano; nitro; C1-C3alkyl;
C1-C2haloalkyl; or C1-C3alkoxycarbonyl;
R3 is hydrogen; chlorine; fluorine; or C1-C3alkyl;
R4 is C1-C5alkyl; C1-C4alkoxy, C1-C4alkylthio; cyclopropyl; phenyl;
furan-2-yl; thiophen-2-yl; cyano; C1-C3haloalkoxy; C1-C2alkoxy-C1-C2-alkyl; C1-C2alkoxy-C1-C2alkoxy; methylsulfinyl; methylsulfonyl; or C2-C3haloalkenyl;
R5 is C1-C3alkyl; fluorine; chlorine; bromine; C1-C3haloalkyl; or C1-C3haloalkoxy; and n is 0, 1 or 2.
C1-C3alkyl; C1-C2haloalkyl; C1-C4alkoxycarbonyl; carbamoyl; difluoro-methylthio or -PO[O-(CI-C2)-alkyl]2;
R2 is hydrogen; fluorine; chlorine; bromine; cyano; nitro; C1-C3alkyl;
C1-C2haloalkyl; or C1-C3alkoxycarbonyl;
R3 is hydrogen; chlorine; fluorine; or C1-C3alkyl;
R4 is C1-C5alkyl; C1-C4alkoxy, C1-C4alkylthio; cyclopropyl; phenyl;
furan-2-yl; thiophen-2-yl; cyano; C1-C3haloalkoxy; C1-C2alkoxy-C1-C2-alkyl; C1-C2alkoxy-C1-C2alkoxy; methylsulfinyl; methylsulfonyl; or C2-C3haloalkenyl;
R5 is C1-C3alkyl; fluorine; chlorine; bromine; C1-C3haloalkyl; or C1-C3haloalkoxy; and n is 0, 1 or 2.
13. A urea according to claim 1 in which R1 is halogen; methyl; trifluoromethyl; trifluoromethoxy; difluoro-methoxy; C1-C3alkoxy; methylthio; methylsulfinyl; methylsulfonyl; cyano;
C1-C4alkoxycarbonyl; carbamoyl; difluoromethylthio; or -PO(O-C2H5)2;
R2 is hydrogen; fluorine; chlorine; bromine; nitro; athyl; methyl;
trifluoromethyl; methoxy; or C1-C3alkoxycarbonyl;
R3 is hydrogen; chlorine; or methyl;
R4 is C1-C5alkyl; C1-C4alkoxy; C1-C4alkylthio; cyclopropyl; phenyl;
furan-2-yl; thiophen-2-yl; cyano; 1,1,2,2-tetrafluoroethoxy; 2-chloro-ethoxy; methoxymethyl; 2-methoxy-ethoxy; methylsulfinyl; mathylsulfonyl;
or 2,2-dichlorovinyl;
R5 is C1-C3alkyl; fluorine; chlorine; bromine; difluoromethoxy; tri-fluoromethyl; pentafluoroethyl; chlorodifluoromethyl; difluoromethyl;
dichloromethyl; chlorofluoromethyl; 1,1-dichloro-2,2,2-trifluoroethyl;
1,1-dichloroethyl; or heptafluoropropyl.
C1-C4alkoxycarbonyl; carbamoyl; difluoromethylthio; or -PO(O-C2H5)2;
R2 is hydrogen; fluorine; chlorine; bromine; nitro; athyl; methyl;
trifluoromethyl; methoxy; or C1-C3alkoxycarbonyl;
R3 is hydrogen; chlorine; or methyl;
R4 is C1-C5alkyl; C1-C4alkoxy; C1-C4alkylthio; cyclopropyl; phenyl;
furan-2-yl; thiophen-2-yl; cyano; 1,1,2,2-tetrafluoroethoxy; 2-chloro-ethoxy; methoxymethyl; 2-methoxy-ethoxy; methylsulfinyl; mathylsulfonyl;
or 2,2-dichlorovinyl;
R5 is C1-C3alkyl; fluorine; chlorine; bromine; difluoromethoxy; tri-fluoromethyl; pentafluoroethyl; chlorodifluoromethyl; difluoromethyl;
dichloromethyl; chlorofluoromethyl; 1,1-dichloro-2,2,2-trifluoroethyl;
1,1-dichloroethyl; or heptafluoropropyl.
14. A urea according to claim 1 in which R1 is fluorine; chlorine; bromine iodine; trlfluoromethyl; methyl;
difluoromethoxy; methoxy; methylthio; PO(OC2H5)2; methoxycarbonyl;
methylsulfonyl; or cyano;
R2 is hydrogen; fluorine; chlorine; bromine nitro; methyl; trifluoro-methyl; or methoxycarbonyl;
R3 is hydrogen; or methyl;
R4 is C1-C5alkyl; butylthio; thiophen-2-yl; furan-2-yl; C1-C4alkoxy;
methylthio; methylsulfinyl; methylsulfonyl; or cyclopropyl; and R5 is methyl; chlorine; dichloromethyl; pentafluoroethyl; difluoromethyl;
chlorofluoromethyl; trifluoromethyl; or chlorodifluoromethyl.
difluoromethoxy; methoxy; methylthio; PO(OC2H5)2; methoxycarbonyl;
methylsulfonyl; or cyano;
R2 is hydrogen; fluorine; chlorine; bromine nitro; methyl; trifluoro-methyl; or methoxycarbonyl;
R3 is hydrogen; or methyl;
R4 is C1-C5alkyl; butylthio; thiophen-2-yl; furan-2-yl; C1-C4alkoxy;
methylthio; methylsulfinyl; methylsulfonyl; or cyclopropyl; and R5 is methyl; chlorine; dichloromethyl; pentafluoroethyl; difluoromethyl;
chlorofluoromethyl; trifluoromethyl; or chlorodifluoromethyl.
l5. A urea according to claim 1 in which R1 is fluorine, chlorine, bromine, trlfluoromethyl, cyano, difluoro-methoxy, trifluoromethoxy, metllyl or methoxy, each bonded in the 2-position of the phenyl ring, R2 and R3 are each hydrogen, R4 is methyl, furan-2-yl or cyclopropyl, and R5 is chlorino, methyl, trifluoromethyl or chlorodifluoromethyl.
16. A urea according to claim 1 in which R1 is fluorine, chlorine, bromine, trifluoromsthyl, difluoromethoxy, trifluoromethoxy, cyano or methoxy, each bonded in the 2-position of the phenyl ring, R2 is fluorine or chlorine, each bonded in the 3-, 5- or 6-position of the phenyl ring, R4 is methyl, furan-2-yl or cyclopropyl, and R5 is chlorine, methyl, trifluoromethyl or chlorodifluoromethyl.
l7. A urea according to claim 1 in which R1 is chlorine bonded in the 3-position of the phenyl ring, R2 is chlorine bonded in the 5-positlon of thc phenyl ring, R4 is methyl, furan-2-yl or cyclopropyl, and R5 is chlorine, methyl, trifluoromethyl or chlorodifluoromethyl.
l8. N-(2-bromophenyl)-N-(4-chloro-6-methyl-pyrimidin-2-yl)-urea, N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-N-(2-trifluoromethyl-phenyl)-urea, N-(2,3-dichlorophenyl)-N-(4-methyl-6-trifluoromethylpyrimidin-2-yl)-urea, N-(2,5-dichlorophenyl)-N-(4,6-dimethyl-pyrimidin-2-yl)-urea, N-(4-chloro-6-methyl-pyrimidin-2-yl)-N-(2,5-dichlorophenyl)-urea, N-(2,5-dichlorophenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-[4-(chlorodifluoromethyl)-6-methyl-pyrimidin-2-yl]-N-(2,5-dichloro-phenyl)-urea, N-(4-chloro-6-methyl-pyrimidin-2-yl)-N-(2,6-dichlorophenyl)-urea, N-(2,6-dichlorophenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(4-cyclopropyl-6-trifluoromethyl-pyrimidin-2-yl)-N-(2,6-dichloro-phenyl)-urea, N-(3,5-dichlorophenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(5-chloro-2-methyl-phenyl)-N-(4-chloro-6-methyl-pyrimidin-2-yl)-urea, N-(5-chloro-2-methoxyphenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2-iodophenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2-chloro-6-methylphenyl)-N-(4-chloro-6-methyl-pyrimidin-2-yl)-urea, N-(3-chloro-2-methoxyphenyl)-N-(4-methyl-6-trifluoromethylpyrimidin-2-yl)-urea, N-(2,6-difluorophenyl)-N-(4-methyl-6-trifluoromethylpyrimidin-2-yl)-urea N-(2,5-dlfluorophenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2-cyanophenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2-bromophenyl)-N-(4-cyclopropyl-6-trifluoromethyl-pyrimidln-2-yl)-urea, N-(4-isopropyl-6-trifluoromethyl-pyrimidin-2-yl)-N-(2-trifluoromethyl-phenyl)-urea, N-(2-fluorophenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2-fluorophenyl)-N-(4-isopropyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2,5-dichlorophenyl)-N-(4-ethyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2,6-dichlorophenyl)-N-(4-difluoromethyl-6-methyl-pyrimidin-2-yl)-urea, N-(2,6-dichlorophenyl)-N-(4-methylthio-6-trifluoromethyl-pyrimldin-2-yl)-urea, N-(2,6-dichloro-3-methyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2,6-dichloro-3-methylphenyl)-N-(4-isopropyl-6-trifluoromethylpyrimidin-2-yl)-urea, N-(2-chloro-6-trifluoromethyl-phenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2-chloro-6-methyl-phenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2-methyl-6-trifluoromethyl-phenyi)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(5-chloro-2-difluoromethoxy-phenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2-methylthio-phenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(4-cyclopropyl-6-trifluoromethyl-pyrimidin-2-yl)-N-(2,5-difluoro-phenyl)-urea, N-(2,6-difluorophenyl)-N-(4-ethyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(6-chloro-2-fluoro-phenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)urea, N-(6-chloro-2-fluoro-phenyl)-N-(4-cyclopropyl-6-trifluoromethyl-pyrimi-din-2-yl)-urea, N-(2-difluoromethoxyphenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)urea, N-(6-chloro-2-methoxycarbonyl-phenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea, N-(2-bromophenyl)-N-[4-(furan-2-yl)-6-trifluoromethyl-pyrlmidin-2-yl]-urea, N-(2-chloro-6-methyl-phenyl)-N-(4-methoxymethyl-6-trifluoromethyl-pyrimidin-2-yl)-urea and N-(2-difluoromethoxy-6-methyl-phenyl)-N-(4-methyl-6-trifluoromethyl-pyrimidin-2-yl)-urea.
- 67 - 2l489-7698
- 67 - 2l489-7698
19. A process for preparing a urea according to any one of claims 1 to 18 which comprises a) reacting an aniline of formula II with phosgene to form a carbamoyl chloride of formula III and reacting this with NH3 in a second step (II) (III) III + NH3 I
to form a urea of formula I, or b) reacting an aniline of formula II with a halosulfonyl isocyanate IX to form a halosulfonylurea of formula IV
(II) (IV) IV + 2HzO I
and hydrolysing this in a second step, or directly, to a compound of formula 1, Y being a group that can be removed under the reaction conditions.
to form a urea of formula I, or b) reacting an aniline of formula II with a halosulfonyl isocyanate IX to form a halosulfonylurea of formula IV
(II) (IV) IV + 2HzO I
and hydrolysing this in a second step, or directly, to a compound of formula 1, Y being a group that can be removed under the reaction conditions.
20. A process for preparing a urea according to claim 19 wherein Y is chlorine.
21. A herbicidal composition containing as active ingredient a compound of formula I according to any one of claims 1 to 18, together with a herbicidally acceptable adjuvant or carrier.
22. A plant growth-regulating composition containing as active ingredient a compound of formula I according to any one of claims 1 to 18, together with a plant growth-regulating acceptable adjuvant or carrier.
23. A method of controlling undesired plant growth which comprises allowing a herbicidally effective amount of a compound according to any one of claims 1 to 18 to act on the plant to be controlled or the locus thereof.
24. A method according to claim 23 for the pre- or post-emergence control of undesired plant growth in crops of useful plants.
25. A method according to claim 23 for the pre- or post-emergence control of undesired plant growth in cereals, cotton, soybeans, sun-flowers, rape, maize or rice.
26. A method of influencing plant growth which comprises allowing an amount of a compound according to any one of claims l to 18 that is effective in plant growth regulation, to act on the plant or the locus thereof.
27. The use of a compound of formula I according to any one of claims I
to 18 for regulating the growth of intersown plants in maize crops or for regulating the growth of grasses.
FO 7.5/HH/kg*
to 18 for regulating the growth of intersown plants in maize crops or for regulating the growth of grasses.
FO 7.5/HH/kg*
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH133688 | 1988-04-12 | ||
| CH1336/88-0 | 1988-04-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1314546C true CA1314546C (en) | 1993-03-16 |
Family
ID=4208099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000596184A Expired - Fee Related CA1314546C (en) | 1988-04-12 | 1989-04-10 | Ureas |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US4966622A (en) |
| EP (1) | EP0337943A3 (en) |
| JP (1) | JPH01308265A (en) |
| CA (1) | CA1314546C (en) |
Families Citing this family (57)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI95376C (en) * | 1989-03-22 | 1996-01-25 | Ciba Geigy Ag | Microbicidal 2-anilino-pyrimidine derivatives |
| EP0401168A3 (en) * | 1989-06-02 | 1991-11-06 | Ciba-Geigy Ag | Herbicides |
| IL97026A (en) * | 1990-02-07 | 1995-01-24 | Ciba Geigy | Pyrimidinylphenyl hydroxylamine derivatives, their preparation and their use as microbicides |
| AU644159B2 (en) * | 1990-05-17 | 1993-12-02 | Novartis Ag | 2-anilino-4-cyanopyrimidine derivatives |
| US5521184A (en) * | 1992-04-03 | 1996-05-28 | Ciba-Geigy Corporation | Pyrimidine derivatives and processes for the preparation thereof |
| GB9212673D0 (en) * | 1992-06-15 | 1992-07-29 | Celltech Ltd | Chemical compounds |
| GB9222253D0 (en) * | 1992-10-23 | 1992-12-09 | Celltech Ltd | Chemical compounds |
| GB9304919D0 (en) * | 1993-03-10 | 1993-04-28 | Celltech Ltd | Chemical compounds |
| GB9304920D0 (en) * | 1993-03-10 | 1993-04-28 | Celltech Ltd | Chemical compounds |
| ES2262137T3 (en) * | 1993-10-01 | 2006-11-16 | Novartis Ag | PHARMACOLOGICALLY ACTIVE PIRIMIDINAMINE DERIVATIVES AND PROCEDURES FOR THEIR PREPARATION. |
| RU2135491C1 (en) * | 1993-10-01 | 1999-08-27 | Новартис Аг | Derivatives of n-phenyl-2-pyrimidineamine, method of their synthesis, pharmaceutical composition on said and method of inhibition (treatment) of tumor |
| US5612340A (en) * | 1993-10-01 | 1997-03-18 | Ciba-Geigy Corporation | Pyrimidineamine derivatives and processes for the preparation thereof |
| DE69433594T2 (en) * | 1993-12-22 | 2004-08-05 | Celltech R&D Ltd., Slough | TRISUBSTITUTED PHENYL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF AS PHOSPHODIESTERASE (TYPE IV) INHIBITORS |
| GB9326699D0 (en) * | 1993-12-22 | 1994-03-02 | Celltech Ltd | Chemical compounds |
| US5786354A (en) * | 1994-06-21 | 1998-07-28 | Celltech Therapeutics, Limited | Tri-substituted phenyl derivatives and processes for their preparation |
| US6245774B1 (en) | 1994-06-21 | 2001-06-12 | Celltech Therapeutics Limited | Tri-substituted phenyl or pyridine derivatives |
| GB9412571D0 (en) * | 1994-06-22 | 1994-08-10 | Celltech Ltd | Chemical compounds |
| GB9412573D0 (en) * | 1994-06-22 | 1994-08-10 | Celltech Ltd | Chemical compounds |
| GB9412672D0 (en) * | 1994-06-23 | 1994-08-10 | Celltech Ltd | Chemical compounds |
| GB9523675D0 (en) * | 1995-11-20 | 1996-01-24 | Celltech Therapeutics Ltd | Chemical compounds |
| GB9526246D0 (en) * | 1995-12-21 | 1996-02-21 | Celltech Therapeutics Ltd | Chemical compounds |
| GB9526245D0 (en) * | 1995-12-21 | 1996-02-21 | Celltech Therapeutics Ltd | Chemical compounds |
| GB9526243D0 (en) * | 1995-12-21 | 1996-02-21 | Celltech Therapeutics Ltd | Chemical compounds |
| GB9608435D0 (en) * | 1996-04-24 | 1996-06-26 | Celltech Therapeutics Ltd | Chemical compounds |
| US6252076B1 (en) | 1996-05-04 | 2001-06-26 | Yuhan Corporation | Process for preparation of pyrimidine derivatives |
| RU2174978C2 (en) * | 1996-05-04 | 2001-10-20 | Юхан Корпорейшн | Method of synthesis of pyrimidine derivative, intermediate compounds and method of their synthesis |
| GB9619284D0 (en) * | 1996-09-16 | 1996-10-30 | Celltech Therapeutics Ltd | Chemical compounds |
| WO1998014434A1 (en) * | 1996-10-04 | 1998-04-09 | Ube Industries, Ltd. | 4-substituted 5-chloro-6-alkylpyrimidine compounds, process for the preparation of them, and pesticide or acaricide compositions containing the same |
| GB9622363D0 (en) * | 1996-10-28 | 1997-01-08 | Celltech Therapeutics Ltd | Chemical compounds |
| GB9625184D0 (en) * | 1996-12-04 | 1997-01-22 | Celltech Therapeutics Ltd | Chemical compounds |
| WO1998028281A1 (en) | 1996-12-23 | 1998-07-02 | Celltech Therapeutics Limited | Fused polycyclic 2-aminopyrimidine derivatives, their preparation and their use as protein tyrosine kinase inhibitors |
| GB9705361D0 (en) * | 1997-03-14 | 1997-04-30 | Celltech Therapeutics Ltd | Chemical compounds |
| IN188411B (en) | 1997-03-27 | 2002-09-21 | Yuhan Corp | |
| GB9713087D0 (en) * | 1997-06-20 | 1997-08-27 | Celltech Therapeutics Ltd | Chemical compounds |
| MY132496A (en) * | 1998-05-11 | 2007-10-31 | Vertex Pharma | Inhibitors of p38 |
| KR100272471B1 (en) | 1998-11-17 | 2000-11-15 | 김선진 | Novel pyrimidine derivatives and processes for the preparation thereof |
| JP2003506312A (en) * | 1998-11-30 | 2003-02-18 | 石原産業株式会社 | Meta-nitrophenol derivative and method for producing the same |
| GB9914258D0 (en) | 1999-06-18 | 1999-08-18 | Celltech Therapeutics Ltd | Chemical compounds |
| GB9924862D0 (en) * | 1999-10-20 | 1999-12-22 | Celltech Therapeutics Ltd | Chemical compounds |
| US7122544B2 (en) | 2000-12-06 | 2006-10-17 | Signal Pharmaceuticals, Llc | Anilinopyrimidine derivatives as IKK inhibitors and compositions and methods related thereto |
| US7129242B2 (en) * | 2000-12-06 | 2006-10-31 | Signal Pharmaceuticals, Llc | Anilinopyrimidine derivatives as JNK pathway inhibitors and compositions and methods related thereto |
| ATE420077T1 (en) | 2001-05-29 | 2009-01-15 | Bayer Schering Pharma Ag | CDK INHIBITORY PYRIMIDINES, THEIR PREPARATION AND USE AS MEDICINAL PRODUCTS |
| WO2003000186A2 (en) * | 2001-06-21 | 2003-01-03 | Ariad Pharmaceuticals, Inc. | Novel phenylamino-pyrimidines and uses thereof |
| CA2463822A1 (en) * | 2001-11-01 | 2003-05-08 | Janssen Pharmaceutica N.V. | Heteroaryl amines as glycogen synthase kinase 3beta inhibitors (gsk3 inhibitors) |
| CA2463823A1 (en) * | 2001-11-01 | 2003-05-08 | Janssen Pharmaceutica N.V. | Aminobenzamide derivatives as glycogen synthase kinase 3.beta. inhibitors |
| TW200302728A (en) * | 2002-02-01 | 2003-08-16 | Novartis Ag | Substituted amines as IgE inhibitors |
| US7351729B2 (en) * | 2002-03-08 | 2008-04-01 | Signal Pharmaceuticals, Llc | JNK inhibitors for use in combination therapy for treating or managing proliferative disorders and cancers |
| US20040034084A1 (en) * | 2002-05-24 | 2004-02-19 | Celgene Corporation | Methods for using JNK inhibitors for treating or preventing disease-related wasting |
| US6818631B1 (en) | 2003-08-15 | 2004-11-16 | Nippon Soda Co. Ltd. | Fungicidal pyrimidine derivatives |
| EA029131B1 (en) | 2008-05-21 | 2018-02-28 | Ариад Фармасьютикалз, Инк. | Phosphorous derivatives as kinase inhibitors |
| US9273077B2 (en) | 2008-05-21 | 2016-03-01 | Ariad Pharmaceuticals, Inc. | Phosphorus derivatives as kinase inhibitors |
| WO2012087980A1 (en) | 2010-12-21 | 2012-06-28 | Agraquest, Inc. | Sandpaper mutants of bacillus and methods of their use to enhance plant growth, promote plant health and control diseases and pests |
| US9834518B2 (en) | 2011-05-04 | 2017-12-05 | Ariad Pharmaceuticals, Inc. | Compounds for inhibiting cell proliferation in EGFR-driven cancers |
| MX2014002890A (en) | 2011-09-12 | 2015-01-19 | Bayer Cropscience Lp | Methods of enhancing health and/or promoting growth of a plant and/or of improving fruit ripening. |
| AU2013204563B2 (en) | 2012-05-05 | 2016-05-19 | Takeda Pharmaceutical Company Limited | Compounds for inhibiting cell proliferation in EGFR-driven cancers |
| US9611283B1 (en) | 2013-04-10 | 2017-04-04 | Ariad Pharmaceuticals, Inc. | Methods for inhibiting cell proliferation in ALK-driven cancers |
| JPWO2014174745A1 (en) * | 2013-04-26 | 2017-02-23 | 国立大学法人京都大学 | Eg5 inhibitor |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2748122A (en) * | 1954-05-06 | 1956-05-29 | Searle & Co | 2-anilino-4, 6-dimethylpyrimidines |
| GB1245085A (en) * | 1967-10-02 | 1971-09-02 | Ici Ltd | Fungicidal processes and compositions |
| DD151404A1 (en) * | 1980-06-13 | 1981-10-21 | Friedrich Franke | FUNGICIDAL AGENTS |
| US4659363A (en) * | 1983-07-25 | 1987-04-21 | Ciba-Geigy Corporation | N-(2-nitrophenyl)-2-aminopyrimidine derivatives, the preparation and use thereof |
| EP0172786B1 (en) * | 1984-06-25 | 1991-01-30 | Ciba-Geigy Ag | Pyrimidine derivatives active as parasiticides |
| DE3751742T3 (en) * | 1986-01-13 | 2002-11-21 | American Cyanamid Co | 4,5,6-substituted 2-pyrimidinamines |
| US4788195A (en) * | 1986-01-13 | 1988-11-29 | American Cyanamid Company | 4,5,6-substituted-N-(substituted-phenyl)-2-pyrimidinamines |
| DE3614060A1 (en) * | 1986-04-23 | 1987-10-29 | Schering Ag | PYRIMIDINE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
| DE3788494D1 (en) * | 1986-10-13 | 1994-01-27 | Ciba Geigy | Ureas. |
| JPH0784445B2 (en) * | 1986-12-03 | 1995-09-13 | クミアイ化学工業株式会社 | Pyrimidine derivatives and agricultural and horticultural fungicides |
| DE3882821D1 (en) * | 1987-06-11 | 1993-09-09 | Ciba Geigy Ag | MICROBICIDES. |
-
1989
- 1989-04-03 US US07/332,193 patent/US4966622A/en not_active Expired - Fee Related
- 1989-04-04 EP EP19890810251 patent/EP0337943A3/en not_active Withdrawn
- 1989-04-10 CA CA000596184A patent/CA1314546C/en not_active Expired - Fee Related
- 1989-04-12 JP JP1092804A patent/JPH01308265A/en active Pending
-
1990
- 1990-08-17 US US07/569,319 patent/US5159078A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US4966622A (en) | 1990-10-30 |
| EP0337943A2 (en) | 1989-10-18 |
| JPH01308265A (en) | 1989-12-12 |
| US5159078A (en) | 1992-10-27 |
| EP0337943A3 (en) | 1991-09-04 |
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