CA1202962A - Substituted n-phenyl-n'-benzoyl ureas and their use as insecticides and acaricides - Google Patents
Substituted n-phenyl-n'-benzoyl ureas and their use as insecticides and acaricidesInfo
- Publication number
- CA1202962A CA1202962A CA000438469A CA438469A CA1202962A CA 1202962 A CA1202962 A CA 1202962A CA 000438469 A CA000438469 A CA 000438469A CA 438469 A CA438469 A CA 438469A CA 1202962 A CA1202962 A CA 1202962A
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- Prior art keywords
- compound
- hydrogen
- alkyl
- halogen atom
- independently
- Prior art date
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Classifications
-
- 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<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
Abstract
ABSTRACT OF THE DISCLOSURE
Novel N-phenyl-N'-benzoyl ureas, e.g., N-(2,6--difluorobenzoyl)-N-(4-phenylazophenyl) urea, process for their preparation and their use as arthropodicides, e.g., for the control of Spodoptera littoralis, Plutella xylostella and Heliothis virescens.
Novel N-phenyl-N'-benzoyl ureas, e.g., N-(2,6--difluorobenzoyl)-N-(4-phenylazophenyl) urea, process for their preparation and their use as arthropodicides, e.g., for the control of Spodoptera littoralis, Plutella xylostella and Heliothis virescens.
Description
NOV~T. SI~TTTUT~D N-PIl~NYI.-N'B~NZ~YT.
~REAS AND THEIR USE AS
INSECTICIDES AND ACARICIDES
The present in~ention relates to certain novel N-phenyl N'benzoylureas, to a process for their preparation and to their use as arthropodicides, expecially as insecticides and acaricides.
The invention provides, as new compounds, the N-phenyl-N'benzoylureas of the general formula ~--CONHCONH--~ ~ ~5 : Rl R3/ N=N--R6 wherein R and Rl are each independently a hydrogen or halogen atom, a Cl-c4 alkyl or halogeno Cl-C4 alkyl ; group; R2 and R3 are each independently a hydrogen or halogen atom or a Cl-C4 alkyi group; R4 and R5 are each independently a hydrogen or halogen atom, or an alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkenyl, halogenoalkenyl, alkenyloxy, halogenoalkenyloxy or alkynyl group;
R6 is ~ or R8 R7 F3C Rg .
wherein R7 and R8 are each independently a hydr~gen or halogen atom, or a nitro, alkyl, halogenoalkyl or cyano group; and Rg is a halogen atom or an alkyl or halogenoalkyl group The present invention also provides processes for the preparation of the benzoylureas of for~ula I.
In the first of these processes, process (a), a phenylazoaniline of the general formula:
R4 R~
R6N=N /~
wherein R2, R3, R~, R5 and R6 are as defined above is reacted with a benzoylisocyanate of the general formula ~ CONCO III
Rl wherein R and Rl are as above defined in the presence of an appropriate solvent.
In the second of these processes, process (b) a 4-arylazophenylisocyanate of the general formula 5 ~
~ ~ NC0 IY
R6N= R3 , ~ ~
i2 wherein R2, R3, R4, R5 and R6 are as above defined is reacted with a benzamide of the formula R
~-- } V
Rl wherein R and Rl are as above defined in the presence of an appropriate solvent If using process (a) 4-phenylazoaniline and
~REAS AND THEIR USE AS
INSECTICIDES AND ACARICIDES
The present in~ention relates to certain novel N-phenyl N'benzoylureas, to a process for their preparation and to their use as arthropodicides, expecially as insecticides and acaricides.
The invention provides, as new compounds, the N-phenyl-N'benzoylureas of the general formula ~--CONHCONH--~ ~ ~5 : Rl R3/ N=N--R6 wherein R and Rl are each independently a hydrogen or halogen atom, a Cl-c4 alkyl or halogeno Cl-C4 alkyl ; group; R2 and R3 are each independently a hydrogen or halogen atom or a Cl-C4 alkyi group; R4 and R5 are each independently a hydrogen or halogen atom, or an alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkenyl, halogenoalkenyl, alkenyloxy, halogenoalkenyloxy or alkynyl group;
R6 is ~ or R8 R7 F3C Rg .
wherein R7 and R8 are each independently a hydr~gen or halogen atom, or a nitro, alkyl, halogenoalkyl or cyano group; and Rg is a halogen atom or an alkyl or halogenoalkyl group The present invention also provides processes for the preparation of the benzoylureas of for~ula I.
In the first of these processes, process (a), a phenylazoaniline of the general formula:
R4 R~
R6N=N /~
wherein R2, R3, R~, R5 and R6 are as defined above is reacted with a benzoylisocyanate of the general formula ~ CONCO III
Rl wherein R and Rl are as above defined in the presence of an appropriate solvent.
In the second of these processes, process (b) a 4-arylazophenylisocyanate of the general formula 5 ~
~ ~ NC0 IY
R6N= R3 , ~ ~
i2 wherein R2, R3, R4, R5 and R6 are as above defined is reacted with a benzamide of the formula R
~-- } V
Rl wherein R and Rl are as above defined in the presence of an appropriate solvent If using process (a) 4-phenylazoaniline and
2,6-difluorobenzoylisocyanate are used as the starting materials and using process variant (b) 4-phenyl-azophenylisocyanate and 2,6-difluorobenzamide are used as starting materials~, the courses of the reaction can be represented by the following equations :-~ -CONCO + H2N ~ ~ N=N ~ ~
20 ~ CONHCONH- ~ N=N ~ .
F
~ coNH2+0Nc~ 3 N = N ~
~ ~ -CONHCONH- ~ N = N- ~
96~
The processes for the preparation of the compounds of the invention are preferably carried out in the presence of suitable solvents and diluents.
~ractically all inert organic solvents can be used for this purpose, especially aliphatic and aromatic optionally chlorinated hydrocarbons, ethers, Ketones and nitriles.
The reaction temperature may be varied within a fairly wide range. In general the reaction is carried out at a temperature in the range of from 0 to 130C.
In general the reaction takes place at atmospheric pressure.
To carry out these processes the reactants are preferably employed in equimolar amounts The compounds of the present invention are normally crystalline solids having a low solubility in water and having a moderate solubility in many organic solvents. The compounds have low phytotoxicity and have exceptional activity in the control of various undesirable agricultural, household and veterinary insect pests.
--5~
E.~amples of the various insects which can be controlled by the active compounds of the present invention are members o~ the orders Lepidoptera, Coleoptera, Diptera, Orthoptera, Homoptera, Thysanoptera and Acarina. They are active against normall~ sensitive and resistant species at some stages of development.
Examples of insect pests comprising the above include the tobacco budworm (Heliothis virescens), the beet armyworm (Spodoptera exigua), the Egyptian cotton leafworm (Spodoptera littoralis), the American boll-worm (Heliothis armigera~, the diamond-back moth ~lutella maculipennis), the gypsy moth (Lymantria dispar), the cutworm (Agrotis segetum), the Mediter-ranean flour moth (Ephestia Keuhniella), the Colorado potato beetle (Leptinotarsa decimlineata), the mustard beetle (Phaedon cochleariae), the cotton boll weevil (Anthomomus grandis, the Mexican bean beetle (Epilachnavarivestis), the khapra beetle (Trogoaerma granarium), he housefl~ (Musca domestica), the lesser housefly (Fannia canicularis), the Mediterranean fruit fly (~eratitis capitata), the black blow fly (Phormia regina), the cabbage rootfly (Hylemya brassicae), the yellow fever mosquito (Aedes aegypti), the malaria mos~uito (Anopheles stephensi), the desert locust (Schistocerca gregaria), the migratory locust (Locusta migratoria), the German cockroach (Blattella germanica), the American cockroach (Periplaneta americana), -" ~2~Z~62 the pear psylla (Psylla pyricola), the onion thrips (Thrips tabaci), and the citrus rust mite (Phyllocoptruta oleivora).
The compounds of the present invention are highly active and can be employed to kill insects outright and~or to prevent adult emergence from the juvenile forms of the insect. In such applications, the insect to be controlled and~or its habitat is contacted or treated with an insectlcidal amount of one or more of the compounds of the present invention. The compounds may be administered orally to warm blooded animals from which they are excreted unchanged and they effectively combat the larvae of certain insPcts which inhabit faeces, e.g., the face fly, horn fly and buffalo fly.
- For all such uses, the compounds of the present invention can be employed in unmodified form. However, the present invention also includes within its scope the use of an insecticidally-effective amount of the active ingredient in composition form with a material known in the art as a diluent or carrier.
Thus, for example, compositions employing one or a comblnation of these active lngredlents can be ln the form of a liquid or a dust, and the adjuvant , ..:
employed can be any one of a plurality of materials including aromatic solvents, petroleum distillates, water or other liquid carriers, propellant substances, surface-active dispersing agents, light absor~ers and finely-divided carrier solids.
The exact concentration of one or a combina-tion of the compounds of the present invention in a composition thereof with an adjuvant therefore can vary; it is only necessary that one or a combination of the compounds be present in a sufficient amount so as to make possible the application of an i.nsectici-dally-effective or inactivating dosage.
Generally, for practical applications, one or a combination of these active ingredients can be broadly applied to the insect larvae or their habitat in compositions cont~;n;ng from 0.0001 to 98 percent by weight, preferably 5 to 50 percent by weight, of the compo~nds7 The compounds of the present invention or compositions containing them can advantageously be be employed in combination with one or more additional pesticidal compounds. Such additional pesticidal compounds may be insecticides, nematocides, acaricldes, herbicides, fungicides or bactericides which are compatible with the compounds of the present invention in the medium selected for application and not antagonistic to the activity of compounds.
Accordingly, in such embodiments, the pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use, or as an additi~e. The compounds used in combination with the compounds of the invention are generally present in a ratio from 1 to 100 parts of the compound of the present invention to from 100 to 1 parts of the additional compound(s).
The compounds of this invention are, or tend to be, slow acting, i.e., they disrupt the molting of the insect, thereby killing it. ~s a result, some time can pass before the insects are killed. Accordingly, an increased benefit can be obtained by combining the compounds of this invention with quicker acting insecticides such as, for example, organophos~horus compounds, carbamates and pyrethroids. Because of this different mode of action, the compounds of this invention kill or control the more common insecticides and thus they inhibit or delay the de~elopment of resistance to such insecticides.
Z91~2 g The present invention will be further illustrated with reference to the following Examples:
Preparation of Anilines Preparation 1 (a~ The preparation of 3-methyl-4-phenylazoaniline Aniline (11.5g, 0.124 mol) was dissolved with stirring in a mixture of conc. hydrochloric acid (30mls) and water (30 mls) and the resultant solution cooled to 0C. To this was added a solution of sodium nitrite (8.52g, 0.123 mol) in water 30mls)~ the temperature of the reaction mixture being maintaine~ at <5C by the addition of ice. Upon completion of the addition, the mixture was stirred at 0-5C for half an hour.
The cooled solution of benzenediazonium chloride was then added grad`ually to a cooled (<10C), stirred solution of m-toluidine (11.92g, 0.111 mol) in ethanol (50mls) and the mixture stirred for two hours at <10C. It was then filtered, the ochre precipitate washed with water, dried and re-crystallised from petroleum ether ~60-80C) to give 3-methyl-4-phenyl-azoaniline (10.93g, 46%), m.p. 66-69C ~ max (Nujol) 3390, 3320, 1604, 1378, 1262 cm; SH (DMSO-d6) 2.55 (3H,s),6-0 (2~, br.s) 6.61 (2H, m) 7.1-8.0 (6H, br.m) ppm.
~2~ Z
(Found: C,73.87; H, 6.35; N, 19.90~. C13H13N3 requires C,73.91; H, 6.20; N, l9.~9~
The anilines listed in Table l were prepared in a similar manner.
.
) TABL~ 1 EXAMPLE COMPOUND YIELD M~Po ~ FOUND ~ CALCULATED
( ~) ( C) C H N C H N
lb 3,5-dlmethyl-4-phenyl-azoaniline 5767-8 74.59 6.71 18.5674.64 6.71 l8.65 lc 3,5-dimethy;-4-(3-nltro-phenylazo)anlline 43 167-9 61.92 5.4820.59 62.21 5.22 20.73 ld 3-methyl-4-(4-nitrophenyl-azo)aniline 23154-661.08 4.66 21.8360.93 4.72 21.86 le 3,5-dimethyl-4-(4-nitro- C~
phenylazo)aniline 49 159-61 62.26 5.0920.8362.21 5.22 20.73 ~, lf 3-methyl-4-(4-chlorophenyl-azo)anlllne 30 oil 63.29 5.01 17.4263.55 4.92 17.10 lg 3,5-dimethyl-4-(3,5-dimethylphenylazo)aniline 37 93-5 76.76 6.15 16.70 76.77 6.44 16.79 lh 3,5-dimethyl-4-(4-chloro-3-nitrophenylazo)aniline 54 166-755.10 4.50 18.48 55.18 4.30 16.39 li 3,5-dlmethyl-4-(4-chloro-2-cyanophenylazo)aniline 33 170-363.06 4.83 20.53 63.27 4.60 19.~8 ~2~;Z
Preparation 2 (a) The preparation of 3- ~ oro-4-(4-nitrophenylazo)amline 4-Nitroaniline 8.9g, 0.064 mo~ was dissolved with warming in a mixture of concentrated hydrochloric acid (20 mls) and water (20 mls) and the solution poured onto stirred ice (52g). This was cooled to <5C and a solution of sodium nitrite (5g, 0.072 mol) in water (15 mls) added with stirring, the reaction temperature being maintained a~ <5C. The reaction mixture was then stirred at 0-5C for half ~n hour and sodium acetate trihydrate (20g) added.
The buffered solutlon of the diazonium salt was added to a vigorously stirred, cooled solution of sodium 3-chloroanilinomethanesulphonate (17.5g, 0.072 mol) in water (250 mls). The reaction mixture was refrigerated overnight and filtered. The red solid was slurried in 5% sodium hydroxide solution (400 mls) and gradually heated to 95C ovex two hours.
This was cooled, filtered and the solid crystallised from dilute ethanol to give 3-chloro-4-(4-nitro-phenylazo)aniline (12.6g, 71%), M.P. 207-9C.-~ max (Nujol) 3500, 3406, cm~'. ~H (DMSO-d6) 6.2 (2H, br.s), 6.5-6.9 (2H, m), 7.7-8.5 (5H, m) ppm.
(Found: C, 52.14; H, 3,34; N, 20.28. C~2HgClN~02 requires C, 52.09; H, 3.29; N, 20.25%) ~;2029~;~
(b) 3,5-Dimethyl-4-(4-chlorophenylazo)aniline was prepared in a similar manner (red oil, 37%).
Found: C, 64.48; H, 5.20; N,16.48. C14H,4ClN3 requires C, 64.74; H, 5.43; N,16.18%
(c) 4-(4-Nitrophenylazo)-3-(1,1,2,2-tetrafluoroethoxy)-aniline was prepared in a similar manner (red crystals, 33%) M.P. 168C. 0 Found: C, 47.12; H, 2.78; N, 15.76. C1~H10F4N403 requires: C,46.94,` H,2.81; N, 15.64%.
Preparation 3 ~a) The preparation of 3-phenylazoaniline
20 ~ CONHCONH- ~ N=N ~ .
F
~ coNH2+0Nc~ 3 N = N ~
~ ~ -CONHCONH- ~ N = N- ~
96~
The processes for the preparation of the compounds of the invention are preferably carried out in the presence of suitable solvents and diluents.
~ractically all inert organic solvents can be used for this purpose, especially aliphatic and aromatic optionally chlorinated hydrocarbons, ethers, Ketones and nitriles.
The reaction temperature may be varied within a fairly wide range. In general the reaction is carried out at a temperature in the range of from 0 to 130C.
In general the reaction takes place at atmospheric pressure.
To carry out these processes the reactants are preferably employed in equimolar amounts The compounds of the present invention are normally crystalline solids having a low solubility in water and having a moderate solubility in many organic solvents. The compounds have low phytotoxicity and have exceptional activity in the control of various undesirable agricultural, household and veterinary insect pests.
--5~
E.~amples of the various insects which can be controlled by the active compounds of the present invention are members o~ the orders Lepidoptera, Coleoptera, Diptera, Orthoptera, Homoptera, Thysanoptera and Acarina. They are active against normall~ sensitive and resistant species at some stages of development.
Examples of insect pests comprising the above include the tobacco budworm (Heliothis virescens), the beet armyworm (Spodoptera exigua), the Egyptian cotton leafworm (Spodoptera littoralis), the American boll-worm (Heliothis armigera~, the diamond-back moth ~lutella maculipennis), the gypsy moth (Lymantria dispar), the cutworm (Agrotis segetum), the Mediter-ranean flour moth (Ephestia Keuhniella), the Colorado potato beetle (Leptinotarsa decimlineata), the mustard beetle (Phaedon cochleariae), the cotton boll weevil (Anthomomus grandis, the Mexican bean beetle (Epilachnavarivestis), the khapra beetle (Trogoaerma granarium), he housefl~ (Musca domestica), the lesser housefly (Fannia canicularis), the Mediterranean fruit fly (~eratitis capitata), the black blow fly (Phormia regina), the cabbage rootfly (Hylemya brassicae), the yellow fever mosquito (Aedes aegypti), the malaria mos~uito (Anopheles stephensi), the desert locust (Schistocerca gregaria), the migratory locust (Locusta migratoria), the German cockroach (Blattella germanica), the American cockroach (Periplaneta americana), -" ~2~Z~62 the pear psylla (Psylla pyricola), the onion thrips (Thrips tabaci), and the citrus rust mite (Phyllocoptruta oleivora).
The compounds of the present invention are highly active and can be employed to kill insects outright and~or to prevent adult emergence from the juvenile forms of the insect. In such applications, the insect to be controlled and~or its habitat is contacted or treated with an insectlcidal amount of one or more of the compounds of the present invention. The compounds may be administered orally to warm blooded animals from which they are excreted unchanged and they effectively combat the larvae of certain insPcts which inhabit faeces, e.g., the face fly, horn fly and buffalo fly.
- For all such uses, the compounds of the present invention can be employed in unmodified form. However, the present invention also includes within its scope the use of an insecticidally-effective amount of the active ingredient in composition form with a material known in the art as a diluent or carrier.
Thus, for example, compositions employing one or a comblnation of these active lngredlents can be ln the form of a liquid or a dust, and the adjuvant , ..:
employed can be any one of a plurality of materials including aromatic solvents, petroleum distillates, water or other liquid carriers, propellant substances, surface-active dispersing agents, light absor~ers and finely-divided carrier solids.
The exact concentration of one or a combina-tion of the compounds of the present invention in a composition thereof with an adjuvant therefore can vary; it is only necessary that one or a combination of the compounds be present in a sufficient amount so as to make possible the application of an i.nsectici-dally-effective or inactivating dosage.
Generally, for practical applications, one or a combination of these active ingredients can be broadly applied to the insect larvae or their habitat in compositions cont~;n;ng from 0.0001 to 98 percent by weight, preferably 5 to 50 percent by weight, of the compo~nds7 The compounds of the present invention or compositions containing them can advantageously be be employed in combination with one or more additional pesticidal compounds. Such additional pesticidal compounds may be insecticides, nematocides, acaricldes, herbicides, fungicides or bactericides which are compatible with the compounds of the present invention in the medium selected for application and not antagonistic to the activity of compounds.
Accordingly, in such embodiments, the pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use, or as an additi~e. The compounds used in combination with the compounds of the invention are generally present in a ratio from 1 to 100 parts of the compound of the present invention to from 100 to 1 parts of the additional compound(s).
The compounds of this invention are, or tend to be, slow acting, i.e., they disrupt the molting of the insect, thereby killing it. ~s a result, some time can pass before the insects are killed. Accordingly, an increased benefit can be obtained by combining the compounds of this invention with quicker acting insecticides such as, for example, organophos~horus compounds, carbamates and pyrethroids. Because of this different mode of action, the compounds of this invention kill or control the more common insecticides and thus they inhibit or delay the de~elopment of resistance to such insecticides.
Z91~2 g The present invention will be further illustrated with reference to the following Examples:
Preparation of Anilines Preparation 1 (a~ The preparation of 3-methyl-4-phenylazoaniline Aniline (11.5g, 0.124 mol) was dissolved with stirring in a mixture of conc. hydrochloric acid (30mls) and water (30 mls) and the resultant solution cooled to 0C. To this was added a solution of sodium nitrite (8.52g, 0.123 mol) in water 30mls)~ the temperature of the reaction mixture being maintaine~ at <5C by the addition of ice. Upon completion of the addition, the mixture was stirred at 0-5C for half an hour.
The cooled solution of benzenediazonium chloride was then added grad`ually to a cooled (<10C), stirred solution of m-toluidine (11.92g, 0.111 mol) in ethanol (50mls) and the mixture stirred for two hours at <10C. It was then filtered, the ochre precipitate washed with water, dried and re-crystallised from petroleum ether ~60-80C) to give 3-methyl-4-phenyl-azoaniline (10.93g, 46%), m.p. 66-69C ~ max (Nujol) 3390, 3320, 1604, 1378, 1262 cm; SH (DMSO-d6) 2.55 (3H,s),6-0 (2~, br.s) 6.61 (2H, m) 7.1-8.0 (6H, br.m) ppm.
~2~ Z
(Found: C,73.87; H, 6.35; N, 19.90~. C13H13N3 requires C,73.91; H, 6.20; N, l9.~9~
The anilines listed in Table l were prepared in a similar manner.
.
) TABL~ 1 EXAMPLE COMPOUND YIELD M~Po ~ FOUND ~ CALCULATED
( ~) ( C) C H N C H N
lb 3,5-dlmethyl-4-phenyl-azoaniline 5767-8 74.59 6.71 18.5674.64 6.71 l8.65 lc 3,5-dimethy;-4-(3-nltro-phenylazo)anlline 43 167-9 61.92 5.4820.59 62.21 5.22 20.73 ld 3-methyl-4-(4-nitrophenyl-azo)aniline 23154-661.08 4.66 21.8360.93 4.72 21.86 le 3,5-dimethyl-4-(4-nitro- C~
phenylazo)aniline 49 159-61 62.26 5.0920.8362.21 5.22 20.73 ~, lf 3-methyl-4-(4-chlorophenyl-azo)anlllne 30 oil 63.29 5.01 17.4263.55 4.92 17.10 lg 3,5-dimethyl-4-(3,5-dimethylphenylazo)aniline 37 93-5 76.76 6.15 16.70 76.77 6.44 16.79 lh 3,5-dimethyl-4-(4-chloro-3-nitrophenylazo)aniline 54 166-755.10 4.50 18.48 55.18 4.30 16.39 li 3,5-dlmethyl-4-(4-chloro-2-cyanophenylazo)aniline 33 170-363.06 4.83 20.53 63.27 4.60 19.~8 ~2~;Z
Preparation 2 (a) The preparation of 3- ~ oro-4-(4-nitrophenylazo)amline 4-Nitroaniline 8.9g, 0.064 mo~ was dissolved with warming in a mixture of concentrated hydrochloric acid (20 mls) and water (20 mls) and the solution poured onto stirred ice (52g). This was cooled to <5C and a solution of sodium nitrite (5g, 0.072 mol) in water (15 mls) added with stirring, the reaction temperature being maintained a~ <5C. The reaction mixture was then stirred at 0-5C for half ~n hour and sodium acetate trihydrate (20g) added.
The buffered solutlon of the diazonium salt was added to a vigorously stirred, cooled solution of sodium 3-chloroanilinomethanesulphonate (17.5g, 0.072 mol) in water (250 mls). The reaction mixture was refrigerated overnight and filtered. The red solid was slurried in 5% sodium hydroxide solution (400 mls) and gradually heated to 95C ovex two hours.
This was cooled, filtered and the solid crystallised from dilute ethanol to give 3-chloro-4-(4-nitro-phenylazo)aniline (12.6g, 71%), M.P. 207-9C.-~ max (Nujol) 3500, 3406, cm~'. ~H (DMSO-d6) 6.2 (2H, br.s), 6.5-6.9 (2H, m), 7.7-8.5 (5H, m) ppm.
(Found: C, 52.14; H, 3,34; N, 20.28. C~2HgClN~02 requires C, 52.09; H, 3.29; N, 20.25%) ~;2029~;~
(b) 3,5-Dimethyl-4-(4-chlorophenylazo)aniline was prepared in a similar manner (red oil, 37%).
Found: C, 64.48; H, 5.20; N,16.48. C14H,4ClN3 requires C, 64.74; H, 5.43; N,16.18%
(c) 4-(4-Nitrophenylazo)-3-(1,1,2,2-tetrafluoroethoxy)-aniline was prepared in a similar manner (red crystals, 33%) M.P. 168C. 0 Found: C, 47.12; H, 2.78; N, 15.76. C1~H10F4N403 requires: C,46.94,` H,2.81; N, 15.64%.
Preparation 3 ~a) The preparation of 3-phenylazoaniline
3-Aminoacetanilide (lOg, 0.067 mol) was dissolved in a mixture of acetic acid (12 mls) and ethanol (64 mls) and cooled to 5C. To this was added a cooled (5C) solution of nitrosobenzene (7.65g 0.071 mol) in ethanol (50 mls) with stirring. The reaction-mixture was stirred at 5C for two hours, allowed to warm to room temperature and poured into water (100 mls).
The resulting mixture was then filtered, the black solid dried and purified by chromatography (silica gel: dichloromethane) and recrystallization from petroleum ether (80:100) to givç 3-phenylazoacet anilide (8.33g, 53%) M.P. 133-4C.
~;~CI 29~2 This solid ~5g, 0. 021 mol) was heated under reflux with potassium hydroxide (2.95g, 0 053 mol) in water (5 mls) and ethanol (50 mls) to give, after work-up, 3-phenylazoaniline (3.7g, 89%), M.P. 54-6C.-In a similar manner, 5-amino-2-fluoroacetanilide was condensed with nitrosobenzene to give 2-fluoro-5-phenylaæoacetanilide in 17% yield, M.P. 165-166C.
(Found: C, 65.27; H, 4.70; N, 16.32%. C14H12FN3O
requires C, 65. 6; H, 4.70; N, 16.33%. This was then hydrolysed with potassium hydroxide in aqueous methanol to give 2-fluoro-5-phenylazoaniline (3b) in quantitative yield which was used without further purification.
PREPARATION OF SUB~ u~ ~ N-BENZOYL-N' PH~ZOPHE~IrU~S
Example 1 (a) The preparation of N-(2,6-difluorobenzoyl)-N'-(4-phenylazophenyl)-urea A solution of 4-phenylazoaniline (3.35g, 0.017 mole) in toluene (50 ml) was added to a stirred solution of 2l6-difluorobenzoylisocyanate (3.42g, 0.0187 mole) in toluene (3.5 mls). The resulting precipitate was filtered and washed firstly with chilled toluene~
and then petroleum ether (40-60). Yield 5.64g, M.P.
241-243C.
~z~ z Found: C, 63.23i H, 3.69; N, 14.70. C20H F2N4O2 ~ired: C, 63.16; H, 3.71; N, 14.73~
Employing the above procedure and appropriate substituted phenylazonilines and isocyanate compounds such as 2-fluorobenzoylisocyanate, 2-chlorobenzoyl-isocyanate, 2,6-dichlorobenzoylisocyanate, 3-chloro-benzoylisocyanate t 4-chlorobenzoylisocyanate, benzoylisocyanate, 2-methylbenzoylisocyanate, 2,6-dimethylbenzoylisocyanate, 2-trifluoromethylbenzoyl-isocyanate and 3-trifluoromethyl-benzoylisocyanate, examples 2-84 were prepared. The results are detailed in Table 2.
~) The preparation of N-(2,6-difluorobenzoyl)-N'-(4-phenylazophenyl) -urea A mixture of 4-phenylazoaniline hydrochloride (23.37g, 0.1 molel and trichloromethyl chloroformate (14.84g, 0.075 moles) in 1,4-Dioxan (100 ml) was heated with stirring under reflux for 4 hours. The solvent and excess trichloromethyl chloroformate were distilled off under atmospheric pressure to a maximum pot temperature of 130C. The resultant oil was cooled and a thin film infra red spectra showed the presence of a strong absorption at 2275 cm 1 (characteristic of -N=C=O absorption). The crude isocyanate was : ~ .
Z96~
diluted with a mixture of toluene (100 ml) and 2,6-difluorobenzamide (15.71g, 0.1 mole) and the reaction mixture heated with stirring under reflux for 1.5 hrs. After cooling, the resultant solid was collected by filtration and washed with chilled toluene and then 40-60 petroleum ether. The crude solid was recrystallised from ethyl methyl ketone to yield an orange crystalline solid. Yield 22.7g, 60%, 241-242C.
Required for C20H14F2N42 Found: C, 63.39; H, 3O73; N, 14.82 , ~
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INSECTICIDAL EVALUATION
Test Procedure I
Spodoptera littoralis (Egyptian cotton leafworm) Larvicide assessments Cotton plants are grown to four true leaves of 7-8 cm diameter. The test compound was prepared as an aqueous/
acetone solution or suspension at the required concentra-tion. The foliar parts of the cotton plant are dipped in the test medium for a 10 second period. After drying they were kept in a glasshouse at a temperature of 20 to 25C with a minimum photoperiod of 12 hours~
Individual leaves from each treatment were removed and placed in separate 9 cm diameter plastic petri dishes where they were infested with ten, 3rd instar larvae of Spodoptera littoralis. The experimental units were kept in an environmental room at 25C, 70~ humidity with a photoperiod of 16 hours. The leaves in each unit were replaced daily with leaves from plants of the same treatment i.e., 0, 1, 2 and 3 days.
Assessment was made on the fourth day as a comparison of treated with untreated controls and expressed as a percentage mortality~
In a similar manner the third instar larvae of Plutella z xylostella (Diamond-backed moth) wexe tested and Heliothis viriscen5 (tobacco budworm~.
The results of the test procedures were assessed upon a scale of 1 - 5, where 1 = 90-100~ mortality 2 = 75-89 3 = 50-74
The resulting mixture was then filtered, the black solid dried and purified by chromatography (silica gel: dichloromethane) and recrystallization from petroleum ether (80:100) to givç 3-phenylazoacet anilide (8.33g, 53%) M.P. 133-4C.
~;~CI 29~2 This solid ~5g, 0. 021 mol) was heated under reflux with potassium hydroxide (2.95g, 0 053 mol) in water (5 mls) and ethanol (50 mls) to give, after work-up, 3-phenylazoaniline (3.7g, 89%), M.P. 54-6C.-In a similar manner, 5-amino-2-fluoroacetanilide was condensed with nitrosobenzene to give 2-fluoro-5-phenylaæoacetanilide in 17% yield, M.P. 165-166C.
(Found: C, 65.27; H, 4.70; N, 16.32%. C14H12FN3O
requires C, 65. 6; H, 4.70; N, 16.33%. This was then hydrolysed with potassium hydroxide in aqueous methanol to give 2-fluoro-5-phenylazoaniline (3b) in quantitative yield which was used without further purification.
PREPARATION OF SUB~ u~ ~ N-BENZOYL-N' PH~ZOPHE~IrU~S
Example 1 (a) The preparation of N-(2,6-difluorobenzoyl)-N'-(4-phenylazophenyl)-urea A solution of 4-phenylazoaniline (3.35g, 0.017 mole) in toluene (50 ml) was added to a stirred solution of 2l6-difluorobenzoylisocyanate (3.42g, 0.0187 mole) in toluene (3.5 mls). The resulting precipitate was filtered and washed firstly with chilled toluene~
and then petroleum ether (40-60). Yield 5.64g, M.P.
241-243C.
~z~ z Found: C, 63.23i H, 3.69; N, 14.70. C20H F2N4O2 ~ired: C, 63.16; H, 3.71; N, 14.73~
Employing the above procedure and appropriate substituted phenylazonilines and isocyanate compounds such as 2-fluorobenzoylisocyanate, 2-chlorobenzoyl-isocyanate, 2,6-dichlorobenzoylisocyanate, 3-chloro-benzoylisocyanate t 4-chlorobenzoylisocyanate, benzoylisocyanate, 2-methylbenzoylisocyanate, 2,6-dimethylbenzoylisocyanate, 2-trifluoromethylbenzoyl-isocyanate and 3-trifluoromethyl-benzoylisocyanate, examples 2-84 were prepared. The results are detailed in Table 2.
~) The preparation of N-(2,6-difluorobenzoyl)-N'-(4-phenylazophenyl) -urea A mixture of 4-phenylazoaniline hydrochloride (23.37g, 0.1 molel and trichloromethyl chloroformate (14.84g, 0.075 moles) in 1,4-Dioxan (100 ml) was heated with stirring under reflux for 4 hours. The solvent and excess trichloromethyl chloroformate were distilled off under atmospheric pressure to a maximum pot temperature of 130C. The resultant oil was cooled and a thin film infra red spectra showed the presence of a strong absorption at 2275 cm 1 (characteristic of -N=C=O absorption). The crude isocyanate was : ~ .
Z96~
diluted with a mixture of toluene (100 ml) and 2,6-difluorobenzamide (15.71g, 0.1 mole) and the reaction mixture heated with stirring under reflux for 1.5 hrs. After cooling, the resultant solid was collected by filtration and washed with chilled toluene and then 40-60 petroleum ether. The crude solid was recrystallised from ethyl methyl ketone to yield an orange crystalline solid. Yield 22.7g, 60%, 241-242C.
Required for C20H14F2N42 Found: C, 63.39; H, 3O73; N, 14.82 , ~
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l69l Z8-Z1 9Z-SSO-99 z p z zz ~z ~ ~ E E
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~v~
INSECTICIDAL EVALUATION
Test Procedure I
Spodoptera littoralis (Egyptian cotton leafworm) Larvicide assessments Cotton plants are grown to four true leaves of 7-8 cm diameter. The test compound was prepared as an aqueous/
acetone solution or suspension at the required concentra-tion. The foliar parts of the cotton plant are dipped in the test medium for a 10 second period. After drying they were kept in a glasshouse at a temperature of 20 to 25C with a minimum photoperiod of 12 hours~
Individual leaves from each treatment were removed and placed in separate 9 cm diameter plastic petri dishes where they were infested with ten, 3rd instar larvae of Spodoptera littoralis. The experimental units were kept in an environmental room at 25C, 70~ humidity with a photoperiod of 16 hours. The leaves in each unit were replaced daily with leaves from plants of the same treatment i.e., 0, 1, 2 and 3 days.
Assessment was made on the fourth day as a comparison of treated with untreated controls and expressed as a percentage mortality~
In a similar manner the third instar larvae of Plutella z xylostella (Diamond-backed moth) wexe tested and Heliothis viriscen5 (tobacco budworm~.
The results of the test procedures were assessed upon a scale of 1 - 5, where 1 = 90-100~ mortality 2 = 75-89 3 = 50-74
4 = 25-49
5 = 0-24 These data are summarised in Table 3.
0~ 2 4-Phenylazo Derivatives - Insecticidal Data - Larvicides Spodoptera littoralis Plutella xylostella Heliothis viriscens 400 mg/1 10 mg/1 400 mg/1 10 mg/1 480 mg/1
0~ 2 4-Phenylazo Derivatives - Insecticidal Data - Larvicides Spodoptera littoralis Plutella xylostella Heliothis viriscens 400 mg/1 10 mg/1 400 mg/1 10 mg/1 480 mg/1
6 1 1 1 5 21 1 5 - h 3~ 2 5 ~ ~o ~I ~ ~ ~ ~ ~ ~ o ~ ~ (n w ~ o c~ n .P w ~
- J
~ -:n oo -- l ~
,~ ~
O
w ~ n , n~
2~6;~
3~Phenylazo Derivatives Spodoptera littoralis Plutella xylostella Heliothis viriscens 400 mg/l 10 mg/1 400 mg/1 10 mg/1 480 mg/1 ~2~2~62 Test Procedure III
Spodoptera littoralis (Egyptian cotton leafworm) Ovicidal assessments One day old eggs of high viability were obtained from S, littoralis adults, suitable masses of approximately 200 eggs being taken from those laid on blotting paper cylinders. Upper layers of eggs were removed by brushing until the mass was reduced to a single layer. Each egg mass was then divided into two halves and mounted on microscope slides using double sided adhesive tape. One half of each mass was untreated and served as a control, the other half was chemically treated.
The test compound was prepared as an aqueous/acetone solution or suspension at the required concentration.
The egg mass was then dipped for a 3 second period into the test solution at the desired concentration. The treated and untreated eggs were kept in an incubator at 2~C and 90% humi~ity for 4-5 days. The treated egg masses were assessed for percent hatch and compared for control mo~tality with the complementary untreated mass.
Corrections for control mortality were made by application of Abbotts formula and the results expressed according to a scale of 1-5, where 1 -- 90-100~ mortality 2 = 75-89 3 = 50-74 4 = 25-49 5 = 0-2~
These data are summarised in Table 4.
Z~6Z
4~Phenylazo derivatives - Insecticidal Data - Ovicide Spodoptera littoralis 400 mg/1 10 mg~1 3-Phenylazo Derivatives ::,
- J
~ -:n oo -- l ~
,~ ~
O
w ~ n , n~
2~6;~
3~Phenylazo Derivatives Spodoptera littoralis Plutella xylostella Heliothis viriscens 400 mg/l 10 mg/1 400 mg/1 10 mg/1 480 mg/1 ~2~2~62 Test Procedure III
Spodoptera littoralis (Egyptian cotton leafworm) Ovicidal assessments One day old eggs of high viability were obtained from S, littoralis adults, suitable masses of approximately 200 eggs being taken from those laid on blotting paper cylinders. Upper layers of eggs were removed by brushing until the mass was reduced to a single layer. Each egg mass was then divided into two halves and mounted on microscope slides using double sided adhesive tape. One half of each mass was untreated and served as a control, the other half was chemically treated.
The test compound was prepared as an aqueous/acetone solution or suspension at the required concentration.
The egg mass was then dipped for a 3 second period into the test solution at the desired concentration. The treated and untreated eggs were kept in an incubator at 2~C and 90% humi~ity for 4-5 days. The treated egg masses were assessed for percent hatch and compared for control mo~tality with the complementary untreated mass.
Corrections for control mortality were made by application of Abbotts formula and the results expressed according to a scale of 1-5, where 1 -- 90-100~ mortality 2 = 75-89 3 = 50-74 4 = 25-49 5 = 0-2~
These data are summarised in Table 4.
Z~6Z
4~Phenylazo derivatives - Insecticidal Data - Ovicide Spodoptera littoralis 400 mg/1 10 mg~1 3-Phenylazo Derivatives ::,
Claims
I
wherein R and R1 are each independently a hydrogen or halogen atom, a C1-c4 alkyl or halogeno C1-C4 alkyl group; R2 and R3 are each independently a hydrogen or halogen atom or a C1-C4 alkyl group; R4 and R5 are each independently a hydrogen or halogen atom, or an alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkenyl, halogenoalkenyl, alkenyloxy, halogenoalkenyloxy or alkynyl group;
R6 is wherein R7 and R8 are each independently a hydrogen or halogen atom, or a nitro, alkyl, halogenoalkyl or cyano group; and R9 is a halogen atom or an alkyl or halogenoalkyl group.
2. A compound as claimed in claim 1 having the general formula (C1-C4 alkyl)n wherein R, R1, R7 and R8 are as defined in Claim 1 and n is 1 or 2.
3. A compound as claimed in claim 2 wherein R
and R1 are each independently a hydrogen, fluorine or chlorine atom or a methyl group.
4. A compound as claimed in claim 2 or claim 3 wherein R7 and R8 are each a hydrogen atom.
5. A compound as claimed in claim 2 wherein the C1-4 alkyl group(s) is(are) at position(s) 3 and/or 5 of the phenyl ring.
6. A compound as claimed in claim 5 wherein the alkyl group(s) is(are) methyl.
7. A compound as claimed in claim 1 having the general formula wherein R, R1, R7 and R8 are as defined in claim 1 and n is 1 or 2, 8. A compound as claimed in claim 7 wherein R
and R1 are each independently a hydrogen, fluorine or chlorine atom or a methyl group.
9. A compound as claimed in claim 7 or claim 8 wherein R7 and R8 are each a hydrogen atom.
10. A compound as claimed in claim 7 wherein the halogen atom(s) is(are) at positions 3 and/or 5 of the phenyl ring.
11. A compound as claimed in claim 10 wherein the halogen atom(s) is(are) fluorine or chlorine atoms.
12. A process for the preparation of a compound as claimed in claim 1 which process comprises reacting a phenylazoaniline of the general formula:
II
wherein R2, R3, R4, R5 and R6 are as defined in claim 1 with a benzoylisocyanote of the general formula III
wherein R and R1 are as defined in claim 1 in the presence of an appropriate solvent.
13. A process for the preparation of a compound as claimed in claim 1 which process comprises reacting a 4-arylazophenylisocyanate of the general formula IV
wherein R2, R3, R4, R5 and R6 are as defined in claim 1 with a benzamide of the formula V
wherein R and R1 are as above defined in the presence of an appropriate solvent.
14. A method of killing or controlling insects which comprises applying to the insect and/or its habitat an insecticidal amount of at least one compound as claimed in Claim 1.
15. A method of killing or controlling insects which comprises applying to the insect and/or its habitat a composition containing an insecticidal amount of at least one compound as claimed in
Claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8229874 | 1982-10-19 | ||
| GB8229874 | 1982-10-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1202962A true CA1202962A (en) | 1986-04-08 |
Family
ID=10533700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000438469A Expired CA1202962A (en) | 1982-10-19 | 1983-10-06 | Substituted n-phenyl-n'-benzoyl ureas and their use as insecticides and acaricides |
Country Status (13)
| Country | Link |
|---|---|
| US (2) | US4800195A (en) |
| EP (1) | EP0109172A1 (en) |
| JP (1) | JPS5989654A (en) |
| AU (1) | AU2014083A (en) |
| BR (1) | BR8305825A (en) |
| CA (1) | CA1202962A (en) |
| DK (1) | DK480783A (en) |
| GB (1) | GB2128995B (en) |
| GR (1) | GR78711B (en) |
| NZ (1) | NZ205973A (en) |
| PH (1) | PH19702A (en) |
| TR (1) | TR21696A (en) |
| ZA (1) | ZA837747B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0504419A1 (en) * | 1990-10-05 | 1992-09-23 | Seiko Epson Corporation | Photosensitive azo compound and image forming device utilizing the same |
| US5610276A (en) * | 1991-05-17 | 1997-03-11 | Chiron Corporation | Polypeptides and antibodies derived from GAP associated protein, p62 |
| US6264915B1 (en) | 1992-09-13 | 2001-07-24 | The President And Fellows Of Harvard College | Process for detecting potential carcinogens |
| US5633149A (en) | 1994-12-07 | 1997-05-27 | Incyte Pharmaceuticals, Inc. | Polynucleotide encoding novel chemokine expressed in inflamed adenoid |
| US7005509B1 (en) | 1995-02-17 | 2006-02-28 | Incyte Corporation | Chemokine PANEC-1 polynucleotides and compositions and methods related thereto |
| US6916646B1 (en) * | 1997-06-23 | 2005-07-12 | Genencor International, Inc. | Enterobacteriaceae fermentation strains |
| US6197502B1 (en) | 1997-11-17 | 2001-03-06 | Cytos Biotechnology Ag | Expression cloning processes for the discovery characterization, and isolation of genes encoding polypeptides with a predetermined property |
| WO2000077179A2 (en) * | 1999-06-16 | 2000-12-21 | Icos Corporation | Human poly(adp-ribose) polymerase 2 materials and methods |
| US20030108927A1 (en) * | 2000-04-03 | 2003-06-12 | Kathryn Leishman | Compositions and methods for the prevention, treatment and detection of tuberculosis and other diseases |
| GB0025132D0 (en) * | 2000-10-13 | 2000-11-29 | Medical Res Council | Method |
| GB0101762D0 (en) * | 2001-01-23 | 2001-03-07 | Medical Res Council | Method |
| US7332585B2 (en) | 2002-04-05 | 2008-02-19 | The Regents Of The California University | Bispecific single chain Fv antibody molecules and methods of use thereof |
| CA2668457C (en) * | 2006-11-02 | 2016-10-04 | Veridex, Llc | Imaging of activated vascular endothelium using immunomagnetic mri contrast agents |
| WO2009059115A1 (en) * | 2007-10-31 | 2009-05-07 | Trustees Of The University Of Pennsylvania | Culture based screening assay and methods of use thereof to identify agents which modulate tumor development, invasion and differentiation |
| WO2009140679A2 (en) | 2008-05-16 | 2009-11-19 | The Children's Hospital Of Philadelphia | Genetic alterations on chromosomes 21q, 6q and 15q and methods of use thereof for the diagnosis and treatment of type i diabetes |
| AU2011312504B2 (en) | 2010-09-27 | 2016-12-22 | The Children's Hospital Of Philadelphia | Compositions and methods useful for the treatment and diagnosis of inflammatory bowel disease |
| WO2012112578A2 (en) | 2011-02-14 | 2012-08-23 | The Children's Hospital Of Philadelphia | Improved aav8 vector with enhanced functional activity and methods of use thereof |
| WO2013078400A1 (en) | 2011-11-22 | 2013-05-30 | The Children's Hospital Of Philadelphia | Virus vectors for highly efficient transgene delivery |
| SI2839014T1 (en) | 2012-04-18 | 2021-05-31 | The Children's Hospital Of Philadelphia | Composition and methods for highly efficient gene transfer using aav capsid variants |
| US10077474B2 (en) | 2012-05-29 | 2018-09-18 | Abbott Molecular, Inc. | Method of designing primers, method of detecting single nucleotide polymorphisms (SNPs), method of distinguishing SNPs, and related primers, detectable oligonucleotides, and kits |
| CA2902167A1 (en) | 2013-03-15 | 2014-09-25 | Abbott Molecular Inc. | Method for amplification and assay of rna fusion gene variants, method of distinguishing same and related primers, probes, and kits |
| US9365902B2 (en) | 2013-03-15 | 2016-06-14 | Abbott Molecular Inc. | Detection of bisulfite converted nucleotide sequences |
| US9840719B2 (en) | 2013-07-22 | 2017-12-12 | The Children's Hospital Of Philadelphia | Variant AAV and compositions, methods and uses for gene transfer to cells, organs and tissues |
| JP2017522015A (en) | 2014-06-24 | 2017-08-10 | アボツト・モレキユラー・インコーポレイテツド | Detection of single nucleotide polymorphisms in human KRAS |
| WO2016077078A1 (en) | 2014-10-29 | 2016-05-19 | The Children's Hospital Of Philadelphia | Diagnosis and treatment of genetic alterations associated with eosinophilic esophagitis |
| CA2989326A1 (en) | 2015-06-15 | 2016-12-22 | The Children's Hospital Of Philadelphia | Methods of diagnosing and treating autism |
| WO2017035017A1 (en) | 2015-08-21 | 2017-03-02 | The Children's Hospital Of Philadelphia | Methods of treating autoimmune conditions in patients with genetic variations in dcr3 or in a dcr3 network gene |
| US20190376127A1 (en) | 2017-01-09 | 2019-12-12 | The Children's Hospital Of Philadelphia | Compositions and methods targeting the th2 pathway for the treatment of asthma |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR799316A (en) * | 1935-03-07 | 1936-06-11 | Ig Farbenindustrie Ag | Process for preparing azo dyes |
| US3379716A (en) * | 1965-06-16 | 1968-04-23 | Eastman Kodak Co | Aromatic monoazo dyestuffs |
| US3810932A (en) * | 1968-03-18 | 1974-05-14 | Ciba Geigy Ag | Styryl dyestuffs |
| EP0016729B1 (en) * | 1979-03-13 | 1984-07-25 | Ciba-Geigy Ag | Substituted n-(p-aminophenyl)-n'-benzoyl ureas, process for their preparation, compositions containing them and their use as pesticides; alkenyl-substituted p-amino aniline derivatives |
| JPS57175158A (en) * | 1981-04-20 | 1982-10-28 | Mitsubishi Chem Ind Ltd | Benzoylurea derivative and insecticide comprising it as active ingredient |
| JPS57188561A (en) * | 1981-05-16 | 1982-11-19 | Mitsubishi Chem Ind Ltd | Benzoylurea derivative and insecticide containing said derivative as active component |
-
1983
- 1983-10-06 CA CA000438469A patent/CA1202962A/en not_active Expired
- 1983-10-07 GB GB08326936A patent/GB2128995B/en not_active Expired
- 1983-10-07 EP EP83306090A patent/EP0109172A1/en not_active Withdrawn
- 1983-10-13 US US06/541,768 patent/US4800195A/en not_active Expired - Fee Related
- 1983-10-13 AU AU20140/83A patent/AU2014083A/en not_active Abandoned
- 1983-10-14 NZ NZ205973A patent/NZ205973A/en unknown
- 1983-10-17 GR GR72715A patent/GR78711B/el unknown
- 1983-10-18 ZA ZA837747A patent/ZA837747B/en unknown
- 1983-10-19 PH PH29720A patent/PH19702A/en unknown
- 1983-10-19 BR BR8305825A patent/BR8305825A/en unknown
- 1983-10-19 JP JP58195936A patent/JPS5989654A/en active Pending
- 1983-10-19 DK DK480783A patent/DK480783A/en not_active Application Discontinuation
- 1983-10-19 TR TR21696A patent/TR21696A/en unknown
-
1988
- 1988-03-04 US US07/164,142 patent/US4795746A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| TR21696A (en) | 1985-03-05 |
| AU2014083A (en) | 1984-05-03 |
| GB8326936D0 (en) | 1983-11-09 |
| EP0109172A1 (en) | 1984-05-23 |
| ZA837747B (en) | 1985-06-26 |
| US4795746A (en) | 1989-01-03 |
| JPS5989654A (en) | 1984-05-23 |
| DK480783A (en) | 1984-04-20 |
| DK480783D0 (en) | 1983-10-19 |
| PH19702A (en) | 1986-06-16 |
| NZ205973A (en) | 1987-05-29 |
| GB2128995B (en) | 1986-09-10 |
| BR8305825A (en) | 1984-05-29 |
| GR78711B (en) | 1984-09-27 |
| GB2128995A (en) | 1984-05-10 |
| US4800195A (en) | 1989-01-24 |
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