CA1079285A - N-benzoyl n'-pyridyloxy phenylurea and preparation thereof - Google Patents
N-benzoyl n'-pyridyloxy phenylurea and preparation thereofInfo
- Publication number
- CA1079285A CA1079285A CA301,811A CA301811A CA1079285A CA 1079285 A CA1079285 A CA 1079285A CA 301811 A CA301811 A CA 301811A CA 1079285 A CA1079285 A CA 1079285A
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- Prior art keywords
- urea
- phenyl
- oxy
- halogen atom
- chloro
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives 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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pyridine Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The invention provides N-benzoyl N'-pyridyloxy phenyl urea having the formula
The invention provides N-benzoyl N'-pyridyloxy phenyl urea having the formula
Description
The present invention relates to N-benzoyl N'-pyridyloxy phenyl ureas useful as insecticides and the process for producing the same.
Most of the conventional insecticides impart neuro-toxicity and contact toxicity to all types of insects. It has been necessary to find selective insecticidal compounds without toxicity to useful insects such compounds include N-benzoyl N'-phenyl ureas disclosed in USP 3,748,356 and N-benzoyl N'-phenoxy-phenyl ureas (no pyridyloxy group) disclosed in USP 4,005,223.
The N-benzoyl N'-pyridyloxyphenyl ureas of the present invention have a substantially better selective insect-icidal action than the above described known compounds.
The present invention provides selective insecticidal compositions which are very effective to selected injurious in-sects without affecting useful insects and have a low toxicity to animals.
According to the present invention there are provided I N-benzoyl N'-pyridyloxy phenyl ureas having the formula Xl X3 X5 ¦ ~ CONHCONH ~ ~ O ~~ X6 (I~
wherein Xl represents a halogen atom or methyl group; X2 repre-sents hydrogen or halogen atom; X3 and X4 respectively represent hydrogen or halogen atom; X5 represents hydrogen or halogen atom;
and X6 represents a halogen atom or nitro or trifluoromethyl group.
10792~
Compound Suitable compounds having the formula (I) include:
No.
1 N-(2-chlorobenzoyl)N'-~3-chloro-4-(5-bromopyridyl-2-oxy) phenyl]urea m.p. 196 to 199C
Most of the conventional insecticides impart neuro-toxicity and contact toxicity to all types of insects. It has been necessary to find selective insecticidal compounds without toxicity to useful insects such compounds include N-benzoyl N'-phenyl ureas disclosed in USP 3,748,356 and N-benzoyl N'-phenoxy-phenyl ureas (no pyridyloxy group) disclosed in USP 4,005,223.
The N-benzoyl N'-pyridyloxyphenyl ureas of the present invention have a substantially better selective insect-icidal action than the above described known compounds.
The present invention provides selective insecticidal compositions which are very effective to selected injurious in-sects without affecting useful insects and have a low toxicity to animals.
According to the present invention there are provided I N-benzoyl N'-pyridyloxy phenyl ureas having the formula Xl X3 X5 ¦ ~ CONHCONH ~ ~ O ~~ X6 (I~
wherein Xl represents a halogen atom or methyl group; X2 repre-sents hydrogen or halogen atom; X3 and X4 respectively represent hydrogen or halogen atom; X5 represents hydrogen or halogen atom;
and X6 represents a halogen atom or nitro or trifluoromethyl group.
10792~
Compound Suitable compounds having the formula (I) include:
No.
1 N-(2-chlorobenzoyl)N'-~3-chloro-4-(5-bromopyridyl-2-oxy) phenyl]urea m.p. 196 to 199C
2 N-(2-chlorobenzoyl)N'-[3-chloro-4-(5-nitropyridyl-2-oxy) ~
phenyl]urea m.p. 209 to 212C -~ -
phenyl]urea m.p. 209 to 212C -~ -
3 N-(2-chlorobenzoyl)N'-[4-(3,5-dibromopyridyl-2-oxy) ;
phenyl]urea m.p. 185 to 188C
phenyl]urea m.p. 185 to 188C
4 N-(2-chlorobenzoyl)N'-[3-chloro-4-(3,5-dibromopyridyl-2-oxy)phenyl]urea m.p. 223 to 224C
N-(2-chlorobenzoyl)N'-[4-(3,5-dichloropyridyl-2-oxy) -phenyl]urea m.p. 216 to 218C
6 N-(2-chlorobenzoyl)N'-[3-chloro-4-(3,5-dichloropyridyl-2-oxy)phenyl]urea m.p. 225 to 228C
7 N-(2-chlorobenzoyl)N'-[3,5-dichloro-4-(3,5-dichloro-pyridyl-2-oxy)phenyl]urea ~ m.p. 221 to 223C
8 N-(2-chlorobenzoyl)N'-[4-(5-bromopyridyl-2-oXy)phenyll urea m.p. 179 to 180C ;;
~ 9 N-(2-chlorohenzoyl)N'-~[3-chloro-4-(5-chlorpyridyl-2-oxy) ~ phenyl]urea m.p. 198 to 200C
~ 10 N-(2-chlorobenzoyl)N'-13,5-dichloro-4-(5-chloropyridyl-, ~ .
~ 2-oxy)phenyl]urea m.p. 147 to 148C
. .
11 N-(2-chlorobenzoyl)N'-l4,(5-trifluoromethylpyridyl-2-oxy)phenyl]urea m.p. 149 to 151C
12 N-(2-chlorobenzoyl)N'-[3-chloro-4-(5-trifluoromethyl-pyridyl-2-oxy)phenyl]urea m.p. 182 to 185C
13 N-(2-chlorobenzoyl)N'-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)phenyl]urea m.p. 186 to 187C
14 N-(2-chlorobenzoyl)N'-[3,5-dichloro-4-(5-trifluoromethyl-pyridyl-2-oxy)phenyl]urea m.p. 206 to 208C
N-(2-chlorobenzoyl)N'-[3,5-dichloro-4-(3-chloro-5-tri-fluoromethylpyridyl-2-oxy)phenyl]urea m.p. 140 to 144C
. . , .: , .. . . ..
-' ~079Z8~5 16 N-(2-chlorobenzoyl)N'-[3-chloro-4-(3-chloro-5-trifluoro-methylpyridyl-2-oxy)phenyl]urea m.p. 224 to 226C
17 N-(2,6-dichlorobenzoyl)N'-[4-t3,5-dichloropyridyl-2-oxy)phenyl]urea m.p. 228 to 230C
18 N-(2,6-dichlorobenzoyl)N'-[3-chloro-4-(3,5-dichloro-pyridyl-2-oxy)phenyl]urea m.p. 214 to 216C
19 N-(2,6-dichlorobenzoyl)N'-[3,5-dichloro-4-(3,5-dichloro-pyridyl-2-oxy)phenyl]urea m.p. 273 to 275C
N-(2,6-difluorobenzoyl)N'-~4-(3,5-dichloropyridyl-2-oxy)phenyl]urea m.p. 184 to 185C
21 N-(2,6-difluorobenzoyl)N'-~3-chloro-4-(3,5-dichloro-pyridyl-2-oxy)phenyl]urea m.p. 230 to 231C
22 N-(2,6-difluorobenzoyl)N'-[3-chloro-4-(5-chloropyridyl-2-oxy)phenyl~urea m.p. 210 to 212C
23 N-(2,6-difluorobenzoyl)N'-[4-(5-trifluoromethylpyridyl-2-oxy)phenyl~urea m.p. 185 to 188C
24 N-(2,6-difluorobenzoyl)N'-~4-(3-chloro-5-trifluoro-methylpyridyl-2-oxy)phenyl]urea m.p. 190 to 192C `
N-(2,6-difluorobenzoyl)N'-[3-chloro-4-(5-trifluoromethyl-pyridyl-2-oxy)phenylJurea m.p. 195 to 198C ~
26 N-(2,6-difluorobenzoyl)N'-[3,-5-dichloro-4-(5-trifluoro- -~-methylpyridyl-2-oxy)phenyl]urea m.p. 209 to 212C
27 N-(2,6-difluorobenzoyl)N'-[3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridyl-2-oxy)phenyl]urea m.p.
203 to 205C
28 N-(2,6-difluorobenzoyl)N'-[3-chloro-4-(3-chloro-5-tri-fluoromethylpyridyl-2-oxy)phenyl]urea m.p. 187 ;~
to 190C
29 N-(2-methylbenzoyl)N'-[4-t5-chloropyridyl-2-oxy)phenyl]
urea m.p. 198 to 200C
N-(2-methylbenzoyl)N'-[4-(5-bromopyridyl-2-oxy)phenyl urea m.p. 188 to 191C
31 N-(2-methylbenzoyl)N'-[4-(5-trifluoromethylpyridyl-2-oxy)phenyl]urea m.p. 140 to 142C
32 N-(2-methylbenzoyl)N'-13-chloro-4-(5-bromopyridyl-2-oxy) phenyl]urea m.p. 207 to 209C
33 N-(2-methylbenzoyl)N'-[3-chloro-4-(5-trifluoromethyl-pyridyl-2-oxy)phenyl]urea m.p. 188 to 191C
34 N-(2-methylbenzoyl)N'-~3-chloro-4-(3,5-dichloropyridyl-2-oxy)phenyl]urea m.p. 213 to 215C
N-(2-methylbenzoyl)N'-[3,5-dichloro-~-(3-chloro-5-~tri-fluoromethylpyridyl-2-oxy)phenyl]urea m.p. 214 to 217C
36 N-(2-methylbenzoyl)N'-[3-bromo-4-(3,5-dichloropyridyl-2-oxy)phenyl]urea m.p. 222 to 224C
37 N-(2-methylbenzoyl)N'-~4-(3,5-dichloropyridyl-2-oxy) phenyl]urea m.p. 216 to 219C
38 N-(2-methylbenzoyl)N'-[4-(3,5-dibromopyridyl-2-oxy) phenyl]urea m.p. 219 to 221C
39 N-(2-methylbenzoyl)N'-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)phenyl]urea m.p. 171 to 173C
, ~ .
:~20 40 N- (2-methylbenzoyl)N'-[3,5-dichloro-4-(5-trifluoromethyl-pyridyl-2-oxy)phenyl]urea m.p. 219 to 221C
:~ . . .
41 N (2-methylbenzoyl)N'-[3-chloro-4-(3-chloro-5-trifluoro-methylpyridyl-2-oxy)phenyl]urea m.p. 156 to 159C -The N~benzoyl N'-pyridyloxy phenyl ureas having the -~
formula (I) may be produced by reacting a compound having the formula - .
~ - 4 - ~
-' 10792~35 ~_ CO-Rl 2 (II) wherein Xl represents a halogen atom or methyl group; X2 repre-sents hydrogen or halogen atom; R1 represents amino or isocyanate group with a compound having the formula -~
1 o R2 ~ _~J 6 wherein X3 and X4 are the same and different and respectively represent hydrogen or halogen atom; X5 represents hydrogen or ~ -halogen atom; X6 represents halogen atom or nitro or trifluoro- ..
methyl group; and R2 represents an amino or isocyanate group; :~ .
R2 being an amino group when-Rl is an isocyanate group and R2 is an isocyanate group when Rl is an amino group.
In particular, the compounds having the formula (I) can be produced by the following processes (1) and (2). :
~20 (1) the reaction of benzoyl isocyanate having the formula ~ .
Xl ,'~
CO-NCO
with pyridyloxy aniline having the formula ':
,`-. ~-:, ' '' - 4a -., ,--.. ~ , with pyridyloxy aniline having the formula 1~ X2, X3, X4, X5 and X6 are defined above) or ~2) the reaction of benzamide having the formula Xl \~ CO--NH2 \~
with pyridyloxy phenyl isocyanate having the formula OC21-~ 0 ~N~x6 Y
! 4 1' X2, X3, X4, X5, and X6 are defined above) The reaction is preferably carried out in the pre-sence of a solvent. Suitable solvents include benzene, toluene, xylene and pyridine. The reaction temperature is usually in a l~ range of 0 to 120C and the reaction time is usually in a range l~ f 0.1 to 24 hours. The reaction is preferably carried out at the i 20 temperature from 50C to a refluxing temperature for 1 to 5 hours.
., .s The present invention wili be further illustrated ~;
by way of the following Examples.
Example 1 Preparation of N-(2-chlorobenzoyl)N'-13-chloro-4-. ~ .
(3,5-dichloro-pyridyl-2-oxy)phenyl]urea A solution prepared by dissolving 2.9 g of 3-chloro-4-(3,5-dichloro-pyridyl-2-oxy) aniline in 50 ml of toluene was heated to 80C. A solution prepared by dissolving 1.8 g of 2- -chlorobenzoyl isocyanate in 20 ml of toluene was added dropwise ii to the former solution with stirring and the reaction was carried out for 1 hour. After the reaction, the reaction mixture was cooled and the precipitate was filtered, washed and toluene, then ., ., . .:
washed with petroleum ether and dried to obtain 3.2 g of N-(2-chlorobenzoyl)N'-[3-chloro-4-(3,5-dichloropyridyl-2-oxy)phenyl]
urea (m.p. 225 to 228C).
Example 2 Preparation of N-(2,6-dichlorobenzoyl)N'-[4-(3,5-dichloropyridyl-2-oxy)phenyl~ urea In accordance with the procedure of Example 1, except using 2.5 g of 4-(3,5-dichloropyridyl-2-oxy) aniline instead of 3-chloro-4-(3,5-dichloropyridyl-2-oxy) aniline and using 2.4 g of 2/6-dichlorobenzoyl isocyanate instead of 2-chlorobenzoyl iSQ-cyanate and reacting at 30C for 8 hours instead of 80C for 1 -- -hours, 3.8 g of N-(2,6-dichlorobenzoyl)N'-[4-(3,5-dichloropyridyl- -? 2-oxy) phenyl] urea (m.p. 228 to 230C) were obtained.
: .
The compounds of the present invention have an excel-lent selective insectidal effect as will be clearly seen from N
t ~ the following.
Exam~le 3 Preparation of N-(2,6-difluorobenzoyl)N'-[4-(3-chloro-
N-(2-chlorobenzoyl)N'-[4-(3,5-dichloropyridyl-2-oxy) -phenyl]urea m.p. 216 to 218C
6 N-(2-chlorobenzoyl)N'-[3-chloro-4-(3,5-dichloropyridyl-2-oxy)phenyl]urea m.p. 225 to 228C
7 N-(2-chlorobenzoyl)N'-[3,5-dichloro-4-(3,5-dichloro-pyridyl-2-oxy)phenyl]urea ~ m.p. 221 to 223C
8 N-(2-chlorobenzoyl)N'-[4-(5-bromopyridyl-2-oXy)phenyll urea m.p. 179 to 180C ;;
~ 9 N-(2-chlorohenzoyl)N'-~[3-chloro-4-(5-chlorpyridyl-2-oxy) ~ phenyl]urea m.p. 198 to 200C
~ 10 N-(2-chlorobenzoyl)N'-13,5-dichloro-4-(5-chloropyridyl-, ~ .
~ 2-oxy)phenyl]urea m.p. 147 to 148C
. .
11 N-(2-chlorobenzoyl)N'-l4,(5-trifluoromethylpyridyl-2-oxy)phenyl]urea m.p. 149 to 151C
12 N-(2-chlorobenzoyl)N'-[3-chloro-4-(5-trifluoromethyl-pyridyl-2-oxy)phenyl]urea m.p. 182 to 185C
13 N-(2-chlorobenzoyl)N'-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)phenyl]urea m.p. 186 to 187C
14 N-(2-chlorobenzoyl)N'-[3,5-dichloro-4-(5-trifluoromethyl-pyridyl-2-oxy)phenyl]urea m.p. 206 to 208C
N-(2-chlorobenzoyl)N'-[3,5-dichloro-4-(3-chloro-5-tri-fluoromethylpyridyl-2-oxy)phenyl]urea m.p. 140 to 144C
. . , .: , .. . . ..
-' ~079Z8~5 16 N-(2-chlorobenzoyl)N'-[3-chloro-4-(3-chloro-5-trifluoro-methylpyridyl-2-oxy)phenyl]urea m.p. 224 to 226C
17 N-(2,6-dichlorobenzoyl)N'-[4-t3,5-dichloropyridyl-2-oxy)phenyl]urea m.p. 228 to 230C
18 N-(2,6-dichlorobenzoyl)N'-[3-chloro-4-(3,5-dichloro-pyridyl-2-oxy)phenyl]urea m.p. 214 to 216C
19 N-(2,6-dichlorobenzoyl)N'-[3,5-dichloro-4-(3,5-dichloro-pyridyl-2-oxy)phenyl]urea m.p. 273 to 275C
N-(2,6-difluorobenzoyl)N'-~4-(3,5-dichloropyridyl-2-oxy)phenyl]urea m.p. 184 to 185C
21 N-(2,6-difluorobenzoyl)N'-~3-chloro-4-(3,5-dichloro-pyridyl-2-oxy)phenyl]urea m.p. 230 to 231C
22 N-(2,6-difluorobenzoyl)N'-[3-chloro-4-(5-chloropyridyl-2-oxy)phenyl~urea m.p. 210 to 212C
23 N-(2,6-difluorobenzoyl)N'-[4-(5-trifluoromethylpyridyl-2-oxy)phenyl~urea m.p. 185 to 188C
24 N-(2,6-difluorobenzoyl)N'-~4-(3-chloro-5-trifluoro-methylpyridyl-2-oxy)phenyl]urea m.p. 190 to 192C `
N-(2,6-difluorobenzoyl)N'-[3-chloro-4-(5-trifluoromethyl-pyridyl-2-oxy)phenylJurea m.p. 195 to 198C ~
26 N-(2,6-difluorobenzoyl)N'-[3,-5-dichloro-4-(5-trifluoro- -~-methylpyridyl-2-oxy)phenyl]urea m.p. 209 to 212C
27 N-(2,6-difluorobenzoyl)N'-[3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridyl-2-oxy)phenyl]urea m.p.
203 to 205C
28 N-(2,6-difluorobenzoyl)N'-[3-chloro-4-(3-chloro-5-tri-fluoromethylpyridyl-2-oxy)phenyl]urea m.p. 187 ;~
to 190C
29 N-(2-methylbenzoyl)N'-[4-t5-chloropyridyl-2-oxy)phenyl]
urea m.p. 198 to 200C
N-(2-methylbenzoyl)N'-[4-(5-bromopyridyl-2-oxy)phenyl urea m.p. 188 to 191C
31 N-(2-methylbenzoyl)N'-[4-(5-trifluoromethylpyridyl-2-oxy)phenyl]urea m.p. 140 to 142C
32 N-(2-methylbenzoyl)N'-13-chloro-4-(5-bromopyridyl-2-oxy) phenyl]urea m.p. 207 to 209C
33 N-(2-methylbenzoyl)N'-[3-chloro-4-(5-trifluoromethyl-pyridyl-2-oxy)phenyl]urea m.p. 188 to 191C
34 N-(2-methylbenzoyl)N'-~3-chloro-4-(3,5-dichloropyridyl-2-oxy)phenyl]urea m.p. 213 to 215C
N-(2-methylbenzoyl)N'-[3,5-dichloro-~-(3-chloro-5-~tri-fluoromethylpyridyl-2-oxy)phenyl]urea m.p. 214 to 217C
36 N-(2-methylbenzoyl)N'-[3-bromo-4-(3,5-dichloropyridyl-2-oxy)phenyl]urea m.p. 222 to 224C
37 N-(2-methylbenzoyl)N'-~4-(3,5-dichloropyridyl-2-oxy) phenyl]urea m.p. 216 to 219C
38 N-(2-methylbenzoyl)N'-[4-(3,5-dibromopyridyl-2-oxy) phenyl]urea m.p. 219 to 221C
39 N-(2-methylbenzoyl)N'-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)phenyl]urea m.p. 171 to 173C
, ~ .
:~20 40 N- (2-methylbenzoyl)N'-[3,5-dichloro-4-(5-trifluoromethyl-pyridyl-2-oxy)phenyl]urea m.p. 219 to 221C
:~ . . .
41 N (2-methylbenzoyl)N'-[3-chloro-4-(3-chloro-5-trifluoro-methylpyridyl-2-oxy)phenyl]urea m.p. 156 to 159C -The N~benzoyl N'-pyridyloxy phenyl ureas having the -~
formula (I) may be produced by reacting a compound having the formula - .
~ - 4 - ~
-' 10792~35 ~_ CO-Rl 2 (II) wherein Xl represents a halogen atom or methyl group; X2 repre-sents hydrogen or halogen atom; R1 represents amino or isocyanate group with a compound having the formula -~
1 o R2 ~ _~J 6 wherein X3 and X4 are the same and different and respectively represent hydrogen or halogen atom; X5 represents hydrogen or ~ -halogen atom; X6 represents halogen atom or nitro or trifluoro- ..
methyl group; and R2 represents an amino or isocyanate group; :~ .
R2 being an amino group when-Rl is an isocyanate group and R2 is an isocyanate group when Rl is an amino group.
In particular, the compounds having the formula (I) can be produced by the following processes (1) and (2). :
~20 (1) the reaction of benzoyl isocyanate having the formula ~ .
Xl ,'~
CO-NCO
with pyridyloxy aniline having the formula ':
,`-. ~-:, ' '' - 4a -., ,--.. ~ , with pyridyloxy aniline having the formula 1~ X2, X3, X4, X5 and X6 are defined above) or ~2) the reaction of benzamide having the formula Xl \~ CO--NH2 \~
with pyridyloxy phenyl isocyanate having the formula OC21-~ 0 ~N~x6 Y
! 4 1' X2, X3, X4, X5, and X6 are defined above) The reaction is preferably carried out in the pre-sence of a solvent. Suitable solvents include benzene, toluene, xylene and pyridine. The reaction temperature is usually in a l~ range of 0 to 120C and the reaction time is usually in a range l~ f 0.1 to 24 hours. The reaction is preferably carried out at the i 20 temperature from 50C to a refluxing temperature for 1 to 5 hours.
., .s The present invention wili be further illustrated ~;
by way of the following Examples.
Example 1 Preparation of N-(2-chlorobenzoyl)N'-13-chloro-4-. ~ .
(3,5-dichloro-pyridyl-2-oxy)phenyl]urea A solution prepared by dissolving 2.9 g of 3-chloro-4-(3,5-dichloro-pyridyl-2-oxy) aniline in 50 ml of toluene was heated to 80C. A solution prepared by dissolving 1.8 g of 2- -chlorobenzoyl isocyanate in 20 ml of toluene was added dropwise ii to the former solution with stirring and the reaction was carried out for 1 hour. After the reaction, the reaction mixture was cooled and the precipitate was filtered, washed and toluene, then ., ., . .:
washed with petroleum ether and dried to obtain 3.2 g of N-(2-chlorobenzoyl)N'-[3-chloro-4-(3,5-dichloropyridyl-2-oxy)phenyl]
urea (m.p. 225 to 228C).
Example 2 Preparation of N-(2,6-dichlorobenzoyl)N'-[4-(3,5-dichloropyridyl-2-oxy)phenyl~ urea In accordance with the procedure of Example 1, except using 2.5 g of 4-(3,5-dichloropyridyl-2-oxy) aniline instead of 3-chloro-4-(3,5-dichloropyridyl-2-oxy) aniline and using 2.4 g of 2/6-dichlorobenzoyl isocyanate instead of 2-chlorobenzoyl iSQ-cyanate and reacting at 30C for 8 hours instead of 80C for 1 -- -hours, 3.8 g of N-(2,6-dichlorobenzoyl)N'-[4-(3,5-dichloropyridyl- -? 2-oxy) phenyl] urea (m.p. 228 to 230C) were obtained.
: .
The compounds of the present invention have an excel-lent selective insectidal effect as will be clearly seen from N
t ~ the following.
Exam~le 3 Preparation of N-(2,6-difluorobenzoyl)N'-[4-(3-chloro-
5-trifluoromethylpyridyl-2-oxy) phenyl] urea ~ 20 In accordance with the procedure of Example 1, except ¦~ using 1.0 g of 4-(3-chloro-5-trifluoromeyhylpyridyl-2-oxy) aniline instead of 3-chloro-4-(3,50dichloropyridyl-2-oxy) aniline and using 0.64 g of 2,6-difluorobenzoyl isocyanate instead of 2-chlorobenzoyl isocyanate and reacting at room temperature for 3 hours instead of 80C for 1 hour, 0.5 g of N-(2,6-difluorobenzoyl) N'-[4-(3-chloro-5-trifluoromethylpyridyl-2-oxy) phenyl] urea (m.p. 190 to 192C)were obtained.
Example 4 Preparation of N-(2-methylbenzoyl)N'-[4-(5-trifluoro-methyl-pyridyl-2-oxy) phenyl] urea A solution was prepared by dissolving 0.5 g of 4-(S-trifluoromethylpyridyl-2-oxy) aniline in 20 ml of toluene. A
solution prepared by dissolving 0.32 g of 2-methylbenzoyl isocyanate in 20 ml of toluene was added dropwise to the former solution with stirring and the reaction was carried out at room temperature for 1 hour. After the reaction, the reaction mixture was cooled, the precipitate was filtered and washed with hexane and then recrystallized from ethanol to obtain 0.3 g of N-(2-methylbenzoyl) N'-[4-(5-trifluoromethylpyridyl-2-oxy) phenyl] urea (m.p. 140 to 142C).
Most of the conventional insecticides have a rapid effect of neutrotoxicity and contact toxicity. However, the compounds of the present invention have a delayed effect, the compounds affecting molting (ecdysis) and metamorphosis of specific insects which orally take in the compound in their feed or water whereby the death of the specific insects is caused.
The compounds of the present invention have remarkable insecticidal effect on larvae of Lepidoptera, Coleoptera, Hymeno-ptera and Diptera, for example, larvae of the following insects:
diamondback moth (Plutella xylostella), common white (Pieris rape crucivora), cabbage armyworm (Mamesta brassicae), cabbage looper tPlusia nigrisigma), tobacco cutworm (Prodenia litura), smoller citrus dog (Papilio xuthus~, small blackish cochlid (Seopelodes contracta), fall webworm (hyphantria cunea), gypsy moth (Lymantria dispar), rice stem borer (Chilo suppressalis), bollworm (Heliothis zea), tobacco budworm tHeliothis virescens), bollweevil (Anthonomus grandis), confused flour beetle (Tribolium -confusum), colorado potato bettle (Leptinotarsa decemlineata), sawfly tNeurotoma irdescens), Culex mosquito (Culex pipiens pallens), and mosquito (Culex pipiens molestus).
The compounds of the present invention do not sub-stantially have an insecticidal effect on adults~ are ineffective or natural enemies such as predatory insects and have a low toxicity in animals.
. .
When the compounds are used as active ingredients in the insecticidal composition, it is possible to prepare various forms of the compositions such as dusts, wettable powders, emul-sifiable concentrates, invert emulsions, oil solutions, and aerosol preparations, with adjuvants for agricultural use. The -~
compositions can be used with or witout dilution in suitable concentrations.
Suitable adjuvants include powdery carriers such as talc, kaolin, bentonite, diatomaceous earth, silicon dioxide, clay and starch; liquid diluents such as water, xylene, toluene, dimethylsulfoxide, dimethyl formamide, acetonitrile, and alcohol;
emulsifiers, dispersing agents and spreaders. The concentration of the active ingredient in the selective insecticidal composition is usually 5 to 80 wt.% in the case of the oily concentrates; ;
from 0.5 to 30 wt.% fo~ dusts; and from 5 to 60 wt.% for wettable powders. It is also possible to include other agricultural ingredients such as the other insecticides, miticides, plant growth regulators. Synergistic effects are sometimes found.
The selective insecticides of the present invention are effective for inhibiting various injurious insects and they are usually applied at a concentration of the active ingredients of from 5 to ~10,000 ppm preferably 20 to 2,000 ppm. When the active ingredient of the present invention is applied to noxious insects in water the composition having said concentration can be applied to inhibit them, whereby the concentration of the active ingredient in water can be lower than said concentration.
` The compounds of the present invention have an excellent selective insecticidal effect as will be clearly seen from the following.
Experiment 1 The active ingredients were respectively dispersed in water to prepare dispersions having specified concentrations.
.
~ 10792~35 Cabbage leaves were dipped into the dispersions for about 10 seconds taken out and dried under an air flow.
A piece of moistened filter paper was put on each Petri dish (diameter 9 cm), the dried leaves of cabbage were put on the filter paper and larvae of the diamondback moth in 2nd or 3rd instar were placed thereon. The Petri dishes were covered and kept in constant temperature at 28C with lighting. After 8 days from the treatment with the dispersion, the dead larvae were measured and the mortality rates were calculated by the f~llowing equation:
Mortality rate = dead larvae x 100 total larvae ~ ' ; 20 Table 1:
Compoun~ (conccntration) Compoun~ ~lortality rate (~O) No.2()0 ppm100 p~m o. (concent ]~)() ppm 1 100 100 20 100 l00_ -2 100 10~ 21 1()() l()() 3 100 100 22 100 100 :
_ 4 100 100 23 100 10n . 100 100 24 100 ~ . 100 .~ , .....
lV 6 100 100 25 100 100 7 100 80 2~ 100 100 'i ; 8 1()0 100 27 10n ]()n _ , 9 10() 100 28 100 100 .
]00 60 3~. lno ; ll 100 80 1 3~ 1~0 .100 . ~ .
l 12 100 100 3~ 100 1()0 l . ....
13 100 100 ~5 1n0 lP0 ~
.
14 100 100 3~i 100 100 .~, .
~' 15. 100 100 38 100 1~0 16 100 100 3() 100 1()0 ,, .
. 17 1()0 1~0 ~l() ln0 100 . 18 100 100 41 100 100 ! 19 80 60 . .
~ Experiment 2 ¦ On radish young seedlings grown in unglazed pots, adults ¦ of diamondback moth were placed and kept for 24 hours to blow ova. One day later, aqueous dispersions of the active ingre-dients (500 ppm) were respectively sprayed on the young seedlings ~ 30 to fall as dr~ps of the dispersion and the seed~ings were dried ¦ and kept in glass greenhouse. After 10 days from the treatment ¦ with the dispersion, the dead larvae were measured and the .. ..
`--- 107928~
mortality rates were calculated by the equation Mortality rate = dead larvae x lO0.
total hatched larvae ~:
The results are shown in Table 2.
Table 2 .~ .
. . . . . -i Compound No. Mortality rate (~) . _. ... _ ~ 2 80 .
~- lO 4 lO0 .3~ . _ ._ .~ _ 6 100 . ' .
Experiment 3 ...
About 20 cc of germinated rice seeds were put into cups :
(diameter : 9 cm, height : 3 cm) to grow. When they grew to : seedlings having a height of l to 2 cm, aqueous dispersions at specified concentrations were respectively sprayed at a rate of : 2cc per cup and dried. Larvae of the rice stem borer (just hatchedJ
were then fed and the cups were covered. After lO days from the treatment with the dispersion, the dead larvae were measured and 20~
the mortality rates were calculated by the equation of Experiment l. The results are shown in Table 3.
Table 3 Compound~~1Orta1~ity rate (~) ~: N (concentr~tion) . o. . 200 ppm l()0 ppm--2 100 lO0 4 lO0 lO0
Example 4 Preparation of N-(2-methylbenzoyl)N'-[4-(5-trifluoro-methyl-pyridyl-2-oxy) phenyl] urea A solution was prepared by dissolving 0.5 g of 4-(S-trifluoromethylpyridyl-2-oxy) aniline in 20 ml of toluene. A
solution prepared by dissolving 0.32 g of 2-methylbenzoyl isocyanate in 20 ml of toluene was added dropwise to the former solution with stirring and the reaction was carried out at room temperature for 1 hour. After the reaction, the reaction mixture was cooled, the precipitate was filtered and washed with hexane and then recrystallized from ethanol to obtain 0.3 g of N-(2-methylbenzoyl) N'-[4-(5-trifluoromethylpyridyl-2-oxy) phenyl] urea (m.p. 140 to 142C).
Most of the conventional insecticides have a rapid effect of neutrotoxicity and contact toxicity. However, the compounds of the present invention have a delayed effect, the compounds affecting molting (ecdysis) and metamorphosis of specific insects which orally take in the compound in their feed or water whereby the death of the specific insects is caused.
The compounds of the present invention have remarkable insecticidal effect on larvae of Lepidoptera, Coleoptera, Hymeno-ptera and Diptera, for example, larvae of the following insects:
diamondback moth (Plutella xylostella), common white (Pieris rape crucivora), cabbage armyworm (Mamesta brassicae), cabbage looper tPlusia nigrisigma), tobacco cutworm (Prodenia litura), smoller citrus dog (Papilio xuthus~, small blackish cochlid (Seopelodes contracta), fall webworm (hyphantria cunea), gypsy moth (Lymantria dispar), rice stem borer (Chilo suppressalis), bollworm (Heliothis zea), tobacco budworm tHeliothis virescens), bollweevil (Anthonomus grandis), confused flour beetle (Tribolium -confusum), colorado potato bettle (Leptinotarsa decemlineata), sawfly tNeurotoma irdescens), Culex mosquito (Culex pipiens pallens), and mosquito (Culex pipiens molestus).
The compounds of the present invention do not sub-stantially have an insecticidal effect on adults~ are ineffective or natural enemies such as predatory insects and have a low toxicity in animals.
. .
When the compounds are used as active ingredients in the insecticidal composition, it is possible to prepare various forms of the compositions such as dusts, wettable powders, emul-sifiable concentrates, invert emulsions, oil solutions, and aerosol preparations, with adjuvants for agricultural use. The -~
compositions can be used with or witout dilution in suitable concentrations.
Suitable adjuvants include powdery carriers such as talc, kaolin, bentonite, diatomaceous earth, silicon dioxide, clay and starch; liquid diluents such as water, xylene, toluene, dimethylsulfoxide, dimethyl formamide, acetonitrile, and alcohol;
emulsifiers, dispersing agents and spreaders. The concentration of the active ingredient in the selective insecticidal composition is usually 5 to 80 wt.% in the case of the oily concentrates; ;
from 0.5 to 30 wt.% fo~ dusts; and from 5 to 60 wt.% for wettable powders. It is also possible to include other agricultural ingredients such as the other insecticides, miticides, plant growth regulators. Synergistic effects are sometimes found.
The selective insecticides of the present invention are effective for inhibiting various injurious insects and they are usually applied at a concentration of the active ingredients of from 5 to ~10,000 ppm preferably 20 to 2,000 ppm. When the active ingredient of the present invention is applied to noxious insects in water the composition having said concentration can be applied to inhibit them, whereby the concentration of the active ingredient in water can be lower than said concentration.
` The compounds of the present invention have an excellent selective insecticidal effect as will be clearly seen from the following.
Experiment 1 The active ingredients were respectively dispersed in water to prepare dispersions having specified concentrations.
.
~ 10792~35 Cabbage leaves were dipped into the dispersions for about 10 seconds taken out and dried under an air flow.
A piece of moistened filter paper was put on each Petri dish (diameter 9 cm), the dried leaves of cabbage were put on the filter paper and larvae of the diamondback moth in 2nd or 3rd instar were placed thereon. The Petri dishes were covered and kept in constant temperature at 28C with lighting. After 8 days from the treatment with the dispersion, the dead larvae were measured and the mortality rates were calculated by the f~llowing equation:
Mortality rate = dead larvae x 100 total larvae ~ ' ; 20 Table 1:
Compoun~ (conccntration) Compoun~ ~lortality rate (~O) No.2()0 ppm100 p~m o. (concent ]~)() ppm 1 100 100 20 100 l00_ -2 100 10~ 21 1()() l()() 3 100 100 22 100 100 :
_ 4 100 100 23 100 10n . 100 100 24 100 ~ . 100 .~ , .....
lV 6 100 100 25 100 100 7 100 80 2~ 100 100 'i ; 8 1()0 100 27 10n ]()n _ , 9 10() 100 28 100 100 .
]00 60 3~. lno ; ll 100 80 1 3~ 1~0 .100 . ~ .
l 12 100 100 3~ 100 1()0 l . ....
13 100 100 ~5 1n0 lP0 ~
.
14 100 100 3~i 100 100 .~, .
~' 15. 100 100 38 100 1~0 16 100 100 3() 100 1()0 ,, .
. 17 1()0 1~0 ~l() ln0 100 . 18 100 100 41 100 100 ! 19 80 60 . .
~ Experiment 2 ¦ On radish young seedlings grown in unglazed pots, adults ¦ of diamondback moth were placed and kept for 24 hours to blow ova. One day later, aqueous dispersions of the active ingre-dients (500 ppm) were respectively sprayed on the young seedlings ~ 30 to fall as dr~ps of the dispersion and the seed~ings were dried ¦ and kept in glass greenhouse. After 10 days from the treatment ¦ with the dispersion, the dead larvae were measured and the .. ..
`--- 107928~
mortality rates were calculated by the equation Mortality rate = dead larvae x lO0.
total hatched larvae ~:
The results are shown in Table 2.
Table 2 .~ .
. . . . . -i Compound No. Mortality rate (~) . _. ... _ ~ 2 80 .
~- lO 4 lO0 .3~ . _ ._ .~ _ 6 100 . ' .
Experiment 3 ...
About 20 cc of germinated rice seeds were put into cups :
(diameter : 9 cm, height : 3 cm) to grow. When they grew to : seedlings having a height of l to 2 cm, aqueous dispersions at specified concentrations were respectively sprayed at a rate of : 2cc per cup and dried. Larvae of the rice stem borer (just hatchedJ
were then fed and the cups were covered. After lO days from the treatment with the dispersion, the dead larvae were measured and 20~
the mortality rates were calculated by the equation of Experiment l. The results are shown in Table 3.
Table 3 Compound~~1Orta1~ity rate (~) ~: N (concentr~tion) . o. . 200 ppm l()0 ppm--2 100 lO0 4 lO0 lO0
6 . 100 100 1 1 100 1()0 ,. .
12 lO0 100 23 100 ]()0 Y . 24 .. _ _ _ ~ 1079Z8S
Experiment 4 In a cup (diameter of 9 cm; hei~ht of 3 cm), about 20 cc of emerged rice seeds were bred to grow to young seedlings having height of 1.5 to 2 cm and then, 2 cc of each composition having 400 ppm a concentration of each active ingredient was sprayed per cup, and dried, and larvae of the rice stem borer in 3rd instar were fed thereon and Petri dish was co~ered. After 10 days from the treatment, the dead larvae were measured and the mortality rates were calculated in accordance with the method of Experiment l. The results are shown in Table 4.
Table 4: ~-,, .
Mortality rate Compound No. (%) ~,, .~
.
Experiment 5 N-(2-chlorobenzoyl)N'-[4-(3,5-dibromopyridyl-2-oxy)phenyl]
urea (Compound No. 3) was used to prepare the aqueous dispersions at specified concentrations. The effects of the dispersions to various insects were tested. The mortality rates after lO days from the treatments were obtained in accordance with the process of Experiment l.
The results are shown in Table 5.
' ,.
- 107g28`5 -:
,~ ` , ~.
Tab1e 5:
f Insects TreatmentConcentration rate . .
.~ cabbage armyworm: cabbage leaf 50 ,~ 2nd instar larvac di~ing 100 (Lcpidoptera) .s, ._. .__ _ confused flour beetle: wheat flour Znd larval instar blending 200 100 larvae (Coleoptera) .~ 10 1 sp. of sawfly cherry ~ranch ~ :
3rd instar larvae spraying 250 lO0 (llymenoptera) :'1 t Experiment 6 Leaves of azalea were dipped in an aqueous solution of ., ,.~ each active ingredient (50 ppm) for lO seconds, and they were ' dried in air and charged in a wide mouth glass bottle, and larvae "'I
. of gypsy moth in 2nd instar were fed thereon. The mouth of the ¦ bottle was covered with a gauze and was kept in a thermostat constant temperature bath with lighting at 28C. After 6 days from the treatment, the dead larvae were measured and the mortality rates were calculated in accordance with the method of Experiment ! 1 The results are shown in Table 6.
3~
:j ,, Table 6 , . Compound No. ~lortality rate :~
, .
100 :.
._ ._ _ . '--:
i 12 100 .:
~ -; 20 100 -: --i~ , 11 100 ~, .
I 23 ~
10() .
27 1-00 . -:-'' I00 : -~:
. . .. 1 0 0 Experiment 7 Cabbage leaves were dipped in an aqueous solution of each ~ active ingredient (50 ppm) for lO seconds, and they were dried in ~ ~ 20~ air. A wet filter paper was disposed in each Petri dish (diameter of 9 cm) and each leaf was put on it and larvae of the tabacco ~ cutworm in 2nd or 3rd instar were fed and the Petri dish was : .~ covered and was kept in a thermostat constant temperature bath with light at 28C. After 7 days from the treatment, the dead larvae were measured and the mortality rates were calculated in , , .
: . accordance with the method of Experiment l. The results are shown ~- in Table 7. - . .
~.:
~:
. - 14 ~
~" ~
--" 1079Z85 Tab3e 7 Compound No. ~ortality rate . 3 100 : -. 4 100 -::
.. .
_ : 1 Z 100 ~:
~ 10 , 21 100 1~ :
. . 24 100 ~' .~ 25 300 , ,, .
100 :~ -: 39 100 ,, ,~
Experiment 8 In each cup (diameter of 9 cm), about 250 ml of an aqueous solution of each active ingredient (100 ppb) was charged, the larvae of mosquito (Culex pipiens molestus) in 3rd instar were charged and the cup was covered and was kept in a thermostat constant temperature bath with lighting at 28C. After 10 days from the treatment, the dead larvae were measured and the mortality :~ rates were calculated in accordance with the method of Experiment : 1. The results are shown in Table 8.
~ ~- 1079285 Table 8:
Mortality ratc ~ Compound No. (%) ,, :
i 3 100 ,~, . 1()0 ~., 1 1 1 00 ~, , i 12 100 1()~
... :,..
~ 23 100 "j~ 24 100 .~
`~ 39 100 ' , .,~
Composition 1 (a) N-(2-chlorobenzoyl)N'-[3-chloro-4-(3,5-dichloropyridyl-2-oxy)phenyl~urea 20 wt. parts (b) Dimethyl sulfoxide 70 wt. parts (c) Polyoxyethylenealkylphenyl ether 10 wt. parts The components were uniformly blended to dissolve the ingredient to prepare an emulsifiable concentrate.
~; Composition 2 ~
(a) N-(2-chlorobenzoyl)Nl[4-(3,5-dichloropyridyl-2-oxy) -phenyl]urea 5 wt. parts -(b) Talc 92 wt. parts :
(c) Sodium naphthalene sulfonate ¦ formaldehyde condensate 3 wt. parts - The mixture was pulverized to uniformly mix them to prepare a dust.
Composition 3 .
(a) N-(2,6-dichlorobenzoyl)N'-14-(3,5-dichloropyridyl-2-oxy)phenyl]urea 50 wt. parts tb) Jeeklite (fine divided clay) 45 wt. parts (c) Sodium ligninsulfonate 5 wt. parts The components were pulverized to uniformly mix them to prepare a wettable powder.
Composition 4 (a) N-(2,6-difluorobenzoyl)N'-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)phenyl]urea 20 wt. parts (b) N,N-dimethylformamide 70 wt. parts (c) Polyoxyethylenealkylphenyl ether 10 wt. parts The components were uniformly blended to dissolve the ingredient to prepare an emulsifiable concentrate.
Composition 5 (a) N-(2-chlorobenzoyl)N'-[3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridyl-2-oxy)phenyl3urea 5 wt. parts (b) Talc 95 wt. parts The mixture was pulverized to uniformly mix them to prepare a dust.
Composition 6 la) N-(2-methylbenzoyl)N'-[3-chloro-4-(3-chloro-5-trifluoro-methyl-pyridyl-2-oxy)phenyl~urea 5 wt. parts (b) Talc 95 wt. parts The mixture was pulverized to uniformly mix them to prepare a dust.
12 lO0 100 23 100 ]()0 Y . 24 .. _ _ _ ~ 1079Z8S
Experiment 4 In a cup (diameter of 9 cm; hei~ht of 3 cm), about 20 cc of emerged rice seeds were bred to grow to young seedlings having height of 1.5 to 2 cm and then, 2 cc of each composition having 400 ppm a concentration of each active ingredient was sprayed per cup, and dried, and larvae of the rice stem borer in 3rd instar were fed thereon and Petri dish was co~ered. After 10 days from the treatment, the dead larvae were measured and the mortality rates were calculated in accordance with the method of Experiment l. The results are shown in Table 4.
Table 4: ~-,, .
Mortality rate Compound No. (%) ~,, .~
.
Experiment 5 N-(2-chlorobenzoyl)N'-[4-(3,5-dibromopyridyl-2-oxy)phenyl]
urea (Compound No. 3) was used to prepare the aqueous dispersions at specified concentrations. The effects of the dispersions to various insects were tested. The mortality rates after lO days from the treatments were obtained in accordance with the process of Experiment l.
The results are shown in Table 5.
' ,.
- 107g28`5 -:
,~ ` , ~.
Tab1e 5:
f Insects TreatmentConcentration rate . .
.~ cabbage armyworm: cabbage leaf 50 ,~ 2nd instar larvac di~ing 100 (Lcpidoptera) .s, ._. .__ _ confused flour beetle: wheat flour Znd larval instar blending 200 100 larvae (Coleoptera) .~ 10 1 sp. of sawfly cherry ~ranch ~ :
3rd instar larvae spraying 250 lO0 (llymenoptera) :'1 t Experiment 6 Leaves of azalea were dipped in an aqueous solution of ., ,.~ each active ingredient (50 ppm) for lO seconds, and they were ' dried in air and charged in a wide mouth glass bottle, and larvae "'I
. of gypsy moth in 2nd instar were fed thereon. The mouth of the ¦ bottle was covered with a gauze and was kept in a thermostat constant temperature bath with lighting at 28C. After 6 days from the treatment, the dead larvae were measured and the mortality rates were calculated in accordance with the method of Experiment ! 1 The results are shown in Table 6.
3~
:j ,, Table 6 , . Compound No. ~lortality rate :~
, .
100 :.
._ ._ _ . '--:
i 12 100 .:
~ -; 20 100 -: --i~ , 11 100 ~, .
I 23 ~
10() .
27 1-00 . -:-'' I00 : -~:
. . .. 1 0 0 Experiment 7 Cabbage leaves were dipped in an aqueous solution of each ~ active ingredient (50 ppm) for lO seconds, and they were dried in ~ ~ 20~ air. A wet filter paper was disposed in each Petri dish (diameter of 9 cm) and each leaf was put on it and larvae of the tabacco ~ cutworm in 2nd or 3rd instar were fed and the Petri dish was : .~ covered and was kept in a thermostat constant temperature bath with light at 28C. After 7 days from the treatment, the dead larvae were measured and the mortality rates were calculated in , , .
: . accordance with the method of Experiment l. The results are shown ~- in Table 7. - . .
~.:
~:
. - 14 ~
~" ~
--" 1079Z85 Tab3e 7 Compound No. ~ortality rate . 3 100 : -. 4 100 -::
.. .
_ : 1 Z 100 ~:
~ 10 , 21 100 1~ :
. . 24 100 ~' .~ 25 300 , ,, .
100 :~ -: 39 100 ,, ,~
Experiment 8 In each cup (diameter of 9 cm), about 250 ml of an aqueous solution of each active ingredient (100 ppb) was charged, the larvae of mosquito (Culex pipiens molestus) in 3rd instar were charged and the cup was covered and was kept in a thermostat constant temperature bath with lighting at 28C. After 10 days from the treatment, the dead larvae were measured and the mortality :~ rates were calculated in accordance with the method of Experiment : 1. The results are shown in Table 8.
~ ~- 1079285 Table 8:
Mortality ratc ~ Compound No. (%) ,, :
i 3 100 ,~, . 1()0 ~., 1 1 1 00 ~, , i 12 100 1()~
... :,..
~ 23 100 "j~ 24 100 .~
`~ 39 100 ' , .,~
Composition 1 (a) N-(2-chlorobenzoyl)N'-[3-chloro-4-(3,5-dichloropyridyl-2-oxy)phenyl~urea 20 wt. parts (b) Dimethyl sulfoxide 70 wt. parts (c) Polyoxyethylenealkylphenyl ether 10 wt. parts The components were uniformly blended to dissolve the ingredient to prepare an emulsifiable concentrate.
~; Composition 2 ~
(a) N-(2-chlorobenzoyl)Nl[4-(3,5-dichloropyridyl-2-oxy) -phenyl]urea 5 wt. parts -(b) Talc 92 wt. parts :
(c) Sodium naphthalene sulfonate ¦ formaldehyde condensate 3 wt. parts - The mixture was pulverized to uniformly mix them to prepare a dust.
Composition 3 .
(a) N-(2,6-dichlorobenzoyl)N'-14-(3,5-dichloropyridyl-2-oxy)phenyl]urea 50 wt. parts tb) Jeeklite (fine divided clay) 45 wt. parts (c) Sodium ligninsulfonate 5 wt. parts The components were pulverized to uniformly mix them to prepare a wettable powder.
Composition 4 (a) N-(2,6-difluorobenzoyl)N'-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy)phenyl]urea 20 wt. parts (b) N,N-dimethylformamide 70 wt. parts (c) Polyoxyethylenealkylphenyl ether 10 wt. parts The components were uniformly blended to dissolve the ingredient to prepare an emulsifiable concentrate.
Composition 5 (a) N-(2-chlorobenzoyl)N'-[3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridyl-2-oxy)phenyl3urea 5 wt. parts (b) Talc 95 wt. parts The mixture was pulverized to uniformly mix them to prepare a dust.
Composition 6 la) N-(2-methylbenzoyl)N'-[3-chloro-4-(3-chloro-5-trifluoro-methyl-pyridyl-2-oxy)phenyl~urea 5 wt. parts (b) Talc 95 wt. parts The mixture was pulverized to uniformly mix them to prepare a dust.
Claims (38)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. N-benzoyl N'-pyridyloxy phenyl urea having the formula (I) wherein X1 represents a halogen atom or methyl group; X2 repre-sents hydrogen or halogen atom; X3 and X4 respectively represent hydrogen or halogen atom; X5 represents hydrogen or halogen atom;
X6 represents a halogen atom or nitro or trifluoromethyl group.
X6 represents a halogen atom or nitro or trifluoromethyl group.
2. A urea according to Claim 1 which has the formula wherein X7 and X8 respectively represent hydrogen or halogen atom;
X9 represents hydrogen or halogen atom; X10 represents a halogen atom or trifluoromethyl group.
X9 represents hydrogen or halogen atom; X10 represents a halogen atom or trifluoromethyl group.
3. A compound as claimed in claim 1 which is N-(2-chlorobenzoyl) N'-[4-(3,5-dibromopyridyl-2-oxy)phenyl]urea.
4. A compound as claimed in claim 1 which is N-(2-chlorobenzoyl)N'-[4-(3,5-dichloropyridyl-2-oxy)phenyl]urea.
5. A compound as claimed in claim 1 which is N-(2-chlorobenzoyl)N'-[3-chloro-4-(3,5-dichloropyridyl--2-oxy)phenyl]
urea.
urea.
6. A urea according to Claim 2 which has the formula wherein X7, X8 and X9 are defined in Claim 2.
7. A compound as claimed in claim 1 which is N-(2-chlorobenzoyl)N'-[4-(3-chloro-5-trifluoromethyl-pyridyl-2-oxy) phenyl]urea.
8. A compound as claimed in claim 1 which is N-(2-chlorobenzoyl)N'-[3,5-dichloro-4-(5-trifluoromethyylpyridyl-2-oxy)phenyl]urea.
9. A compound as claimed in claim 1 which is N-(2-chlorobenzoyl)N'-[3,5-dichloro-4-(3-chloro-5-triflluoromethyl-pyridyl-2-oxy)phenyl]urea.
10. A compound as claimed in claim 1 which is N-(2-chlorobenzoyl)N'-[3-chloro-4-(3-chloro-5-trifluoroomethylpyridyl-2-oxy)phenyl]urea.
11. A urea according to Claim 1 which has the formula wherein X7 and X8 respectively represent hydrogen or halogen atom;
X9 represents hydrogen or halogen atom; X10 represents a halogen atom or trifluoromethyl group.
X9 represents hydrogen or halogen atom; X10 represents a halogen atom or trifluoromethyl group.
12. A compound as claimed in claim 1 which is N-(2,6-difluorobenzoyl)N'-[4-(3,5-dichloropyridyl-2-oxy)phenyl] urea.
13. A compound as claimed in claim 1 which is N-(2,6-difluorobenzoyl)N'-[3-chloro-4-(3,5-dichloropyridyl-2-oxy)phenyl urea.
14. A urea according to Claim 11 which has the formula wherein X7, X8 and X9 are defined in Claim 11.
15. A compound as claimed in claim 1 which is N-(2,6-difluorobenzoyl)N'-[4-(3-chloro-5-trifluoromethylppyridyl-2-oxy) phenyl]urea.
16. A compound as claimed in claim 1 which is N-(2,6-difluorobenzoyl)N'-[3,5-dichloro-4-(5-trifluoromethylpyridyl-2-oxy)phenyl]urea.
17. A compound as claimed in claim 1 which is N-(2,6-difluorobenzoyl)N'-[3,5-dichloro-4-(3-chloro-5-triifluoromethyl-pyridyl-2-oxy)phenyl] urea.
18. A compound as claimed in claim 1 which is N-(2,6-difluorobenzoyl)N'-[3-chloro-4-(3-chloro-5-trifluooromethylpyridyl-2-oxy)phenyl] urea.
19. A urea according to Claim 1 which has the formula wherein X7 and X8 respectively represent hydrogen or halogen atom;
X9 represents hydrogen or halogen atom; X10 represents a halogen atom or trifluoromethyl group.
X9 represents hydrogen or halogen atom; X10 represents a halogen atom or trifluoromethyl group.
20. A compound as claimed in claim 1 which is N-(2-methylbenzoyl)N'-[3-chloro-4-(3,5-dichloropyridyl-2-oxy)phenyl]
urea.
urea.
21. A urea according to Claim 19 which has the formula wherein X7, X8 and X9 are defined in Claim 19.
22. A compound as claimed in claim 1 which is N-(2-methylbenzoyl)N'-[3-chloro-4-(5-trifluoromethylpyrridyl-2-oxy)phenyl]
urea.
urea.
23. A compound as claimed in claim 1 which is N-(2-methylbenzoyl)N'-(3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridyl-2-oxy)phenyl] urea.
24. A compound as claimed in claim 1 which is N-(2-methylbenzoyl)N'-[4-(3-chloro-5-trifluoromethylpyrridyl-2-oxy) phenyl] urea.
25. A compound as claimed in claim 1 which is N-(2-methylbenzoyl)N'-13-chloro-4-(3-chloro-5-trifluoroomethylpyridyl-2-oxy) phenyl] urea.
26. A process for producing N-benzoyl N'-pyridyloxy phenyl urea which comprises reacting a compound having the formula wherein X1 represents a halogen atom or methyl group; X2 represents hydrogen or halogen atom; and R1 represents amino or isocyanate group; with a compound having the formula wherein X3 and X4 respectively represent hydrogen or halogen atom;
X5 represents hydrogen or halogen atom; X6 represents a halogen atom, nitro or trifluoromethyl group; R2 represents amino or isocya-nate group and R2 is amino group in the case that R1 is isocyanate group, R2 is isocyanate group in the case that R1 is amino group.
X5 represents hydrogen or halogen atom; X6 represents a halogen atom, nitro or trifluoromethyl group; R2 represents amino or isocya-nate group and R2 is amino group in the case that R1 is isocyanate group, R2 is isocyanate group in the case that R1 is amino group.
27. A process according to Claim 26 wherein the reaction is carried out in a solvent at a temperature from room temperature to the refluxing temperature.
28. A process according to Claim 26 which comprises reacting benzoyl isocyanate having the formula with pyridyloxy aniline having the formula wherein X1, X2, X3, X4, X5 and X6 are defined in Claim 26.
29. A process as claimed in claim 26 which comprises reacting benzamide having the formula with pyridyloxy phenyl isocyanate having the formula wherein X1, X2, X3, X4, X5 and X6 are defined in Claim 26.
30. A method of selectively killing injurious insects which comprises applying thereto a urea as claimed in claim 1, 2 or 3.
31. A method of selectively killing injurious insects which comprises applying thereto a urea as claimed in claim 4, 5 or 6.
32. A method of selectively killing injurious insects which comprises applying thereto a urea as claimed in claim 7, 8 or 9.
33. A method of selectively killing injurious insects which comprises applying thereto a urea as claimed in claim 10, 11 or 12.
34. A method of selectively killing injurious insects which comprises applying thereto a urea as claimed in claim 13, 14 or 15.
35. A method of selectively killing injurious insects which comprises applying thereot a urea as claimed in claim 16, 17 or 18.
36. A method of selectively killing injurious insects which comprises applying thereto a urea as claimed in claim 19, 20 or 21.
37. A method of selectively killing injurious insects which comprises applying thereto a urea as claimed in claim 22, 23 or 24.
38. A method of selectively killing injurious insects which comprises applying thereto a urea as claimed in claim 25.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53012215A JPS5823871B2 (en) | 1978-02-06 | 1978-02-06 | N↓-pyridyloxyphenylurea compounds and insecticides containing them |
| JP2982878A JPS54125677A (en) | 1978-03-17 | 1978-03-17 | N-benzoyl-n'-pyridyloxyphenylurea compound,its preparation,and insecticide containing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1079285A true CA1079285A (en) | 1980-06-10 |
Family
ID=26347785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA301,811A Expired CA1079285A (en) | 1978-02-06 | 1978-04-24 | N-benzoyl n'-pyridyloxy phenylurea and preparation thereof |
Country Status (7)
| Country | Link |
|---|---|
| CA (1) | CA1079285A (en) |
| DK (1) | DK155664C (en) |
| FI (1) | FI70211C (en) |
| NL (1) | NL189293C (en) |
| NO (1) | NO149429C (en) |
| PH (1) | PH16906A (en) |
| SE (1) | SE430249B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4904668A (en) * | 1986-09-29 | 1990-02-27 | Ishihara Sangyo Kaisha Ltd. | Benzoyl urea compound |
| US8828907B2 (en) | 2009-03-25 | 2014-09-09 | Bayer Cropscience Ag | Active ingredient combinations having insecticidal and acaricidal properties |
| CN105010371A (en) * | 2015-02-12 | 2015-11-04 | 四川利尔作物科学有限公司 | Insecticidal composition and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK47476C (en) * | 1930-07-21 | 1933-06-26 | Aga Baltic Radio Ab | Device by Radio Receivers. |
| US3931201A (en) * | 1974-01-22 | 1976-01-06 | The Dow Chemical Company | Substituted pyridinyloxy(thio)phenyl -acetamides, -ureas and urea derivatives |
| GB1460419A (en) * | 1975-02-06 | 1977-01-06 | Bayer Ag | Benzoylureido-diphenyl ethers and their use as insecticides |
-
1978
- 1978-04-21 NL NLAANVRAGE7804264,A patent/NL189293C/en not_active IP Right Cessation
- 1978-04-24 CA CA301,811A patent/CA1079285A/en not_active Expired
- 1978-04-27 FI FI781315A patent/FI70211C/en not_active IP Right Cessation
- 1978-04-28 NO NO781516A patent/NO149429C/en unknown
- 1978-04-28 PH PH21081A patent/PH16906A/en unknown
- 1978-04-28 SE SE7804972A patent/SE430249B/en not_active IP Right Cessation
- 1978-04-28 DK DK187078A patent/DK155664C/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4904668A (en) * | 1986-09-29 | 1990-02-27 | Ishihara Sangyo Kaisha Ltd. | Benzoyl urea compound |
| US8828907B2 (en) | 2009-03-25 | 2014-09-09 | Bayer Cropscience Ag | Active ingredient combinations having insecticidal and acaricidal properties |
| CN105010371A (en) * | 2015-02-12 | 2015-11-04 | 四川利尔作物科学有限公司 | Insecticidal composition and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| NO781516L (en) | 1979-08-07 |
| DK187078A (en) | 1979-08-07 |
| SE430249B (en) | 1983-10-31 |
| NL189293B (en) | 1992-10-01 |
| NL7804264A (en) | 1979-08-08 |
| DK155664B (en) | 1989-05-01 |
| PH16906A (en) | 1984-04-10 |
| SE7804972L (en) | 1979-08-07 |
| NO149429C (en) | 1984-04-25 |
| DK155664C (en) | 1989-10-09 |
| FI70211B (en) | 1986-02-28 |
| NO149429B (en) | 1984-01-09 |
| FI70211C (en) | 1986-09-15 |
| NL189293C (en) | 1993-03-01 |
| FI781315A (en) | 1979-08-07 |
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