JPS63222154A - N-phenyl-n'-benzoylurea compound and insecticide containing said compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (A is CH or N; X is H or halogen; Y1, Y2, Y3 and Y4 are H, halogen, lower alkyl, etc.; Z1 and Z2 are H or halogen; R1 and R2 are H lower alkyl, etc.). EXAMPLE:N-[4-(2-chloro-4-trifluoromethylphenoxyl)-2,3-difluorophenyl]- N'-(2,6-di fluorobenzoyl)-N-methylurea. USE:Insecticide. PREPARATION:A compound of formula I (R1 is lower alkyl and R2 is H) can be produced by reacting an aniline compound of formula II (R1' is lower alkyl) with a benzoylisocyanate compound of formula III at -10-100 deg.C for 0.1-24hr.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to novel N-phenyl-No-benzoylurea compounds, insecticides containing them, and methods for producing them.

(Prior art and background to the present invention) Benzoyl urea compounds are disclosed in, for example, Japanese Patent Publication No. 4 (i-
No. 6550, etc., it is known that it is useful as an active ingredient of insecticides. The chemical structure is widely shown in the general formula in the above literature, but there is a benzoyl group on one nitrogen atom and a benzoyl group on the other nitrogen atom in the two nitrogen atoms that make up the urea part of the chemical structure. Each has a specific phenyl group, and one or both of the nitrogen groups.

What has a lower alkyl group on its atom, ie, certain N-phenyl-No-benzoylureas? llq compound'1
is not specifically disclosed. The present invention provides that a specific N-phenyl-No-benzoyl urea compound exhibits a high insecticidal effect and is easy to decompose (and is safe for aquatic seedling-raising organisms), making it an excellent insecticide. Based on the knowledge that it has certain characteristics.

(Disclosure of the Invention) The present invention relates to N-phenyl-
The present invention relates to No-benzoyl urea compounds, insecticides containing them, and methods for producing them. They also include salts with basic substances.

General formula: [In the formula, A is -(, n = u or a nitrogen atom, X is a hydrogen atom or a halogen atom, Y,, Y,,'Y3 and Y4 are a hydrogen atom, a halogen atom, a lower is an alkyl group or a -COzRs group (in the formula, R1 is a hydrogen atom or a lower alkyl group), 2. and Z! are a hydrogen atom or a halogen atom, and R8 and R8 are a hydrogen atom or a lower alkyl group; , provided that at least one of Zl and Z2 is a halogen atom, and at least one of R1 and R8 is a lower alkyl group] In the general formula (1), YI-Y*, Yx, Y4, R
The alkyl groups represented by +, Rz and R1 include methyl group, ethyl group, n-propyl group, isopropyl convex,
Examples include lower alkyl groups having 1 to 6 carbon atoms such as n-butyl group, isobutyl i, and sec-butyl group. Also, X
-Y +, Y! , Y3, Y4, Zl and Z2 include fluorine atom, chlorine atom, bromine atom and iodine atom.

The compound represented by the general formula (1) can be produced, for example, by the following method.

(A) An aniline compound represented by the general formula (wherein A-X1'j'+ SYz, Ya and Y4 are as described above, and R" is a lower alkyl group) and the general formula: benzoyl isocyanate compound represented by Z, Z, and Z2 are as described above) = 10 to 10
The reaction was carried out at 0°C for 0.1 to 24 hours to form a compound of the general formula (n) (wherein A, XSY+, Yz, Ya -Y4, R'
l, Zl and Zt are as described above)
- A method for producing a phenyl-N'-benzoyl urea compound.

CB) An isocyanate compound represented by the general formula: (wherein A, X, Y+, Yt 1Y2, and Y4 are as described above) and the general formula: , R12 is a lower alkyl group) at -10 to 100°C for 0.1 to 24 hours. Ya, R
'2, Zl and Z2 are as described above)
How to build A.

[C]

General formula (wherein, 8, X, Y, , Y, Y, Y4, Zl and Z
2 is as described above), a compound represented by the general formula (n) or a compound represented by the general formula (nl) and an alkyl halide at -10 to 100°C general formula % formula % (wherein A, ,,Y+,YzSYz,Y4,Z+-Z
z, R'l and R'z are as described above).

The reactions (A), (I3) and (C) are carried out in the presence of an acid acceptor, if necessary. As an acid acceptor, n-
Lithium compounds such as butyllithium, lert-butyllithium, phenyllithium, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkali metals such as sodium, organic compounds such as triethylamine, pyridine, etc. Examples include bases.

Furthermore, these reactions are carried out in the presence of a solvent, if necessary. Examples of solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; cyclic or acyclic aliphatic hydrocarbons such as hexane and cyclohexane; and ethers such as diethyl ether, methyl ethyl ether, dioxane, and tetrahydrofuran. Examples include aprotic polar solvents such as nitriles such as niacetonitrile, propionitrile, and acrylonitrile, dimethylpolamide, dimethyl sulfoxide, sulporan, and hexamethylphosphoric triamide.

Next, specific production examples of the compounds of the present invention will be described.

Production Example I N (4(2-chloro-4-trifluoromethylphenol-1-cy)-2,3-difluorophenyl-N'
- Synthesis of (2.6-difluorobenzoyl)-N-methylurea (compound 4) (1) 2.1 g of 2.3-difluoro-4-methoxynitrobenzene was added to 80 ml of 60% hydrobromic acid. This) u suspension was heated to 90-100℃ overnight for 11 hours per night! continued.

After the reaction was completed, the reaction 1 shell was cooled, extracted with dichloromethane and water, and the organic layer was washed with saturated saline.

Then, it was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 2.3-difluoro-4-nitrophenol 1. having a melting point of 128-133°C. f33g was obtained.

(n) 2,3-difluoro- obtained in the above step (1)
1.2g of 4-nitrophenol in 40ml of ethanol! 0.05 g of 10% palladium-carbon was added to the solution dissolved in the solution, and the mixture was stirred at room temperature under a hydrogen atmosphere for 3 hours.

After the reaction was completed, the reaction solution was filtered to remove the catalyst, and the solvent was distilled off under reduced pressure to obtain 4-amino-2 as a solid.

0.89 g of 3-difluoro-phenol was obtained.

CII+) 4-amino-2 obtained in the above step C11)
.

A solution of 0.42 g of 3-difluorophenol and 0.62 g of 3,4-dichloropenzotrifluoride dissolved in 10 ml of dimethyl sulfoxide was added with 0 potassium hydroxide.
．． Added 2g. This mixture was heated to 90 to 1
The mixture was kept at 00°C and stirred for 3 hours.

After the reaction was completed, the reaction solution was cooled and extracted with ethyl acetate and water, and the organic layer was washed with saturated brine. Next, it was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the 4- 0.20 g of (2-chloro-4-trifluoromethylphenoxy)-2,3-difluoroaniline was obtained.

[1v] 4-(2-chloro-4-trifluoromethylphenoxy)-2 obtained in the above step CII [).

0.20 g of 3-difluoroaniline was added to pyridine 8 I
Cool the solution dissolved in 1 ml and add acetyl chloride 0,
10 g was added dropwise and stirred at room temperature for 1 hour.

After the reaction was completed, the reaction solution was extracted with ether and diluted hydrochloric acid, and the a-layer was washed with an aqueous sodium bicarbonate solution and then with saturated brine. Next, it was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure, and then purified by silica gel column chromatography using a developing solvent of n-hexane and ethyl acetate in a ratio of 3:2 to obtain a solid with a melting point of 146-147.
0.21 g of N-(4-(2-chloro-4-trifluoromethylphenoxy)-2,3-difluorophenyl)acetamide was obtained.

(V) Sodium hydride (60% Nujol mixture ￥!l
J> 0.05g of dimethyl sulfoxide 5r+l N
The N- (4- (2-
Ricoro-4-trifluoromethylphenoxy)-2゜3
A solution prepared by dissolving 0.20 g of difluorophenylacetamide in 5 ml of dimethyl sulfoxide was added dropwise. During the dropwise addition, the temperature of the reaction solution was maintained at 15 to 20°C. After the dropwise addition, the mixture was stirred at room temperature for 1 hour, and then 0.20 g of methyl iodide was added. 23g to 15
The mixture was added dropwise at ~20°C, and stirring was continued for 2 hours at room temperature.

After the reaction was completed, the reaction solution was extracted with ethyl acetate and water, and the first layer was washed with saturated brine.Next, it was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. Purified by silica gel column chromatography using a 1:1 developing solvent of n-hexane and ethyl acetate,
0.21 g of N-(4-(2-chloro-4-trifluoromethylphenoxy)-2,3-difluorophenyl-N-methylacetamide) was obtained as an oil.

(Vr) N-(4-(2-chloro-4-trifluoromethylphenoxy)-2,3- obtained in step (V))
difluorophenyl)-N-methylacetamide 0.2
Add 5 ml of concentrated hydrochloric acid to a solution of 1 g dissolved in 10 ml methanol.
mA was added and refluxed for 3 hours.

After the reaction was completed, the reaction solution was cooled, poured into 50 ml of a 10% aqueous potassium hydroxide solution, and extracted with dichloromethane. The organic layer was washed with water, further washed with saturated brine, and then dried over anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure and purified by silica gel column chromatography using a developing solvent of n-hexane and ethyl acetate in a ratio of 3=1 to obtain N-methyl-4 as a solid with a melting point of 37-38°C.
=(2-chloro-4-trifluoromethylphenoxy)
0.18 g of -2,3-difluoroaniline was obtained.

1 [■] N-methyl-4 obtained in the above step (Vl)
, -(2-Chloro-4-trifluoromethylphenoxy)-2,3-difluoroaniline, 0.4 g of 2,6-cyfluoropenzoyl isocyanate was added to a solution of 8 g of dioxane dissolved in 74 ml of dioxane. 2 m
A solution dissolved in A was added at room temperature, and the mixture was stirred at room temperature for 1 hour.

After the reaction was completed, the reaction solution was poured into 30 mff1 of water, extracted with ethyl acetate, and the solution was poured into 30 mff1 of water. j was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure, followed by a 3:2 mixture of n-hexane and ethyl acetate.
The resulting product was purified by silica gel column chromatography using the following developing solvent to obtain 0.26 g of the target compound as a solid with a melting point of 164-166°C.

Production Example 2 N-(4-(2-chloro-4-trifluoromethylphenoxy)-2-fluorophenyl)-N'-(2,6-
Synthesis of (difluorobenzoyl)-N-methylurea (compound 20) (1) A solution of 0.16 g of 4-(2-chloro-4-trifluoromethylphenoxy)-2-fluoroaniline dissolved in 10 mA of pyridine was cooled, To this was added dropwise 0.29 g of acetyl chloride, and the mixture was stirred at room temperature for 1 hour.

After the completion of the reaction, the reaction solution was extracted with ethyl acetate and diluted hydrochloric acid, and the organic solution was washed with an aqueous sodium bicarbonate solution, and then with saturated brine.Then, it was dried over sodium sulfate, and the solvent was distilled off under reduced pressure. , was prepared by silica gel column chromatography using a 1:1 developing solvent of n-hexane and ethyl acetate, and the melting point was 11 as a solid.
0.37 g of N-(4-(2-chloro-4-trifluoromethylphenoxy)-2-fluorophenyl)acetamide having a temperature of 7 to 118°C was obtained.

(Tl) Sodium hydride (60% Nuzidyl mixture)
The above step (r
0.37 g of N-(4-(2-chloro-4-trifluoromethylphenoxy)-2-fluorophenyl)acetamide obtained in ) was mixed with 10 m of dimethyl sulfoxide.
A solution dissolved in l was added dropwise. During the dropwise addition, the temperature of the reaction solution was maintained at 15-20°C. After stirring for 30 minutes after dropping, 0.0% methyl iodide was added. (i g was added dropwise at 15-20°C, and stirring was continued at room temperature for an additional hour.

After the reaction was completed, the reaction solution was extracted with ethyl acetate and water, and the organic layer was further washed with saturated brine. Next, it was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 0.4 g of N-(4-(2-chloro4-trifluoromethylphenoxy)-2-fluorophenyl)-N-methylacetamide as an oil. Obtained.

(III) N-(4-(2) obtained in the step (If)
-chloro-4-trifluoromethylphenoxy)-2-
Fluorophenyl)-N-methylacetamide 0.4
g of concentrated hydrochloric acid to a solution of 2 Qml of methanol.
mj! was added and refluxed for 5 hours.

After the reaction was completed, the reaction solution was cooled, poured into 100 mf of a 10% aqueous potassium hydroxide solution, and then extracted with ethyl acetate. After washing the aN with water and further washing with saturated saline, it was dried over anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure, and a solution of 4:1 of n-hexane and ethyl acetate was added.
The product was purified by silica gel column chromatography using a developing solvent of 1 to obtain 0.13 g of N-methyl-4-(2-chloro-4-trifluoromethylphenoxy)-2-fluoroaniline as an oil.

(IV) N-methyl-4 obtained in the above step (I[l)
-(2-chloro-4-trifluoromethylphenoxy)
-0.13g of 2-fluoroaniline in 5ml of dioxane
What was dissolved in it? In the evening, a solution of 0.2 g of 2,6-cyfluorobenzoyl isocyanate dissolved in 5 ml of dioxane was added at room temperature, and the mixture was stirred at room temperature for 2 hours.

After the reaction was completed, the reaction solution was poured into 3 Qml of water, extracted with ethyl acetate, the a layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. Purification was performed by silica gel column chromatography using a developing solvent of -hexane and ethyl acetate in a ratio of 3:1 to obtain 0.20 g of the target product as an amorphous solid with no clear melting point.

Production Example 3 ・N-[4-(3-chloro-5-trifluoromethyl-
2-pyridyloxy)phenyl)-N'-(2,6
-difluorobenzoyl)-N-methylurea (compound N123) synthesis (1) 4-(3-chloro-5-trifluoromethyl-
A solution of 3.99 g of 2-pyridyloxy)aniline dissolved in 50 ml of pyridine was cooled, and 2.17 g of acetyl chloride was added dropwise thereto, followed by stirring at room temperature for 1 hour.

After the reaction was completed, the reaction solution was extracted with ethyl acetate and diluted hydrochloric acid,
The organic layer was washed with an aqueous sodium bicarbonate solution and further washed with saturated brine.Then, the solvent was distilled off under reduced pressure, and then developed with n-hexane and ethyl acetate in a ratio of 1:2. Purified by silica gel column chromatography using a solvent to obtain a solid with a melting point of 175-1.
N-(4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl)acetamide 3 at 76°C
．． 68g was obtained.

(n) Sodium hydride (60% Nujol mixture)
N-(4-(3-chloro-5
3.68 g of -trifluoromethyl-2-pyridyloxy)phenyl]acetamide was mixed with 4 g of dimethylbormamide.
A solution dissolved in QmJ was added dropwise. During the 0-drop addition, the temperature of the reaction solution was maintained at 15-20°C. After the 0-drop addition, the temperature of the reaction solution was 1.5 at room temperature
After stirring for an hour, 6.3 g of methyl iodide was added at 15-20°C.
The mixture was added dropwise at room temperature, and stirring was continued for 20 hours at room temperature.

After the reaction was completed, the reaction solution was extracted with ethyl acetate and water, and the organic layer was further washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. It was purified by silica gel column chromatography using a l:2 developing solvent with N-(4-(3-chloro-5-trifluoromethyl-2) as an oil.
-Pyridyloxy)phenyl-N-methylacetamide 2.0 (i.g.) was obtained.

[■], N-(4-(3-
2.06 g of chloro-5-trifluoromethyl-2-pyridi-ruoxy)phenyl-N-methylacetamide was dissolved in 4 Qml of methanol for t8.
0 ml was added and refluxed for 4 hours.

After the reaction was completed, the reaction solution was cooled, poured into 200 ml of a 10% aqueous potassium hydroxide solution, and then extracted with ethyl acetate. The a-layer was washed with water, further washed with saturated saline, and then dried over anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure, and a solution of 4:1 of n-hexane and ethyl acetate was added.
Purify by silica gel column chromatography using a developing solvent of 1. N-methyl-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy) as an oil
0.24 g of aniline was obtained.

(IV) N-methyl-4 obtained in the above step (ITI)
-(3-Chloro-5-trifluoromethyl-2-pyridyloxy) 0.24 g of aniline was dissolved in 5 ml of dioxane, and 0.3 g of 2,6-cyfluoropenzoyl isocyanate was dissolved in dioxane 5.J. The solution was added at room temperature and stirred at room temperature for 4 hours.

After the reaction was completed, the reaction solution was poured into 30 ml of water, extracted with ethyl acetate, the amyl was washed with saturated brine, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and n-hexane was added. Purified by silica gel column chromatography using a developing solvent of 3:1 and ethyl acetate,
0.30 ff of the target product with a melting point of 147-149°C was obtained.

Representative compounds of the present invention that can be synthesized in the general synthesis examples and production examples and according to the production examples are shown below.

Representative Compound Examples As shown in the test examples below, the compounds of the present invention exhibit excellent activity as insecticides, especially as active ingredients of insecticides.For example, diamondback moth, armyworm, armyworm, codling moth, ball worm, tobacco Budworm (tabacco budworm), ? Ballweed moth, Colorado potato beetle, ballweevil
evil), agricultural pests such as banks, bee flies, scarab beetles, tamanaya moths, caprayaga moths, cockroaches,
Hygiene pests such as the house fly and Culex mosquito; grain storage pests such as the Japanese brown moth, brunette moth, brown rice beetle, and blackberry; clothing and household pests such as the bur moth, snail beetle, and termites; flies that infest other livestock. It is also effective for types such as It is also effective against various insect pests that are resistant to organophosphates, such as the house fly and catfish.

All of them are highly effective against the larvae, but if adult insects ingest the compounds of the present invention, they will be unable to lay eggs, or even if they are able to lay eggs, they will have the effect of preventing the eggs from hatching. For example, the compound of the present invention exhibits good effects such as being easily decomposed in soil (and being safe to beneficial aquatic organisms).

When using this product as an active ingredient of an insecticide, it should be formulated in various forms such as emulsions, powders, wettable powders, liquids, and pastes together with pesticide adjuvants, as in the case of conventional pesticide formulations. I can do it.

The blending ratio of these is usually 0.5 to eQffi of the active ingredient.
The amount of agricultural chemical adjuvant is 10 to 99.5 parts by weight. When actually using these preparations, either use them as is or
Alternatively, it can be used after being diluted to a predetermined concentration with a diluent such as water.

Agrochemical auxiliaries mentioned here include bicarriers, emulsifiers, Q clouding agents, dispersants, spreading agents, penetrants, wetting agents, thickeners, stabilizers, etc., and may be added as appropriate if necessary. They are divided into solid carriers and liquid carriers, and solid carriers include starch, activated carbon, soybean flour, wheat flour, wood flour, fish meal, animal and vegetable powders such as milk powder, talc, kaolin, bentonite, calcium carbonate, zeolite, and diatomaceous earth. Examples of liquid carriers include water, alcohols such as methyl alcohol and ethylene glycol, ketones such as acetone and methyl ethyl ketone, dioxane,
Ethers such as tetrahydrofuran, aliphatic hydrocarbons such as kerosene and kerosene, aromatic hydrocarbons such as xylene, trimethylbenzene, tetramethylbenzene, cyclohexane, and solvent naphtha, halogenated hydrocarbons such as chloroform and chlorobenzene, dimethyl Examples include acid amides such as formamide, esters such as ethyl acetate, esters, and glycerin esters of fatty acids, nitrites such as acetonitrile, and sulfide-containing metals such as dimethyl sulfoxide.

In addition, it can be used in combination with other a-drugs, such as insecticides, acaricides, nematicides, fungicides, antiviral agents, herbicides, plant growth regulators, etc., if necessary. One in case! Sometimes it shows excellent effects.

For example, as an insecticide, acaricide, or nematocide,
O-(4-fromo2-chlorophenyl)0-ethyl
S-propyl phosphorothioate, 2. 2-Dichlorovinyldimethyl phosphate, ethyl 3-methyl-4-(methylthio)phenyl isopropyl phosphoramidate, 0°0-dimethyl 0-4-nitro-m-
) lyl phosphorothioate, 0-ethyl 0-4-nitrophenyl phenylphosphonothiony), 0.0-
Diethyl 0-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate, 0°, 0-dimethyl 0-(3,5,6-1-lichloro-2-pyridyl)
Phosphoric acid ester compounds such as phosphorothioate, O,S-dimethyl acetyl phosphoramidothioate, 〇-(2,4-dichlorophenyl) 0-ethyl S-propyl phosphorodithioate; 1-naphthyl
Methyl carbamate, 2-isopropoxyphenylmethylcarbamate, 2-methyl-2-(methylthio)propionaldehyde O-methylcarbamoyloxime, 2,3-dihydro-2,2-dimethylbenzofuran-
7-yl methyl carbamate, dimethyl N, N'
−(thiobis[(methylimino)carbonyloxy]]
Bisethanimidothioate, S-methyl N-(methylcarbamoyloxy)thioacetimidate, N,N
-dimethylcarbamoyloxyimino-2-(methylthio)acetamide, 2-(ethylthiomethyl)phenyl methylcarbamate, 2-dimethylamino-5,6-
dimethylpyridin-4-yl direthyl carbamate,
Carbamate compounds such as S, S'-2-dimethyl, minotrimethylene bis(thiocarbamate)!
, 2.2-) dichloro-1,1-bis(4-chlorophenyl)ethanol, 4-chlorophenyl 2.4.5-)
Organochlorine compounds such as dichlorophenyl sulfone;
Organometallic compounds such as tricyclohexyldine hydroxide, (R3)-α-cyano-3-phenoxybenzyl (R3)-2-(4-chlorophenyl)-3-
Methyl butyrate, 3-phenoxybenzyl (IR3
)-cis, trans-3-(2,2-dichlorovinyl)
-2,2-dimethylcyclopropane carboxylate,
(RS)-α-cyano-3-phenoxybenzyl (IR
3)-cis, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, (S)-α-cyano-3-phenoxybenzyl (IR
)-cis-3-(2,2-dibromovinyl)-2,2-
Dimethyl cyclopropane carboxylate, (1?S)
-α-cyano-3-phenoxybenzyl (IR3)-cis, trans-3-(2-chloro-3,3,3-)lifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate, 4-methyl- 2,3,5,6-thitrafluorobenzyl-3-(2-10rho3゜3.3-
) Pyrethroid compounds such as 1t-(4-chlorophenyl)-3-(
2,6-')fluorobenzoyl)urea, 1-(3,
5-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl) -3-(2,
6-difluorobenzoyl)urea, 1-(3,5-
2,4-difluorophenyl) -3-(
Benzoylurea compounds such as 2゜6-difluorobenzoyl)urea; 2-tert-butylimino-3-isopropyl-5-phenyl-3,4゜5.6
-tetrahydro-2H-1,3,5-thiadiazine-4
-one, trans-5-(4-chlorophenyl)-N-
Cyclohexyl-4-methyl-2-oxothiazolidinone-3-carboxamide, N-methylbis(2,4-xylyliminomethyl)amine, N'-(4-chloro-
Compounds such as 〇-tolyl)-N,N-dime, thylformamidine; isopropyl <2E, 4E)-juvenile hormones such as -11-methoxy-3,7,11-trimethyl-2,4-dodecagenoate and other compounds such as dinitro compounds, organic sulfur compounds,
Examples include urea compounds and triazine compounds.

Furthermore, it can also be used in combination with microbial pesticides such as BT agents and insect pathogenic virus agents.

For example, as a fungicide, S-benzyl 0°O-diisopropyl phosphorothioate, o-ethyl S, S
- Organophosphorus compounds such as diphenyl phosphorodithioate and aluminum ethyl hydrogen phosphonate; Organochlorine compounds such as 4,5,6゜7-titrachlorophthalide and tetrachloroisophthalonitrile; Manganese ethylene bis(dithiocarbamate) ), polymers of zinc ethylene bis(dithiocarbamate), complex compounds of zinc and maneb, polymers of zinc bis(dimethyldithiocarbamate), ethylene bis(dithiocarbamate), zinc propylene bis(dithiocarbamate), etc. Dithiocarbamate type compound; 3a, 4.7゜7a-tetrahydro-N-()dichloromethanesulfenyl)phthalimide, 3a, 4.7
, 7a-Tetrahydro N-(1,1,2,2-tetrachloroethanesulfenyl)phthalimide, N-(trichloromethylsulfenyl)phthalimide and other N-halogenothioalkyl compounds; 3-(3,5-dichlorophenyl) -N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide, (R3)-3-(3
,5-dichlorophenyl)-5-methyl-5-vinyl-
1,3-oxazolidine-2,4-dione, N-(3,
Dicarboximide compounds such as 5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide; methyl 1-(butylcarbamoyl)benzimidazol-2-yl ka, -bamate, dimethyl 4,4 ° Benzimidazole compounds such as -(0-phenylene)bis(3-thioallophanate); 1-
(4-chlorophenoxy)-3,3-dimethyl-1-(
IH-1゜2.4-)riazol-1-yl)pukunon, 1-(biphenyl-4-yloxy)-3,3-schif-thyl-1-(11-r-1,2,4-triazole-
1-yl)butan-2-ol, 1-(N-(4-chloro-2-trifluoromethylphenyl)-2-propoxyacetimidoylcoimidazole, 1-(2-(2
,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylmethyl)-1H-1,2,4-1-
Riazole, 1-(2-(2,4-dichlorophenyl)
-4-propyl-1,3-dioxolan-2-ylmethyl]-LH-1,2,4-)riazole, 1-(2-(
2,4-'; dichlorophenylpentyl) -11(-
1,2,4-)Azole compounds such as lyazole; 2
．． 4° -dichloro-α-・(pyrimidin-5-yl)
Benzhydryl alcohol, (±)-2,4゛-difluoro-α-(LH-1,2,4-triazole-1-
Carbinol compounds such as (methyl)benzhydryl alcohol; 3'-isoproboxy-0-toluanilide, α7 α.

Benzanilide compounds such as α-trifluoro-3′-isopropoxy-〇-trianilide; Methyl N-
Acylalanine such as (2-methoxyacetyl) -N-(2°6-xylyl)-DL-alaninate? lJ
3-7o rhoN-(3-chloro-2,6-sinitro-4-α,α,α-trifluorotolyl)-5-)lifluorotolyl)-5-trifluoromethyl-2-pyridinamine Viridinamine compounds; other compounds include piperazine compounds, morpholine compounds, anthraquinone compounds, quinoxaline compounds,
Examples include crotonic acid compounds, sulfenic acid compounds, urea compounds, and antibiotics.

The insecticide of the present invention is effective for controlling various harmful insects, and the application amount is generally 1 to 20,000 ppm, preferably 2 ppm.
0-2. These active ingredient concentrations can be changed appropriately depending on the form of the preparation, the method of application, purpose, timing, location, pest outbreak status, etc. For example, in the case of aquatic pests, The active ingredient concentration range in water is below the above range because it can be controlled by spraying a chemical solution with the above concentration range at the site of occurrence.

The application per unit area is about 0.1 to 5,000 g, preferably 5 to 1,000 g of active ingredient compound per 10a.
000g is used. However, deviations from these ranges are possible in special cases.

The various formulations containing the compounds of the present invention or their dilutions can be applied by commonly used application methods, such as spreading (e.g., spraying, misting, misting, atomizing, water surface application, etc.), soil application ( It can be carried out by mixing, irrigation, etc.), surface application (coating, powder coating, IW, etc.), immersed poison bait, etc.

It is also possible to feed the above-mentioned active ingredient to livestock by mixing it with their feed, and use their excrement to control the emergence and growth of existing pests, particularly harmful insects. It can also be applied by the so-called ultra low-volume method. In this way, 100% active ingredient content is possible.

Next, test examples of the compounds of the present invention will be described.

g 1 Kogajime Each formulation of the auxiliary component C was dispersed in water, and cabbage leaf pieces were immersed in the chemical solution adjusted to a concentration of 10 ppm for about 10 seconds and air-dried. A Petri dish with a diameter of 9 cm was lined with moist filter paper, and the air-dried leaf pieces were placed on top of it. 2nd to 3rd instar diamondback moth larvae were released there, the lid was placed, and the container was left in a lighted incubator at 26°C. The survival rate of the insects was determined at the 7th post-adult stage, and the mortality rate was calculated using the following formula. Representative examples of those test results are shown in Table 1. (Note) Comparative compound: N-(2,6-difluorobenzoyl)-N'-(4-chlorophenyl)urea (described in JP-A-46-6550) 81 12 Spodoptera spp. 1" The test was conducted in the same manner as in Test Example 1 above, except that the 2nd to 3rd instar of the diamondback moth was replaced with the 2nd to 3rd instar of the Spodoptera moth, and the active ingredient concentration of 10 ppm was replaced with 1 ppm. The insect rate was calculated.

Representative examples of those test results are shown in Table 2 (Note) Comparative compounds; same g as in Table 1 3 Housefly! 1 Feed for rearing housefly larvae [manufactured by Oriental Yeast Gl] L
og was placed in an ice cream cup, the active ingredient compound formulation was dispersed in water, and the drug solution adjusted to a concentration of 1100 pp was poured into a 10 ml cup and mixed well. House fly 2nd instar larvae were released into the larvae, and 10 days after treatment, the loss of emerged insects was investigated, and the percentage of unemerged insects was determined using the following formula.

Representative examples of those test results are shown in Table 3.

vinegar.

Table 3 14. Chikayeka'! 11 Test V The formulation of the active ingredient compound was diluted with water to 11 minutes, and the active ingredient concentration was 2.5.
It was adjusted so that ρpb. 200 mJ of this chemical solution was placed in a wide mouth bottle. After 4 days of acetylation, 20 Chikaie larvae were released into this and placed in a thermostat at 26°C. Nine days after the treatment, the number of dead insects was investigated, and the mortality rate was determined using the Keigo gamma formula of Test Example 1. Representative examples of those test results are shown in Table 4.

Table 4 Skim milk and sand) J! Pour 0.5 ml of an acetone solution of the active ingredient compound into 2 g of a mixture of
The concentration was adjusted to 0 μg/g. The poison bait and water were placed in a rearing container, and 20 unmated female adult houseflies were released into the container, and the container was placed in a thermostat at 26°C. After 3 days, the poisoned bait was removed, skim milk and sugar were fed, and 20 unmated female adult house flies were released to mate. After another 3 days, eggs were placed in a mixture of house fly larval feed and water at a ratio of 1:1 for 7 hours. The newly laid eggs were arranged on a wet black filter paper, examined one day later, and the acetylation inhibition rate was determined using the following formula. As a result, the acetylation inhibition rate for compound NO, 14 was 100.
%Met.

°A similarly good acetylation inhibiting effect can be obtained with the compounds N001 and N004.

4 conversion inhibition rate (%) Formulation example 1 (a) Compound AI 201i 1 part (b)
Sickleite 721! ffi part (c) 8 parts by weight or more of sodium lignin sulfonate are uniformly mixed to form a wettable powder.

Formulation Example 2 (a) Compound 1 is uniformly mixed with 45 parts by weight (b) 951 parts or more of talc to form a powder.

Formulation Example 3 (a) Compound 1114 2011 parts by weight (b) N,N'-dimethylformamide 70 parts by weight (c) Polyoxyethylene alkylphenyl ether
10 parts by weight or more are uniformly mixed and dissolved to form an emulsion.

Formulation Example 4 (a) Di-cryte 78'tL 1 part (b) β-naphthalenesulfonic acid soda formalin metal condensate
2IIIfft part (c) Polyoxyethylene alkyl sulfate
5 parts by weight (d) White carbon A mixture of 15 iiffi parts or more of each component and the compound Na2O are mixed at a ratio of 4:1 to form a wettable powder.

Claims (1)

[Claims] 1. General formula: ▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, A is a -CH= group or a nitrogen atom, X is a hydrogen atom or a halogen atom, and Y_1, Y_2 , Y_3
and Y_4 are a hydrogen atom, a halogen atom, a lower alkyl group, or a -CO_2R_3 group (in the formula, R_3 is a hydrogen atom or a lower alkyl group), Z_1 and Z_2 are a hydrogen atom or a halogen atom, and R_1 and R_
2 is a hydrogen atom or a lower alkyl group, provided that Z_1
and at least one of Z_2 is a halogen atom, and at least one of R_1 and R_2 is a lower alkyl group, except when R_1 is a methyl group and R_2 is a hydrogen atom] N-phenyl-N ′−
Benzoylurea compounds. 2. General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A is a -CH= group or a nitrogen atom, X is a hydrogen atom or a halogen atom, and Y_1, Y_2, Y_3
and Y_4 are a hydrogen atom, a halogen atom, a lower alkyl group, or a -CO_2R_3 group (in the formula, R_3 is a hydrogen atom or a lower alkyl group), Z_1 and Z_2 are a hydrogen atom or a halogen atom, and R_1 and R_
2 is a hydrogen atom or a lower alkyl group, provided that Z_1
and at least one of Z_2 is a halogen atom, and at least one of R_1 and R_2 is a lower alkyl group, except when R_1 is a methyl group and R_2 is a hydrogen atom] N-phenyl-N ′−
An insecticide characterized by containing at least one benzoyl urea compound as an active ingredient. 3. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) [In the formula, A is a -CH= group or a nitrogen atom, X is a hydrogen atom or a halogen atom, and Y_1 , Y_2, Y_3
and Y_4 are a hydrogen atom, a halogen atom, a lower alkyl group, or a -CO_2R_3 group (in the formula, R_3 is a hydrogen atom or a lower alkyl group), Z_1 and Z_2 are a hydrogen atom or a halogen atom, and R_1 and R_
2 is a hydrogen atom or a lower alkyl group, provided that Z_1
and at least one of Z_2 is a halogen atom, and at least one of R_1 and R_2 is a lower alkyl group, except when R_1 is a methyl group and R_2 is a hydrogen atom] N-phenyl- N'
In the method for producing a benzoyl urea compound, [
A] When R_1 is a lower alkyl group and R_2 is a hydrogen atom, the general formula is: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A, X, Y_1, Y_2, Y_3 and Y_4 are as described above. (R'_1 is a lower alkyl group)
[B] is obtained by reacting an aniline compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, Z_1 and Z_2 are as described above). When R_1 is a hydrogen atom and R_2 is a lower alkyl group, the general formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A, X, Y_1, Y_2, Y_3, and Y_4
are as described above), and the general formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Z_1 and Z_2 are as described above, and R'_
2 is a lower alkyl group), or when [C]R_1 is a lower alkyl group and R_2 is a lower alkyl group, general formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, A, X, Y_1, Y_2, Y_3, Y_4, Z
_1 and Z_2 are as described above), general formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A, X, Y_1, Y_2, Y_3, Y_4, R
'_1, Z_1, and Z_2 are as described above) Compound or general formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, A, X, Y_1, Y_2, Y_3, Y_4, R
'_2Z_1 and Z_2 are as described above) is reacted with an alkyl halide to produce an N-phenyl-N'-benzoyl urea compound represented by the general formula (I). A method for producing an N-phenyl-N'-benzoylurea compound represented by the general formula (I).