JPS62155248A - N-benzoyl-n'-phenylurea compound and insecticide containing same - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X1 is H or halogen; X2 is halogen; Y is halogen or alkoxy; R is alkyl). EXAMPLE:N-(2,6-difluorobenzoyl)-N'-(3,5-dichloro-2-fluoro-4-methoxyphe nyl)urea. USE:Insecticide effective in controlling various harmful insects. PREPARATION:The compound of formula I can be produced by reacting a benzoylisocyanate compound of formula II with an aniline compound of formula III in a solvent such as benzene at 0-120 deg.C for 0.1-24hr.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to novel N-benzoyl-N'-phenylurea compounds and insecticides containing them.

(Disclosure of the Invention) The compound of the present invention is a novel N-benzoyl-No-phenylurea compound represented by the following general formula (1).

[In the formula, Xl is a hydrogen atom or a halogen atom,
X2 is a halogen atom, Y is a halogen atom or an alkoxy group, and R is an alkyl group] The alkyl portion of the alkoxy group represented by Y in the general formula (1) and the alkyl group represented by R are methyl. group, ethyl group, n-butyl group, 1so-butyl group, 5ac-butyl group, tert-butyl group, etc., and the halogen atom represented by Xl, , iodine atom.

The N-benzoyl-N'-phenylurea compound of the present invention is, for example, a benzoyl isocyanate compound represented by the formula c, in which X and is as described above].

This reaction is carried out in the presence of a solvent such as benzene, toluene, xylene, octane, chlorobenzene, pyridine, dioxane, dimethyl sulfoxide, or ethyl acetate, and the reaction temperature is 0-120°C and the reaction time is 0.1-24°C. It's time.

In addition, the raw material compound represented by the general formula (ffl) (III-1) (Iff-2) (III-3) [wherein, Hal is a halogen atom, and R1 and R2 are alkyl groups] The aniline compound represented by the following formula can be produced, for example, by the following method.

CB) [C] [In the above reaction formula, Hat, R+ and R2 are as described above] Next, specific synthesis examples of the compound of the present invention will be described.

Synthesis Example I N-(2,6-cyfluorohenzoyl)-
Synthesis of N″-(3,5-dichloro-2-fluoro-4-methoxyphenyl)urea (1) Dissolve 9.42 g of 3.5-dichloro-2,4-difluoronitrobenzene in 50 ml of ether and stir Then, 2.45 g of sodium methoxide was added at room temperature and reacted for 1 hour.

After the reaction, 20 On/2 of ether was added to the reaction mixture, washed twice with 100 m/2 of saturated brine, and then dried over anhydrous sodium sulfate. After drying, the ether was distilled off under reduced pressure, and separated and purified using silica gel column chromatography to obtain 3,5
4.5 g of crystals of -dichloro-2-fluoro-4-methoxynitrobenzene and 0.8 g of crystals of 3.5-dichloro-4-dimethoxynitrobenzene were obtained.

[2] 3,5-dichloro-2- obtained in step (1) above
15mj of 2g of fluoro-4-methoxynitrobenzene
After dissolving the mixture in acetic acid (2), the mixture was heated to 80° C., 1.6 g of reduced iron was gradually added thereto, and the mixture was stirred for 15 minutes while maintaining this temperature, and the counterpressure was terminated. After the reaction, the reactants were allowed to age to room temperature,
100 mf of methylene chloride was added, insoluble materials were removed using a filter, and the filtrate was dried over anhydrous sodium sulfate, which had been washed with water, an onodium carbonate solution, and saturated brine. After drying, the filtrate was distilled off under reduced pressure, and purified by silica gel column chromatography to obtain 3,5-di-oo-2-fluoro-4.
-1.52 g of crystals of methoxyaniline were obtained.

[3] 3,5-dichloro-2- obtained in step C2]
A solution of 1.05 g of 2,6-cyfluoropenzoyl isocyanate dissolved in 5 ml of dioxane was added dropwise at mold temperature to a solution of 1 g of fluoro-4-methoxyaniline dissolved in 5 ml of dioxane, and the mixture was heated overnight. The mixture was stirred to complete the reaction.

After the reaction, the reaction product was poured into 20mj+ water, and the formed crystals were collected by filtration and washed with methanol to give a melting point of 239-240°C.
N-(2,6-difluorobenzoyl)-N'-
0.82 g of (3,5-dichloro-2-fluoro-4-methoxyphenyl)1 urea was obtained.

゛ Synthesis Example 2 Synthesis of N-(2,6-difluorobenzoyl)-N"=(3,5-dichloro-2,4-dimethoxyphenyl)urea [1) 3,5-dichloro-2,4-dimethoxynitrobenzene After dissolving 1 g in IOmj' of acetic acid),
The mixture was heated to 80 to 90°C, 0.8 g of reduced iron was gradually added, and stirred for 10 minutes while maintaining this temperature to complete the reaction.

After the reaction, the reaction product was allowed to cool to room temperature, and 50 mj! of methylene chloride was added, insoluble matter was removed by filtration, and the filtrate was diluted with water,
After washing with sodium bicarbonate solution and saturated saline,
It was dried with anhydrous sodium sulfate. After drying, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 0.62 g of an oily substance of 3,5-dichloro-2,4-dimethoxyaniline.

[2] 3,5-dichloro-2, obtained in the above step [1]
0.8g of 4-dimethoxyaniline for 5m! A solution of 0.79 g of 2.6-cyfluoropenzoyl isocyanate dissolved in 5 ml of dioxane was added dropwise to the dioxane solution at room temperature, and the mixture was stirred overnight to complete the reaction.

After the reaction, the reaction product was poured into 20 ml of water, and the formed crystals were collected by filtration and washed with methanol, with a melting point of 201-204℃.
N-(2,6-difluorobenzoyl)-N'-
0.64 g of (3,5-dichloro-2,4-dimethoxyphenyl)urea was obtained.

The following compounds can be synthesized according to the general production method and Synthesis Examples 1 and 2.

Compound Nal N-(2,6-difluorobenzoyl)N'-(3,5-dichloro-2-fluoro-4-methoxyphenyl)urea
Compound N12 N-('2
．． 6-difluorobenzoyl)-N'-(3,5-dichloro-2,4-dimethoxyphenyl)urea Melting point 201-204°C Compound Thtk3 N(2,6-difluorobenzoyl)-N'-(4-methoxy-2゜3・,5−
) IJ dichloroenyl) urea compound ThTh4 N-
(,2,6-difluorobenzoyl)-N'-(2
-bromo-3,5-dichloro-4-methoxyphenyl)
Urea compound Th5 N-(2-chlorobenzoyl)-N'
--(3,5-dichloro-4-ethoxy-2-isobutoxyphenyl)urea The compound of the present invention exhibits excellent activity as an active ingredient of insecticides, especially insecticides, as shown in Test Example B below. . For example, the diamondback moth, armyworm, armyworm, codling moth, ball worm (no Japanese name), yellowtail moth (no Japanese name), gypsy moth, Colorado potato beetle, ball weevil (no Japanese name), grasshoppers, wasp flies, scarab beetles, Agricultural pests such as Tamanaya moth, Kaburaya moth etc.
Hygiene pests such as cockroaches, houseflies, Culex mosquitoes, grain storage pests such as brown moths, silver moths, brown rice beetles, cornstarch, etc., clothing/household pests such as burs, burrs, termites, etc. It is also effective against flies that parasitize livestock. It is also effective against various chemically resistant insect pests such as the house fly, which is resistant to organophosphates.

All of them are highly effective against the larvae, but when the adult insects ingest the compound of the present invention, they have the effect of making them unable to lay eggs, or even if they are able to lay eggs, preventing the eggs from becoming fertile.

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, along with anti-shock agents, as in the case of conventional pesticide formulations. I can do it. The blending ratio of these ingredients is usually 0.5 to 90 parts by weight of the active ingredient and 10 to 99.5 parts by weight of the pesticide auxiliary.
Parts by weight. When actually using these preparations,
It can be used as is or diluted to a predetermined concentration with a diluent such as water.

The agrochemical auxiliary agents mentioned herein include carriers, emulsifiers, suspending agents, dispersants, spreading agents, penetrants, wetting agents, thickeners, stabilizers, etc., and may be added as appropriate if necessary. Carriers 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, hentonite, calcium carbonate, zeolite, Examples include mineral powders such as diatomaceous earth, white carbon, clay, alumina, and sulfur powder. 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, acid amides such as dimethylformamide, esters such as ethyl acetate and glycerin ester of fatty acids, nitriles such as acetonitrile, and sulfur-containing compounds such as dimethyl sulfoxide. Can be mentioned.

In addition, other agricultural chemicals such as insecticides, acaricides, nematicides, fungicides, antiviral agents, attractants, herbicides,
It can be mixed or used in combination with plant growth regulators, etc., and may exhibit even better effects in this case.

For example, as an insecticide, acaricide, or nematicide,
0-(4-bromo-2-chlorophenyl) 0-ethyl S-propyl phosphorothiony), 2,2-dichlorovinyldimethyl phosphate, ethyl 3-methyl-4-(methylthio)phenyl isopropyl phosphoroamidate, 0.0- dimethyl 0-4-nitro-m-)
Lyle phosphorothioate, 0-ethyl 0-4-nitrophenyl phenylphosphonothioate, 0,0-diethyl 0-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate, ol o-dimethyl O-(3,5,6 -Dolichloro-2-pyridyl) phosphorothioate, 0. Organic phosphate ester compounds such as S-dimethyl acetyl phosphoramidothioate, O-(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 dimethylcarbamate,
Carbamate compounds such as S, S'-2-dimethylaminotrimethylene bis(thiocarbamate);
2.2.2-1-dichloro-1,1-bis(4-chlorophenyl)ethanol, 4-chlorophenyl 2,4.5
-organochlorine compounds such as tri')lorophenyl sulfone; organometallic compounds such as tricyclohexyltine hydroxide; (R3)-α-cyano-3-phenoxybenzyl (R3)-2-(4-chlorophenyl )-3-methylbutyrate, 3-phenoxybenzyl (IR3)-cis.

trans-3-(2,2-dichlorovinyl)-2,2-
Dimethyl cyclopropane carboxylate, (RS)-
α-cyano-3-phenoxyhensyl (IR3) −
cis, trans-3-(2,2-dichlorovinyl)-2
゜2-Dimethylcyclopropanecarboxylate, (S
)-α-cyano-3-phenoxyhencyl (IR)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate, (RS)-α-cyano-3-phenoxyhenyl sil(IR3)-cis, trans-3-(2-chloro-3,3°3-trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate, 4-methyl-2,3,5,6-titra Pyrethroid compounds such as fluorobenzyl-3-(2-chloro-3,3,3-trifluoro-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate; ni(4-chlorophenyl) -3-(2,6-
difluorobenzoyl)urea, 1-(3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2)
-pyridyloxy)phenyl)-3-(2,6-difluorobenzoyl)urea, 1-(3,5-dichloro-2
, 4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea; 2 tert-butylimino-3-isopropyl-5-phenyl-3°4.5.6-titrahydro2
H-1,3゜5-thiadiazin-4-one, trans-
5-(4-chlorophenyl)-N-cyclohexyl-4
-Methyl-2-oxothiazolidinone-3-carboxamide, N-methylbis(2,4-xylyliminomethyl)amine, N'-(4-chloro-0-tolyl)-N
, N-dimethylformamidine; isopropyl (2E,4E)-11-methoxy-3,7,1
Juvenile hormone-like compounds such as 1-trimethyl-2,4-dodecagenoate; also, among other compounds,
Examples include dinitro compounds, organic sulfur compounds, urea compounds, and triazine compounds. Furthermore, it can be mixed or used in combination with microbial pesticides such as BT agents, insect pathogenic virus agents, etc.

For example, the fungicides include S-benzyl 0, ○-diisopropyl phosphorothioate, ○-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) polymer, zinc ethylene bis(dithiocarbamate) polymer, zinc and maneb complex, disinc bis(dimethyldithiocarbamate), ethylene bis(dithiocarbamate), zinc propylene bis(dithiocarbamate) dithiocarbamate compounds such as polymers of carbamates); 3a, 4. 7.7a-tetrahydro-N-
(Trichloromethanesulfenyl)phthalimide, 3a
, 4. 7.7a-tetrahuman o-N-(1,1,
N-halogenothioalkyl compounds such as 2,2-tetrachloroethanesulfenyl)phthalimide and N-(trichloromethylsulfenyl)phthalimide;
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-(3,5-dichlorophenyl)-1,2-
Dicarboximide compounds such as dimethylcyclopropane-1,2-dicarboximide: methyl 1-(butylcarbamoyl)benzimidazol-2-yl carbamate, dimethyl 4,4°-(0-phenylene)bis(3- benzimidazole compounds such as thioallophanate; 1-(4-chlorophenoxy)-3,3
-dimethyl=1- (LH-1,2,4-triazol-1-yl)butanone, 1-(biphenyl-4-yloxy)-3,3-dimethyl-1-(IH-1,2,4-
) riazol-1-yl)butan-2-ol, 1-
(N-(4-chloro-2-trifluoromethylphenyl)-2=propoxyacetimidoyl]imidazole,
1-(2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylmethyl)-LH-1
,2,4-)riazole, 1-(2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-ylmethyl)-1H-1,2,4-triazole, 1-(2 azole compounds such as -(2,4-dichlorophenyl)pentyl)-LH-1,2,4-triazole; 2゜4゛ -dichloro-α-(pyrimidine-
carbinol compounds such as 5-′yl)benzhydryl alcohol, (±)-2°4°-difluoro-α-(IH-1,2,4-triazol-1-ylmethyl)benzhydryl alcohol; 3°-isopropoxy-
0-Toluanilide, α, α, α-trifluoro 3°
-Benzanilide compounds such as isopropoxy-0-toluanilide; Acylalanine compounds such as methyl N-(2-methoxyacetyl)-N-(2,6-xylyl)-DL-alaninate; 3-chloro-N −(3
-Chloro-2,6-sinitro-4-α,α,α-trifluorotolyl)-5-trifluorotolyl)-5-1-
Pyridinamine compounds such as lifluoromethyl-2-viridinamine; other compounds include piperazine compounds, morpholine compounds, anthraquinone compounds, quinoxaline compounds, crotonic acid compounds, sulfenic acid compounds, urea compounds, Examples include antibiotics.

The insecticide of the present invention is effective in controlling various harmful insects, and the application rate is generally 1 to 20,000 ppm s, preferably 20 to 2.0 ppm s. It is carried out at an active ingredient concentration of OOOppm. The concentration of these active ingredients depends on the form of the preparation and the method of application;
It can be changed as appropriate depending on the purpose, timing, location, pest outbreak situation, etc. For example, in the case of harmful aquatic insects, the concentration range of the active ingredient in water is below the above range, since it is possible to control aquatic pests by spraying a chemical solution with the above concentration range to the place of occurrence.

The application per unit area is about 0.1 to 5,000 g, preferably 5 to 1,0 g of active ingredient compound per 102
00g 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 using commonly used application methods, such as spreading (e.g., spraying, spraying, misting, atomizing, water surface application, etc.), soil application (contamination), etc. , irrigation, etc.), surface application (painting, powder coating, coating, etc.), immersion of poisonous bait, etc. It is also possible to feed livestock with the foregoing ingredients mixed with their feed, and use their excrement to control harmful insects, particularly in front of their generators. Also, the so-called ultra low-volume spraying method
It can also be applied by. In this way, 100% active ingredient content is possible.

Test Example 1 The formulations of active ingredient compounds No. 1 and 2 were dispersed in water, and cabbage leaf pieces were immersed in the drug solution adjusted to a concentration of 1100 pp for about 10 seconds, then taken out and air-dried. Petri dish (
A moist filter paper (9 cm in diameter) was placed on top of which the leaf pieces were placed.

2nd to 3rd instar Spodoptera larvae were released there, the lid was placed, and the container was left in a lighted incubator at 26°C. The survival rate was determined on the 7th day after release, and the mortality rate was calculated using the following formula, and all results were 100%.

Test Example 2 Replace the 2nd to 3rd instar Spodoptera japonica with the 2nd to 3rd instar diamondback moth,
When the same procedure as in Test Example 1 was carried out, compound No.
The mortality rate of 1 and 2 was 100%.

Formulation Example 1 (a) Compound No. 1 20 parts by weight (b) Diquerite 72 parts by weight (c) 8 parts by weight or more of sodium ligninsulfonate were uniformly mixed to prepare a wettable powder.

Formulation Example 2 (a) Compound No. 2 5 parts by weight (b) Talc 95 parts by weight or more were uniformly mixed to prepare a powder.

Formulation Example 3 (a) Compound No. 1 20wt (b)
70 parts by weight of N,N'-dimethylformamide (c) 10 parts by weight or more of polyoxyethylene alkylphenyl ether were uniformly mixed and dissolved to form an emulsion.

Formulation example 4 (a) Zeekrite ゛ 78 parts by weight (b)
β-nafucrene sulfonic acid soda pomarin condensate
2 parts by weight (c) Polyoxyethylene alkyl sulfate 5 parts by weight (d) White carbon A mixture of 15 parts by weight or more of each component and Compound No. 0.2 are mixed at a weight ratio of 4:l, and hydrated. It was used as a drug.

Claims (1)

[Claims] 1. General formula: ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X_1 is a hydrogen atom or a halogen atom,
X_2 is a halogen atom, Y is a halogen atom or an alkoxy group, and R is an alkyl group]. 2. General formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X_1 is a hydrogen atom or a halogen atom,
X_2 is a halogen atom, Y is a halogen atom or an alkoxy group, and R is an alkyl group. and insecticides.