JPS61207367A - Benzoylurea derivative, production thereof, and insecticide containing same as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R<1> is H, or halogen; R<2> is halogen; R<3> is R<2>, or lower alkyl; R<4> is group shown by the formula II, formula III, or formula IV). EXAMPLE:N-2, 6-Difluorobenzoyl-N'-4-(2,3,5-trifluorophenoxy)-3,5-dimethylphenyl urea. USE:An insecticide, having more improved insecticidal effect than well-known diflubenzuron, especially effective against lepidopterous larvae such as diamondback moth, Mamestra brassica Linne, etc., dipterous larvae such as Culex pipiens pallens, Musca domestica Linne, etc., coleopteran larvae, etc. An application amount is 5-500g/10a, when an emulsion, wettable powder, etc., is diluted with water, an application concentration is 10-1,000ppm and dust, oil, etc., can be used as it is in preparation without being diluted. PREPARATION:For example, a benzoyl cyanate compound shown by the formula V is reacted with a novel aniline compound shown by the formula VI in a solvent such as preferably toluene, etc., at 0-80 deg.C for 1-50hr under normal pressure to give a compound shown by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a benzoyl urea derivative represented by the following general formula (I), a method for producing the same, and an insecticide containing the same as an active ingredient.

R2Rs [wherein R1 represents a hydrogen atom or a halogen atom,
R2 represents a halogen atom, R4 represents a halogen atom or a lower alkyl group, and R4 represents a ' group represented by the formula. ] The present inventors have conducted numerous studies to develop excellent insecticides, and as a result, the benzoyl urea derivative represented by the above general formula CI (hereinafter referred to as the compound of the present invention) has been found to be effective against insect larvae. They discovered that it has excellent properties such as high insecticidal efficacy and can be produced at a relatively low cost, leading to the completion of the present invention.

As a benzoyl urea derivative insecticide, diflubenzuron is known and commercially available.

However, it has recently been found that the compound of the present invention has superior insecticidal efficacy to that compound.

Specific pest insects to which the compounds of the present invention are particularly effective include Lepidoptera larvae such as the diamondback moth, Japanese caterpillar moth, and armyworm, Diptera larvae such as Culex mosquito, and house fly, and Coleoptera larvae.

In the compound of the present invention represented by the general formula (I), the stone represents, for example, a hydrogen atom, a fluorine atom or a chlorine atom, and R2
represents, for example, a fluorine atom or a chlorine atom, and R3
represents, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group or an ethyl group, and R4 represents a 2-fluorophenyl group, 8-fluorophenyl group, 4-fluorophenyl group, 2,8.5-) -Lifluorophenyl! , 2.4.5-) represents a trifluorophenyl group.

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

(Manufacturing corporation) General formula (n) [In the formula, R1 and R2 represent the same meanings as above. ] A benzoyl isocyanate compound represented by the general formula (m) R3 [wherein R3 and R4 have the same meanings as above. ] is reacted with the aniline compound shown below.

(Manufacturing method B) General formula CPI) [In the formula, R1 and R2 represent the same meanings as above. ] A pendamide type compound shown by the general formula 3 [wherein R3 and R4 represent the same meanings as above. ] is reacted with the isocyanate compound shown below.

In production company and production method B, the reaction is advantageously carried out in the presence of an inert solvent.

Suitable solvents include hydrocarbons such as benzene,
Toluene, xylene, chlorobenzene, carbon tetrachloride, chloroform, methylene chloride, 1°2-dichloroethane,
Nitromethane, ethers such as diethyl ether, tetrahydrofuran, dioxane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, polar organic solvents such as dimethyl sulfoxide,
Dimethylformamide, sulfolane etc. and 2 of these
Examples include mixed solvents of more than one species.

The reaction in manufacturing company and manufacturing method B can generally be carried out under normal pressure and is usually completed in 1 to 50 hours. Furthermore, although it is generally advantageous to use the reaction components in equimolar ratios, it is also possible to use an excess amount of one component.

The reaction temperature at the manufacturing company is not particularly limited, but is generally between 0 and 80°C, more generally between room temperature and 6°C.
The temperature is between 0°C.

The reaction temperature in Production Method B is not particularly limited, but is generally between room temperature and 160°C, more generally 80°C.
The temperature is between 180°C and 180°C.

The obtained compound of the present invention can be purified by means such as column chromatography and recrystallization, if necessary.

In this production method, the benzoyl isocyanate compound represented by the general formula (II) and the pendzamide compound represented by the general formula (IV) are known compounds.

The aniline compound represented by the general formula (In) is a new compound, and can be produced, for example, by the following method.

(VI) Furthermore, the isocyanate compound represented by the general formula (V) can be easily produced by normally reacting the aniline compound represented by the general formula (III) with phosgene.

Next, the present invention will be explained in more detail by showing production examples and reference examples.

Production Example 1 4-(2,8,5-trifluorophenoxidine-3,
Dissolve 0.267 P of 5-dimethylaniline in 20- toluene, and add 0.183 P of 2,6-cyfluoropenzoyl isocyanate to this with stirring. A solution prepared by dissolving 10% of toluene was added dropwise over 10 minutes. After stirring overnight at room temperature, n-hexane 50- was added, the insoluble matter was taken out, and washed with a small amount of n-hexane to give N-2,6-cyfluorobenzoyl-N-4-(2,8, 5-Trifluorophenoxy)-3,5-dimethylphenylurea 0168P was obtained as a white powder (fnP 208.1''C).

Production Example 2 2.6-cyfluorobenzamide 0.157? , 4-(
A mixture of 2,4,rotrifluorophenoxy)-8,5-dichlorophenylisocyanate 0184P and xylene 80- was heated under reflux for 24 hours. After the reaction is complete,
After cooling, the precipitated crystals were collected, and the obtained crystals were recrystallized from 77 tons to obtain N-2,6-cyfluorobenzoyl-N-4-(2,4,5-trifluorophenoxy) -
8,6-dichlorophenylurine [0,818P was obtained as white crystals (InPl 72, 6°C).

Reference Example 1 4-Amino-2,6-dimethylphenol 6-00?
, 1.2.8.5-tetrafluorobenzene 24.0O
f, anhydrous potassium carbonate tt, o4r, anhydrous cuprous chloride 0
．． 50? By heating and refluxing the mixture of 50 and anhydrous dimethyl sulfoxide for 6 hours, the internal temperature rose from 120°C to 150°C. After the reaction was completed, the mixture was cooled to room temperature, 200 ml of cold water and 100 ml of toluene were added, and after stirring for 30 minutes, insoluble matter was removed by filtration through Celite, and the resulting toluene layer was washed with water and dried over anhydrous sodium sulfate. Toluene was distilled off under reduced pressure, and methylene chloride/n-hexane=
Purification by silica gel column chromatography using 174 as a developing solvent gave 4-(2,8,5-)lifluorophenoxy)-8,5-dimethylaniline 10.52
? was obtained as yellow-white crystals (mP 118.6°C).

Next, Table 1 shows some of the compounds of the present invention produced according to the production examples.

When using the compound of the present invention as an active ingredient of an insecticide,
Although it may be used as is without adding any other ingredients, it is usually mixed with solid carriers, liquid carriers, surfactants, other formulation auxiliaries, baits, etc. to form emulsions, wettable powders, powders, and granules. It is used in formulations such as oils, fogging agents, poison baits, etc.

These preparations contain 0.01% to 95% by weight of the compound of the present invention as an active ingredient. As a solid carrier,
Fine powders or granules such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, synthetic hydrous silicon oxide, etc. Liquid carriers include aliphatic hydrocarbons such as kerosene and kerosene, aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene, dichloroethane,
Halogenated hydrocarbons such as trichlorethylene and carbon tetrachloride, alcohols such as methanol, ethanol, isopropanol, ethylene glycol, and cellosolve, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and isophorone, ethers such as diethyl ether, dioxane, and tetrahydrofuran, and acetic acid. Examples include esters such as ethyl, nitriles such as acetonitrile and isobutyronitrile, acid amides such as cumethylformamide and dimethylacetamide, dimethyl sulfoxide, and vegetable oils such as soybean oil and cottonseed oil. Surfactants used for emulsification, dispersion, wet layer, etc. include alkyl sulfate ester salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, naphthalene sulfones. Examples include anionic surfactants such as acid formalin condensates, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Formulation aids such as fixing agents and dispersants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, molasses, casein, gelatin, and CMC (carboxymethylcellulose).
, pine oil, agar, etc., and as a stabilizer, PAP
(acidic isopropyl phosphate), alkyl phosphate such as TOP ('J-9-cresyl phosphate), vegetable oil, epoxidized moiety, the above-mentioned surfactants, antioxidants such as BIllT and BEEmu, sodium oleate, stearate. Examples include fatty acid salts such as calcium phosphate, fatty acid esters such as methyl oleate, and methyl stearate.

Examples of formulations are shown below. The compounds of the present invention are indicated by compound numbers in Table 1. Parts represent parts by weight.

Formulation Example 1 A compound of the present invention (0.2 parts), 2 parts of cyclohexanone, and 97.8 parts of white kerosene are mixed to obtain an oil solution.

Formulation Example 2 10 parts of the compounds (1) to (b) of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium F-decylbenzenesulfonate, 85 parts of xylene and 85 parts of dimethylformamide are thoroughly mixed to obtain an emulsion. .

, Formulation Example 8 20 parts of the present compound (1), fenitrothion 1011
S, 8 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate, and 65 parts of synthetic hydrated silicon oxide are thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 4 1 part of the compound (2) of the present invention, 2 parts of carbaryl, 87 parts of kaolin clay and 10 parts of talc are thoroughly ground and mixed to obtain a powder.

Formulation Example 5 5 parts of the compound of the present invention (4), 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 80 parts of bentonite and 62 parts of kaolin clay were thoroughly ground and mixed, water was added, and the mixture was thoroughly kneaded. Granulate and dry to obtain granules.

These preparations can be used as they are or diluted with water. In addition, other insecticides, acaricides, nematicides, fungicides,
It can also be used in combination with herbicides, plant growth regulators, fertilizers, top conditioners, etc.

When the compound of the present invention is used as an insecticide, the application rate is usually 5? ~500t, emulsion,
When applying wettable powders diluted with water, the application concentration is 1 ppm to 1"000 ppm; powders, granules, oils, etc. can be applied without diluting in any way. do.

Next, a test example is shown. Among the test compounds, the compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 2.

Table 2 Compound Symbol Structural Formula Name Test Example 1 An emulsion of the following compound of the present invention obtained according to Formulation Example 2 was diluted with water to a concentration of Jl-5 ppm. diluted liquid 100
- was placed in a 180 sd polycup, and 20 Culex Culex entangled larvae were released.

The mice were fed and reared until emergence, and the emergence rate was determined (2 repetitions).

The results are shown in Table 8.

Table 8 Test Example 2 A diluted solution 2- of the emulsion of the following present compound and control compound obtained according to Formulation Example 2 with water at a predetermined concentration was diluted with 181 ml of water.
P's Hasmonyo □ Soaked in artificial feed for tow, diameter 1
1- in a polyethylene cup. We released 10 fourth-instar Spodoptera larvae into the larvae, and examined whether they were alive or dead after 6 days.
The LCso value (50% lethal concentration) was determined (2 replicates). The results are shown in Table 4.

Table 4 Test Example 8 Artificial feed 5 for snailfish prepared in accordance with Formulation Example 2 and prepared in a polyethylene cup with a diameter of 5°51 and containing a diluted solution 1- of the emulsion of the present invention compound with water at a predetermined concentration.
? I let it soak inside. 10 10-day-old nymphs were released into the cage, and after 8 days, they were examined for survival and LCs.

The value (50% lethal concentration) was determined (2 replicates).

The results are shown in Table 5.

Table 5

Claims (4)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R_1 represents a hydrogen atom or a halogen atom, R_2 represents a halogen atom, R_3 represents a halogen atom or a lower alkyl group, and R_4 represents a formula ▲Math,
Represents a group represented by ▼, ▲There are chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ] A benzoyl urea derivative represented by. (2) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R_1 represents a hydrogen atom or a halogen atom, and R_2 represents a halogen atom. ] Benzoyl isocyanate compounds represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_3 represents a halogen atom or lower alkyl group, and R_4 is the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Represents a group represented by. [In the formula, R_1, R_2, R_3 and R_4 have the same meanings as above. ] A method for producing a benzoyl urea derivative. (3) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R_1 represents a hydrogen atom or a halogen atom, and R_2 represents a halogen atom. ] Benzamide compounds represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_3 represents a halogen atom or lower alkyl group, and R_4 is the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Represents a group represented by. [In the formula, R_1, R_2, R_3 and R_4 have the same meanings as above. ] A method for producing a benzoyl urea derivative. (4) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R_1 represents a hydrogen atom or a halogen atom, R_2 represents a halogen atom, R_3 represents a halogen atom or a lower alkyl group, and R_4 represents a formula ▲Math,
Chemical formulas, tables, etc. are available ▼, ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ or ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ Represents a group represented by. ] An insecticide characterized by containing a benzoyl urea derivative represented by the following as an active ingredient.