JPH05132480A - Imidazole derivative, its production and insecticide containing the same as active ingredient - Google Patents

Abstract

PURPOSE:To provide a new compound useful as an insecticide against Hemiptera insect pests, Lepidoptera insect pests, Diptera insect pests, Anoplura insect pests, etc. CONSTITUTION:A compound of formula I (R<1> is halogen, nitro, trifluoromethyl; R<2> is 1-3C haloalkyl, 1-3C haloalkoxy; R<3> is 1-3C alkyl; R<4> is tert-butyl, 1-4C haloalkyl). For example, 1-(3-chloro-5-trifluoromethyl-pyridin-2-yl)-5-methyl-4- pentafluoroethylimidazole. The compound of formula I is obtained by reacting a compound of formula II (A is halogen) with a compound of formula III in a solvent such as hexane in the presence of a base such as triethylamine.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel imidazole derivative, a process for producing the same and an insecticide containing the same as an active ingredient.

[0002]

2. Description of the Related Art Certain imidazole derivatives,
For example, 4-tert-butyl-1-dimethylcarbamoyl-2-methylimidazole is described in U.S. Pat. No. 3,868,458 and U.S. Pat. No. 3,940,484 as 4-tert-butyl-1.
It is described in U.S. Pat. No. 3,996,366 that dimethylcarbamoyl-2-methylthioimidazole can be used as the active ingredient of insecticides.

[0003]

However, these compounds are not always sufficient as active ingredients of insecticides.

[0004]

[Means for Solving the Problems] In view of the above situation, the present inventors have conducted diligent studies to find a compound having a superior insecticidal effect, and as a result, have found that the imidazole derivative represented by the following general formula Have a very high insecticidal effect, and have completed the present invention. That is, the present invention provides a compound represented by the general formula

[0005]

[Chemical 5]

[Wherein R ¹ is a halogen atom, a nitro group or a trifluoromethyl group, R ² is a haloalkyl group having 1 to 3 carbon atoms or a haloalkoxy group having 1 to ³ carbon atoms, and R ³ is a carbon atom. 1 to 3 alkyl groups, R ⁴ is te
represents an rt-butyl group or a haloalkyl group having 1 to 4 carbon atoms. ] The imidazole derivative shown by these (henceforth compound of this invention), its manufacturing method, and the insecticide which contains it as an active ingredient are provided.

In the compound of the present invention, the halogen atom is
Fluoro atom, chlorine atom, bromine atom, iodine atom and the like, and the haloalkyl group having 1 to 3 carbon atoms represented by R ² includes, for example, trifluoromethyl group, pentafluoromethyl group, heptafluoropropyl group and the like. And R ²
The haloalkoxy group having 1 to 3 carbon atoms represented by
For example, a trifluoromethoxy group, a difluoromethoxy group, a tetrafluoroethyl group, and the like, and the alkyl group having 1 to 3 carbon atoms represented by R ³ is a methyl group, an ethyl group, a propyl group, or an isopropyl group. , R ⁴ represents a haloalkyl group having 1 to 4 carbon atoms, for example, a trifluoromethyl group, a pentafluoroethyl group,
2-chloro-1,1,2,2-tetrafluoroethyl group, 2-
Bromo-1,1,2,2-tetrafluoroethyl group, 1,1,2,2
-A tetrafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, etc. can be mentioned. Among the compounds of the present invention, R ¹ is preferably a fluorine atom, chlorine atom or nitro group, R ² is a carbon atom containing at least one fluorine atom as a halogen atom 1
To 3 haloalkyl groups, R ³ is an alkyl group having 1 to ³ carbon atoms, R ⁴ is a tert-butyl group or 1 to 3 carbon atoms containing at least one fluorine atom, chlorine atom or bromine atom as a halogen atom. The imidazole derivative which represents the haloalkyl group of is mentioned. More preferred compounds are R ¹ is a fluorine atom or chlorine atom, R ² is a trifluoromethyl group, R ³ is a methyl group, and R ⁴ is a carbon atom containing at least one fluorine atom, chlorine atom or bromine atom as a halogen atom. Examples include imidazole derivatives that represent 1 to 3 haloalkyl groups. More preferred compounds are R ¹ is a chlorine atom, R ² is a trifluoromethyl group, R ³ is a methyl group, R ⁴ is a haloalkyl group represented by the formula —CF ₂ CF ₂ X, where X is a hydrogen atom and fluorine. And an imidazole derivative which represents an atom, a chlorine atom or a bromine atom. The most preferable compound is R ¹ is a chlorine atom, R ² is a trifluoromethyl group, R ³ is a methyl group, R ⁴ is a haloalkyl group represented by the formula —CF ₂ CF ₂ X, where X is a fluorine atom and chlorine. And an imidazole derivative that represents an atom or a bromine atom. The compound of the present invention has the general formula:

[0008]

[Chemical 6]

[In the formula, R ¹ and R ² have the same meanings as described above, and A represents a halogen atom. ] The halide compound represented by

[0010]

[Chemical 7]

[In the formula, R ³ and R ⁴ have the same meanings as described above. ] It can manufacture by reacting with the imidazole shown by these.

In this reaction, in a solvent, in the presence of a dehydrohalogenating agent, at about -5 ° C to 150 ° C, for 1 hour to 24 hours.
It can be produced by reacting for about a time.

The amount of the reagent used in the reaction is 1 to 2 equivalents of the halide compound represented by the general formula 6 and 1 to 4 equivalents of the dehydrohalogenating agent with respect to 1 equivalent of the imidazole represented by the general formula. It is equivalent.

Examples of the solvent used in the above reaction include aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, chloroform, carbon tetrachloride, dichloroethane and chlorobenzene. , Halogenated hydrocarbons such as dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, acetone, ketones such as methyl ethyl ketone, methyl isobutyl ketone, isophorone and cyclohexanone, esters such as ethyl acetate and butyl acetate. Nitrates such as nitroethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, pyridine, triethylamine, N, N-diethylaniline, and Butylamine, tertiary amines such as N- methylmorpholine, formamide, N, N- dimethylformamide, N, acid amides such as N- dimethylacetamide, dimethyl sulfoxide, sulfur compounds or mixtures thereof, such as sulfolane and the like.

Examples of the dehydrohalogenating agent include organic bases such as pyridine, triethylamine and N, N-diethylaniline, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, calcium carbonate and hydrogenation. Examples thereof include inorganic bases such as sodium and alkali metal alkoxides such as sodium methoxide and sodium ethoxide.

After completion of the reaction, usual post treatment is carried out, and if necessary, purification can be carried out by chromatography, distillation, recrystallization and the like.

The imidazole represented by the general formula (7), which is a raw material of the compound of the present invention, is a compound of US Pat. No. 3,868,458, US Pat. No. 3,940,484, and US Pat.
6,366, J. Org. Chem., 47 , 2867 (1982) and JP-A-61-286370, the halide compounds represented by the general formula 6 are described in US Pat. No. 3,888,932,
U.S. Pat.No. 3,928,416, European Patent 23,1
00, European Patent 34,402, West German Patent 2,606,393, West German Patent 3,545,570, U.S. Patent 4,184,041, British Patent 2,00.
2,368, British Patent 1,121,211, J. Or
g. Chem., 25 , 1710 (1960) and JP-A-59-20,269, respectively, or can be produced by methods equivalent thereto.

Examples of the compounds of the present invention include those listed in Tables 1 to 3 below.

(Table 1) (Table 2) (Table 3)

[0020]

[Chemical 8]

[0021]

[Table 1]

[Table 2]

[Table 3]

Examples of pests on which the compound of the present invention exerts excellent effects include the following.

Hemiptera Pests Planthoppers such as the brown leafhopper, the brown planthopper, and the brown planthopper, leafhoppers such as the leafhopper leafhopper, the Taiwan leafhopper leafhopper, aphids, stink bugs, whiteflies, scale insects, humpback bugs, psyllids, etc.

Lepidopteran pests Nikameiga (Nikameichu), Rhododendron dachaensis and other moths, Spodoptera litura, Spodoptera litura, Spodoptera litura, such as Pieris rapae, Sedum moth, etc.
Pests of the genus Agrotis ( Agrothis spp.), Such as leaf worms, hemlocks, mosquitos, cabbage moths, and Tamana moths, Heliothis spp., Diamondback moth, moths, carp moths, etc.

Diptera Pests Culex pipiens, Culex pipiens, Culex pipiens, Aedes aegypti, Aedes albopictus, Anopheles mosquito, etc. Onion fly and other fruit flies, fruit flies, fruit flies, fruit flies, flies, gnats, sand flies, etc.

Coleoptera pests Western corn rootworms, Southern corn rootworms and other corn rootworms, Rana buoy buoy, Scarabaeidae, chafer beetles, Weevil weevils, Weevil weevil, Weevil beetle, etc. Beetle beetles, beetle beetle, beetle beetle and other beetles, beetle beetles, Epipilachna ( Epilach-na spp.) Species such as Nijuyahochitentou, flat beetle beetles, long beetle beetles, long beetle beetle, beetle beetle, etc.

Pests of the order Lepidoptera, German cockroaches, Black cockroaches, American cockroaches, Black cockroaches, Cockroaches, etc.

Pests of the order Thysanoptera, Thrips palmi Thrips, Thrips thrips, etc.

Hymenoptera pests Ants, wasps, wasps, wasps such as turnips, etc.

Orthoptera pests such as moss, grasshopper, etc.

Insecta pest Human flea etc.

Lice pests Human lice, lice, etc.

It is highly effective against insects such as Yamato termites, and termites.

Further, it is extremely effective against pests that have developed resistance against existing insecticides.

When the compound of the present invention is used as an active ingredient of an insecticide, it may be used as it is without adding any other ingredients, but it is usually used as a solid carrier, liquid carrier, gaseous carrier, bait or the like. Mix and add surfactants and other formulation aids if necessary to formulate oils, emulsions, wettable powders, flowables, granules, powders, aerosols, fumes (fogging, etc.), poison baits, etc. To use.

These formulations usually contain the compound of the present invention as an active ingredient in an amount of 0.01% to 95% by weight.

Examples of solid carriers used for formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.), talcs, ceramics, and other inorganic minerals (sericite). , Quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), chemical fertilizers (ammonium sulfate, phosphorous ammonium, ammonium nitrate, urea, ammonium salt, etc.), etc. Water, alcohols (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene) , Light oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile) Isobutyronitrile), ethers (diisopropyl ether, dioxane, etc.),
Acid amides (N, N-dimethylformamide, N, N-
Dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, soybean oil, cottonseed oil, and other vegetable oils, and the like, and examples of gaseous carriers, that is, propellants include freon gas, butane gas. , LPG (liquefied petroleum gas),
Examples include dimethyl ether and carbon dioxide gas.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylene compounds thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohols. Examples include derivatives.

Examples of auxiliary agents for formulation such as a sticking agent and a dispersant are casein, gelatin, polysaccharides (starch powder, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonites, sugars, synthetic water-soluble polymers. (Polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, etc.) and the like, and examples of the stabilizer include PAP (isopropyl acid phosphate) and BH.
T (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil , Surfactants, fatty acids or esters thereof, and the like.

Examples of base materials for poison baits include bait ingredients such as cereal flour, vegetable essential oils, sugars and crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, and capsicum. Examples include edible foods such as powdered foods, cheese flavor, and onion flavor.

The preparation thus obtained is used as it is or after diluted with water or the like. Also other pesticides,
It can be used simultaneously with or without mixing with nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil improvers, animal feeds and the like.

When the compound of the present invention is used as an agricultural insecticide, the application rate is usually 0.1 g per 10 ares.
~ 100g, when using emulsion, wettable powder, flowable agent, etc. diluted with water, the application concentration is usually 0.1 pp
m ~ 500 ppm, and granules, powders, etc. are applied as they are without any dilution. When used as an insecticide for epidemics, emulsions, wettable powders, flowable agents, etc.
Usually, it is diluted with water to a concentration of 0.1 ppm to 500 ppm and applied, and oils, aerosols, fumes, poison baits, etc. are applied as they are.

The application amount and application concentration depend on the kind of formulation, application time, application site, application method, type of pest, degree of damage, etc., and may be increased without regard to the above range. It can be reduced.

[0044]

EXAMPLES The present invention will be described in more detail below with reference to production examples, formulation examples and test examples, but the present invention is not limited to these examples. First, production examples of the compound of the present invention will be shown.

Production Example 1 (Production of Compound (1) of the Present Invention) A solution of 5-methyl-4-pentafluoroethylimidazole (0.6 g, 3 mmol) in N, N-dimethylformamide (5 ml) was added with 60% oiliness. Sodium hydride (1
(20 mg, 3 mmol) was added little by little under ice cooling. After stirring at the same temperature for 10 minutes, the temperature was brought to room temperature, and 2,3-dichloro-5-trifluoromethylpyridine (0.65 g, 3 mmol) was added dropwise. After the addition was completed, the mixture was stirred at the same temperature for 9 hours. After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. Further, it was washed with saturated saline and dried over magnesium sulfate. The residue obtained by concentration under reduced pressure was subjected to silica gel column chromatography to give 1- (3
0.5 g of -chloro-5-trifluoromethyl-pyridin-2-yl) -5-methyl-4-pentafluoroethylimidazole was obtained. m. p. 71.0 ° C

Production Example 2 (Production of Compound (2) of the Present Invention) 4- (2-Bromo-1,1,2,2-tetrafluoroethyl)-
To a solution of 5-methylimidazole (1.0 g, 3.8 mmol) in N, N-dimethylformamide (5 ml), 60%
Oily sodium hydride (150 mg, 3.8 mmol) was added in small portions under ice cooling. After stirring at the same temperature for 10 minutes, the temperature was brought to room temperature, and 2,3-dichloro-5-trifluoromethylpyridine (0.82 g, 3.8 mmol) was added dropwise. After the addition was completed, the mixture was stirred at the same temperature for 9 hours. After the reaction,
The reaction mixture was poured into water and extracted with ethyl acetate. Further, it was washed with saturated saline and dried over magnesium sulfate. The residue obtained by concentration under reduced pressure was subjected to silica gel column chromatography to give 4- (2-bromo-1,1,2,2-tetrafluoro) ethyl-1- (3-chloro-5-tri 0.8 g of fluoromethyl-pyridin-2-yl) -5-methylimidazole was obtained. n _D ^22.1 1.4829

Production Example 3 (Production of Compound (3) of the Present Invention) 5-Methyl-4- (1,1,2,2-tetrafluoroethyl) imidazole (1.0 g, 5 mmol) N, N-dimethyl To a formamide (5 ml) solution, 60% oily sodium hydride (200 mg, 5 mmol) was added little by little under ice cooling. After stirring at the same temperature for 10 minutes, bring the temperature to room temperature, and
3-dichloro-5-trifluoromethylpyridine (1.
08 g, 5 mmol) was added dropwise. After the addition is complete
The mixture was stirred at the same temperature for 9 hours. After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. Further, it was washed with saturated saline and dried over magnesium sulfate. The residue obtained by concentration under reduced pressure was subjected to silica gel column chromatography to give 1- (3-chloro-5-trifluoromethyl-pyridin-2-yl) -5-methyl-4- (1,1 0.9 g of 2,2,2-tetrafluoro) ethylimidazole was obtained. n _D ^24.5 1.4744

Production Example 4 (Production of Compound (4) of the Present Invention) A solution of 5-methyl-4-trifluoromethylimidazole (0.50 g, 3 mmol) in N, N-dimethylformamide (5 ml) was added with 60% oiliness. Sodium hydride (133 mg, 3 mmol) was added in small portions under ice cooling.
After stirring at the same temperature for 10 minutes, the temperature was brought to room temperature, and 2,3-dichloro-5-trifluoromethylpyridine (0.62 g,
3 mmol) was added dropwise. 8 at the same temperature after addition
Stir for hours. After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. Further, it was washed with saturated saline and dried over magnesium sulfate. The residue obtained by concentration under reduced pressure was subjected to silica gel column chromatography, 1-
(3-chloro-5-trifluoromethylpyridine-2-
0.48 g of (yl) -5-methyl-4-trifluoromethylimidazole was obtained. m. p. 59.4 ° C

Production Example 5 (Production of Compound (5) of the Invention) 4-heptafluoropropyl-5-methylimidazole (0.6 g, 2.4 mmol) in N, N-dimethylformamide (5 ml) solution was added to 60 % Oily sodium hydride (100 mg, 2.4 mmol) was added portionwise under ice cooling. After stirring at the same temperature for 10 minutes, bring the temperature to room temperature, and
-Dichloro-5-trifluoromethylpyridine (0.52
g, 2.4 mmol) was added dropwise. After the addition is complete
The mixture was stirred at the same temperature for 9 hours. After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. Further, it was washed with saturated saline and dried over magnesium sulfate. The residue obtained by concentration under reduced pressure was subjected to silica gel column chromatography to give 1- (3-chloro-5-trifluoromethyl-pyridin-2-yl) -4-heptafluoropropyl-5.
0.4 g of methyl imidazole was obtained. m. p. 62.5 ° C

Production Example 6 (Production of Compound (6) of the Present Invention) A solution of 5-methyl-4-nonafluorobutylimidazole (0.6 g, 2 mmol) in N, N-dimethylformamide (5 ml) was added with 60% oiliness. Sodium hydride (8
(0 mg, 2 mmol) was added little by little under ice cooling. After stirring at the same temperature for 10 minutes, the temperature was brought to room temperature, and 2,3-dichloro-5-trifluoromethylpyridine (0.37 g, 2 mmol) was added dropwise. After the addition was completed, the mixture was stirred at the same temperature for 9 hours. After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. Further, it was washed with saturated saline and dried over magnesium sulfate. The residue obtained by concentration under reduced pressure was subjected to silica gel column chromatography to give 1- (3-
Chloro-5-trifluoromethylpyridin-2-yl)
0.5 g of -5-methyl-4-nonafluorobutylimidazole was obtained. n _D ^25.0 1.4385

Production Example 7 (Production of Compound (7) of the Present Invention) A solution of 5-methyl-4-pentafluoroethylimidazole (0.5 g, 2.5 mmol) in N, N-dimethylformamide (5 ml) was added with 60 parts. % Oily sodium hydride (100 mg, 2.5 mmol) is added portionwise under ice cooling. After stirring for 20 minutes at the same temperature, 2-chloro-3,5-di (trifluoromethyl) pyridine (0.62 g, 2.5 mmol) is added. After the addition is complete, stir at room temperature for 9 hours. After completion of the reaction, the reaction mixture is poured into water and extracted with ethyl acetate. Further, it is washed with saturated saline and dried over magnesium sulfate. The residue obtained by concentration under reduced pressure was subjected to silica gel column chromatography to give 1- [3,5-
Di (trifluoromethyl) pyridin-2-yl] -5-
Methyl-4-pentafluoroethylimidazole is obtained.

Production Example 8 (Production of the compound (8) of the present invention) A solution of 5-methyl-4-pentafluoroethylimidazole (0.5 g, 2.5 mmol) in N, N-dimethylformamide (5 ml) was added with 60 parts. % Oily sodium hydride (100 mg, 2.5 mmol) is added portionwise under ice cooling. After stirring at the same temperature for 20 minutes, 2,3-dichloro-5-
Difluoromethoxypyridine (0.50 g, 2.5 mmol) is added dropwise. After the addition is complete, stir at room temperature for 9 hours. After completion of the reaction, the reaction mixture is poured into water and extracted with ethyl acetate. Further, it is washed with saturated saline and dried over magnesium sulfate. The residue obtained by concentration under reduced pressure was subjected to silica gel column chromatography to give 1- (3-chloro-5-difluoromethoxypyridin-2-yl)-
5-Methyl-4-pentafluoroethylimidazole is obtained.

Production Example 9 (Production of Compound (9) of the Present Invention) 4-tert-butyl-5-methylimidazole (0.5
g, 3.6 mmol) in N, N-dimethylformamide (5 ml) solution, 60% oily sodium hydride (150 ml)
mg, 3.7 mmol) in small portions under ice cooling. After stirring for 20 minutes at the same temperature, 2,3-dichloro-5-trifluoromethylpyridine (0.71 g, 3.6 mmol) is added dropwise. After the addition is complete, stir at room temperature for 9 hours. After completion of the reaction, the reaction mixture is poured into water and extracted with ethyl acetate. Further, it is washed with saturated saline and dried over magnesium sulfate. The residue obtained by concentration under reduced pressure was subjected to silica gel column chromatography to give 4-tert-butyl-1.
-(3-chloro-5-trifluoromethylpyridine-2
-Yl) -5-methylimidazole is obtained.

Formulation examples are shown below. The parts are parts by weight, and the compounds of the present invention are represented by the above compound numbers.

Formulation Example 1 Emulsion 10 parts of each of the compounds (1) to (9) of the present invention were dissolved in 35 parts of xylene and 35 parts of dimethylformamide, and polyoxyethylene styryl phenyl ether 14 was added thereto.
Parts and 6 parts of calcium dodecylbenzene sulfonate are added and well mixed with stirring to obtain 10% emulsions of each.

Formulation Example 2 Wettable Powder 20 parts of each of the compounds (1) to (9) of the present invention, 4 parts of sodium lauryl sulfate and 2 parts of calcium ligninsulfonate.
Parts, 20 parts of synthetic hydrous silicon oxide fine powder and 54 parts of silicon earth are added to the mixture and mixed by stirring with a juice mixer to obtain 20% wettable powder of each.

Formulation Example 3 Granules 5 parts of each of the compounds (1), (4) and (5) of the present invention, 5 parts of synthetic hydrous silicon oxide fine powder, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and clay. 5
Add 5 parts and mix thoroughly with stirring. Then, an appropriate amount of water is added to these mixtures, further stirred, and granulated by a granulator,
Ventilate dry to obtain each 5% granule.

Formulation Example 4 Granules To 5 parts of each of the compounds (2), (3) and (6) of the present invention, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 60 parts of clay are added and mixed thoroughly with stirring.
Then, an appropriate amount of water is added to these mixtures, and the mixture is further stirred, granulated by a granulator, and air-dried to obtain each 5% granule.

Formulation Example 5 Powders 1 part of the compounds (1) to (9) of the present invention is dissolved in an appropriate amount of acetone, and 5 parts of synthetic hydrous silicon oxide fine powder and PAP0.
3 parts of clay and 93.7 parts of clay were added, and the mixture was stirred and mixed with a juice mixer to remove acetone by evaporation to obtain a 1% powder.

Formulation Example 6 Flowable Agent 20 parts of each of the compounds (1), (4) and (5) of the present invention and 1.5 parts of sorbitan trioleate were mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol. Then, after finely pulverizing with a sand grinder (particle size: 3μ or less), 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate is added, and 10 parts of propylene glycol is further added and stirred. Mix to obtain each 20% suspension in water.

Formulation Example 7 Flowable Agent 10 parts of each of the compounds (2), (3) and (6) of the present invention were added.
In addition to 40 parts of an aqueous solution containing 6 parts of polyvinyl alcohol,
Stir with a mixer to obtain a dispersant. To this, 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate was added, and further 10 parts of propylene glycol was added and mixed by stirring to obtain 10% of each.
Obtain a suspension in water.

Formulation Example 8 Oil formulation 0.1 part of each of the compounds (1) to (9) of the present invention was mixed with 5 parts of xylene.
Parts and 5 parts of trichloroethane, and mixed with 89.9 parts of deodorized kerosene to obtain each 0.1% oil.

Formulation Example 9 Oily aerosol 0.1 parts each of the compounds (1) to (9) of the present invention, 0.2 parts tetramethrin, 0.1 part d-phenothrin, 10 parts trichloroethane and 59.6 parts deodorizing kerosene were prepared. After mixing and dissolving, filling into an aerosol container and attaching a valve portion, 30 parts of a propellant (liquefied petroleum gas) is filled under pressure through the valve portion to obtain each oil-based aerosol.

Formulation Example 10 Aqueous Aerosol 0.2 parts of each of the compounds (1) to (9) of the present invention, 0.2 part of d-allethrin, 0.2 part of d-phenothrin, 5 parts of xylene,
Aerosol container was filled with 3.4 parts of deodorized kerosene and 1 part of emulsifier {Atmos 300 (registered trade name of Atlas Chemical Co.)} and pure water was filled in an aerosol container, and a valve part was attached, and through the valve part 40 parts of propellant (liquefied petroleum gas) is charged under pressure to obtain each aqueous aerosol.

Formulation Example 11 Mosquito coiling incense sticks 0.3 g of each of the compounds (1) to (9) of the present invention was added with 0.3 g of d-allethrin and dissolved in 20 ml of acetone to prepare a carrier for mosquito coiling sticks (tab powder: lees). Powder: Wood flour is mixed at a ratio of 4: 3: 3) 99.4 g of the mixture is uniformly mixed with stirring, 120 ml of water is added, and the mixture is sufficiently kneaded and dried to obtain each mosquito coil.

Formulation Example 12 Electric Mosquito Repellent Mat Acetone was added to 0.4 g of each of the compounds (1) to (9) of the present invention, 0.4 g of d-allethrin and 0.4 g of pipenyl butoxide to dissolve them, and the total was dissolved. To 10 ml. This solution
0.5 ml was uniformly impregnated into a 2.5 cm × 1.5 cm, 0.3 cm thick base for an electric mat (a fibril mixture of cotton linter and pulp was hardened into a plate), and each was impregnated with it. Get an electric mosquito repellent mat.

Formulation Example 13 Heating Smoke Agent 100 mg of each of the compounds (1) to (9) of the present invention is dissolved in an appropriate amount of acetone and impregnated into a porous ceramic plate of 4.0 cm × 4.0 cm and 1.2 cm in thickness. To obtain each heated smoking agent.

Formulation Example 14 Poison bait 10 mg of each of the compounds (1) to (9) of the present invention was dissolved in acetone of 0.
It is dissolved in 5 ml, and this solution is treated with 5 g of animal solid feed powder (solid feed powder for breeding and breeding CE-2, trade name of CLEA Japan, Inc.) and mixed uniformly. Then, it is air-dried with acetone to obtain each 0.5% poison bait.

Next, it will be shown by test examples that the compound of the present invention is useful as an active ingredient of an insecticide. The compounds of the present invention are indicated by the above compound numbers, and the compounds used for comparison and control are indicated by the following compound symbols.

Compound No. (A) 4-tert-butyl-
1-N, N-dimethylcarbamoyl-2-methylimidazole (U.S. Pat. Nos. 3,868,458 and 3,940,484
Compounds described in No.) Compound No. (B) 4-tert-butyl-1-N, N-
Dimethylcarbamoyl-2-methylthioimidazole
(Compounds described in US Pat. No. 3,996,366)

Test Example 1 Insecticidal test against larvae of the brown planthopper, an emulsion of the test compound obtained according to Formulation Example 1 was diluted with water (500, 50 or 0.5 ppm) to a rice stem (length: about 12 cm). Was soaked for 1 minute. After air-drying, put rice stalks in a test tube and put about 30 larvae of the brown planthopper in it.
After letting go of the head, the life and death was investigated 6 days later. The criteria are: a: No live insects are found. b: Five or less surviving insects are recognized. c: Six or more live insects are recognized. The results are shown in Table 4.

[0072]

[Table 4] Further, the compounds (1) and (2) of the present invention had a test concentration of 0.
At 5 ppm, a was shown in the above criteria. The untreated section was c.

Test Example 2 Insecticidal test against Southern corn rootworm A filter paper of the same size was placed on the bottom of a polyethylene cup having a diameter of 5.5 cm, and an emulsion of the test compound obtained according to Formulation Example 1 was diluted with water. 1 ml (500 or 50 ppm) was dropped on a filter paper, and one corn sprouting was put as a bait. Approximately 30 Southern corn rootworm eggs were placed therein, the lid was put on, and 8 days later, the life and death of hatched larvae were examined. The criteria for effect evaluation are: a: No live insects are observed. b: Five or less surviving insects are recognized. c: Six or more live insects are recognized. As a result, the compounds (1), (2), (3) and (4) of the present invention showed a in the above judgment criteria at a test concentration of 500 or 50 ppm. The untreated section was c.

Test Example 3 Insecticidal test against Culex pipiens A test compound was made into an emulsion according to Formulation Example 1, diluted with water, and 0.7 ml of the solution was added to 100 ml of ion-exchanged water (concentration of active ingredient: 3. 5 ppm). 20 dead larvae of Culex pipiens were released in it, and the mortality rate one day later was investigated. The criteria for effect evaluation were as follows: A: 90% or more mortality, B: 10% or more and less than 90% mortality, C: Less than 10% mortality. As a result, the compounds of the present invention (1), (2),
(3), (4), (5) and (6) are test concentrations of 3.5
In ppm, A was shown in the above criteria. The untreated section was C.

Test Example 4 Insecticidal test against German cockroach Cockroaches of the same size were laid on the bottom of a polyethylene cup having a diameter of 5.5 cm, and the emulsion of the test compound obtained according to Formulation Example 1 was diluted with water (500 ppm). 0.7 ml was dropped on a filter paper, and 30 mg of sucrose was uniformly added as a bait. Ten adult German cockroaches were released therein, the lid was put on, and the life and death thereof were examined 6 days later, and the mortality rate was calculated. The results are shown in Table 5.

[0076]

[Table 5]

Test Example 5 Insecticidal test against housefly A polyethylene cup having a diameter of 5.5 cm is covered with a filter paper of the same size, and an emulsion of the test compound obtained according to Formulation Example 1 is diluted with water (500 ppm). 0.7 ml was dropped on a filter paper, and 30 mg of sucrose was uniformly added as a bait. Ten adult housefly females were released therein, the lid was put on, 48 hours later, the life and death thereof were investigated, and the mortality rate was calculated (2 repetitions). As a result, the compounds (1), (2), (3), (4) and (5) of the present invention
Showed 100% mortality at a test concentration of 500 ppm. The untreated area was 0%.

[0078]

INDUSTRIAL APPLICABILITY The compound of the present invention is used for hemiptera pests, lepidopteran pests, diptera pests, coleopteran pests, reticule pests, total pests pests, orthoptera pests, hymenoptera pests, hidden pests. It has an excellent insecticidal effect against pests such as eye pests, lice pests, and ptera pests.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroaki Fujimoto 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Takao Ishiwata 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Chemical Industry Co., Ltd. (72) Inventor Hiroshi Kishida 4-2-1 Takashi Takarazuka City, Hyogo Prefecture Sumitomo Chemical Industry Co., Ltd.

Claims (4)

[Claims] 1. A general formula: ## STR1 ## [In the formula, R ¹ is a halogen atom, a nitro group or a trifluoromethyl group, R ² is a haloalkyl group having 1 to 3 carbon atoms or a haloalkoxy group having 1 to ³ carbon atoms, and R ³ is 1 to ³ carbon atoms. number of the alkyl group, R ⁴ represents a tert- butyl group, or 1 to 4 carbon atoms haloalkyl groups. ] The imidazole derivative shown by these. 2. A general formula: ## STR2 ## [Wherein R ¹ is a halogen atom, a nitro group or a trifluoromethyl group, R ² is a haloalkyl group having 1 to 3 carbon atoms or a haloalkoxy group having 1 to 3 carbon atoms, R ³ is a methyl group, R ⁴ Is a tert-butyl group or 1 to 4 carbon atoms
Represents one haloalkyl group. ] The imidazole derivative shown by these. 3. The general formula: ## STR3 ## [In the formula, R ¹ represents a halogen atom, a nitro group or a trifluoromethyl group, R ² represents a haloalkyl group having 1 to 3 carbon atoms or a haloalkoxy group having 1 to 3 carbon atoms, and A represents a halogen atom. ] And a halide compound represented by the general formula: [In the formula, R ³ is an alkyl group having 1 to ³ carbon atoms, and R ⁴ is
It represents a tert-butyl group or a haloalkyl group having 1 to 4 carbon atoms. ] It reacts with the imidazole shown by these, The manufacturing method of the imidazole derivative of Claim 1 characterized by the above-mentioned. 4. An insecticide containing the imidazole derivative according to claim 1 as an active ingredient.