JPH0324062A - Imidazole derivative, production thereof and use of same derivative as pesticide - Google Patents

Abstract

NEW MATERIAL:An imidazole derivative expressed by formula I (R<1> is H or lower alkyl; R<2>, R<3> and R<4> are H, halogen, lower alkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy, lower alkylthio, cyano or phenoxy may be substituted with halogen, furthermore, R<2>, R<3> and R<4> are able to form methylene dioxy group in joining of neighboring groups; X<1> and X<2> are halogen; m is 0 or 1; n is 0-4). EXAMPLE:2-(4-methoxybenzylthio)-4,5-dichloroimidazole. USE:Useful as pesticide. Exhibits strong insect-killing activity with low toxicity. Exhibits effectiveness against harmful insect insensitive to pyrethroid. Exhibits excellent effect as aerosol agent or fumigant, etc. PREPARATION:A compound expressed by formula II is treated by acid to afford the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel imidazole derivative, its production method, and its use as an insecticide. <Prior art> Certain imidazole derivatives, such as 2-(5-(N
, N-dimethylsulfdemoyl)-2chenylteo]-
The usefulness of 4,Is-dibromoidazole as an active ingredient in insecticides is described in European Patent No. 42,781.

Problems to be Solved by the Invention However, this compound cannot always be said to be sufficient as an active ingredient of the insecticide targeted by the present invention. Furthermore, from a safety standpoint, there are expectations for the development of insecticides with strong insecticidal activity and low toxicity.

Means for Solving the Problems> In view of the above circumstances, the present inventors have made intensive studies to develop a strong insecticide, and have found that the general formula (1) [wherein R is a hydrogen atom or a lower alkyl represents a group. RM, Rl and R'f & same or different, hydrogen atom, halogen atom, lower alkyl group, lower alkoxy group, lower haloalkyl group, lower haloalkoxy group, lower alkylthio group,
Represents a cyano group or a phenoxy group which may be substituted with a halogen atom. Also, R*, B. a. R4 is
Adjacent groups may join together to form a methylenedioxy group.

x1 and x3 represent the same or different halogen atoms. m represents 0 or 1, and n represents an integer of 0 to 4. ] The imidazole derivative (hereinafter referred to as the compound of the present invention) represented by: 1. It has extremely high insecticidal efficacy.

2. It has excellent knockdown and lethal effects.

8. Demonstrates remarkable insecticidal efficacy against pests with low pyrethroid susceptibility.

4. Highly effective as an oil or aerosol agent.

6. Highly effective as a fumigant or smog agent. It was discovered that it has extremely excellent insecticidal properties such as, and the present invention was developed based on this discovery.

The compound of the present invention has an insecticidal effect against various sanitary pests such as insect pests of the order Apoptera and pests of the order Dimata, and many agricultural pests,
It is particularly effective against cockroaches such as the German cockroach, the German cockroach, the black cockroach, the brown cockroach, and the black cockroach.

Therefore, the compound of the present invention can be used as an active ingredient of an insecticide effective against pests that are problematic in many situations.

The compound of the present invention represented by the general formula (1) has the general formula (2) [wherein R1, R*, R Hatake, R4, X1, X8, m and n represent the same meanings as punishment, and R6 Represents a lower alkyl group. ] It can be obtained by treating the ikadazole compound represented by the following with an acid, that is, by allowing the acid to coexist.

The amount of the reagent used in the reaction is 0.00% of the acid per equivalent of the imidazole compound represented by the general formula (6). oot to 1 equivalent, and these are reacted at 0 to 150°C for about 1 to 24 hours.

This reaction is usually carried out in an inert solvent, and the solvents used include, for example, aliphatic hydrocarbons such as hexane, hebutane, ligroin, and petroleum ether, aromatic hydrocarbons such as benzene, toluene, and xylene, chloroform, Halogenated hydrocarbons such as carbon chloride, dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as ethyl ether, diisobrobyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; Esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate, nitrides such as nitroethane and nitrobenzene, nitriles such as acetonitrile and isoptylonitrile,
Formamide, N,N-dimethylformamide, N,
Examples include acid amides such as N-dimethylacetate, sulfur compounds such as dimethyl sulfoxide and sulfolane, alcohols such as methyl alcohol, ethyl alcohol, and isobrobyl alcohol, water, and mixtures thereof.

Examples of acids include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid, and perchloric acid;
Examples include organic acids such as p-toluenesulfonic acid.

After the reaction is completed, usual post-treatments are carried out, and if necessary, vN can be produced by chromatography, 'tX distillation, recrystallization, etc.

The imidazole compound represented by the general formula (4), which is a raw material compound, is described in J. Chem, Soc. , C
l1exn. Common-un. , 1428 (198
It can be manufactured by the manufacturing method described in 5).

When using the compound of the present invention as an active ingredient of an insecticide,
Usually, it is mixed with a solid carrier, liquid carrier, gaseous carrier, bait, or impregnated into a substrate such as a mosquito coil or mat, and if necessary, a surfactant, powder, aerosol, mosquito coil, etc. Heating fumigants such as electric mosquito repellent mat Nomat, self-combusting fumigants. Chemically reactive smoke agents, heating smoke agents such as porous ceramic plate smoke agents, non-heat transpiration agents such as resin transpiration agents, impregnated paper evaporation agents, fogging agents such as fogging agents, ULV agents, poison baits, etc. use.

These preparations usually contain 0.001 to 96% by weight of the compound of the present invention as an active ingredient.

Solid carriers used in formulation include, for example, clays (kaolin clay, diatomaceous earth, synthetic hydrated 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, ammonium phosphorus, ammonium nitrate, urea, ammonium chloride, etc.), and other fine powders or granules.As liquid carriers, for example, water, alcohol, etc. (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.), nitrile gjIC acetonitrile, isobutyronitrile, etc.), ethers (diisobrobyl ether, dioxane, etc.), acid amides (
(N,N-dimethylformamide, N,N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethylsulfoxide, vegetable oils such as soybean oil, cottonseed oil, etc. Examples of the carrier, that is, the propellant, include chlorofluorocarbon gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas, and the like.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkylaryl ethers and polyoxyethylenized products thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives, etc. can be given.

Examples of formulation aids such as fixing agents and dispersants include casein, gelatin, polysaccharides (starch powder, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers (polyvinyl (alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.), and examples of stabilizers include PAP (isobrobyl acid phosphate), BHT (2,6-diter
t-butyl-4-methylphenol) s B H A
(a mixture of 2tert-butyl-4-methoxyphenol and 9-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil, surfactant, fatty acid or its ester, and the like.

Examples of the base material for mosquito coils include mixtures of raw plant powders such as wood flour and lees powder and binders such as tab flour, starch, and gluten.

Examples of the base material for the electric mosquito repellent mat include cotton linters or fiprils of a mixture of cotton linters and pulp hardened into a plate shape.

Examples of base materials for self-combusting smoke agents include nitrates, nitrites, guanidine salts, potassium chlorate, nitrocellulose, ethylcellulose, combustion exothermic agents such as wood flour, alkali metal salts, alkaline earth metal salts, heavy Pyrolysis stimulators such as chromate, chromate, oxygen supply agents such as potassium nitrate,
Examples include combustion supporting agents such as melamine and wheat starch, fillers such as diatoms, and binders such as synthetic glues.

The base materials for chemically reactive smoke agents include, for example, exothermic agents such as alkali metal sulfides, polysulfides, hydrosulfides, hydrated salts, and calcium oxide, and catalyst agents such as carbonaceous substances, iron carbide, and activated clay. , azodicarbonamide, benzenesulfonyl hydrazide, dinitrosopentamethylenetetratin, polystyrene, polyurethane, and other organic blowing agents, natural fiber pieces, synthetic IiaMi pieces, and other fillers.

Examples of the base material of the non-heating transpiration agent include thermoplastic resin,
Examples include p-paper and Japanese paper.

Examples of base materials for poison bait include grain flour, vegetable essential oil, sugar,
Examples include bait ingredients such as crystalline cellulose, attractants such as dibutylhydroxytoluene, nordihydroguaia flavoring, onion flavoring, and peanut oil.

The formulation of flowables (suspensions or emulsions in water) generally consists of a compound of 1 to 7596, a dispersing agent of 0.6 to 1696, and a suspending agent of 0.1 to 1096 (for example, a retentive colloid or an emulsion). Compound that imparts thixotropic properties), OS-
1 (L) of suitable sleeve aids (e.g. defoamers, rust preventives, stabilizers, spreading agents, penetration aids, antifreeze agents, anti-corrosion agents, anti-corrosion agents,
f'ilz agent, etc.) in water. It is also possible to use an oil in which the compound hardly dissolves instead of water to form a clouding agent in oil. Examples of protective colloids used include gelatin, casein, gums, cellulose ether, and polyvinyl alcohol. Examples of compounds that impart thixotropy include bentonite, aluminum magnesium silicate, xanthan gum, and polyacrylic acid.

The preparation thus obtained is used as it is or diluted with water or the like. It may also be used with or without mixing with other insecticides, acaricides, nematicides, soil pest control agents, fungicides, herbicides, plant growth regulators, synergists, fertilizers, and soil conditioners. It can also be used at the same time.

When the compound of the present invention is used as an active ingredient of an agricultural insecticide, the application rate is usually 6 to 500 per 10 are.
F. When applying emulsions, wettable powders, floor pull agents, etc. diluted with water, the application concentration is 10 to 2000 p.
pm, and granules, powders, etc. should be applied as they are without any dilution. In addition, when used as an active ingredient in insecticides for household use and epidemic prevention, emulsions, wettable powders, flowables, etc. should be diluted with water to 10 to 00 ppm before application, and oils, aerosols, fumigants, fs smoke agent, fume agent,
ULV agents, poison baits, etc. can be applied as is.

These application amounts and concentrations vary depending on the type of formulation, application time, application location, application method, type of pest, degree of damage, etc., and may be increased or decreased without regard to the above range. can do.

Examples> The present invention will be explained 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, a production example of the compound of the present invention will be shown.

Production Example 1C Production of Compound (1) of the Present Invention) 1-Ethoxymethyl-2-(4-methoxybenzylthio)-4. 5
- dichloroimidazole (0.69F, 2 mmol),
Concentrated hydrochloric acid (0.2F) and methyl alcohol (5mj)
The mixture was heated under reflux for 8 hours. It was concentrated under reduced pressure and ethyl acetate (80mj) was added. This was washed with saturated sodium bicarbonate solution (50 mjX2). The organic layer was dried over magnesium sulfate and concentrated. Thus 2-
(4-methoxybenzylthio)-4,5-dichloroimidazole 0.86F was obtained.

m-1). 128°C (dec.) Next, Table 1 shows some of the compounds of the present invention produced according to this production method.

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

Formulation Example 1 10 parts each of emulsion compounds (1) to (43) were dissolved in 35 parts of xylene and 35 parts of dimethylformamide, 14 parts of polyoxyethylene styrylphenyl ether and 6 parts of calcium dodecylbenzenesulfonate were added, and the mixture was stirred well. Mix to obtain each 10% emulsion.

Formulation Example 2 20 parts of wettable powder E compound (1) was added to 4 parts of sodium lauryl sulfate.
1 part, 2 parts of calcium lignosulfonate, 20 parts of synthetic hydrated silicon oxide fine powder, and 54 parts of silicate clay, and the mixture was stirred and mixed with a jet mixer to obtain 2096 wettable powder.

Formulation Example 8 To 6 parts of Granule Compound (9), 6 parts of synthetic hydrous silicon oxide fine powder, 6 parts of sodium dodecylbenzenesulfonate, 80 parts of bentonite and 66 parts of clay are added and mixed with thorough stirring.

Then, an appropriate amount of water is added to the mixture, which is further stirred, granulated using a granulator, and dried through ventilation to obtain 65% granules.

Formulation Example 4 Dissolve 1 part of powder compound (11) in an appropriate amount of acetone, add 6 parts of synthetic hydrated silicon oxide fine powder, 0.8 part of PAP, and 98.7 parts of clay, and stir and mix with a juice mixer. Acetone is removed by evaporation to obtain a 1% powder.

Formulation Example 5 20 parts of floor pull agent compound (15) and 1.6 parts of sorbitan trioleate were mixed with 28.6 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and the mixture was finely ground with a sand grinder (particle size of 8 μm or less). After that, add xanthan gum 0.0
6 parts and 0.1 aluminum magnesium silicate
40 parts of an aqueous solution containing 2096 were added thereto, and further 10 parts of propylene glycol were added and mixed with stirring to obtain a suspension of 2096 in water.

Formulation Example 6 Oil agent 0.1 part of each of the compounds (1> to (48)) is dissolved in 10 parts of trichloroethane, and this is mixed with 89.9 parts of kerosene to obtain a 0.191; oil agent.

Formulation Example 7 Oil-based aerosol compound (16) 0. 1 part of tetramethrin, 0.2 parts of d-phenothrin, 10 parts of trichloroethane, and 69.6 parts of kerosene are mixed and dissolved, filled into an aerosol container, and a valve part is attached. 80 parts of propellant C (liquefied petroleum gas) is charged under pressure to obtain an oil-based aerosol.

Formulation Example 8 Mosquito coil compound (18) 0. 8 f d - 7 lex
! J n0. Add a f +, add ##L to 20mj of acetone, and carrier for mosquito coil (tab powder: lees powder: wood flour: 4:
After uniformly stirring and mixing with 99.4F (mixed at a ratio of 8:8), 120 mJ of water was added, and the thoroughly kneaded mixture was molded and dried to obtain a mosquito coil.

Formulation Example 9 100 mF of each of the heated smoke agent compounds (1) to (48) was dissolved in an appropriate amount of acetone, and 4, O al X 4, Q c
IIR, thickness 1. Temporarily impregnated with 2 cps of porous ceramic to obtain hot smoke agent.

Next, test examples demonstrate that the compounds of the present invention are useful as active ingredients of insecticides. In addition, the compound of the present invention is the first
The compound number shown in the table is the compound used for comparison.
Indicated by compound symbol in the table.

Table 2 Test Example 1 Diameter 5. Place a piece of paper of the same size on the bottom of a 5 ffi polyethylene cup, and dilute the emulsion of the test compound obtained according to Formulation Example 1 100 times with water (1000 ppm).

7 mj was dropped onto furnace paper, and 80 mF of sulfur sugar was evenly added as bait. Release 10 adult female house flies into it.
After 48 hours with the lid on, the insects were examined to see if they were alive or dead, and the mortality rate was determined (repeat twice).

The results are shown in Table 8.

Table 8 Test Example 2 10 adult German cockroaches (5 males and 5 females) were placed in a 93 mm diameter polyethylene cup with a thin layer of Vaseline applied to the wall.
were released and covered with 16-mesh nylon gauze.
It was installed at the bottom of an acrylic cylinder with an inner diameter of 106,111 and a height of 87 mm. o. of the wiping compound obtained according to Formulation Example 6. Apply 0.6 mJ each of t96 oil to a pressure of 0. Sprayed directly from the top of the cylinder at 6 atmospheres. After 20 minutes, the test insects were collected in a new container, given water and food, and the survival rate was determined after 8 days to determine the mortality rate (2
repetition).

The results are shown in Table 4.

Test Example 8 10 adult German cockroaches (5 males and 5 females) of a pyrethroid-insensitive strain were released into a polyethylene cup with a diameter of 93 mm and the walls were thinly coated with Vaseline, and the cup was covered with a 16-mesh nylon gauze. It was installed at the bottom of an acrylic cylinder with 87 scratches in height. o. of the test compound obtained according to Formulation Example 6. is oil agent each 0.6m
J was sprayed directly from the top of the cylinder using a spray gun at a pressure of 0.6 atmospheres. After 20 minutes, the number of test insects knocked down was investigated, and the knockdown insect rate was determined (2
repetition).

The results are shown in Table 6.

Table 5: Effects of the Invention> The compounds of the present invention exhibit high insecticidal activity against various insect pests such as insect pests of the order Recipoptera and pests of the order Diptera, and are particularly excellent in quick-acting properties.

Claims (4)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R^1 represents a hydrogen atom or a lower alkyl group. R^2, R^3 and R^4 are the same or different and are a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, a lower alkylthio group, a cyano group or a halogen atom represents a phenoxy group which may be substituted with Also,
Adjacent groups of R^2, R^3, and R^4 may be combined to form a methylenedioxy group. X^1
and X^2 represent the same or different halogen atoms. m represents 0 or 1, and n represents an integer of 0 to 4. ] An imidazole derivative represented by (2) General formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R^1 represents a hydrogen atom or a lower alkyl group. R^2, R^3 and R^4 are the same or different and are a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, a lower alkylthio group, a cyano group or a halogen atom represents a phenoxy group which may be substituted with Also,
Adjacent groups of R^2, R^3, and R^4 may be combined to form a methylenedioxy group. R^5
represents a lower alkyl group, and X^1 and X^2 represent the same or different halogen atoms. m represents 0 or 1, and n represents an integer of 0 to 4. ] The method for producing an imidazole derivative according to claim 1, characterized in that the imidazole compound represented by these is treated with an acid. (3) An insecticide containing the imidazole derivative according to claim 1 as an active ingredient. (4) An insecticidal method using the imidazole derivative according to claim 1.