JPH0429974A - Trihaloimidazole derivative, its preparation and insecticidal, acaricidal agent containing the same as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [X is halogen; R is cyano, halogenothio, group of formula II, SO2R<1>, etc., (R<1> is alkyl, benzyl, phenoxymethyl, phenyl etc.,)]. USE:An insecticidal, acaricidal agent exhibiting excellent insecticidal, acaricidal activity against various injurious insects such as the Hemiptera and Diptera and injurious mites, especially against the Blatteriae. PREPARATION:A trihaloimidazole of formula III is made to react with a halogen compound of formula: Y-R (Y is halogen) in the presence of a hydrohalogenic acid-removing agent in a solvent such as toluene at 0-150 deg.C to prepare the compound of formula I. The halide compound and the hydrohalogenic acid-removing agent are employed in amounts of 1-2 equivalents and 1-8 equivalents, respectively, per equivalent of the compound of formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel tribaloimidazole derivative, a method for producing the same, and an insecticide and acaricide containing the same as an active ingredient.

<Prior art> Trivaloimidazole derivatives similar to the compounds of the present invention, such as those described in 1-(4-nitrobenzoyl)-169192, and 1-n-propoxycarbonyl-2,4,5-) The fact that bromoimidazole can be used as an active ingredient in insecticides and acaricides was reported in the 4th B.
It is described in No. 17748.

On the other hand, it has been shown in British Patent No. 1,816,665 and in the U.S. Patent No. Patent No. 8,
674,874, etc.

<Problems to be Solved by the Invention> However, these compounds cannot always be said to be sufficient as active ingredients for insecticides and acaricides.

<Means for solving the problem> In view of the above situation, the present inventors have developed a better insecticide,
As a result of intensive studies to find a compound having acaricidal effect, -formation CI] [wherein, X represents a halogen atom, and R represents a cyano group]. R is an alkyl group, an alkoxyalkyl group, a haloalkyl group, a benzyl group which may have a substituent,
It represents a phenoxymethyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a naphthyl group, which may have a substituent, or a phenyl group, which may have a substituent.

R2 and R8 are the same, or R2, R8 and the nitrogen atom may be taken together to form a morpholino ring, piperidino ring or pyrrolidino ring. ] The trivaloimidazole derivative (hereinafter referred to as the compound of the present invention) represented by the following: 1. has extremely high insecticidal and acaricidal efficacy.

2. Excellent knockdown efficacy and lethal efficacy.

8. Demonstrates remarkable insecticidal and acaricidal efficacy against pests that are not sensitive to pyrethroids.

4. Highly effective as a smoking agent.

It was discovered that it has completely new insecticidal and acaricidal properties, such as, and led to the present invention.

The compound of the present invention has insecticidal and acaricidal effects against many pests such as various sanitary pests such as Apiptera pests, Hemiptera pests, and Diptera pests, agricultural pests, and harmful mites, and in particular, German cockroaches, It is effective against cockroaches such as the American cockroach, black cockroach, brown cockroach, and small cockroach.

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

In the compound of the present invention represented by the general formula [υ], when R1 is a benzyl group, phenoxymethyl group or phenyl group which may have a substituent, examples of the substituent on the benzene ring include an alkyl group, a halogen atom,
Alkoxy group, nitro group, cyano group, cycloalkyl group, phenyl group, dialkylamino group, acetamido group,
Examples include benzyloxy group, phenoxy group, haloalkyl group, benzyl group, acetyl group, formyl group, benzoyl group, halogen-substituted benzoyl group, and alkylsulfonyl group.

The compound of the present invention shown in one country is
It can be produced by the methods described in Japanese Patent Publication No. 9192 and Japanese Patent Publication No. 17748/1984.

That is, the compound of the present invention is formed by -formation (2) [wherein, X represents the same meaning as above]. ] Trivaloimidazole and one-forming field Y-R [ ] [In the formula, Y represents a halogen atom and R represents the same meaning as above. ] It can be produced by reacting a halide represented by the following in the presence of a dehydrohalogenating agent.

The reagent used in the reaction is tribaloimidazole (3)
1 to 2 equivalents of the halide and 1 to 8 equivalents of the dehydrohalogenation agent are used per equivalent, and these are mixed in a solvent with 0 to 1
React at 50°C for about 1 to 24 hours.

Examples of the trivaloimidazole represented by the general formula (3) include 2-brot-4,5-dichloroimidazole and trichloroimidazole. Among these raw material compounds, 2-promo-4,5-dichloroimidazole is disclosed in U.S. Patent No. 8,409,606;
Trichloroimidazole is disclosed in U.S. Patent No. 8,485,05.
They can be easily manufactured by the manufacturing methods described in the OM specification.

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, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, ethyl formate, ethyl acetate. , esters such as butyl acetate and diethyl carbonate, nitrides such as nitroethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, pyridine,
Tertiary amines such as triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine, formamide, N,N-dimethylformamide, N,
Examples include acid amides such as N-dimethylacetamide, sulfur compounds such as dimethylsulfoxide and sulfolane, and mixtures thereof.

Examples of the acid catalyst include organic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid.

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

Examples of the compounds of the present invention include those listed in Table 1 below.

(lO) Table When the compound of the present invention is used as an active ingredient of an insecticide or acaricide, it is usually mixed with a solid carrier, liquid carrier, gaseous carrier, bait, etc., or it is mixed with a mosquito coil, mat, plate, etc. If necessary, surfactants and other formulation auxiliaries are added to form flowable agents such as oils, emulsions, wettable powders, suspensions/emulsions in water, and granules. agents, powders, aerosols, heating fumigants such as mosquito coils, electric mosquito repellent mats, and no-mats, heating fumigants such as self-combustion type smokers, chemical reaction type smokers, and electric heating type smokers, and resin evaporation. non-heating transpiration agents such as impregnated paper evaporation agents, fogging agents such as fogging agents, LILV agents,
It is used as a poison bait etc.

These preparations usually contain 0.001 to 95% 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 hydrous silicon oxide, bentonite, fubasamiclay, 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. (ethanol, methanol, 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, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N, N
-dimethylformamide, N,N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, vegetable oils such as soybean oil, cottonseed oil, etc.; Examples of the agent include chlorofluorocarbon gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether,
Examples include carbon dioxide gas.

Examples of surfactants include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkylaryl ethers and their polyoxyethylenic products, 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 molecules (polyvinyl alcohol, , polyvinylpyrrolidone, polyacrylic acids, etc.), and examples of stabilizers include PAP (
Isoflovir acid phosphate), B) iT (2,6-sheet t
ert-butyl-4-methylphenol), BHA (
2-tert-butyl-4-methoxyphenol and 8
-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids or esters thereof, 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 fibrils of cotton linters or a mixture of cotton linters and pulp solidified into a plate shape.

Examples of base materials for self-combusting smoke agents include nitrates, nitrites, guanidine salts, potassium salts, nitrocellulose, ethyl cellulose, wood powder, etc., combustion exothermic agents, 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 diatomaceous earth, 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, dinitrosopentamethylenetetramine, polystyrene, polyurethane, and other organic blowing agents; and fillers such as natural fiber pieces and synthetic mineral fiber pieces.

Examples of the base material for the hot-type smokeless agent include porous ceramic plates, asbestos plates, pulp plates, and porous glass plates.

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

Examples of base materials for poison bait include grain flour, vegetable essential oil, sugar,
Feed ingredients such as crystalline cellulose, oxidative anti-pressure agents such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, agents to prevent accidental ingestion such as capsicum powder,
Examples include attractants such as cheese flavoring, onion flavoring, and peanut oil.

Flowable formulations (suspensions or emulsions in water) generally contain 1 to 75% of the active ingredient compound and 0.5 to 15% of the active ingredient.
dispersant, 0.1-10% suspension aid (e.g., protective colloid or compound imparting thixotropy), 0-10%
Finely dispersed in water containing 10% of suitable adjuvants (e.g. antifoaming agents, rust preventives, stabilizers, spreading agents, penetration aids, antifreeze agents, antibacterial agents, antifungal agents, etc.) obtained by letting

It is also possible to use an oil in which the active ingredient is hardly soluble instead of water to form a suspension in oil.

Examples of protective colloids include gelatin, casein,
Gums, cellulose ether, polyvinyl alcohol, etc. are used. 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 mixed with other insecticides, acaricides, nematicides, soil pest control agents, pest repellents, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners, etc. , or can be used simultaneously without mixing.

When the compound of the present invention is used as an active ingredient for agricultural insecticides and acaricides, the application rate is usually 5 to
When applying 500F, emulsions, wettable powders, flowables, etc. diluted with water, the application concentration is 10 to 2000 pI.
)m, and granules, powders, etc. are applied as they are without any dilution.

In addition, when used as an active ingredient in insecticides and acaricides for home and epidemic prevention, emulsions, wettable powders, flowables, etc.
Apply after diluting to 0,000 ppm, and apply as is for oils, aerosols, fumigants, smoke agents, fog agents, ULV agents, poison baits, etc.

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 using 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 1 (Production of compound (1) of the present invention) 2-bromo-
To a mixture of 4,5-dichloroimidazole (1,08F, 5 mmol), triethylamine (0,51F, 5 mmol) and toluene (2°- limol) was added at room temperature.

After stirring at room temperature for 4 hours, the crystals were separated from the furnace and the furnace liquid was concentrated. The oil obtained by concentration was subjected to silica gel chromatography to obtain the compound (1) of the present invention having a concentration of 0.45F.

1281.5796 Table 2 shows the physical properties of the compound produced according to the method shown in Production Example 1. Compound numbers correspond to those in Table 1.

Table 2 shows formulation examples. 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 (7) were dissolved in 85 parts of xylene and 85 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 compound (1) were added to a mixture of 4 parts of sodium lauryl sulfate, 2 parts of calcium lignin sulfonate, 20 parts of synthetic hydrated silicon oxide fine powder, and ±54 parts of diatom, and mixed with a juice mixer. Stir and mix to obtain a 20% hydrating powder.

Formulation Example 8 6 parts of synthetic hydrous silicon oxide fine powder, 5 parts of sodium dodecylbenzenesulfonate, 80 parts of bentonite, and 55 parts of clay are added to 5 parts of granule compound (8), and the mixture is thoroughly stirred and mixed.

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 5% granules.

Formulation Example 4 Dissolve 1 part of powder compound (2) in an appropriate amount of acetone, add 5 parts of synthetic hydrated silicon oxide fine powder, 0.8 part of P A P and 98.7 parts of clay, and stir with a juice mixer. Mix and evaporate the acetone to obtain a 1% powder.

Formulation Example 570 Able Compound (4) 20 parts and sorbitan trioleate 1.
5 parts and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol.
．． 6 parts and finely pulverize with a sand grinder (particle size 8
μ or less), to this was added 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate, and further added 10 parts of propylene glycol and mixed with stirring to form a 20% suspension in water. obtain.

Formulation Example 6 Oil agent 0.1 part of each of compounds (1,) to (7) is dissolved in 10 parts of trichloroethane, and this is mixed with 89.9 parts of kerosene to obtain each 0.1% oil agent.

Formulation Example 7 Oil-based aerosol compound (5) 0.1 part, tetramethrin 0.2 part, d
- Mix and dissolve 0.1 part of phenothrin, 10 parts of trichloroethane, and 59.6 parts of phantom oil, fill it into an aerosol container, attach the valve part, and then add 80 parts of propellant (liquefied petroleum gas) through the valve part. Pressure filling to obtain an oil-based aerosol.

Formulation Example 8 Add 0.8 f of d-allethrin to 0.8 y of mosquito coil compound (6), dissolve it in 20 mm of acetone, and prepare a carrier for mosquito coil (Tab powder: lees powder: wood flour at 4:8: Mixed at a ratio of 8) 99.42
After stirring and mixing uniformly, 120% of water was added, and the mixture was thoroughly kneaded and dried to obtain a mosquito coil.

Formulation Example 9 100 μm of each of heat-smoking agent compounds (1) to (7) was dissolved in an appropriate amount of acetone, and impregnated into a porous ceramic plate measuring 4.0 m×4°Q cm and 1.2 mm thick to form each of the heat smoker compounds (1) to (7). Obtain a heated smoker.

Next, test examples demonstrate that the compounds of the present invention are useful as active ingredients for insecticides and acaricides. 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 8.

Table Test Example 1 A 10,000-fold dilution with water of an emulsion of the following test compound obtained according to Formulation Example 1 (101) pm) 100
- into a 180- poly cup, Culex entangled larva 2
0 animals were released. The mice were fed and reared, and 8 days later, their survival and death were investigated to determine the mortality rate (2 repetitions). The result is the fourth
Shown in the table.

Table Test Example 2 Place ceramic paper of the same size on the bottom of a polyethylene cup with a diameter of 5.5 crn, and prepare a 200-fold dilution (500 pl) of the emulsion of the test compound obtained according to Formulation Example 1 with water. )0,
7 ml was dropped onto a filter paper, and 80"v of sila sugar was evenly added as bait. 10 female adult house flies of a pyrethroid-insensitive strain were released into the filter, and the lid was placed on the filter paper. After 48 hours, their survival and death were examined. (2 replicates to calculate the mortality rate).

The results are shown in Table 5.

Table 1 Test Example 8 Rice stems (length approximately 149+w) were immersed for 1 minute in a 200-fold dilution (500 ppm) of the test compound emulsion obtained according to Formulation Example 1 with water. After air-drying, the rice stems were placed in a test tube and 10 adult leafhoppers of a resistant strain were released, and one day later, their viability was determined to determine the survival rate (
2 repetitions). The results are shown in Table 6.

Table Test Example 4 Each of the test compounds was added to acetone at a predetermined concentration (0.1% w/
v) and locally apply 1 μj of the diluted solution per adult male German cockroach on the thorax and abdominal plate,
The treatment dose was set to 1 μf/ton. After treatment, the test insects were placed in a polyethylene cup and given water and food, and 8 days later, their survival was investigated to determine the mortality rate.
head 2 repetitions).

The results are shown in Table 7.

Table Test Example 5 A total of four polyethylene cups (inner diameter 10 m, height 3 cm) each with butter applied to the inner surface were installed in the four corners of the bottom of a 70 c1n cubic glass chamber (0.84 m), In each cup, place 10 male and 10 female adult German cockroaches of a pyrethroid-insensitive strain in duplicate.
The heads were released in duplicate. An electric heater was installed at the center bottom of the chamber, and a porous ceramic plate mat smoking agent (
18.7"9/myto, 40 Wi/m ) was placed, energized for 20 minutes, and heated to approximately 200°C. 80 minutes after the start of energization, the cup containing the test insect was removed from the chamber, and water was poured into it. After 2 days, the number of live and dead animals was investigated, and the mortality rate was calculated (2 repetitions).

The results are shown in Table 8.

Table 8 Test Example 6 -
10 adult female spider mites per leaf, 2
It was placed in a constant temperature room at 5°C. After 6 days, an emulsion of the test compound obtained according to Formulation Example 1 was diluted 200 times with water (5
00 ppm) was sprayed on a turntable at 15 kg per pot, and at the same time 2 kg of the same wave was poured into a clay pond. After 8 days, the degree of damage caused by spider mites on each plant was investigated (2 repetitions).
. Criteria for evaluating effectiveness: Almost no damage is observed.

12 A little damage was observed.

Ox: The same damage as in the untreated area is observed.

Closed. The results are shown in Table 9.

Table 9 <Effects of the Invention> The compounds of the present invention have excellent insecticidal and acaricidal effects against various pests such as Apiptera pests, Hemiptera pests, and Diptera pests, and harmful mites such as spider mites. shows.

Claims (3)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X represents a halogen atom, R is a cyano group, haloalkylthio group, or formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Numerical formulas, There are chemical formulas, tables, etc. ▼, ▲mathematical formulas,
Chemical formulas, tables, etc. available ▼, -SO_2R^1 or ▲ Numerical formulas, chemical formulas, tables, etc. available ▼ Represents a group. R^1 is an alkyl group, an alkoxyalkyl group, a haloalkyl group, a benzyl group that may have a substituent, a phenoxymethyl group that may have a substituent, an alkenyl group, an alkynyl group, a cycloalkyl group, or a naphthyl group. Represents a phenyl group which may have a group or a substituent. R
^2 and R^3 are the same or different and represent an alkyl group or a phenyl group, or R^2, R^3 and a nitrogen atom together form a morpholino ring, piperidino ring or pyrrolidino ring; Good too. ] A trihaloimidazole derivative represented by (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X represents a halogen atom. ] Trihaloimidazole represented by the general formula Y-R [In the formula, Y represents a halogen atom, and R represents a cyano group, a haloalkylthio group, or a formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Numerical formulas, chemical formulas, tables, etc. There are ▼, ▲mathematical formulas, etc.
Chemical formulas, tables, etc. available ▼, -SO_2R^1 or ▲ Numerical formulas, chemical formulas, tables, etc. available ▼ Represents a group. R^1 is an alkyl group, an alkoxyalkyl group, a haloalkyl group, a benzyl group that may have a substituent, a phenoxymethyl group that may have a substituent, an alkenyl group, an alkynyl group, a cycloalkyl group, or a naphthyl group. Represents a phenyl group which may have a group or a substituent. R
^2 and R^3 are the same or different and represent an alkyl group or a phenyl group, or R^2, R^3 and a nitrogen atom together form a morpholino ring, piperidino ring or pyrrolidino ring; Good too. ] The method for producing a trihaloimidazole derivative according to claim 1, characterized in that the halide represented by these is reacted in the presence of a dehydrohalogenating agent. (3) An insecticide or acaricide containing the trihaloimidazole derivative according to claim 1 as an active ingredient.