JPH0482877A - Trihaloimidazole derivative, production thereof and insecticide and acaricide containing the same as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula (R is alkyl, alkynyl or haloalkynyl). EXAMPLE:1-Methyl-2-bromo-4,5-dichloroimidazole. USE:An insecticide and acaricide. PREPARATION:2-Bromo-4,5-dichloroimidazole is reacted with a halide expressed by the formula Y-R (Y is halogen) in the presence of a dehydrohalogenating agent to afford the compound expressed by the formula. When the compound expressed by the formula is used as an active ingredient for agricultural insecticides and acaricides, the amount thereof applied is normally 5-500 g based on 10 ares. When an emulsion, wettable powder, flowable, etc., are diluted with water for application, the concentration of application is 10-2000ppm. Granules, dusts, etc., in a state of a formulation are directly applied without any dilution thereof.

Description

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

<Prior Art> It has been known that certain trihaloimidazole derivatives can be used as active ingredients of insecticides, such as in Belgian Patent No. 788,755, and as acaricides, West German Patent No. 2,081. , 400, etc., and the extracorporeal parasitic agent is described in West German Patent No. 1,950,991, etc.

Also, 1-n-pentyloxymethyl-2゜4,5-
) That dichloroimidazole can be used as an active ingredient in insecticides, especially insecticides for cockroaches, has been shown in British Patent No. 1,816,665 and US Pat.
, 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 extensive research to find a compound with acaricidal activity, we found a compound of the general formula CI) [wherein R represents an alkyl group, an alkynyl group, or a haloalkynyl group]. ] The trihaloimidazole 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.

3. 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.

The compound of the present invention represented by general formula [1] is disclosed in Belgian Patent No. 788.755 and West German Patent No. 1,9
It can be produced according to the method described in No. 50,991.

That is, 2-bromo-4,5-dichloroimidazole and a halide represented by the general formula [1'lD Y -R(fD [wherein R represents the same meaning as above]] were subjected to dehydrohalogenation. It can be produced by reacting in the presence of an agent.

The amount of reagent used in the reaction is 1 equivalent of halide [■] per 1 equivalent of 2-bromo-4゜5-dichloroimidazole.
~2 equivalents, and the dehydrohalogenating agent is 1 to 8 equivalents, and these are reacted in a solvent at 0 to 150°C for about 1 to 24 hours.

The raw material 2-bromo-4,5-dichloroimidazole can be easily produced by the production method described in US Pat. No. 8,409,606.

Examples of the electric medium used in this reaction include aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether, aromatic hydrocarbons such as benzene, toluene, and xylene, chloroform, carbon tetrachloride, dichloroethane, Halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone, ethyl formate, acetic acid Esters such as ethyl, butyl acetate, 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 I
Examples include acid amides such as N-dimethylacetamide, sulfur compounds such as dimethylsulfoxide and sulfolane, and mixtures thereof.

Examples of the dehydrohalogenation agent include organic bases such as pyridine, triethylamine, and N,N-diethylaniline; inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydride;
Examples include alkali metal alcohols such as sodium methoxide and sodium ethoxide.

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

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 impregnated into a substrate such as a mosquito coil, cloak, or noblate. If necessary, surfactants and other formulation auxiliaries may be added to formulate oils, emulsions, wettable powders, suspensions in water, emulsions in water, etc., flowables, granules, powders, aerosols, and insecticides. Heating fumigants such as incense sticks and electric mosquito repellent mats e-Nomat, heating fumigants such as self-combustion type fumigants, chemical reaction type fumigants, and electric heating type fumigants, resin transpiration agents, impregnated paper evaporation agents, etc. non-heating transpiration agents, fogging agents, LJLV 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, fubasamikle, acid clay, etc.), talcs,
Fine powders or granules such as ceramics, 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.) Liquid carriers include, for example, water, alcohols (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 Class (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 sulfate esters, alkyl sulfonates, alkylaryl sulfonates, alkylaryl ethers and polyoxyethylenic products thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol conductors, 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 conductors, bentonite, sugars, synthetic water-soluble polymers (polyvinyl (alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.), and examples of stabilizers include PAP (isopropyl acid phosphate), BHT (2°6-sheet
t-butyl-4-methylphenol), BHA (2-t
ert-butyl-4-methylphenol 3-tert
Examples include mixtures with -phthyl-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 cloak 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 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 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. , organic blowing agents such as azodicarbonamide, benzenesulfonyl hydrazide, dinitrosopentamethylenetetramine, polystyrene, and polyurethane, and fillers such as natural fiber pieces and synthetic fiber pieces.

Examples of the base material for the electrothermal smoke agent include porous ceramic plates, asbestos plates, pulp plates, porous glass materials, and the like.

Examples of the base material of the non-heating transpiration agent include thermoplastic resin,
Examples include 11 Kushi, Japanese paper, etc.

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

Flowable formulations (suspensions or emulsions in water) generally contain 0.5 to 15% of the active ingredient compound.
dispersant, 0.1-10% suspension aid (e.g., protective colloid or compound imparting thixotropy), 0-10%
microscopically in water containing 10% of suitable adjuvants (e.g. antifoaming agents, rust inhibitors, stabilizers, spreading agents, soaking aids, antifreeze agents, antibacterial agents, antifungal agents, etc.). Obtained by dispersing. 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 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. In addition, other rice pesticides, acaricides,
Radiocides, soil insect control agents, insect repellents, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners. Can be used simultaneously with or without mixing. .

When the compound of the present invention is used as an active ingredient of an agricultural insecticide or acaricide, the application amount is usually 5 to 5 g per 10 are.
00y, when applying emulsions, wettable powders, flowables, etc. diluted with water, the application concentration is 10-20001)p
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. should be diluted with water to 10 to 10,000 ppm, and applied as oils, aerosols, etc. Fumigants, smoke agents, haze agents, LILV agents, poison baits, etc. should 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 1 (Production of compound (1) of the present invention) 2-bromo-
A DMF solution (10 m/l) of the sodium salt of 2bromo-4,5-dichloroimidazole prepared from 4,5-dibromoimidazole (1,08&, 5 mmol) and sodium hydride (0,12f, 5 mmol) Methyl iodide (0.71y, 5 mmol) was added dropwise at room temperature. After stirring at room temperature for 4 hours, water (100rn1) was added.

It was extracted twice with ether (50 m) and dried over magnesium sulfate. The oil obtained by concentration was subjected to silica gel chromatography to obtain 1-methyl-2-bromo-4,
0.929 of 5-dichloroimidazole was obtained.

Some of the compounds prepared by the manufacturing methods such as m, p, 72.5° are shown in Table 1.

Table 1 General Formula % Formula % Next, formulation examples are shown. 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 Dissolve 10 parts each of emulsion compounds (1) to (4) in 85 parts of xylene and 35 parts of dimethylformamide, add 14 parts of polyoxyethylene styrylphenyl ether and 6 parts of calcium dodecylbenzenesulfonate, and stir well. Mix to obtain each 10% emulsion.

Formulation Example 2 20 parts of wettable powder compound (1), 4 parts of sodium lauryl sulfate,
Add 2 parts of calcium lignin sulfonate, 20 parts of synthetic hydrated silicon oxide fine powder, and 54 parts of diatomaceous earth to a mixture,
Stir and mix with a juice mixer to obtain a 20% hydrating powder.

Formulation Example 3 5 parts of synthetic hydrated silicon oxide fine powder, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite, and 55 parts of clay are added to 5 parts of granule compound (3), and the mixture is sufficiently 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, 8 parts of PAPo, and 93.7 parts of clay, and stir and mix with a juice mixer. Acetone is removed by evaporation to obtain a 1% powder.

Formulation Example 570 Able Compound (4) 20 parts and sorbitan trioleate 1.
5 parts and 28 parts of polyvinyl alcohol.
．． 5 parts and finely grind it with a sand grinder (particle size 8
μ or less), 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate were added thereto, followed by 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 (4) is dissolved in 10 parts of trichloroethane, and this is mixed with 899 parts of kerosene to obtain each 0.1% oil agent.

Formulation Example 7 0.1 part of oil-based aerosol compound (1), 0.2 parts of tetramethrin, 0.1 part of d-phenothrin, 10 parts of trichloroethane and 59.6 parts of kerosene were mixed and filled into an aerosol container,
After removing the valve part, 30 parts of a propellant (liquefied petroleum gas) is pressurized and filled through the valve part to obtain an oil-based aerosol.

Sinter production example 8 Mosquito coil compound (2) 0.89 was added with d-allethrin o and ay, dissolved in 20 ml of acetone, and a carrier for mosquito coil (Tab powder: Kasu powder: Mokkuri 4:8: Mixed at a ratio of 8) 99.49
After stirring and mixing uniformly, add 120 ml of water, mix thoroughly, and mold and dry to obtain a mosquito coil.

Formulation Example 9 100 μm of each of heat-smoking agent compounds (1) to (4) were dissolved in an appropriate amount of acetone, and 4. Ocm x 4. Ocrn1 thickness 1
．． Each hot smoke agent was obtained by impregnating a 2 cm porous ceramic plate.

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 2.

Table 2 Test Example 1 The following emulsion of the present compound obtained according to Formulation Example 1:
io, oooo diluted solution with water (10ppm) 10
0- was placed in a 180-polycup, and 20 Culex Culex entangled larvae were released. The animals were fed and reared, and 8 days later, their survival and death were investigated to determine the mortality rate (2 repetitions). The results are shown in Table 3.

Table 8 Test Example 2 A filter paper of the same size was placed at the bottom of a polyethylene cup with a diameter of 5.5 mm, and an emulsion of the test compound obtained according to Formulation Example 1 was prepared.
200 times diluted solution with water (500ppm) 0.7 m
l! was dropped onto filter paper, and 30 Ilv of sucrose was evenly added as bait. Ten female adult house flies of a pyrethroid-insensitive strain were released into the container, and the container was covered with a lid. After 48 hours, their survival and death were determined to determine the mortality rate (2 repetitions). The results are shown in Table 4.

It was applied topically onto the fourth top plate at a treatment dose of 1 μf/head. After treatment, the test insects were placed in a polyethylene cup,
Water and food were provided, and the animals were examined for survival and death after 8 days to determine the mortality rate (10 animals per group, 2 replicates).

The results are shown in Table 5.

Table 5 Test Example 3 Each test compound was added to acetone at a predetermined concentration (0.1% W/
V) and applied 1μβ of the diluted solution per adult male German cockroach to the four corners of the bottom of a 70crn cubic glass chamber (0.84i), and butter was applied to the inner surface. A total of 4 polyethylene cups (inner diameter 10 ctn, height 8 m) were installed, and in each cup, pyrethroid-insensitive adult German cockroaches were placed in 2 rows with 10 males and 2 rows with 10 females. were released into the wild. An electric heater was installed at the center bottom of the chamber, and a porous ceramic plate mat smoking agent (dose 1B, 7W9/Vt40"9/yr) of the test compound obtained according to Formulation Example 9 was placed on top of the electric heater. /')
Electricity was applied for 20 minutes and the mixture was heated to about 200'C. 80 minutes after the start of electricity application, the cup containing the test insects was taken out from the chamber, water and food were given, and two days later, the number of live and dead insects was investigated and the mortality rate was calculated (two repetitions).

The results are shown in Table 6.

Table 6 Test Example 5 -
Each leaf was infested with 10 female adult spider mites, and 2
It was placed in a constant temperature room at 5°C. After 6 days, the emulsion of the test compound obtained according to Formulation Example 1 was diluted 200 times with water (
500ppm) per pot on a turntable.
At the same time, 2 ml of the same wave was applied to the soil. After 8 days, the degree of damage caused by spider mites to each plant was investigated (2 repetitions). Criteria for evaluating effectiveness: Almost no damage is observed.

+: Slight damage is observed.

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

Closed. The results are shown in Table 7.

Table 7 <Effects of the Invention> The compounds of the present invention have excellent insecticidal and acaricidal effects against various insect pests such as Apiptera pests, Hemiptera pests, and Diptera pests, and harmful mites such as spider mites. shows.

(25 completed)

Claims (3)

[Claims] (1) General formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R is an alkyl group, an alkynyl group or or haloalkynyl group. ] A trihaloimidazole derivative represented by (2) 2-bromo-4,5-dichloroimidazole and general formula Y-R [wherein R represents an alkyl group, an alkynyl group or a haloalkynyl group, and Y represents a halogen atom. ] 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.