JPH02311466A - Trihaloimidazole derivative, its production and use of the same derivative as insecticide or miticide - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (X<1> to X<3> are halogen; Y is CO or SO2; R is lower alkyl, lower alkenyl or cycloalkyl capable of having substituting group). EXAMPLE:1-{3-(2,2-dimethylvinyl)-2,2-dimethylcyclopropyl carbonyl}-2,4,5- tribromoimidazole. USE:Insecticide or miticide especially effective against cockroaches exhibiting excellent insecticidal and mite-killing activity on various harmful insects such as harmful insect of Dictyoptera, harmful insect of Hemiptera or harmful insect of Diptera and harmful mites such as Tetranychidae. PREPARATION:A compound expressed by formula II is reacted with a compound expressed by the formula Z-Y-R (Z is halogen) in the presence of dehydrohalogenation agent to afford the compound expressed by formula I. Said compound has exceedingly high insecticidal and mite-killing activity, both of knock-down efficiency and fatal efficiency, exceedingly high in the abovementioned effect against harmful insect having low sensitivity to pyrethroid and high efficiency as smoking agent.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel trihaloimidazole derivative, a method for producing the same, and its use as an insecticide or acaricide.

<Prior Art> Certain trihaloimidazole derivatives, such as 1-n
-Pentyloxymethyl-2,4゜6-dolichloride-based dazole can be used as an active ingredient in insecticides, acaricides, especially insecticides for cockroaches, as disclosed in British Patent No. 1,816,665 and U.S. Pat. Patent%8,6
It is described in the specification of No. 74,874, 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 with acaricidal effect, we found a compound with the general formula CI)-R [wherein X, X and X represent the same or different halogen atoms, and Y represents a carbonyl group or a sulfonyl group]. , R represents a lower alkyl group, a lower alkenyl group, or a cycloalkyl group which may have a substituent. ] 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.

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

4. Highly effective as a smoking agent.

We have discovered completely new insecticidal and acaricidal properties such as, and have led to the present invention.

The compound of the present invention has insecticidal and acaricidal effects against many pests and harmful mites, including sanitary pests such as Apiptera pests, Hemiptera pests, and Diptera pests, and agricultural pests, and in particular against German cockroaches. , the American cockroach, the black cockroach, the brown cockroach, the black cockroach, and other cockroaches. Therefore, the compound of the present invention is effective as an insecticide and acaricide against pests and harmful mites that are problematic in many situations. It can be used as an active ingredient.

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

That is, general formula (n) [wherein, Xl, X2 and X8 represent the same meanings as above]. ] Trihaloimidazole represented by the general formula [■] Z-Y
-R [In the formula, 2 represents a halogen atom, and Y and R have the same meanings as above. ] The acid halide represented by these is reacted in the presence of a dehydrohalogenating agent.

The amount of reagent used for the reaction is trihaloimidazole (n)
The acid halide (nl) is 1 to 2 equivalents and the dehydrohalogenation agent is 1 to 8 equivalents per equivalent, and these are heated at about 0 to 160°C for 1 to 24 hours in a solvent or without a solvent. Let it react for about an hour.

Examples of the trihaloimidazole represented by the general formula (n) include tribromoimidazole, 2-bromo-4,
Examples include 5-cyclooimidazole and trichloroimidazole. Among these raw material compounds, for example, 2
-Bromo-4゜5-cyclooimidazole is easily produced by the manufacturing method described in U.S. Patent No. 8,409,606, and trichloroimidazole is described in U.S. Patent No. 8,485,050. be able to.

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,
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, ethyl acetate, and acetic acid. Esters such as butyl and diethyl carbonate, nitrites such as nitroethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, pyridine, triethylamine, N,N-diethylaniline, tributylamine, N
- Tertiary amines such as methylmorpholine, formamide, etc.
Examples include acid amides such as N,N-dimethylformamide and N,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; sodium methoxide; Examples include alkali metal alkoxides such as 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, or bait, or impregnated into a substrate such as a mosquito coil or mat, and then If necessary, add surfactants and other formulation auxiliaries to prepare oils, emulsions, wettable powders, flowables such as suspensions and emulsions in water, granules, powders, aerosols, mosquito coils, etc. Heating fumigants such as electric mosquito repellent mats and no-mats, heating fumigants such as self-combustion type fumigants, chemical reaction type fumigants, and porous ceramic plate fumigants, non-heating fumigants such as resin transpiration agents, impregnated paper evaporation agents, etc. It is used in formulations such as heating evaporation agents, fogging agents, ULV agents, poison baits, etc.

These preparations usually contain the compound of the present invention as an active ingredient in a weight ratio of 0.001 to 95! %contains.

Solid carriers used in formulation include, for example, clays (kaolin clay, diatomaceous earth, synthetic hydrated silicon oxide, bentonite, fubasamiclay, acid clay, etc.), talcs, serazyli, 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 carrier, that is, the propellant include chlorofluorocarbon gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas, and the like.

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 give.

Examples of formulation auxiliaries 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, etc.) , polyvinylpyrrolidone, polyacrylic acids, etc.), and examples of stabilizers include PAP (isopropyl acid phosphate), BIT (2.

6-tert-butyl-4-methylphenol),
Examples include BHA (a mixture of 2-tert-butyl-4-methoxyphenol and s-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 plant powders such as wood flour and lees powder with binders such as tab powder, starch, and gluten.

Examples of the base material for the electric pattern mat include fibrils of cotton linters or a mixture of cotton linters and bulbs 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 of the non-heating transpiration agent include thermoplastic resin,
Examples include filter paper and Japanese paper.

Examples of base materials for poison bait include general food flour, plant essential oils, sugar,
Feed ingredients such as cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, pre-ingestion prevention such as capsicum powder, cheese flavoring, onion flavoring, peanut oil, etc. Examples include attractants.

The formulation of flowables (suspensions or emulsions in water) generally consists of 1-76% compound, 0.5-15% dispersing agent, 0.1-10% suspending aid (e.g. It is obtained by finely dispersing it in water containing colloids, thixotropic additives, penetration aids, antifreeze agents, antibacterial agents, antifungal agents, etc.). It is also possible to use an oil in which the compound hardly dissolves instead of water to form a suspension in oil. Examples of protective colloids that can be 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 or acaricide, the application rate is usually 5 to 5 per 10 are.
When applying 00y-1 emulsion, wettable powder, flowable agent, etc. diluted with water, the application concentration is 10 to 2000 pp.
Granules, powders, etc. are applied as they are without any dilution. In addition, when used as an active ingredient in insecticides and acaricides for household epidemic prevention, emulsions, wettable powders, flowables, etc. should be diluted with water to a concentration of 10 to 10.00 lpm before application, and oils, aerosols, and fumigants should be applied. , smoke agent, fume agent, UL
V agents, poison baits, etc., can be applied as is.

The amount and concentration of these applications vary depending on the circumstances such as the covering of the preparation, the application time, the application location, the application method, the type of pest, and the degree of damage, and may be increased or decreased regardless of the above range. You can

<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) 2.4.5-
tribromoimidazole (1,221,4 mmol),
Chrysanthemum acid chloride (0,75P) was added to a mixture of triethylamine (0,40F, 4 mmol) and toluene (20m).
, 4 mmol) were added at room temperature. After stirring at room temperature for 2 hours, the crystals were separated by F and the furnace liquid was concentrated. Obtained by concentrating
The resulting oil was purified by silica gel chromatography to obtain 0.575' 1-(8-(2,2-dimethylvinyl)
-2,2-dimethylcyclopropylcarbonyl)-2,
4,5-tribromoimidazole (compound of the present invention (1)
) was obtained. Be’lbu6/! Table 1 shows some of the compounds produced by such a production method.

Trihaloimidazole derivatives shown in Table 1-R 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 10 parts each of Milk Formula Compounds (1) to α-fathom 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 thoroughly dissolved. Stir and mix to obtain each 10% emulsion.

Formulation Example 2 Add 20 parts of wettable powder compound (1) 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 diatomaceous earth, and stir with a juice mixer. Mix to obtain 20% hydrating powder.

Formulation Example 8 5 parts of synthetic hydrous silicon oxide fine powder, 5 parts of sodium dodecylbenzenesulfonate, 80 parts of bentonite, and 56 parts of clay are added to 5 parts of granule compound (9), 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, 8 parts of PAPo, 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 a flowable agent compound and 1.5 parts of sorbitan trioleate are mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and after finely pulverizing the mixture with a sand grinder (particle size of 8 μm or less), 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate are added thereto, followed by 10 parts of propylene glycol and mixed with stirring to obtain a 20% suspension in water.

Formulation Example 6 Oil Agent 0.1 part of each of Compounds (1) to α4 is dissolved in 10 parts of trichloroethane and mixed with 89.9 parts of kerosene to obtain each 0.1% oil agent.

Formulation Example 7 Oil-based aerosol compound (310.1 part, tetramethrin 0.2 part, d-
Mix and dissolve 0.1 part of phenothrin, 1 part of trichloroethane, and 59.6 parts of kerosene, fill it into an aerosol container, attach the valve part, and pressurize 80 parts of propellant (liquefied petroleum gas) through the valve part. Fill to obtain oil-based aerosol.

Formulation Example 8 Mosquito coil compound (4) 0. BP to d-arethri: / 0.
8? 'Add, dissolve in acetone 20111, stir and mix uniformly with 99.4F of mosquito coil carrier (mixing tab powder: lees powder: wood flour in the ratio of 4:8:8), and then add 120 d of water.
The mixture is thoroughly kneaded and then molded and dried to obtain mosquito coils.

Formulation Example 9 100fi7 of each of heat-smoking agent compounds (1) to α◆ was dissolved in an appropriate amount of acetone, 4.0cIII×4.0cIII, thickness 1
．． 2 (11) Obtain each heated smoking agent by impregnating a porous ceramic board.

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 A filter paper of the same size was placed at the bottom of an ethylene cup with a diameter of 6.63 mm, and an emulsion of the test compound obtained according to Formulation Example 1 was diluted 200 times with water (500 ppm) o. 7d was dropped onto the filter paper, and 80 tons of mushroom sugar 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 8.

Table 8 Test Example 2 Rice stems (about 1 liter in length) were immersed for 1 minute in a 200-fold dilution of the emulsion of the test compound obtained according to Formulation Example 1 with water (5001) pm). After air-drying, the rice stems were placed in a test tube and 10 adult leafhoppers of a resistant strain were released.After one day, their survival and death were investigated to determine the mortality rate (
2 repetitions).

The results are shown in Table 4.

Test Example 8 Each test compound was diluted with acetone at a predetermined concentration (0.1% W/
M5.1 to adult male German cockroaches.
Head 7. Rio. The diluted solution was applied locally onto the thorax and abdominal plate at a treatment dose of 1 μP/head. After treatment,
Place the test insects in a polyethylene cup, give them water and food,
After 8 days, the animals were examined to see if they were alive or dead, and the mortality rate was calculated (10
2 repetitions) 7, and the results are shown in Table 5.

Table 6 Test Example 4 70c11 cubic glass chamber (0,84772)
A total of four polyethylene cups (inner diameter 10 (Ig, height 8 cgI)) with butter applied to the inner surface were placed in the four corners of the bottom of the 10 males in 2 rows,
Ten rings were released in two rows. An electric heater was installed at the center bottom of the chamber, and a porous ceramic plate mat fumigation agent (18.7 gl9/ret: 40 sp/m) of the test compound obtained according to Formulation Example 9 was placed on it. , and heated to about 200°C by applying electricity for 20 minutes. 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 Potted green beans (first leaf stage) 7 days after sowing,
- Infest each leaf with 10 female adult spider mites,
It was housed in a constant temperature room at 25°C. After 6 days, the milk of the test compound obtained according to Formulation Example 1 was mixed with water to add 500 pp of the active ingredient.
15 m 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). The criteria for evaluating effectiveness is 1: 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.

<Effects of the Invention> The compound of the present invention exhibits excellent insecticidal and acaricidal efficacy against various insect pests such as Apiptera pests, Hemiptera pests, and Diptera pests, and harmful mites such as spider mites. .

Claims (4)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X^1, X^2 and X^3 represent the same or different halogen atoms, Y represents a carbonyl group or a sulfonyl group, R represents a lower alkyl group, a lower alkenyl group, or a cycloalkyl group which may have a substituent. ] A trihaloimidazole derivative represented by (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X^1, X^2 and X^3 represent the same or different halogen atoms. ] Trihaloimidazole represented by the general formula Z-Y-R [wherein, Z represents a halogen atom, Y represents a carbonyl group or a sulfonyl group, and R has a lower alkyl group, a lower alkenyl group, or a substituent; Represents an optionally cycloalkyl group. ] The general formula is characterized by reacting the acid halide represented by the following in the presence of the dehalogenating base agent ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X^1, X^2 , X^3 and R have the same meanings as above. ] A method for producing a trihaloimidazole derivative. (3) An insecticide or acaricide containing the trihaloimidazole derivative according to claim 1 as an active ingredient. (4) An insecticidal or acaricidal method using the trihaloimidazole derivative according to claim 1.