JPH0413344B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [] [In the formula, X and Y represent halogen atoms,
n represents an integer from 4 to 6. ] The trihaloimidazole derivative (hereinafter referred to as
It is called the compound of the present invention. ) Regarding its production method and insecticides containing it as an active ingredient. The halogen atoms represented by X and Y include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom, respectively. The present inventors have conducted extensive studies to find a compound with superior insecticidal efficacy, and as a result, the compound of the present invention represented by the general formula [] has: 1. Extremely high insecticidal efficacy. 2. Particularly effective against cockroaches, with excellent knockdown and lethal activity. 3. Demonstrates a remarkable insecticidal effect against pyrethroid-insensitive German cockroaches. 4. Highly effective as a smoking agent. 5. Relatively low toxicity to humans and animals. It was discovered that it has excellent properties such as. Certain trihaloimidazole derivatives, such as 1-pentyloxymethyl-2,4,5-trichloroimidazole, 1-isopropoxymethyl-2,4,5-trichloroimidazole, 1-
(2-bromoethyl)oxymethyl-2,4,5
- The fact that tribromoimidazole and the like can be used as active ingredients of insecticides and acaricides is disclosed in British Patent No. 1316665 and US Patent No. 3674874.
It is stated in the specification etc. The compound of the present invention is included in the general formula described in U.S. Pat. As shown, the compound of the present invention not only has extremely high insecticidal efficacy compared to the green compounds described in the specification, but also has an insecticidal effect against pyrethroid-insensitive German cockroaches and an effect as a smoking agent. In this regard, they have discovered that they have completely new insecticidal properties, leading to the present invention. The compound of the present invention can be used as an active ingredient of an insecticide that is effective against pests that are problematic in many situations, and in particular, cockroaches (Japanese cockroaches, German cockroaches,
It is expected to be used as an active ingredient in fumigants for controlling American cockroaches, black cockroaches, etc.). Among the compounds of the present invention, those with particularly high insecticidal efficacy as insecticides for cockroaches include 1-(4-bromobutoxymethyl)-2,4,5
-Trichloroimidazole 1-(4-chlorobutoxymethyl)-2,4,5
-Trichloroimidazole 1-(4-bromobutoxymethyl)-2,4,5
-Tribromoimidazole 1-(4-chlorobutoxymethyl)-2,4,5
-tribromoimidazole 1-(6-bromohexyloxymethyl)-2,
4,5-trichloroimidazole 1-(6-bromohexyloxymethyl)-2,
Examples include 4,5-tribromoimidazole. The compound of the present invention has the general formula [] [In the formula, X represents a halogen atom. ] Trihaloimidazole represented by the general formula [] ZCH ₂ O (CH ₂ ) _o Y [] [wherein, Y and Z represent a halogen atom,
n represents an integer from 4 to 6. ] in a solvent and in the presence of a dehydrohalogenating agent at about 0°C to 150°C.
It can be produced by reacting for about 24 hours to 24 hours. Here, examples of the halogen atom represented by Z include a chlorine atom and a bromine atom. 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, nitrites such as nitroethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, pyridine, triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine, etc. Examples include tertiary amines, formamide, 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, etc. 2,4,5-tribromoimidazole, which is a raw material for the compound of the present invention, can be produced by brominating imidazole.
and Swiss Patent No. 485,733. Production Example 1 (Production of compound (1) of the present invention) 2,4,5-trichloroimidazole (1.03
g), 4-bromobutoxymethyl bromide (1.48 g) was added dropwise to a mixture of triethylamine (0.61 g) and toluene (approx. 30 ml) at room temperature. After stirring the mixture at room temperature for 2 hours, the crystals were separated and washed with about 10 ml of toluene. The liquid thus obtained was concentrated under reduced pressure, and the remaining oil was purified by silica gel column chromatography to obtain 1-(4-bromobutoxymethyl)-
0.78 g of 2,4,5-trichloroimidazole was obtained. n ^23.7 _D 1.5337 Production Example 2 (Production of compound (2) of the present invention) 2,4,5-trichloroimidazole (0.69
4-chlorobutoxymethyl chloride (0.63 g) was added dropwise at room temperature to a solution of the sodium salt prepared from g) and 60% oily sodium hydride (0.16 g) in N,N-dimethylformamide (5 ml). After stirring at room temperature for 3 hours, 50 ml of water was added and the mixture was extracted three times with 30 ml of ether. The ether layer was dried over magnesium sulfate and concentrated. The obtained oil was purified by silica gel column chromatography to obtain 0.83 g of 1-(4-chlorobutoxymethyl)-2,4,5-trichloroimidazole. n ^26.3 _D 1.5140 Production Example 3 (Production of compound (3) of the present invention) 2,4,5-tribromoimidazole (1.22
4-bromobutoxymethyl bromide (1.23 g) was added dropwise at room temperature to a solution of the sodium salt prepared from g) and 60% oily sodium hydride (0.16 g) in N,N-dimethylformamide (5 ml). After stirring at room temperature for 3 hours, 50 ml of water was added and the mixture was extracted three times with 30 ml of ether. The ether layer was dried over magnesium sulfate and concentrated. The obtained oil was purified by silica gel column chromatography to obtain 0.74 g of 1-(4-bromobutoxymethyl)-2,4,5-tribromoimidazole. n ^21.7 _D 1.5797 Some of the compounds of the present invention that can be produced by such a production method are shown in Table 1.

[Table] When the compound of the present invention is used as an active ingredient of an insecticide, it may be used as is without adding any other ingredients, but it is usually used in combination with a solid carrier, liquid carrier, gaseous carrier, surfactant, or other It can be mixed with formulation auxiliaries, baits, etc., or impregnated into base materials such as incense sticks and mats to produce emulsions, wettable powders, powders, granules, oils, aerosols, mosquito coils, electric mosquito mats, and porous ceramics. It is formulated into heating fumigants such as board pine, fogging agents such as fogging, non-heating fumigants, poison baits, etc. These preparations contain 0.001% to 95% by weight of the compound of the present invention as an active ingredient. Examples of solid carriers include fine powders such as kaolin clay, attapalgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corncob powder, walnut shell powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Examples of liquid carriers include aliphatic hydrocarbons such as kerosene and kerosene, aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene, and halogenated substances such as dichloroethane, trichloroethylene, and carbon tetrachloride. Hydrocarbons, alcohols such as methanol, ethanol, isopropanol, ethylene glycol, cellosolve, ketones such as acetone, methyl ethyl ketone, cyclohexanone, isophorone, ethers such as diethyl ether, dioxane, tetrahydrofuran, esters such as ethyl acetate, acetonitrile , nitriles such as isobutyronitrile, acid amides such as dimethylformamide and dimethylacetamide, dimethyl sulfoxide, vegetable oils such as soybean oil and cottonseed oil, etc. Gaseous carriers include:
Examples include chlorofluorocarbon gas, LPG (liquefied petroleum gas), and dimethyl ether. Examples of surfactants used for emulsification, dispersion, wetting, etc. include alkyl sulfate salts, alkyl (aryl) sulfonate salts, dialkyl sulfosuccinate salts, polyoxyethylene alkylaryl ether phosphate salts, and naphthalene. Examples include anionic surfactants such as sulfonic acid formalin condensates, and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Examples of formulation aids such as fixing agents and dispersants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, molasses, casein, gelatin, CMC (carboxymethylcellulose), pine oil, agar, etc. Stabilizers include alkyl phosphates such as PAP (isopropyl acid phosphate) and TCP (tricresyl phosphate), vegetable oils, epoxidized oils, the above-mentioned surfactants, antioxidants such as BHT and BHA, sodium oleate, Examples include fatty acid salts such as calcium stearate, fatty acid esters such as methyl oleate, and methyl stearate. Examples of formulations are shown below. In addition, the compound of the present invention is the first
Indicated by compound number in the table. Parts mean parts by weight. Formulation Example 1 An oil solution is obtained by mixing 0.2 parts of the compound of the present invention (1), 2 parts of xylene, and 97.8 parts of white kerosene. Formulation Example 2 10 parts each of the compounds (1) to (7) of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 70 parts of xylene are thoroughly mixed to obtain each emulsion. Formulation Example 3 20 parts of the compound of the present invention (2), 10 parts of fenitrothion,
3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 65 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain a wettable powder. Formulation Example 4 1 part of the compound of the present invention (1), 2 parts of carbaryl, 37 parts of kaolin clay and 10 parts of talc are thoroughly ground and mixed to obtain a powder. Formulation Example 5 5 parts of the compound of the present invention (1), 1 part of synthetic hydrated silicon oxide,
2 parts of calcium ligninsulfonate, 30 parts of bentonite and 62 parts of kaolin clay are thoroughly ground and mixed, water is added and the mixture is thoroughly kneaded, followed by granulation and drying to obtain granules. Formulation example 6 0.05 part of the compound of the present invention (1), 0.2 part of tetramethrin,
Mix and dissolve 0.05 parts of resmethrin, 7 parts of xylene, and 32.7 parts of deodorized kerosene, fill it into an aerosol container, and attach the valve part. Then, pressurize and fill 60 parts of propellant (liquefied petroleum gas) through the valve part to create an aerosol. get. Formulation Example 7 Add 0.3 g of d-trans primary chrysanthemum acid ester of allethrin to 0.3 g of the compound (1) of the present invention, and add methanol
Dissolve in 20ml and add carrier for mosquito coil (tab powder: lees powder:
Mix 99.4g of wood flour (mixed at a ratio of 3:5:1) with stirring, evaporate methanol, and add 150g of water.
ml, mix thoroughly and mold and dry to obtain mosquito coils. Formulation Example 8 100 mg of each of the compounds (1) to (7) of the present invention are dissolved in an appropriate amount of acetone and impregnated into a porous ceramic plate measuring 4.0 cm x 4.0 cm and 1.2 cm thick to obtain each heat fumigant. These preparations can be used as they are or diluted with water. It can also be used in combination with other insecticides, acaricides, nematicides, fungicides, herbicides, plant growth regulators, fertilizers, soil conditioners, and the like. When using the compound of the present invention as an insecticide, in the case of emulsions and wettable powders, the application concentration is 10 ppm to
The concentration is 10,000 ppm, and powders, granules, oils, aerosols, etc. should be applied in their original form without any dilution. Next, a test example is shown. The compounds used for comparison are indicated by compound symbols in Table 2.

〔result〕

The acute oral toxicity to mice and the insecticidal efficacy against German cockroaches of the test compounds are shown in Table 3. In addition, in order to further clarify the characteristics of the compound of the present invention in the same table that it has low toxicity to warm-blooded animals and high efficacy against target pests, the following safety coefficient was calculated based on the results of this test. I asked for it. Safety factor = Mouse toxicity (LD ₅₀ mg/Kg) / Insecticidal efficacy (
LD ₅₀ mg/Kg) As a result of this calculation, the safety coefficients of the compounds (1) and (2) of the present invention are both approximately 50 or more. This means it is more than 50 times safer for warm-blooded animals.
In contrast, the safety factor of the reference compound is (C)
16, (D) was 18, and (E) was 5.6.

[Table] Test Example 2 Each of the compounds of the present invention and a comparative compound was diluted with acetone and applied topically to the thorax and abdomen of adult male black cockroaches in an amount of 10 μg per head. After treatment, the insects were kept in a polyethylene cup while being provided with food and water, and two days later, the insects were examined for survival and mortality to determine the mortality rate (5 animals per group, 2 replicates).

[Table] Test Example ³ A total of 4 polyethylene cups (inner diameter 10 cm, height 8 cm) with butter coated on the inner surface were placed in each of the four corners of the bottom of a 70 cm cubic glass chamber (0.34 m 3 ).
In each cup, adult German cockroaches of a pyrethroid-low susceptibility strain were released in two rows of 10 males and two rows of 10 females. Install an electric heater at the center bottom of the chamber,
A fumigation agent for porous ceramic mat boards impregnated with the compound of the present invention obtained according to Formulation Example 8 and a comparative compound (13.7 mg/mat: 40 mg/m ³ )
was heated to approximately 200°C by applying electricity for 20 minutes. The number of knockdown insects was observed over time, and KT ₅₀ (50% knockdown time) was determined. 80 minutes after the start of energization, the cup containing the test insect was removed from the chamber.
Water and food were given, and the number of living and dead insects was investigated two days later, and the mortality rate was calculated (two repetitions). The results are shown in Table 5.

[Table] Test example 4 183 cm cubic peat gradient chamber (6.1
Three polyethylene cups (inner diameter 10 cm, height 8 cm ⁾ coated with butter on the inner surface were placed at the bottom of a pyrethroid-insensitive cockroach. Male and female
10 animals) were released at a time. An electric heater was installed at the center bottom of the chamber, and a fumigant (61 mg/mat: 10 mg/m ³ ) and turn on the power for 70 minutes, approximately 200
heated to ℃. The number of knockdown insects was observed over time, and the KT ₅₀ value (50% knockdown time) was determined.
80 minutes after the start of electricity application, the cup containing the test insects was taken out from the chamber and fed with water and food.After 3 days, the number of living and dead insects was examined and the mortality rate was calculated. The results are shown in Table 6.

[Table] Test Example 5 10 adult German cockroaches of the susceptible strain and pyrethroid non-susceptible strain (5 of each sex) were released in a polyethylene cup with a diameter of 9 cm with a thin layer of Vaseline applied to the wall, and 16 meshes of nylon gauze were placed. Cover with a lid and place it at the bottom of a glass cylinder with an inner diameter of 10 cm and a height of 37 cm. 0.6 ml each of the 0.1% oil solutions of the present compound and the control compound obtained according to Formulation Example 1 were directly sprayed from the top of the cylinder at a pressure of 0.6 atmospheres using a spray gun, and the number of knockdown insects was observed over time. ₅₀ value (50% knockdown time) was determined (2 repetitions). The results are shown in Table 7. Table 7

【table】

Claims (1)

[Claims] 1. General formula [In the formula, X and Y represent halogen atoms,
n represents an integer from 4 to 6. ] A trihaloimidazole derivative represented by 2 General formula [In the formula, X represents a halogen atom. ] Trihaloimidazole represented by the general formula ZCH ₂ O(CH ₂ ) _o Y [wherein, Y and Z represent a halogen atom,
n represents an integer from 4 to 6. ] A general formula characterized by reacting a halomethyl ether represented by in the presence of a dehydrohalogenating agent. [In the formula, X, Y and n represent the same meanings as above. ] A method for producing a trihaloimidazole derivative. 3 General formula [In the formula, X and Y represent halogen atoms,
n represents an integer from 4 to 6. ] An insecticide characterized by containing a trihaloimidazole derivative represented by the following as an active ingredient. 4 Claim No. 3 which is a smoking agent for cockroaches
Insecticides listed in section.