JPH0367060B2 - - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to the general formula () [In the formula, R ₁ is a hydrogen atom, a fluorine atom, a chlorine atom,
It represents a bromine atom or a methyl group, and R ₂ represents a hydrogen atom or a fluorine atom. R ₃ has 2 or more carbon atoms
represents an alkyl group of 4 or a 2,2,2-trifluoroethyl group. A represents an oxygen atom or an imino group. ] The present invention relates to an ether compound represented by the following and insecticides and acaricides containing the same as an active ingredient. The present inventors have conducted intensive studies to develop excellent insecticidal and acaricidal agents, and have discovered that the ether compound represented by the above general formula () has high insecticidal and acaricidal effects, and has developed the present invention. It was completed. Specific pests to which the compound of the present invention is effective include Hemiptera such as planthoppers, leafhoppers, aphids, and stink bugs; Lepidoptera such as mealybugs and armyworms; Coleoptera such as weevils and black beetles; Culex mosquitoes and houseflies. Examples include Diptera, such as the Orthoptera, and Orthoptera, such as the Japanese locust and Japanese cockroach. The compound of the present invention has the general formula () [In the formula, R ₁ , R ₂ and A have the same meanings as above, and Z represents a halogen atom. ] Benzyl halide shown by and the general formula () [In the formula, R ₃ has the same meaning as above. ] It is obtained by reacting the alcohol represented by the formula () with an alkali metal salt, and more specifically, the alcohol represented by the general formula () is reacted with an alkali metal salt in an aprotic polar solvent (e.g. dimethylformamide, dimethyl sulfoxide, etc.). It is reacted with a metal hydride to form an alkali metal salt, and a benzyl halide represented by the general formula () is added to the alkali metal salt.
It can be produced by reacting at a temperature of 1 to 50°C for 1 to 12 hours. Examples of the alcohol represented by the general formula () include the following. 1-(4-ethoxyphenyl)cyclopropyl-1-carbinol 1-(4-n-propyloxyphenyl)cyclopropyl-1-carbinol 1-(4-iso-propyloxyphenyl)cyclopropyl-1 -Carbinol 1-(4-n-butyloxyphenyl)cyclopropyl-1-carbinol 1-(4-(2,2,2-olifluoroethoxy)phenyl)cyclopropyl-1-carbinol Above alcohol The class is J.Amer.Chem.Soc.
93(17), 4237-4242 (1971), KhimFarm.Zh.
14(2), 40-45 (1980), etc., by reducing 1-phenylcyclopropanecarboxylic acids or esters thereof with a reducing agent such as lithium aluminum hydride. Furthermore, the following benzyl halides represented by the general formula () can be mentioned. 3-Phenoxybenzyl bromide 4-fluoro-3-phenoxybenzyl chloride 3-(4-fluorophenoxy)benzyl bromide 3-(4-chlorophenoxy)benzyl bromide 3-(4-bromophenoxy)benzyl bromide 3-(4-methylphenoxy)benzyl chloride 4-fluoro-3-(4-fluorophenoxy)
Benzyl chloride 4-fluoro-3-(4-chlorophenoxy)
Benzyl chloride 4-fluoro-3-(4-methylphenoxy)
Benzyl bromide 4-fluoro-3-(4-bromophenoxy)
Benzyl bromide 3-anilinobezyl bromide 3-(4-fluoroanilino)benzyl chloride 3-(4-chloroanilino)benzyl bromide 3-(4-bromoanilino)benzyl bromide 3-(4-methylanilino)benzyl bromide (3-anilino) -4-fluoro)benzyl bromide 4-fluoro-3-(4-fluoroanilino)
Benzyl chloride 4-fluoro-3-(4-chloroanilino)benzyl chloride 4-fluoro-3-(4-bromoanilino)benzyl bromide 4-fluoro-3-(4-methylanilino)benzyl bromide Next, production examples of the compounds of the present invention will be described. show. Production Example Synthesis of Compound (1) 114 mg (2.86 mmol) of sodium hydride (60% oil suspension) was suspended in 5 ml of dimethylformamide, and 1-(4
A solution of 549 mg (2.86 mmol) of dimethylformamide (3 ml) of dimethylformamide (-ethoxyphenyl)cyclopropyl-1-carbinol is added dropwise, and the internal temperature is maintained at 50 to 80°C until hydrogen generation is complete. Then, cool to room temperature and 3-phenoxy-4-
Fluorobenzyl chloride 615 mg (2.60 mmol)
3 ml of dimethylformamide solution was added dropwise, and the mixture was stirred overnight at room temperature. Next, the reaction mixture solution was poured into 50 ml of water, extracted twice with 20 ml of ether,
After drying the ether layer over anhydrous magnesium sulfate, the ether was distilled off, and the ether layer was separated and purified by column chromatography packed with silica gel.
Phenoxy-4-fluorobenzyl 1-(4-ethoxyphenyl)cyclopropyl methyl ether
805 mg was obtained as a colorless liquid. Table 1 summarizes some of the compounds of the present invention that can be produced in the same manner as in the above production examples. [Table] Reference example Synthesis of 1-(4-ethoxyphenyl)cyclopropyl-1-carbinol 445 mg (11.7 mmol) of lithium aluminum hydride was added to tetrahydrofuran under a nitrogen stream.
Make a suspension with 40ml and add 1-(4-
ethoxyphenyl)cyclopropanecarboxylic acid
2.41g (11.7mmol) of tetrahydrofuran 20ml
Add the solution dropwise while stirring under ice-cooling, and after the completion of dropping
Stir at room temperature for an hour. Next, the reaction solution was carefully poured into a mixture of a large amount of ice and concentrated hydrochloric acid while stirring, and extracted several times with diethyl ether. After drying the ether layer over anhydrous magnesium sulfate, the solvent was distilled off, and 1-( 4-ethoxyphenyl)cyclopropyl-1-carbinol
2.13 g was obtained as a pale yellow liquid. Physical properties n ^21.0 _D 1.5382 When the compound of the present invention is used as an active ingredient in insecticides or acaricides, it is usually used in the presence of solid carriers, liquid carriers, gaseous carriers, or other formulation auxiliaries (e.g., surfactants, dispersants, moisturizers, etc.). (spreading agents, stabilizers, etc.) to produce various preparations such as emulsions, wettable powders, powders, granules, oils, aerosols, thermal fumigants, (mosquito coils,
Use electric mosquito repellents, etc.), fumigants such as fogging, non-heating fumigants, poison baits, etc. The active ingredient content in these preparations ranges from 0.1% to 95%
It is. Solid carriers include fine powders or powders such as clays (e.g. kaolin, bentonite, acid clay, pyrophyllite, sericite), talcs, and other inorganic minerals (e.g. hydrated silicon dioxide, pumice, diatomaceous earth, sulfur powder, activated carbon). Things can be mentioned. Liquid carriers include alcohols (e.g. methyl alcohol), ketones (e.g. acetone,
methyl ethyl ketone), ethers (e.g. ethyl ether, dioxane, cellosolve, tetrahydrofuran), aromatic hydrocarbons (e.g. benzene, toluene, xylene, methylnaphthalene),
Examples include aliphatic hydrocarbons (eg, kerosene, kerosene), esters, nitriles, acid amides (eg, dimethylformamide, dimethylacetamide), halogenated hydrocarbons (eg, dichloroethane, trichloroethylene, carbon tetrachloride), and the like. Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, polyethylene glycol ethers, and polyhydric alcohol esters. Furthermore, usable fixing agents and dispersants include casein, gelatin, starch powder, CMC, gum arabic, alginic acid, lignin sulfonate,
Stabilizers include bentonite, molasses, polyvinyl alcohol, pine oil, agar, etc.
Examples include PAP (isopropyl phosphate), TCP (tricresyl phosphate), tall oil, epoxidized oil, various surfactants, and various fatty acids or their esters. Examples of formulations are shown below. Formulation Example 1 Each of the compounds (1) to (10) of the present invention is dissolved in white kerosene in an amount of 0.5 parts to make a total of 100 parts to obtain each oil solution. Formulation Example 2 Add 10 parts each of the compounds (1) to (10) of the present invention, 10 parts emulsifier {Solpol 3005X (registered trademark name of Toho Chemical)}, and 70 parts xylol, and stir and mix them well to form each compound. An emulsion is obtained. Formulation example 3 0.2 parts of the compound of the present invention (1), 0.3 parts of tetramethrin,
Mix and dissolve 5 parts of xylol and 44.5 parts of deodorized kerosene,
After filling an aerosol container and attaching a valve part, an aerosol is obtained by filling 50 parts of a propellant (liquefied petroleum gas) under pressure through the valve part. Formulation Example 4 0.2 parts of the compound of the present invention (2), 0.3 parts of the d-trans acid form of allethrin, 8.5 parts of deodorized kerosene, and 1 part of an emulsifier {Atmos 300 (registered trademark of Atlas Chemical Co., Ltd.)} were mixed, and the mixture was mixed with 60 parts of pure water. A water-based aerosol is obtained by emulsifying the mixture and filling it into an aerosol container with 30 parts of a 3:1 mixture of deodorized butane and deodorized propane. Formulation Example 5 Dissolve 0.6 g of the compound (1) of the present invention in 20 ml of methanol and stir uniformly with 99.4 g of carrier for mosquito coils (mixture of tab powder: lees powder: wood flour in a ratio of 3:5:1). After mixing and evaporating the methanol, add 150 ml of water, mix well, mold and dry to obtain each mosquito coil. Formulation Example 6 Add 0.08g of BHF to 0.08g of the compound (1) of the present invention,
Dissolve in an appropriate amount of chloroform and evenly absorb onto a piece of paper 3.5cm x 1.5cm and 0.3cm thick. A fiber fumigation composition heated on an electric heating plate is thus obtained. Formulation Example 7 10 parts each of the compounds (4) and (5) of the present invention were thoroughly mixed with 5 parts of an emulsifier {Solpol 5029-0 (registered trademark name of Toho Chemical)}, and 85 parts of 300 mesh diatomaceous earth was added and mixed thoroughly with stirring. Then you will get each hydrating agent. Formulation Example 8 0.5 parts of each of the compounds (1) to (10) of the present invention are dissolved in an appropriate amount of acetone, 99.5 parts of 300 ml of turquoise are added thereto, and the mixture is thoroughly stirred and mixed.The acetone is then evaporated off to obtain each powder. The compounds of the present invention can be widely used as insecticides and acaricides for agricultural and horticultural purposes such as paddy fields, fields, orchards, tea gardens, mulberry gardens, lawns, pastures, forests, etc., and can also be used as insecticides and acaricides for epidemic prevention. Next, test examples will be given to 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 as comparative controls are indicated by the following compound symbols. [Table] Test Example 1 A piece of paper of the same size was placed at the bottom of a polyethylene cup with a diameter of 5.5 cm. 0.7 ml of a 200-fold diluted solution of the emulsion obtained in Formulation Example 2 in water (equivalent to 500 ppm) was dropped onto the paper. 30 mg of sucrose was placed on the paper as bait. Release 10 female adult house flies into the container, put the lid on, and
After some time, we examined whether they were alive or dead and determined the adult rate (2
repetition). [Table] Test Example 2 Aqueous dilutions of predetermined concentrations of emulsions of compounds (1) and (2) of the present invention obtained in Formulation Example 2 and control compounds (A) and (B) obtained in the same manner were tested. The treatment was carried out in the same manner as in Example 1, and the LC ₅₀ value (median lethal concentration) for female adult domesticated grass was determined. (2 repetitions) [Table] Test Example 3 200% of the emulsion of the present compound obtained in Formulation Example 2
2 ml of the diluted solution (equivalent to 500 ppm) was soaked into 15 g of artificial feed for Spodoptera japonica and placed in a polyethylene cup with a diameter of 11 cm. Ten third instar Spodoptera larvae were released into the larvae, and 24 hours later, they were examined to see if they were alive or dead, and the mortality rate was determined. (2 repetitions) [Table] [Table] Test example 4 1 for 4 leaves of potted chinensis 5 days after sowing
Each leaf was infested with 10 mag female adult spider mites and stored in a constant temperature room at 27°C. After 6 days, a 200-fold diluted emulsion in water (500 ppm (equivalent) was sprayed on a turntable at 10 ml per pot. After 6 days, female adult spider mites on the plants were counted. The effectiveness criteria were ++ 1 leaf infested with 0 to 9 female adults + 10 to 30 - 31 or more. The results are shown below. 【table】

Claims (1)

[Claims] 1 General formula () [In the formula, R ₁ is a hydrogen atom, a fluorine atom, a chlorine atom,
It represents a bromine atom or a methyl group, and R ₂ represents a hydrogen atom or a fluorine atom. R ₃ has 2 or more carbon atoms
represents an alkyl group of 4 or a 2,2,2-trifluoroethyl group. A represents an oxygen atom or an imino group. ] An ether compound represented by 2 General formula () [In the formula, R ₁ is a hydrogen atom, a fluorine atom, a chlorine atom,
It represents a bromine atom or a methyl group, and R ₂ represents a hydrogen atom or a fluorine atom. R ₃ has 2 or more carbon atoms
represents an alkyl group of 4 or a 2,2,2-trifluoroethyl group. A represents an oxygen atom or an imino group. ] An insecticide and acaricide characterized by containing an ether compound represented by the following as an active ingredient.