JPH04234829A - Alcohol derivative - Google Patents

Abstract

PURPOSE:To provide a new alcohol derivative useful as a production intermediate for an ether compound having high insecticidal and miticidal activities. CONSTITUTION:The compound of formula I (R is lower alkyl other than methyl or 2,2,2-trifluoromethyl), e.g. 1-(4-ethoxyphenyl) cyclopropyl-1-carbinol. The compound can be produced by reducing a 1-phenylcyclopropanecarboxylic acid of formula II or its ester with a reducing agent such as aluminum lithium hydride. The compound is useful as an intermediate for ether compounds of formula III (R1 is H, F, Cl, Br or methyl; R2 is H or F; A is O or NH), e.g. 3-phenoxy-4-fluorobenzyl 1-(4-ethoxyphenyl)cyclopropylmethyl ether.

Description

[Detailed description of the invention]

The present invention is directed to the general formula 2 which is useful as an intermediate for insecticides and acaricides.

0002

[Case 2]

[In the formula, R represents a lower alkyl group other than a methyl group or a 2,2,2-trifluoroethyl group. ] Regarding the alcohol derivative shown. The inventors
As a result of intensive research to develop excellent insecticides and acaricides, the general formula 3 was developed.

0004

[Chemical formula 3]

[In the formula, R1 is a hydrogen atom, a fluorine atom,
It represents a chlorine atom, a bromine atom or a methyl group, and R2 represents a hydrogen atom or a fluorine atom. A represents an oxygen atom or an imino group. R represents the same meaning as above. ]
It was discovered that the ether compound represented by (hereinafter referred to as ether compound) has high insecticidal and acaricidal efficacy,
Furthermore, the inventors discovered that the alcohol derivative represented by the above formula 2 (hereinafter referred to as the compound of the present invention) is a useful intermediate for ether compounds, and completed the present invention. In this application, a lower alkyl group other than a methyl group has 2 carbon atoms.
~4 alkyl groups, such as ethyl group, n-
Examples include propyl group, iso-propyl group, and n-butyl group. The compound of the present invention has the general formula:

[0006]

[C4]

[In the formula, R has the same meaning as above. ]
It can be easily obtained by reducing the 1-phenylcyclopropanecarboxylic acids or esters thereof with a reducing agent such as lithium aluminum hydride. Next, production examples of the compounds of the present invention will be shown. Production Example 1 Lithium aluminum halide 44 under nitrogen flow
5 mg (11.7 mmol) in tetrahydrofuran
Make a suspension with 40 ml, and add 2.41 g of 1-(4-ethoxyphenyl)cyclopropanecarboxylic acid.
A solution of (11.7 mmol) in 20 ml of tetrahydrofuran was added dropwise with stirring under ice cooling, and after the addition was completed, the mixture was stirred at room temperature for 2 hours. 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-( 2.13 g of 4-ethoxyphenyl)cyclopropyl-1-carbinol was obtained as a pale yellow liquid. n21.0 D 1.5382 Production Example 2 In Production Example 1, 1-(4-n-propyloxy)cyclopropanecarboxylic acid was used instead of 1-(4-ethoxyphenyl)cyclopropanecarboxylic acid, and 1- (
4-n-propyloxyphenyl)cyclopropyl-1
- Carbinol was obtained. Production Example 3 In Production Example 1, 1-(4-iso
1-(4-iso-propyloxyphenyl)cyclopropyl-1-carbinol was obtained using -propyloxyphenyl)cyclopropanecarboxylic acid. Production Example 4 In Production Example 1, 1-(4-n-butyloxyphenyl)cyclopropanecarboxylic acid was used instead of 1-(4-ethoxyphenyl)cyclopropanecarboxylic acid,
1-(4-n-butyloxyphenyl)cyclopropyl-1-carbinol was obtained. Production Example 5 In Production Example 1, 1-{4-(2,2
, 2-trifluoroethoxy)phenyl)cyclopropanecarboxylic acid to obtain 1-(4-(2,2,2-trifluoroethoxy)phenyl)cyclopropyl-1-carbinol. The 1-phenylcyclopropanecarboxylic acids represented by the general formula 4, which are raw materials for producing the compounds of the present invention, are described in J. Amer. Chem. So
c. , 93(17), 4237-4242 (19
71), Khim-Farm, Zh. ,14 (2)
, 40-45 (1980). The compound of the present invention and its alkali metal salt have the following general formula:

[0008]

[C5]

[In the formula, R1, R2 and A have the same meanings as above, and Z represents a halogen atom. ] By reacting with the benzyl halide represented by the above formula, the ether compound represented by the general formula 3 can be easily obtained. More specifically, the compound of the present invention represented by the general formula 2 is reacted with an alkali metal hydride in an aprotic polar solvent (e.g. dimethylformamide, dimethyl sulfoxide, etc.) to form an alkali metal salt, The benzyl halide represented by chemical formula 5 is 0
An ether compound can be produced by reacting at a temperature of 1 to 50°C for 1 to 12 hours. Next, an example of producing an ether compound will be shown. Reference production example Sodium hydride (60% oil suspension) 11
4 mg (2.86 mmol) in dimethylformamide 5
ml to make a suspension, and 1-(4-ethoxyphenyl)cyclopropyl-1-carbinol 549m
g (2.86 mmol) of dimethylformamide 3 ml
Add the solution dropwise and keep the internal temperature at 50-80°C until hydrogen generation ends.
Keep it. Then, cool to room temperature and 3-phenoxy-4-
A solution of 615 mg (2.60 mmol) of fluorobenzyl chloride in 3 ml of dimethylformamide is added dropwise, and the mixture is stirred overnight at room temperature. Next, add the reaction mixture solution to 5 liters of water.
The ether layer was dried over anhydrous magnesium sulfate, the ether was distilled off, and the 3-phenoxy-4-fluoro 805 mg of benzyl 1-(4-ethoxyphenyl)cyclopropyl methyl ether was obtained as a colorless liquid. Table 1 summarizes some of the ether compounds that can be produced in the same manner as in the above production examples. Specific pests for which ether compounds are particularly effective include hemiptera such as planthoppers, leafhoppers, aphids, and stink bugs, mealybugs,
Examples include Lepidoptera such as armyworms, Coleoptera such as weevils and beetles, Diptera such as Culex mosquitoes and houseflies, and Orthoptera such as locust locusts and German cockroaches.

When an ether compound is used as an active ingredient of an insecticide or acaricide, it is usually used as a solid carrier, liquid carrier, gaseous carrier, or other formulation auxiliary agent (such as a surfactant, dispersant, wetting agent, etc.). (stabilizers, etc.) to produce various preparations, such as emulsions, wettable powders, powders, granules, oils, aerosols, heated fumigants, (mosquito coils, electric mosquito repellents, etc.), fogging agents, etc. Use non-heated fumigant, poison bait, etc. The active ingredient content in these formulations is between 0.1% and 95%. Solid carriers include clays (e.g. kaolin, bentonite, acid clay, pyrophyllite, sericite), talcs, and other inorganic minerals (e.g. hydrated silicon dioxide, pumice,
Examples include fine powders or powders such as diatomaceous earth, sulfur powder, and activated carbon. 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), aliphatic hydrocarbons (e.g. kerosene, kerosene), esters, nitriles, acid amides (e.g. dimethylformamide, dimethylacetamide), halogenated Examples include hydrocarbons (eg dichloroethane, trichloroethylene, carbon tetrachloride). 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, and CM.
C, gum arabic, alginic acid, lignin sulfonate, bentonite, molasses, polyvinyl alcohol, pine oil, agar, etc. Stabilizers include, for example, PAP (isopropyl phosphate), TCP (tricresyl phosphate), tall oil, Examples include epoxidized oil, various surfactants, various fatty acids or their esters. Next, examples of formulations of ether compounds will be shown.

Reference Formulation Example 1 Each oil agent is obtained by dissolving 0.5 parts of each of the ether compounds (1) to (10) in white kerosene to make a total of 100 parts. Reference Formulation Example 2 Add 10 parts each of ether compounds (1) to (10), 10 parts emulsifier {Solpol 3005X (registered trademark of Toho Chemical)}, and 70 parts xylol, and stir and mix these to each. An emulsion is obtained. Reference formulation example 3 Ether compound (1) 0.2 parts, tetramethrin 0.3
After mixing and dissolving 1 part, 5 parts of xylene, and 44.5 parts of deodorized kerosene, filling it into an aerosol container and attaching a valve part, 50 parts of a propellant (liquefied petroleum gas) is pressurized and filled through the valve part to form an aerosol. get. Reference Formulation Example 4 0.2 parts of ether compound (2), 0.3 parts of d-trans acid form of allethrin, 8.5 parts of deodorized kerosene, and 1 part of emulsifier {Atmos 300 (registered trademark name of Atlas Chemical Co., Ltd.)}. A water-based aerosol is obtained by mixing the mixture, emulsifying it by adding 60 parts of pure water, and filling it into an aerosol container with 30 parts of a 3:1 mixture of deodorized butane and deodorized propane. Reference Formulation Example 5 Add 0.6 g of ether compound (1) to 20 ml of methanol
Dissolve in a carrier for mosquito coils (3 parts: tab powder: lees powder: wood powder).
(Mixed at a ratio of 5:1) 99.4g and stirred uniformly,
After the methanol has been evaporated, 150 ml of water is added and the mixture is sufficiently kneaded and then molded and dried to obtain each mosquito coil. Reference formulation example 6 0.08g of BHF in 0.08g of ether compound (1)
Add it, dissolve it in an appropriate amount of chloroform, and make a 3.5cm x 1
．． Adsorb it uniformly onto a 5 cm, 0.3 cm thick filter paper. A fiber fumigation composition heated on an electric heating plate is thus obtained. Reference Formulation Example 7 Emulsifier {
5 parts of Solpol 5029-0 (registered trademark of Toho Chemical) were thoroughly mixed, 85 parts of 300 mesh diatomaceous earth were added, and the mixture was thoroughly stirred and mixed to obtain each wettable powder. Reference Formulation Example 8 0.5 parts of each of ether compounds (1) to (10) were dissolved in an appropriate amount of acetone, and 300 mesh talc 99.5
After stirring and mixing thoroughly, the acetone is removed by evaporation to obtain each powder.

Ether compounds 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, the usefulness of ether compounds as active ingredients in insecticides and acaricides will be shown with test examples. Ether compounds are indicated by compound numbers in Table 1, and compounds used as comparative controls are indicated by compound symbols in Table 2.

[0013]

[Table 1]

[0014]

[Table 2]

Reference Test Example 1 A filter 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 water dilution (equivalent to 500 ppm) of the emulsion obtained in Reference Formulation Example 2 was dropped onto the filter paper. 30 mg of sucrose was placed on the filter paper as bait. Ten female adult house flies were released into the container, the lid was closed, and 48 hours later, their survival and death were investigated to determine the adult rate (2 repetitions). The results are shown in Table 3.

[0016]

[Table 3]

Reference Test Example 2 Ether compounds (1) and (2) obtained in Reference Formulation Example 2
, and control compounds (A) and (B) obtained in the same manner.
An emulsion diluted with water at a predetermined concentration was treated in the same manner as in Reference Test Example 1, and the LC50 value (median lethal concentration) for female adult house flies was determined. (2 repetitions) The results are shown in Table 4.

[0018]

[Table 4]

Reference Test Example 3 200% of the emulsion of the ether compound obtained in Reference Formulation Example 2
2 ml of the diluted solution (equivalent to 500 ppm) was soaked into 15 g of artificial feed for Spodoptera spp. 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) The results are shown in Table 5.

[0020]

[Table 5]

Reference Test Example 4 5 days after sowing, four leaves of a potted chinensis were infested with 10 female adult spider mites per leaf and stored in a constant temperature room at 27°C. After 6 days, a 200-fold water dilution solution (500 ppm (equivalent) was sprayed at 10 ml per pot on a turntable. After 6 days, female adult spider mites on the plants were counted. The criteria for evaluating effectiveness were set. The results are shown in Table 6.

[0022]

[Table 6]

Claims (1)

[Claims] [Claim 1] General formula: [Formula 1] [In the formula, R is a lower alkyl group other than a methyl group, or 2,
Represents a 2,2-trifluoroethyl group. ] An alcohol derivative represented by