JPH06710B2 - Alcohol derivative - Google Patents

Description

Detailed Description of the Invention

The present invention provides a compound of general formula 2 which is useful as an intermediate for insecticides and acaricides.

[0002]

[Chemical 2]

[In the formula, R represents a lower alkyl group other than a methyl group or a 2,2,2-trifluoroethyl group. ] It is related with the alcohol derivative shown by these. We have
As a result of intensive studies to develop excellent insecticides and acaricides, the general formula 3

[0004]

[Chemical 3]

[In the formula, R ₁ represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a methyl group, and R ₂ represents a hydrogen atom or a fluorine atom. A represents an oxygen atom or an imino group. R has the same meaning as described above. ] It was found that the ether compound represented by (hereinafter, referred to as an ether compound) has high insecticidal and acaricidal efficacy,
Furthermore, the alcohol derivative represented by the above chemical formula 2 (hereinafter,
It is described as the compound of the present invention. ) Has made it a useful intermediate of an ether compound, and completed the present invention. In the present application, a lower alkyl group other than a methyl group has 2 to 2 carbon atoms.
It means four alkyl groups, and examples thereof include an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group. The compound of the present invention has the general formula

[0006]

[Chemical 4]

[In the formula, R has the same meaning as described above. ] It can be easily obtained by reducing 1-phenylcyclopropanecarboxylic acid represented by the following formula or its ester with a reducing agent such as lithium aluminum hydride.
Next, production examples of the compound of the present invention will be shown. Production Example 1 Lithium aluminum halide 445 under nitrogen stream
40 mg of tetrahydrofuran (11.7 mmol)
A suspension was prepared in ml, and 1- (4-ethoxyphenyl) cyclopropanecarboxylic acid 2.41 g (1
A solution of 1.7 mmol of tetrahydrofuran in 20 ml is dropped with stirring under ice cooling, and after completion of dropping, the mixture is stirred at room temperature for 2 hours. Then, the reaction solution was carefully poured into a mixture of a large amount of ice and concentrated hydrochloric acid while stirring, and then extracted several times with diethyl ether, the ether layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off. 2.13 g of 4-ethoxyphenyl) cyclopropyl-1-carbinol was obtained as a pale yellow liquid. n ^21.0 _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. n ^22.0 _D 1.5773 Production Example 3 In Production Example 1, 1- (4-iso- was used instead of 1- (4-ethoxyphenyl) cyclopropanecarboxylic acid.
1- (4-iso-propyloxyphenyl) cyclopropyl-1-carbinol was obtained using propyloxyphenyl) cyclopropanecarboxylic acid. n ^21.5 _D 1.5798 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. n ^20.5 _D 1.5749 Production Example 5 In Production Example 1, instead of 1- (4-ethoxyphenyl) cyclopropanecarboxylic acid, 1- {4- (2,
Using 2,2-trifluoroethoxy) phenyl) cyclopropanecarboxylic acid, 1- (4- (2,2,2-trifluoroethoxy) phenyl) cyclopropyl-1-carbinol was obtained. n ^23.0 _D 1.4659 Incidentally, 1-phenylcyclopropanecarboxylic acids represented by the general formula (4), which is a raw material for producing the compound of the present invention, can be prepared according to J. Amer. Chem. Soc. , 93 (1
7), 4237-4242 (1971), Khim-F
arm, Zh. , 14 (2), 40-45 (1980)
And the like. The compound of the present invention comprises an alkali metal salt and a compound of the general formula

[0008]

[Chemical 5]

[In the formula, R ₁ , R ₂ and A have the same meanings as described above, and Z represents a halogen atom. ] By reacting with a benzyl halide represented by the following formula, the ether compound represented by the general formula 3 can be easily obtained. More specifically, the general formula 2
The compound of the present invention represented by is an aprotic polar solvent (eg, dimethylformamide, dimethylsulfoxide, etc.)
Among them, an ether compound can be produced by reacting with an alkali metal hydride to form an alkali metal salt, and reacting this with the benzyl halide represented by the general formula 5 at 0 ° C to 50 ° C for 1 to 12 hours. Next, production examples of ether compounds will be shown. Reference Production Example Sodium hydride (60% oil suspension) 11
4 mg (2.86 mmol) was suspended with 5 ml of dimethylformamide, and 549 mg (2.8 of 1- (4-ethoxyphenyl) cyclopropyl-1-carbinol) was suspended therein.
6 mmol) of dimethylformamide (3 ml) was added dropwise, and the internal temperature was kept at 50 to 80 ° C. until hydrogen generation was completed. Then, the mixture was cooled to room temperature, a solution of phenoxy-4-fluorobenzyl chloride (615 mg, 2.60 mmol) in dimethylformamide (3 ml) was added dropwise, and the mixture was stirred at room temperature overnight. Then, the reaction mixture solution was poured into 50 ml of water, extracted twice with 20 ml of ether, the ether layer was dried over anhydrous magnesium sulfate, the ether was distilled off, and the residue was separated and purified by column chromatography packed with silica gel. , 3-phenoxy-4-fluorobenzyl 1- (4
-Ethoxyphenyl) cyclopropyl methyl ether 8
05 mg was obtained as a colorless liquid. Table 1 collectively shows some of the ether compounds that can be produced in the same manner as in the above Production Example. Specific pests for which ether compounds are particularly effective include planthoppers, leafhoppers, aphids, hemiptera, such as stink bugs, diamondback moth, lepidoptera, such as Spodoptera,
Coleoptera such as weevil and beetle, Culex pipiens,
Examples include diptera such as housefly and orthoptera such as cockroach and German cockroach.

When an ether compound is used as an active ingredient of an insecticidal or acaricidal agent, it is usually a solid carrier, liquid carrier, gaseous carrier or other auxiliary agent for formulation (eg surfactant, dispersant, wetting agent, Stabilizer etc.) mixed with various preparations such as emulsions, wettable powders, powders, granules, oils, aerosols, fumigants for heating, (mosquito coils, electric mosquito coils, etc.), fumigants such as fogging, Use unheated fumigant, poison bait, etc. The content of the active ingredient in these preparations is 0.1% to 95%. Solid carriers include clays (eg kaolin, bentonite,
Acid clay, pyrophyllite, sericite), talc,
Other examples include fine powders or powdery substances such as inorganic minerals (eg hydrated silicon dioxide, pumice stone, diatomaceous earth, sulfur powder, activated carbon). Liquid carriers include alcohols (eg methyl alcohol), ketones (eg acetone, methyl ethyl ketone), ethers (eg ethyl ether, dioxane, cellosolve, tetrahydrofuran),
Aromatic hydrocarbons (eg benzene, toluene, xylene, methylnaphthalene), aliphatic hydrocarbons (eg kerosene, kerosene), esters, nitriles, acid amides (eg dimethylformamide, dimethylacetamide), halogenated carbonization Hydrogen (for example, dichloroethane, trichloroethylene, carbon tetrachloride) and the like can be mentioned. Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, polyethylene glycol ethers, polyhydric alcohol esters and the like. In addition, examples of fixing agents and dispersants that can be used include casein, gelatin, starch powder, CM
C, gum arabic, alginic acid, lignin sulfonate, bentonite, molasses, polyvinyl alcohol, pine oil, agar and the like, and examples of stabilizers include PAP (isopropyl phosphate), TCP (tricresyl phosphate), tall oil, Examples include epoxidized oil, various surfactants, various fatty acids or their esters, and the like. Next, formulation examples of ether compounds are shown.

Reference Formulation Example 1 0.5 parts of each of the ether compounds (1) to (10) are dissolved in white kerosene and the total amount is 100 parts to obtain each oil solution. Reference formulation example 2 10 parts of each of the ether compounds (1) to (10), 10 parts of each emulsifier {Solpol 3005X (registered trademark of Toho Kagaku)}, and 70 parts of xylol are added to each of them, and they are mixed well with stirring. To obtain an emulsion of. Reference formulation example 3 0.2 part of ether compound (1), 0.3 part of tetramethrin,
5 parts of xylol and 44.5 parts of deodorized kerosene are mixed and dissolved, filled into an aerosol container, a valve portion is attached, and then 50 parts of a propellant (liquefied petroleum gas) is pressure-filled through the valve portion to obtain an aerosol. . Reference formulation example 4 0.2 part of ether compound (2), 0.3 part of d-trans acid form of allethrin, 8.5 parts of deodorized kerosene and emulsifier {Atmos 3
00 (registered trade name of Atlas Chemical Co.)}, and 60 parts of pure water is added to emulsify the mixture, followed by filling the aerosol container with 30 parts of a 3: 1 mixture of deodorized butane and deodorized propane. To get Reference formulation example 5 0.6 g of ether compound (1) is dissolved in 20 ml of methanol, and a carrier for mosquito coil (tab powder: lees powder: wood powder 3: 5:
99.4 g of the mosquito coil is mixed with 19.4 of the above mixture with uniform stirring, methanol is evaporated, 150 ml of water is added, and the mixture is thoroughly kneaded and dried to obtain each mosquito coil. Reference formulation example 6 0.08 g of ether compound (1) was added with 0.08 g of BHF, dissolved in an appropriate amount of chloroform, and uniformly adsorbed on a filter paper of 3.5 cm x 1.5 cm and thickness of 0.3 cm. Thus, the fumigant composition heated on the electric heating plate is obtained. Reference formulation example 7 An emulsifier {Solpol 5029-0 (trade name of Toho Kagaku)} 5 in 10 parts of each of ether compounds (4) and (5)
Well mixed, add 85 parts of 300 mesh diatomaceous earth,
When mixed with sufficient stirring, each wettable powder is obtained. Reference Formulation Example 8 0.5 parts of each of the ether compounds (1) to (10) is dissolved in an appropriate amount of acetone, and 99.5 parts of 300 mesh talc are added and sufficiently stirred and mixed, and then acetone is removed by evaporation. To obtain a powder.

The ether compounds can be widely used as agricultural and horticultural insecticides and acaricides such as paddy fields, fields, orchards, tea gardens, mulberry fields, lawns, meadows, forests, etc., as well as a pesticidal insecticide and acaricide. Next, it will be shown by way of test examples that ether compounds are useful as active ingredients of insecticides and acaricides.
The ether compounds are shown by the compound numbers in Table 1, and the compounds used as comparative controls are shown by the compound symbols in Table 2.

[0013]

[Table 1]

[0014]

[Table 2]

Reference Test Example 1 A polyethylene cup having a diameter of 5.5 cm was covered with a filter paper of the same size. 0.7 ml of a 200 times diluted solution of water (corresponding to 500 ppm) of the emulsion obtained in Reference Formulation Example 2 was dropped on the filter paper. As a bait, 30 mg of sucrose was put on a filter paper. Ten housefly female adults were released therein, the lid was put on, 48 hours later, the life and death thereof were examined, and the adult rate was determined (2 repetitions). The results are shown in Table 3.
Shown in.

[0016]

[Table 3]

Reference Test Example 2 Ether compound (1) obtained in Reference Formulation Example 2,
(2), and a control compound (A) obtained in the same manner,
The emulsion of (B) having a predetermined concentration in water was treated in the same manner as in Reference Test Example 1 to determine the LC ₅₀ value (central lethal concentration) for adult houseflies. (2 iterations) The results are shown in Table 4.
Shown in.

[0018]

[Table 4]

Reference Test Example 3 200 of the emulsion of the ether compound obtained in Reference Formulation Example 2
2 ml of a diluted solution of double water (equivalent to 500 ppm) was soaked in 15 g of an artificial feed for Spodoptera litura and put in a polyethylene cup having a diameter of 11 cm. Ten third-instar larvae of Spodoptera litura were released into the larvae, and after 24 hours, life and death were investigated to determine the mortality rate. (2 repetitions) The results are shown in Table 5.

[0020]

[Table 5]

Reference Test Example 4 Four leaves of potted Thunasiinsen were seeded 5 days after seeding, and 10 female adults of the spider mite mite were infested with each leaf and stored in a constant temperature chamber at 27 ° C. Six days later, a 200-fold water-diluted solution (500 ppm) of the emulsions of the ether compounds (1), (2), (5) and (10) obtained in Reference Formulation Example 2 and the control compound (C) obtained in the same manner (500 ppm). 10 ml per pot was sprayed on the turntable. After 6 days, female adults of the spider mites on the plants were counted. The effect criteria are And The results are shown in Table 6.

[0022]

[Table 6]

Front page continuation (72) Inventor Shin Hata Koshi No. 42-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Chemical Co., Ltd. (72) Inventor Masachika Hirano 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Chemical Gaku Kogyo Co., Ltd.

Claims (1)

[Claims] 1. A general formula: ## STR1 ## [In the formula, R is a lower alkyl group other than a methyl group or 2,
It represents a 2,2-trifluoroethyl group. ] The alcohol derivative shown by these.