JPH0764768B2 - Alcohol compound - 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 the production of insecticides.

[Chemical 2] [In the formula, R ₃ represents a hydrogen atom or a methyl group, and R ₄
Is an ethyl group, n-propyl group, isopropyl group, allyl
Represents a group, a propargyl group or a 3-butynyl group. ]
And an alcohol compound represented by We have
As a result of repeated research aimed at developing a compound having excellent insecticidal activity, an ester compound represented by the following general formula 3 (hereinafter referred to as an ester compound)

[Chemical 3] [In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₁
Is a hydrogen atom, R ₂ has the general formula

[Chemical 4] (Where X and Y are the same or different and are hydrogen atoms,
It represents a methyl group, a halogen atom, or a lower haloalkyl group. ), And when R ₁ represents a methyl group, R ₂ represents a methyl group. R ₃ represents a hydrogen atom or a methyl group, and R ₄ represents a hydrogen atom, a lower alkyl group, a lower alkenyl group or a lower alkynyl group. ], But 1. It acts very quickly against various pests and has a high insecticidal effect. 2. Highly active as a transpiration agent or a smoke agent. 3. It has relatively low toxicity to humans. 4. It is also effective against pests that are resistant to organophosphorus or carbamate agents. 5. It can be manufactured relatively inexpensively. It was found that the alcohol compound represented by the general formula (2) (hereinafter referred to as the compound of the present invention) is a useful intermediate for the production of ester compounds. Was completed. The present invention is broadly included in JP-B-55-42045, but there is no specific description about the compound of the present invention in the publication. The inventors of the present invention have found that the ester compound, as will be apparent from the test example described later, is disclosed in
The present inventors have found that they have extremely high insecticidal efficacy as compared with the similar compounds described in No. 42045, and have completed the present invention.

Pests for which ester compounds are particularly effective include dipteran pests such as housefly and mosquito, indoor-living lepidopteran pests such as squid, and net-pest insects such as German cockroaches. , Has extremely high efficacy as a transpiration agent or a smoke agent. Other pests for which the compound of the present invention is effective, planthoppers, leafhoppers, aphids, stink bugs such as stink bugs, diamondback moth, larvae,
Lepidoptera such as the armyworm, Coleoptera such as the cuticle beetle,
Examples include Orthoptera.

The ester compound has the general formula

[Chemical 5] [In the formula, R ₁ and R ₂ have the same meanings as described above. ]
Can be produced by reacting the carboxylic acid represented by or a reactive derivative thereof with the compound of the present invention in the presence of a suitable solvent, a reaction aid and a catalyst, if necessary. Here, as the reactive derivative of the carboxylic acid represented by the general formula 5,
Examples thereof include acid halides, acid anhydrides and lower alkyl esters. Some ester compounds include optical isomers based on the asymmetric carbon of the carboxylic acid component or alcohol component, and stereoisomers based on the carboxylic acid component, and these isomers are also included in the present invention. Further, an isomer related to the double bond of alcohol may exist, but in this case, it means the (Z) -form. Next, the outline of the method for producing the ester compound is shown below. (Reference Production Method A) Method by Reaction of Carboxylic Acid Halide with Alcohol General Formula 6

[Chemical 6] [In the formula, A represents a halogen atom, and R ₁ and R ₂ have the same meanings as described above. ] An acid halide represented by The desired ester is obtained by reacting at a temperature of -30 ° C to 100 ° C for 30 minutes to 20 hours. (Reference Production Method B) Method by Reaction of Carboxylic Anhydride and Alcohol

[Chemical 7] [In the formula, R ₁ and R ₂ have the same meanings as described above. ]
In an inert solvent (eg, benzene, toluene, hexane, acetone, etc.) in the presence of a base (eg, pyridine, triethylamine, etc.), the carboxylic acid anhydride represented by The desired ester is obtained by reacting at 1 ° C for 20 hours. (Reference Production Method C) Method by Dehydration Reaction of Carboxylic Acid and Alcohol The carboxylic acid represented by the general formula 4 and the compound of the present invention are dehydrated and condensed in a dehydration condensing agent (for example, dicyclohexylcarbodiimide) at an internal temperature of 0 ° C to 150 ° C. The desired ester is obtained by reacting at 30 ° C. for 30 minutes to 10 hours. The ester compound obtained by the above method can be purified by means such as chromatography and distillation, if necessary.

Tables 1 to 3 show examples of ester compounds produced according to the above production method.

[Table 1]

[Table 2]

[Table 3]

The ester compound will be described in more detail with reference to the following reference examples. Reference Example 1: Production of Compound (1) by Reference Production Method A 1.50 g (0.01 mol) of (Z) -3-hydroxy-4-fluoro-4-hepten-1-yne and (1R)-in 50 ml of dry toluene. Trans-2,2-dimethyl-3- (2,2
2.27 g (0.01 mol) of -dichlorovinyl) -cyclopropane-1-carboxylic acid chloride is dissolved, and 1.58 g (0.02 mol) of pyridine is added dropwise under ice cooling. After the dropping, the reaction was completed by stirring at room temperature for 5 hours. The reaction solution was poured into 50 ml of ice water for liquid separation, the toluene layer was separated, and then washed with 5% aqueous hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated brine in this order. After drying over anhydrous sodium sulfate, toluene was distilled off and the residue was converted into ethyl acetate: n-
Hexane = 1: 20 was used as a developing solvent, and it was made to flow down through a column filled with 50 g of silica gel to obtain 2.68 of the target ester.
g (84.0% yield based on the theoretical yield based on the carboxylic acid chloride used) was obtained as a colorless oil. Reference Example 2: Production of Compound (2) by Reference Production Method B (1R) -trans-2,2-dimethyl-3- (2-methyl-1-propenyl) -cyclopropanecarboxylic acid anhydride 1.59 g (5 Mmol) and (Z) -3-hydroxy-
0.32 g (2.5 mmol) of 4-fluoro-4-hepten-1-yne was dissolved in 20 ml of dry toluene, 0.50 g (5 mmol) of triethylamine was added, and the mixture was stirred at 40 ° C. for 10 hours. Next, the reaction solution was poured into 50 ml of ice water to separate the layers, the toluene layer was separated, the aqueous layer was extracted with 20 ml of toluene, and the toluene layers were combined and washed twice with 20 ml of 5% sodium carbonate aqueous solution. The raw carboxylic acid was removed. The toluene layer was further washed with 5% hydrochloric acid water, saturated sodium bicarbonate water, and saturated saline in this order,
It was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was allowed to flow down a column packed with 50 g of silica gel using ethyl acetate: n-hexane = 1: 20 as a developing solvent to give 0.50 g of the target ester (theory for alcohol using Yield 72%). Reference Example 3: Production of Compound (13) by Reference Production Method C (Z) -3-Hydroxy-4-fluoro-4-hepten-1-yne 0.64 g (5 mmol) and (1RS) -trans-2, 2-Dimethyl-3- (2-chloro-2-trifluoromethylvinyl) -cyclopropane-1-carboxylic acid 1.21 g (5 mmol) was dissolved in 20 ml of dry dichloromethane, 2.06 g (10 mmol) of dicyclohexylcarbodiimide. Was added and left overnight. The next day, the mixture was heated under reflux for 4 hours to complete the reaction, and after cooling, the precipitated dicyclohexylurea was filtered off, and the filtrate was concentrated. Targeted ester with 20 developing solvents
1.09 g (62.0% of theoretical yield based on the carboxylic acid used)
Was obtained as a colorless oil. Reference Example 4: Production of compound (17) by Reference Production Method A (-)-(Z) -3-hydroxy- was added to 5 ml of dry toluene.
235 mg of 4-fluoro-4-hupeten-1-yne was dissolved, and 200 mg of pyridine was added thereto. Then. Under ice cooling, (1R) -trans-2,2-dimethyl-3- (2,2)
-Dichlorovinyl) -cyclopropane-1-carboxylic acid chloride (390 mg) was added, and the mixture was stirred at 20 ° C for 10 hr. After that,
Post-treatment was carried out in the same manner as in Reference Example 1 to obtain 490 mg of the desired ester.

The compounds of the present invention are represented by the general formulas
Can be produced from the corresponding aldehyde compound by the synthetic route shown in FIG.

[Chemical 8] [In the formula, R ₃ has the same meaning as described above, and R ₅ represents a lower alkyl group, a lower alkenyl group, or a lower alkynyl group having 4 or more carbon atoms. ]

[Chemical 9]

In the above production method, each aldehyde compound used as a starting material is tetrahedron letters 24
Volume, 3387 pages (1983) and Helvetica Chemika Actor 60.
It can be manufactured according to the method described in Volume 1739 (1977).

The synthetic examples of the compounds of the present invention are shown below. Reference Example 1 (Synthesis of ethyl 2-fluorocrotonate) 4 g of (Z) -2-fluorocrotyl aldehyde was dissolved in 10 ml of acetone, and 45 g of Jones reagent was added thereto under ice cooling.
It was added dropwise at a temperature of not higher than 0 ° C. The reaction solution was stirred at 20 ° C. for 1 hour, 10 ml of isopropyl alcohol was added dropwise thereto, and the mixture was stirred, ice water was added to the reaction solution, and the mixture was extracted twice with diethyl ether. The ether layer was washed with brine, dried over anhydrous magnesium sulfate and then concentrated to obtain 3.5 g of the corresponding carboxylic acid. Then, the carboxylic acid was added to dimethylformamide 10
ml, ethyl bromide 3.6 g and triethylamine 3.3
g, and stirred for 24 hours at 20 ° C. The reaction solution was poured into ice water and extracted twice with ethyl acetate. The ethyl acetate layer was washed successively with water and brine, concentrated and then distilled under reduced pressure to give 2.8
g of the desired product was obtained. Boiling point: 75-82 ° C / 95 mmHg Refractive index: 1.4702 (24 ° C) NMR data (CDCl ₃ ) δ 1.29 (t, 3H, J = 8 Hz) 1.77 (dd, 3H, J = 3 Hz, 8 Hz) 4.23 (q, 2H) 5.7 to 6.6 (dp, 1H, J = 8 Hz, 33 Hz) Reference Example 2 (Synthesis of (Z) -ethyl 4-bromo-2-fluorocrotonate) (Z) -Ethyl 2-fluorocrotonate 9.0 g Was dissolved in 60 ml of carbon tetrachloride, and N-bromosuccinimide was added to the solution.
13.5 g and benzoyl peroxide 10 mg were added and the mixture was heated under reflux for 6 hours. The reaction solution was filtered and then concentrated. The concentrated residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 20: 1) to obtain 8.5 g of the desired product. NMR data (CDCl ₃ ) δ 1.36 (t, 3H, J = 8Hz) 4.0, 4.15 (dd, 2H, J = 9Hz, 2Hz) 4.35 (q, 2H, J = 8Hz) 6 to 6.8 (dt, 1H) , J = 9 Hz, 30 Hz) Reference Example 3 (Synthesis of (Z) -4-bromo-2-fluorocrotylaldehyde) (Z) -Ethyl 4-bromo-2-fluorocrotonate 3.0 g was dissolved in 30 ml of dichloromethane. -60 ℃
Then, a diisobutylaluminum hydride / n-hexane solution (1.3 times the mole of the ester) was added dropwise. After dropping, stir for 30 minutes at the same temperature, then cool the reaction mixture to 10%.
The mixture was poured into hydrochloric acid water and separated. The aqueous layer was extracted once with dichloromethane, combined with the dichloromethane layer, washed once with brine, dried over anhydrous magnesium sulfate and concentrated to obtain the desired product 2.5.
g was obtained as a pale yellow oil. This was a pure product from its NMR data. NMR data (CDCl ₃ ) δ 4.1 to 4.3 (m, 2H) 5.9, 6.4 (dt, 1H, J = 8Hz, 30Hz) 9.13, 9.44 (d, 1H, J = 20Hz) Production Example 1 ((Z) -3-hydroxy-4-fluoro
Synthesis of Oct-4-ene-1,7-diyne) (Z) -4-Bromo-2-fluorocrotylaldehyde
2.5 g of it was dissolved in 20 ml of dry tetrahydrofuran, and a tetrahydrofuran solution of acetylene magnesium bromide (corresponding to 4-fold mole) was added dropwise thereto at 0 ° C. 12 hours after dropping
After stirring at 20 ° C., 200 mg of cuprous chloride was added to the reaction solution, and the mixture was heated under reflux for 6 hours. The reaction solution was poured into 100 ml of ice-cooled hydrochloric acid water and extracted twice with ethyl acetate. The ethyl acetate layer was washed with brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated. The residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 3: 1) to give 1.1.
g of the desired product was obtained as a pale yellow oil. Refractive index: 1.4769 (23.0 ° C.) NMR data (CDCl ₃ ) δ 2.03 (t, 1H, J = 3 Hz) 2.65 (d, 1H, J = 2 Hz) 3.1 (m, 2H) 4.8 to 5.0 (bd, 1H) 5.05 , 5.6 (dt, 1H, J = 8 Hz, 32 Hz) Production Example 2 ((Z) -3-hydroxy-4-fluoro-
(Synthesis of 4-hepten-1-yne) (Z) -2-Fluoro-2-pentenal (13.0 g) was dissolved in dry tetrahydrofuran (30 ml), and the internal temperature under ice cooling was 10
A tetrahydrofuran solution of acetylene magnesium bromide (corresponding to 1.5 times mol) was added dropwise at a temperature of not higher than ° C. Under ice cooling
After stirring for 30 minutes and further at 20 ° C. for 1 hour, the reaction solution was poured into ice-cooled 5% hydrochloric acid water and extracted with ethyl acetate. The ethyl acetate layer was washed with brine, dried over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was distilled under reduced pressure to obtain 9.5 g of the desired product.
Was obtained as a pale yellow oil. Boiling point: 85 to 92 ° C. (30 mmHg) NMR data (CDCl ₃ ) δ 1.00 (t, 3H, J = 8 Hz) 1.8 to 2.2 (m, 2H) 2.56 (d, 1H, 2.5 Hz) 4. 8,5.4 (dt, 1H, J = 8Hz, 3.6Hz) 4.7, 4.9 (dd, 1H, J = 2.5Hz, 12Hz) Production Example 3 ((-)-(Z) -3- Synthesis of hydroxy-4-fluoro-4-hepten-1-yne) (±)-(Z) -3-hydroxy-4-fluoro-4-
Hepten-1-yne 1.0 g and (1R) -cis-3,3-
1.4 g of a lactone of dimethyl-2- (dihydroxymethyl) -cyclopropanecarboxylic acid was dissolved in 50 ml of benzene, 20 mg of p-toluenesulfonic acid was added thereto, and the mixture was heated under reflux for 12 hours with a water separation tube. The reaction solution was washed with 2% potassium carbonate water, the solvent was distilled off, and the residual oil was subjected to preparative thin layer chromatography [Merck Kiesel.
3 times development using gel Art.13792 (8 sheets) (Development solvent:
n-hexane / diethyl ether = 4/1)]. Of the diastereomers separated into upper and lower parts, the part with a low Rf value was scraped off, eluted with ethyl acetate and the solvent was distilled off to give 510 mg of 2
A lactone of-[(4-fluoro-4-hepten-1-yn-3-yloxy) -hydroxymethyl] -3,3-dimethylcyclopropanecarboxylic acid was obtained as an oil. Methanol (10 ml) and p-toluenesulfonic acid (10 mg) were added to this oil and the mixture was allowed to stand for 10 hours. After distilling off methanol, the residual oil was subjected to silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 10 /
1), 235 mg of the target (-)-(Z) -3-hydroxy-4-fluoro-4-hepten-1-yne was obtained. [Α] _D ²³ = −34.4 ° (C = 0.57, chloroform) The obtained alcohol was an ester of 2-methoxy-2-trifluoromethylphenylacetic acid, and then HPLC (column: Lichrosorb SI-60 4 mm × 30 cm, Developing solvent: n
When analyzed by -hexane / ethyl acetate = 500: 2), it was (-): (+) = 96: 4.

When the ester compound is used as an active ingredient of an insecticide, it may be used as it is without adding any other component, but it is usually a solid carrier, a liquid carrier, a gaseous carrier, a surfactant, Emulsion, by mixing with other formulation adjuvants, baits, etc., or impregnating the base material such as incense sticks and mats
Wet powders, powders, granules, oils, aerosols, fumigants such as mosquito coils, electric mosquito mats and perforated ceramic plate mats, fuming agents such as fogging, non-heat fumigants, poison baits, etc. To do. The content of the ester compound as an active ingredient in these preparations is 0.001% to 95% by weight. As the solid carrier, kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, fine powder or particles of synthetic hydrous silicon oxide, etc. As the liquid carrier, kerosene, aliphatic hydrocarbons such as kerosene, benzene, toluene, xylene, aromatic hydrocarbons such as methylnaphthalene, dichloroethane, trichloroethylene, halogenated hydrocarbons such as carbon tetrachloride, methanol, Alcohols such as ethanol, isopropanol, ethylene glycol, cellosolve, acetone, methyl ethyl ketone, cyclohexanone, ketones such as isophorone, diethyl ether,
Examples thereof include ethers such as dioxane and tetrahydrofuran, esters such as ethyl acetate, nitriles such as acetonitrile and isobutyronitrile, acid amides such as dimethylformamide and dimethylacetamide, dimethyl sulfoxide, vegetable oils such as soybean oil and cottonseed oil. Examples of the gaseous carrier include CFC gas, LPG (liquefied petroleum gas), dimethyl ether and the like. Surfactants used for emulsification, dispersion, wet extension, etc. include alkyl sulfate ester salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphate ester salts, naphthalene sulfone. Examples thereof include anionic surfactants such as 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 sticking agents and dispersants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, molasses, casein, gelatin, CMC (carboxymethylcellulose), pine oil, agar, etc. Examples of the agent 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, and stearate. Examples thereof include fatty acid salts such as calcium phosphate, fatty acid esters such as methyl oleate and methyl stearate, and the like.

Next, formulation examples of ester compounds are shown. The ester compounds are shown by the compound numbers in Tables 1 to 3. Parts are parts by weight. Reference formulation example 1 0.2 parts each of ester compounds (1) to (17), 2 parts xylene and 97.8 parts white kerosene are mixed to obtain an oil solution. Reference formulation example 2 10 parts of each of the ester compounds (1) to (17), 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzene sulfonate and 70 parts of xylene are mixed well to obtain an emulsion. Reference formulation example 3 20 parts of ester compound (1), 10 parts of fenitrothion, 3 parts of calcium lignin sulfonate, 2 parts of sodium laurin sulfate and 65 parts of synthetic hydrous silicon oxide are well pulverized and mixed to obtain a wettable powder. Reference Formulation Example 4 Ester compound (2) 1 part, carbaryl 2 parts, kaolin clay 87 parts and talc 10 parts are thoroughly pulverized and mixed to obtain a powder. Reference formulation example 5 5 parts of ester compound (3), 1 part of synthetic hydrous silicon oxide,
2 parts of calcium lignin sulfonate, 30 parts of bentonite and 62 parts of kaolin clay are well pulverized and mixed, water is added and well kneaded, and then granulated and dried to obtain granules. Reference formulation example 6 ester compound (4) 0.05 part, tetramethrin 0.2 part,
Resmethrin 0.05 parts, xylene 7 parts and deodorant kerosene 32.7
After mixing and dissolving the parts, filling the aerosol container with the valve portion and attaching the valve portion, 60 parts of the propellant (liquefied petroleum gas) is filled under pressure through the valve portion to obtain an aerosol. Reference formulation example 7 0.3 g of each of the ester compounds (1) to (17) is dissolved in 20 ml of methanol, and a carrier for mosquito coil (mixing tab powder: meal powder: wood powder at a ratio of 3: 5: 1). After uniformly stirring and mixing with 99.7 g and evaporating methanol, 150 ml of water was added, and a sufficiently kneaded product was molded and dried to obtain each mosquito coil. Reference formulation example 8 100 mg of each of the ester compounds (1) to (17) is dissolved in an appropriate amount of acetone and impregnated into a porous ceramic plate of 4.0 cm × 4.0 and a thickness of 1.2 cm to obtain a fumigant for heating. .

These formulations are used as they are or after diluting with water. Further, it can be used by mixing with other insecticides, acaricides, nematicides, fungicides, herbicides, plant growth regulators, fertilizers, soil conditioners and the like. When an ester compound is used as an agricultural insecticide, its application amount is usually 10
The amount is 5 g to 500 g per are, and when the emulsion, wettable powder, etc. are diluted with water before application, the application concentration is 10 ppm to 10 ppm.
It is 00ppm, and powders, granules, etc. are applied as it is without any dilution. When emulsions, wettable powders, etc. are used as pesticides for epidemic prevention, dilute them with water to a concentration of 10 ppm to 10,000 ppm and spray. Also, apply fumigants and vaporizers such as oils, aerosols, mosquito coils and electric mats as they are.

Next, test examples of ester compounds will be shown. The ester compounds are shown by the compound numbers in Tables 1 to 3, and the compounds used for comparison and control are shown by the compound symbols in Table 4.

[Table 4] Reference Test Example 1 2 ml of a 200-fold diluted water solution (equivalent to 500 ppm) of an emulsion of the following ester compound obtained according to Reference Formulation Example 2 was soaked in 13 g of an artificial bait for Lotus japonicus, and placed in a polyethylene cup having a diameter of 11 cm. . Hasmon Yoto 4 in it
Ten old larvae were released, and after 6 days, life and death were examined to determine the mortality rate (2 repetitions). The results are shown in Table 5.

[Table 5] Reference Test Example 2 Rice stalks (about 12 cm in length) were immersed for 1 minute in a 200-fold diluted solution (equivalent to 500 ppm) of an emulsion of the following ester compound and control compound obtained according to Reference Formulation Example 2 in water. After air-drying, rice stalks were placed in test tubes, 10 resistant leafhopper leafhopper adults were released, and one day later, the viability was investigated and the mortality rate was determined (2 repetitions). The results are shown in Table 6.

[Table 6] Reference Test Example 3 Each of the following ester compounds and control compounds was adjusted to a reagent amount with acetone, and 1 ml each was uniformly treated on the bottom of a glass petri dish (bottom area 63.6 cm ² ) having an inner diameter of 9 cm and a height of 2 cm. To do. Acetone is air-dried, susceptible housefly (C
This treated petri dish was separated by a nylon net (16 mesh) on the top of a polyethylene cup (diameter 9 cm, height 4.5 cm) from which 20 adult females of SMA type) were released. Cover with. After 60 minutes, the number of knockdown insects was observed and the KD ₅₀ value (50
% Knockdown dose) was determined. After another 120 minutes,
The petri dish lid was removed, water and food were fed, and life and death were examined 24 hours later, and the LD ₅₀ (50% lethal drug amount) was determined (duplicate). The results are shown in Table 7.

[Table 7] Reference Test Example 4 0.3% and 0.15% mosquito coil of the ester compound and the reference compound obtained according to Reference Formulation Example 7 are prepared. 70
10 mosquito female mosquitoes and 10 housefly adult adults (♂ / ♀ = 1/1) are released in a cm ³ (0.34 m ³ ) glass chamber. 1g of each mosquito coil in this glass chamber
Was ignited at both ends and the number of knockdown insects was observed with time, and the KT ₅₀ value (50% knockdown time) was determined by the probit method (2 repetitions). The results are shown in Table 8.

[Table 8]

Front page continuation (72) Inventor Toshihiko Yano 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Kagaku Kogyo Co., Ltd. (56) References JP-B-55-42045 (JP, B2)

Claims (1)

[Claims] 1. A general formula: ## STR1 ## [In the formula, R ₃ represents a hydrogen atom or a methyl group, and R ₄
Is an ethyl group, n-propyl group, isopropyl group, allyl
Represents a group, a propargyl group or a 3-butynyl group. ] The alcohol compound shown by these.