JPH0723341B2 - Carboxylic acid ester and insecticide containing the same as active ingredient - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a carboxylic acid ester represented by the following general formula (I) and an insecticide containing the same as an active ingredient.

In the formula, R ₁ represents a hydrogen atom or a methyl group, and when R ₁ represents a hydrogen atom, R ₂ has the formula —CH═C (Me) ₂ , —CH═C.
_{(C1) 2, -CH = CH} (Me), - CH = CF 2, -CH = CC1 (CF
₃₎ or represents a group represented by -CH = CC1 (Me), also 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 an ethyl group, n-propyl group, isopropyl group, allyl group, propargyl group or 3-butynyl group.

The present inventors have conducted extensive research to develop compounds having excellent insecticidal activity, and as a result, the compounds of the present invention represented by the general formula (I) have the following effects: 1. Very rapidly acting against various pests. In addition, the insecticidal effect is high.

2. High activity as a transpiration agent or smoke agent.

3. Relatively low toxicity to humans.

4. It is also effective against harmful insects that are resistant to organic phosphorus agents or carbamate agents.

5. Can be manufactured at relatively low cost.

It has been found to have excellent properties such as.

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 present inventors have made the above general formula (I)
As will be apparent from the test examples described below, the present invention has been found to have an extremely high insecticidal effect as compared with the similar compounds described in JP-B-55-42045, and has arrived at the present invention. .

Examples of pests for which the compound of the present invention is particularly effective include house flies, diptera pests such as Culex pipiens, indoor-living lepidopteran pests such as squid, and reticulo-pests such as German cockroaches. It has extremely high potency as an agent or smoke agent. Other pests for which the compound of the present invention is effective include planthoppers, leafhoppers, aphids, hemiptera such as stink bugs, diamondback moth, lizards, lepidopterans such as Spodoptera, coleoptera such as cutworms, and orthoptera. Can be mentioned.

The compound of the present invention represented by the above general formula (I) has the general formula (I
I) [In the formula, R ₁ and R ₂ have the same meanings as described above. ] The carboxylic acid represented by or its reactive derivative and the general formula (III) [In the formula, R ₃ and R ₄ have the same meanings as described above. ] It can manufacture by making it react with the alcohol shown by these in the presence of a suitable solvent, a reaction auxiliary agent, and a catalyst as needed.

Examples of the reactive derivative of the carboxylic acid represented by the general formula (II) include acid halides, acid anhydrides and lower alkyl esters.

Some of the carboxylic acid esters represented by the general formula (I) have optical isomers based on the asymmetric carbon of the carboxylic acid component or alcohol component, and stereoisomers based on the carboxylic acid component. The esters of are also included in the present invention. Further, isomers related to the double bond of alcohol may exist, but in this case, it means (Z) unit.

Next, the outline of the method for producing the carboxylic acid ester in the present invention is shown below.

(Production Method A) Method by Reaction of Carboxylic Acid Halide with Alcohol General Formula (IV) [In the formula, A represents a halogen atom, and R ₁ and R ₂ have the same meanings as described above. ] The acid halide represented by, preferably an acid chloride and the alcohol represented by the general formula (III) in an inert solvent (eg, benzene, toluene, hexane, ether, etc.), a deoxidizing agent (eg, pyridine, triethylamine). Etc.) at an internal temperature of -30 ° C to 100 ° C for 30 minutes to 20 hours to obtain the desired ester.

(Production Method B) Method by Reaction of Carboxylic Anhydride and Alcohol General Formula (V) [In the formula, R ₁ and R ₂ have the same meanings as described above. ] The carboxylic anhydride represented by and the alcohol represented by the general formula (III) are treated with an inert solvent (for example, benzene,
In toluene, hexane, acetone, etc., a base (eg,
-20 ℃ in the presence of pyridine, triethylamine, etc.)
The desired ester is obtained by reacting at -100 ° C for 1-20 hours.

(Production Method C) Method by Dehydration Reaction of Carboxylic Acid and Alcohol Carboxylic acid represented by the general formula (II) and general formula (II
The alcohol represented by I) is mixed with 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 carboxylic acid ester obtained by the above method can be purified by means such as chromatography and distillation, if necessary.

Example 1 of the compound of the present invention produced based on the above production method
Although shown in the table, the present invention is not limited to only these examples.

The compound of the present invention will be described in more detail with reference to the following examples.

Example 1: Production of compound (1) according to production method A 1.28 g (0.01 mol) of (Z) -3-hydroxy-4-fluoro-4-heptene-1-yne and (1
R) -trans-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropane-1-carboxylic acid chloride 2.
Dissolve 27 g (0.01 mol) and pyridine 1.58 g (0.
02 mol) is added dropwise. 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, and 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 allowed to flow down through a column filled with 50 g of silica gel with ethyl acetate: n-hexane = 1: 20 as a developing solvent, to give 2.68 g of the target ester (carboxamide used). (84.0% yield based on the theoretical yield based on the acid chloride) was obtained as a colorless oil.

Example 2: Production of compound (2) according to 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-4-
Fluoro-4-hepten-1-yne (0.32 g, 2.5 mmol) was dissolved in 20 ml of dry toluene, triethylamine (0.50 g, 5 mmol) 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% aqueous sodium carbonate solution. The raw carboxylic acid was removed. 5% more toluene layer
It was washed with hydrochloric acid water, saturated sodium bicarbonate water, and saturated saline solution in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure,
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 obtain 0.50 g of the desired ester (72% of theoretical yield based on the alcohol used).

Example 3: Preparation of Compound (13) by Preparation 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 the mixture was allowed to stand overnight. The next day, the mixture was heated under reflux for 4 hours to complete the reaction, cooled, and the precipitated dicyclohexylurea was separated, and the liquid was concentrated and the resulting oily substance was applied to a column packed with 60 g of silica gel: ethyl acetate: n-hexane = 1: 1.
The mixture was allowed to flow down with 20 developing solvents to obtain 1.09 g of the desired ester (62.0% of the theoretical yield based on the carboxylic acid used) as a colorless oil.

Example 4: Production of compound (17) according to production method A (-)-(Z) -3-hydroxy- in 5 ml of dry toluene.
235 mg of 4-fluoro-4-hepten-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 temperature was raised to 20 ° C for 10 hours. Thereafter, Example 1
Post-treatment was carried out in the same manner as above to obtain 490 mg of the desired ester.

The alcohol represented by the general formula (III) is a novel compound unknown in the literature, and can be produced, for example, from the corresponding aldehyde compound by the synthetic route shown below.

[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. ] In the above production method, each aldehyde compound as a starting material should be produced according to the method described in Tetrahedron Letters, Vol. 24, page 3387 (1983) and Helvetica Chemika Actor, Volume 60, page 1739 (1977). You can

Below, the synthetic example of alcohol shown by General formula (III) is shown as a reference example.

Reference Example 1 (Synthesis of ethyl 2-fluorocrotonate) 4 g of (Z) -2-fluorocrotyl aldehyde was added to acetone.
Dissolve in 10 ml and add 45 g of Jones Reagent to it at 20 ℃ under ice cooling.
Dropped below. 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 concentrated to obtain 3.5 g of the corresponding carboxylic acid. Then, 10m of dimethylformamide was added to the carboxylic acid.
1, ethyl bromide (3.6 g) and triethylamine (3.3 g) were added, and the mixture was stirred at 20 ° C. for 24 hours. 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 subjected to vacuum distillation to obtain 2.8 g of the desired product.

Boiling point: 75-82 ℃ / 95mmHg Refractive index: 1.4702 (24 ℃) NMR data (CDCl ₃ ) δ 1.29 (t, 3H, J = 8Hz) 1.77 (dd, 3H, J = 3Hz, 8Hz) 4.23 (q, 2H) ) 5.7 to 6.6 (dq, 1H, J = 8Hz, 33Hz) Reference Example 2 (Synthesis of (Z) -ethyl 4-bromo-2-fluorocrotonate) (Z) -ethyl 2-fluorocrotonate 9.0 g Dissolve in 60 ml of carbon chloride and add N-bromosuccinimide 1
3.5 g and benzoyl peroxide 10 mg were added, and the mixture was heated under reflux for 6 hours. The reaction solution was concentrated 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) 6-6.8 (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, and- A diisobutylaluminum hydride / n-hexane solution (1.3 times the mole of the ester) was added dropwise at 60 ° C. After dropping
After stirring at the same temperature for 30 minutes, the reaction solution was poured into chilled 10% 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 2.5 g of the desired product as a pale yellow oil.

This was a pure object 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) Reference Example 4 ((Z) -3 -Hydroxy-4-fluoro
Synthesis of Oct-4-ene-1,7-diyne) (Z) -4-Bromo-2-fluorocrotylaldehyde
Dissolve 2.5 g in 20 ml of dry tetrahydrofuran and add 0 to it.
A tetrahydrofuran solution of acetylene magnesium bromide (corresponding to 4-fold mol) was added dropwise at ° C. 12 hours after dropping 20
After stirring at ℃, add 200 mg of cuprous chloride to the reaction mixture and mix.
Heated to reflux for 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 obtain 1.1 g of the desired product as a pale yellow oil.

Refractive index: 1.4769 (23.0 ° C) NMR data (CDCl ₃ ) δ 2.03 (t, 1H, J = 3Hz) 2.65 (d, 1H, J = 2Hz) 3.1 (m, 2H) 4.8 to 5.0 (bd, 1H) 5.05 , 5.6 (dt, 1H, J = 8Hz, 32Hz) Reference Example 5 ((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 3
After stirring for 0 minutes and then 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 and dried over anhydrous magnesium sulfate, then the melt pump was distilled off and the residue was distilled under reduced pressure to obtain 9.5 g of the desired product as a pale yellow oil.

Boiling point: 85~92 ℃ (30mmHg) NMR data _{(CDCl 3) δ 1.00 (t} , 3H, J = 8Hz) 1.8~2.2 (m, 2H) 2.56 (d, 1H, 2.5Hz) 4.8,5.4 (dt, 1H , J = 8Hz, 36Hz) 4.7,4.9 (dd, 1H, J = 2.5Hz, 12Hz) Reference Example 6 ((-)-(Z) -3-hydroxy-4-fluoro-4-hepten-1-yne Synthesis) (±)-(Z) -3-hydroxy-4-fluoro-4-
1.0 g of hepten-1-yne and 1.4 g of lactone of (1R) -cis-3,3-dimethyl-2- (dihydroxymethyl) -cyclopropanecarboxylic acid were dissolved in 50 ml of benzene, and 20 mg of p-toluenesulfonic acid was added thereto. In addition, with a water separation tube 12
Heated to reflux for hours. 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 Kieselgel Art.13.
792 (8 sheets) was used to develop 3 times (developing melt: n-hexane / diethyl ether = 4/1)]. Of the diastereomers separated into the upper and lower parts, the part having a low Rf value was scraped off, eluted with ethyl acetate and the solvent was distilled off to obtain 510 mg of 2-[(4-fluoro-4-hepten-1-yn-3-yloxy). ) -Hydroxymethyl] -3,3-dimethylcyclopropanecarboxylic acid lactone was obtained as an oil. To this oil, add 10 ml of methanol and 10 mg of p-toluenesulfonic acid, and add 10
Left for hours. After distilling off the methanol, the residual oil was subjected to silica gel column chromatography (developing solvent: n-
Hexane / ethyl acetate = 10/1), the desired (-)-(Z)
-3-Hydroxy-4-fluoro-4-heptene-1-
Yield 235 mg.

▲ [α] ²³ _D ▼ = −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-hexane / ethyl acetate = 500: 2) analyzed (-):
(+) = 96: 4.

When the compound of the present invention is used as an active ingredient of an insecticide,
It may be used as it is without adding any other ingredients,
Usually, it is mixed with a solid carrier, liquid carrier, gaseous carrier, surfactant, other auxiliaries for formulation, bait or the like, or impregnated into a base material such as incense stick, electric mosquito repellent or mat to prepare an emulsion or water. It is used as a fumigant for powders, powders, granules, oils, aerosols, mosquito coils, mats and perforated ceramic plate mats, fuming agents for fugging, non-heat fumigants, poison baits, etc.

The content of the compound of the present invention 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 flour, walnut flour, urea,
Fine powders or granules of ammonium sulfate, synthetic hydrous silicon oxide and the like can be mentioned, and liquid carriers include kerosene, kerosene and other aliphatic hydrocarbons, benzene, toluene, xylene, methylnaphthalene and other aromatic hydrocarbons, dichloroethane, trichloroethylene. , Halogenated hydrocarbons such as carbon tetrachloride, alcohols such as methanol, ethanol, isopropanol, ethylene glycol, cellosolve,
Acetone, methyl ethyl ketone, cyclohexanone, ketones such as isophorone, diethyl ether, dioxane,
Examples thereof include ethers such as tetrahydrofuran, esters such as ethyl acetate, nitriles such as acetonitrile and isobutyronitrile, acid amides such as dimethylformamide and dimethylacetamide, dimethylsulfoxide, 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,
Anionic surfactants such as polyoxyethylene alkylaryl ether phosphoric acid ester salt and naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl ale, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester And nonionic surfactants such as Examples of formulation adjuvants such as sticking agents and dispersants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, molasses, casein, gelatin, CMC (carboxymethyl cellulose), pine oil, and agar, which are stable. 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, fatty acid salts such as sodium oleate and calcium stearate, methyl oleate,
Examples thereof include fatty acid esters such as methyl stearate.

Formulation examples are shown below. The compounds of the present invention are shown by the compound numbers in Table 1. Parts are parts by weight.

Formulation Example 1 0.2 parts of each of the compounds (1) to (17) of the present invention, xylene 2
Part and white kerosene 97.8 parts are mixed to obtain an oil solution.

Formulation Example 2 10 parts of each of the compounds (1) to (17) of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 70 parts of xylene are thoroughly mixed to obtain an emulsion.

Formulation Example 3 20 parts of the compound (1) of the present invention, 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 well pulverized and mixed to obtain a wettable powder.

Formulation Example 4 1 part of the compound (2) of the present invention, 2 parts of carbaryl, 87 parts of kaolin clay and 10 parts of talc are well pulverized and mixed to obtain a powder.

Formulation Example 5 5 parts of the compound (3) of the present invention, 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, and after adding water and kneading well, Granulate and dry to obtain granules.

Formulation Example 6 0.05 part of the compound (4) of the present invention, 0.2 part of tetramethrin, 0.05 part of resmethrin, 7 parts of xylene and 32.7 parts of deodorant kerosene were mixed and dissolved, and the mixture was filled in an aerosol container, and after the valve part was attached, through the valve part Aerosol is obtained by pressure-filling 60 parts of propellant (liquefied petroleum gas).

Formulation Example 7 0.3 g of each of the compounds (1) to (17) of the present invention was added to methanol 20
Dissolve in ml and use the carrier for mosquito coil (tab powder: lees powder: wood powder 3:
99.7 g of the mixture was mixed with stirring at a ratio of 5: 1), methanol was evaporated, 150 ml of water was added, and the mixture was sufficiently kneaded and dried to obtain each incense stick.

Formulation Example 8 100 mg of each of the compounds (1) to (17) of the present invention is dissolved in an appropriate amount of acetone and impregnated into a porous ceramic plate having a size of 4.0 cm × 4.0 cm and a thickness of 1.2 cm to obtain a fumigant for heating.

These formulations are used as they are or diluted with water. In addition, other insecticides, acaricides, nematicides, fungicides,
It can also be used as a mixture with herbicides, plant growth regulators, fertilizers, soil conditioners and the like.

When the compound of the present invention is used as an agricultural insecticide, its application amount is usually 5 g to 500 g per 10 ares, and when the emulsion, wettable powder or the like is diluted and then applied, its application concentration is
It is 10 ppm to 1000 ppm, and powders, granules, etc. are applied as they are without any dilution. When using emulsions, wettable powders, etc. as insecticidal pesticides, 10ppm to 10,000
Dilute to ppm and spray. Also, apply fumigants and vaporizers such as oils, aerosols, mosquito coils and electric mats as they are.

Next, a test example is shown. The compounds of the present invention are shown by the compound numbers in Table 1, and the compounds used for comparison and control are shown by the compound symbols in Table 2.

Test Example 1 2 ml of a 200-fold diluted water solution (corresponding to 500 ppm) of the emulsion of the compound of the present invention obtained according to 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. In it, the 4th instar larvae of Spodoptera litura
10 animals were released, and after 6 days, life and death were investigated and the mortality rate was calculated (2 repetitions).

The results are shown in Table 3.

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 water of the emulsion of the present invention compound and the control compound described below obtained according to Formulation Example 2. After air-drying, put rice stalks in a test tube and put a resistant strain of leafhopper leafhopper adults.
10 animals were released and one day later they were examined for life and death, and the mortality rate was calculated (2
Repeat).

The results are shown in Table 4.

Test Example 3 Each of the following compounds of the present invention 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. After acetone is air-dried, the susceptible housefly (CSMA system)
Polyethylene cup (diameter 9 cm,
The treated petri dish is covered with a nylon net (16 mesh) on the upper part (4.5 cm in height) so that insects do not directly touch the treated surface. After 60 minutes, the number of knockdown insects was observed, and the KD ₅₀ value (50% knockdown dose) was determined by the probit method. After or 120 minutes, remove the dish pigs given water and food, to investigate the life and death after 24 hours, LD _{50 (50}
% Lethal dose) was determined (2 replicates).

The results are shown in Table 5.

Test Example 4 0.3% and 0.15% mosquito coil of the compound of the present invention and the control compound obtained according to Formulation Example 7 are prepared.

Release 10 female mosquitoes and 10 adult houseflies (♂ / ♀ = 1/1) into a 70 cm cubic (0.34 m ³ ) glass chamber.

1 g of each mosquito coil was ignited at both ends in this glass chamber, 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 6.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location C07C 69/747 N 9279-4H (72) Inventor Toshihiko Yano Takashizuka City, Hyogo Prefecture 4-2-1 Issue Sumitomo Kagaku Kogyo Co., Ltd. (56) References Japanese Patent Publication Sho 55-42045 (JP, B2)

Claims (2)

[Claims] 1. A general formula [Wherein, R ₁ represents a hydrogen atom or a methyl group, and when R ₁ represents a hydrogen atom, R ₂ has the formula —CH═C (Me) ₂ , —CH═
_{C (C1) 2, -CH =} CH (Me), - CH = CF 2, -CH = CC1
(CF ₃ ) or a group represented by -CH = CC1 (Me),
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 an ethyl group, n-propyl group, isopropyl group, allyl group, propargyl group or 3-butynyl group. ] The albonic acid ester shown by these. 2. General formula [Wherein, R ₁ represents a hydrogen atom or a methyl group, and when R ₁ represents a hydrogen atom, R ₂ has the formula —CH═C (Me) ₂ , —CH═
_{C (C1) 2, -CH =} CH (Me), - CH = CF 2, -CH = CC1
(CF ₃ ) or a group represented by -CH = CC1 (Me),
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 an ethyl group, n-propyl group, isopropyl group, allyl group, propargyl group or 3-butynyl group. ] An insecticide containing a carboxylic acid ester represented by the following as an active ingredient.