JPS6223740B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula (In the formula, X represents O, S, or NH group, Y ₁ ,
Y ₂ and Y ₃ represent a hydrogen atom or a halogen atom. However, at least one of Y ₁ , Y ₂ and Y ₃ represents a halogen atom. R ₁ represents a lower alkyl group having 1 to 8 carbon atoms, a lower alkenyl group, a haloalkyl group, a haloalkenyl group, and a group represented by the general formula (), (), or ().

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Here, m is an integer of 1 to 3, n is an integer of 2 to 5, and R ₃ is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a haloalkyl group, or an alkoxyl group. R ₂ represents a hydrogen atom, a cyano group or a trifluoromethyl group. ), its optical and geometrical isomers, its production method, and an insecticide characterized by containing this compound as an active ingredient. Various alcohol components of chrysanthemum acid esters have been studied and put to practical use, but they are susceptible to oxidative decomposition by light, which has limited their use outdoors. Recently, research into acid components has become active, and a compound that is more stable to light than conventional pyrethroids by replacing the methyl group with a halogen atom has been discovered. However, when considering issues such as environmental pollution and chronic toxicity, compounds with structures similar to naturally occurring organic compounds, mainly consisting of carbon, hydrogen, oxygen, and nitrogen, are considered to be advantageous as future insecticidal ingredients. As a result of repeated research, the present inventor has found that the compound represented by the above formula () has an extremely excellent insecticidal effect as an insecticidal ingredient against various sanitary pests and agricultural and horticultural pests, and has extremely low toxicity to warm-blooded animals. We learned that it is much more stable against light than conventional pyrethroids. As described above, the compound represented by the above formula () overcomes the drawback of conventional pyrethroids such as being unstable to light, and is an excellent pest control composition that has a wide insecticidal spectrum and low toxicity.
Moreover, the cyclopropanecarboxylic acid constituting the above formula () can be easily obtained at low cost. The present invention was completed based on the above findings. The above formula () used as an active ingredient in the present invention
The compound represented by has the general formula according to the general method for ester production. (In the formula, X represents O, S, or NH group, Y ₁ ,
Y ₂ and Y ₃ represent a hydrogen atom or a halogen atom. However, at least one of Y ₁ , Y ₂ and Y ₃ represents a halogen atom. R ₁ represents a lower alkyl group having 1 to 8 carbon atoms, a lower alkenyl group, a haloalkyl group, a haloalkenyl group, and a group represented by the general formula (), (), or ().

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Here, m is an integer of 1 to 3, n is an integer of 2 to 5, and R ₃ is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a haloalkyl group, or an alkoxyl group. ) or its reactive derivative and the general formula (R ₂ here represents a hydrogen atom, a cyano group, or a trifluoromethyl group) or a reactive derivative thereof. Examples of reactive derivatives of carboxylic acids include acid halides, acid anhydrides, lower alkyl esters, and alkali metal salts. Examples of reactive derivatives of alcohol include chloride. The reaction is carried out in a suitable solvent, optionally in the presence of an organic or inorganic base or acid as a deoxidizer or catalyst, and optionally with heating.
Although what is obtained by a normal production method is a mixture of optical isomers, all of the esters of each isomer constituting this are also included in the present invention. Next, representative examples (shown as a mixture of optical isomers and geometric isomers) are shown, but the present invention is of course not limited to these.

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[Table] The compound of the present invention is a new compound, is solid or liquid at room temperature, and is generally easily soluble in organic solvents. Therefore, it can be used as an insecticide for spraying in the form of emulsions, oils, powders, wettable powders, aerosols, etc. It can also be used as an insecticide for fumigation such as mosquito coils by mixing with wood flour or other suitable base materials. can do. Also, when used as a so-called electric mosquito repellent by dissolving this active ingredient in an appropriate organic solvent and soaking it in a mount, or dissolving it in an appropriate solvent and heating and evaporating it with an appropriate heating element, it is as good as a mosquito coil. Show effectiveness. The compound of the present invention is more stable to light than conventional pyrethroids, has a broader insecticidal spectrum, is less toxic, and is cheaper, so it can be used in agriculture and horticulture as an alternative to conventional organophosphorus agents and organochlorine insecticides. It can be used as an insecticide. The compounds of the present invention can be used against sanitary pests such as flies, mosquitoes, and cockroaches, as well as organophosphorus agent- and carbamate-resistant leafhoppers, planthoppers, stink bugs, stink bugs, armyworm moths, diamondback moths, tobacco moths, bean weevils, nocturnal moths, and cabbage moths. , agricultural pests such as chestnut beetles, leaf beetles, aphids, and scale insects, grain storage pests such as brown elephants,
It is extremely useful for controlling mites, etc. In addition, the compounds of the present invention include N-octylbicycloheptenedicarboximide (trade name MGK-264) and a mixture of N-octylbicycloheptenedicarboximide and an arylsulfonate (trade name MGK-264).
5026), cinepirin 500, octachlorodipropyl ether, piperonyl butoxide, etc., the insecticidal effect can be further enhanced. In addition, other insecticides of the compounds of the present invention, such as organophosphorus agents such as fenitrothion, DDVP, diazinon, propaphos, and pyridafentione,
Carbamates such as NAC, MTMC, BPMC, PHC, conventional pyrethroid insecticides such as pyrethrin, allethrin, phthalthrin, flamethrin, phenothrin, permethrin, cypermethrin, decametrin, fuenvalerate, fuenpropanate, cartap, chlorphenamide Insecticides or acaricides such as gin and methomyl,
By mixing fungicides, nematicides, herbicides, plant growth regulators, fertilizers, and other agricultural chemicals, highly effective multipurpose compositions can be obtained, saving labor and providing sufficient synergy between the drugs. It's something to look forward to. In order to make it clearer that the composition provided by the present invention is excellent, the results of the efficacy test are shown below. Test Example 1 Insecticidal test by spraying A 0.2% white light solution of the compound of the present invention (A), 0.2% and a white light solution of 0.8% piperonyl butoxide (B), 0.1%
The falling and turning rate of houseflies was determined for a white light solution containing 0.1% phthalthrin (C), and a white light solution containing 0.2% each of allethrin and phthalthrin, and the relative effectiveness of the test agent was calculated. The calculated ratio is as follows.

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[Table] Test Example 2 Insecticidal test by fumigation Mosquito coils containing 0.5% of insecticidal ingredients were prepared and tested for their effectiveness in causing adult Culex mosquitoes to fall and roll over. This experiment was published in Insect Control Science Volume 16 (1951).
The relative effectiveness of the incense stick was calculated according to the method of Nagasawa, Katsuta et al., p. 176, and the results were as follows. The sample drug number is the same as that of the active ingredient example above.

[Table] Test Example 3 Insecticidal test by micro-dropping method Each of allethrin and the compound of the present invention and piperonyl butoxide were added to each of them as active ingredients.
An acetone solution with a predetermined concentration was added in twice the amount and applied to the thoracic dorsal plate of adult house flies using a microsyringe, and the mortality rate after 24 hours was determined from the relative insecticidal efficacy against allethrin and the synergistic effect with piperonyl butoxide. I investigated and found the following.

[Table] Next, the method for producing the compound of the present invention will be explained in detail by giving synthesis examples. Synthesis Example 1 2,2-dimethyl-3-trifluoromethyl-
Dissolve 4.3 g of 3-methoxycyclopropanecarboxylic acid in 50 ml of acetone, and add 3-phenoxy-
Add 5.7 g of α-cyanobenzyl bromide.
Add 4 ml of triethylamine under stirring, react at 60-80°C for 3 hours, dissolve in ether, wash the ether solution thoroughly with diluted hydrochloric acid, aqueous sodium bicarbonate, and brine, dry over sulfuric acid, and distill off the ether under reduced pressure. te, 3′-
7.4 g of phenoxy-α-cyanobenzyl 2,2-dimethyl-3-trifluoromethyl-3-methoxycyclopropanecarboxylate was obtained. Synthesis Example 2 2,2-dimethyl-3-fluoromethyl-3-
(2-Methyl-3-bromoallylthio)cyclopropanecarboxylic acid 6.3g and 3-phenoxy-α-
4.8 g of trifluoromethylbenzyl alcohol was dissolved in 50 ml of dry benzene, 6.2 g of dicyclohexylcarbodiimide was added, and the mixture was left sealed overnight. The next day, the reaction was completed by heating under reflux for 4 hours, and after cooling, the precipitated dicyclohexyl urea was filtered off. 100g of the oily substance obtained by concentrating the filtrate
3′-phenoxy-α′-trifluoromethylbenzyl 2,2-
8.8 g of dimethyl-3-fluoromethyl-3-(2-methyl-3-bromoallylthio)cyclopropanecarboxylate was obtained. Synthesis Example 3 2,2-dimethyl-3-trifluoromethyl-
Sodium salt of 3-(2-chloro-4-trifluoromethylanilino)cyclopropanecarboxylic acid
8.0g and 4.5g of 3-phenoxybenzyl chloride
was dissolved in 50 ml of benzene, reacted under reflux for 3 hours in a nitrogen stream, cooled the reaction solution, filtered out the precipitated salt, washed thoroughly with brine, dried over sulfur salt, and removed the benzene under reduced pressure. Distill to give 3'-phenoxybenzyl 2,2-dimethyl-3-trifluoromethyl-3-(2-chloro-4-trifluoromethylanilino)cyclopropanecarboxylate.
9.6g was obtained. Synthesis Example 4 6.3 g of 2,2-dimethyl-3-bromomethyl-3-cyclohexyloxycyclopropanecarboxylic acid chloride was dissolved in 15 ml of dry benzene, and 4.5 g of 3-phenoxy-α-cyanobenzyl alcohol was dissolved in 20 ml of dry benzene. When 3 ml of dry pyridine is added as a condensation aid, pyridine hydrochloride is precipitated. After sealing the cap and leaving it overnight at room temperature, after separating the crystals of pyridine hydrochloride, the benzene solution was dried with sulfuric acid, and the benzene was distilled off under reduced pressure to produce 3'-phenoxy-α'-cyanobenzyl 2,2- Dimethyl-3bromomethyl-
8.4 g of 3-cyclohexyloxycyclopropane carboxylate was obtained. Synthesis Example 5 6.1 g of methyl ester of 2,2-dimethyl-3-fluorochloromethyl-3-bromomethoxycyclopropanecarboxylic acid and 4.2 g of 3-phenoxybenzyl alcohol are heated to 150°C. temperature
When the temperature reached 150°C, 0.25 g of sodium was added and methanol distillation was started. When the distillation of methanol has stopped, 0.25 g of sodium is further added and the above operation is repeated while keeping the temperature around 150° C. until the theoretical amount of methanol is obtained. The mixture is then cooled and
Dissolve in ether, wash the ether solution with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dry with sulfuric acid, and distill off the ether under reduced pressure to obtain 3'-phenoxybenzyl 2,2.
-dimethyl-3-fluorochloromethyl-3-bromomethoxycyclopropanecarboxylate
8.1g was obtained. Synthesis Example 6 2,2-dimethyl-3-fluoromethyl-3-
Methylthiocyclopropanecarboxylic anhydride 7.4
g and 4.5 g of 3-phenoxy-α-cyanobenzyl alcohol were dissolved in 50 ml of dry pyridine and stirred overnight at room temperature. The next day, the reaction solution was poured into 100 g of ice and extracted three times with 20 ml of ether. Combine the ether layers and add 5% sodium hydroxide aqueous solution 20
ml was used to remove by-product carboxylic acid. The ether layer was further washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dried over sulfuric acid, and the ether was removed under reduced pressure to obtain a crude ester, which was injected into activated alumina 20.
3′-phenoxy-α′-
6.5 g of cyanobenzyl 2,2-dimethyl-3-fluoromethyl-3-methylthiocyclopropanecarboxylate was obtained. Synthesis Example 7 1.5 g of sodium metal is dissolved in 50 ml of absolute ethanol, and 100 ml of anhydrous toluene is added thereto. Ethanol and toluene were removed under reduced pressure in a nitrogen stream, and 1,
Add 100ml of 2-dimethoxyethane and add d-
Add 13.0 g of ethyl ester of cis,trans-2,2-dimethyl-3-trifluoromethyl-3-ethoxycyclopropanecarboxylic acid and heat under reflux for 12 hours. After the isomerization is completed, 1,2-dimethoxyethane is distilled off under reduced pressure, and 100 ml of water is added to the residue for ether extraction. The ether solution was thoroughly washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dried over sulfuric acid, distilled off the ether, and then distilled to give d-trans-2,2-dimethyl-3-trifluoromethyl-3-ethoxycyclopropanecarboxylic acid. Ethyl ester of acid (boiling point 120-125℃/30mmHg fraction)
9.6g was obtained. Add 5.2 g of this ethyl ester to 20 ml of acetic acid and 35%
4.7 g of the obtained carboxylic acid was hydrolyzed in 20 ml of an aqueous solution of hydrochloric acid, and 4.5 g of 3-phenoxy-α-cyanobenzyl alcohol was added according to the method of Synthesis Example 2.
3′-phenoxy-α′-cyanobenzyl d-trans-2,2-dimethyl-3-
7.3 g of trifluoromethyl-3-ethoxycyclopropanecarboxylate (n ²⁰ _D 1.5381) were obtained. Synthesis Example 8 d-cis,trans-2,2-dimethyl-3
16.0 g of ethyl ester of trifluoromethyl-3-methoxycyclopropanecarboxylic acid was subjected to repeated precision distillation to obtain ethyl ester of d-trans-2,2-dimethyl-3-trifluoromethyl-3-methoxycyclopropanecarboxylic acid ( Boiling point 75℃/15mmHg) 5.9g and d-cis-2,2-
1.6 g of ethyl ester of dimethyl-3-trifluoromethyl-3-methoxycyclopropanecarboxylic acid (a fraction with a boiling point of 81° C./13 mmHg) was obtained. The latter ethyl ester was treated in the same manner as in Synthesis Example 7 to obtain 3'-phenoxy-α'-cyanobenzyl d-cis-2,2-dimethyl-3-trifluoromethyl-3-methoxycyclopropanecarboxylate (n ^20D _1.5306 ) was obtained. Hereinafter, the symbol A will be added after the compound number to indicate that the acid moiety is the d-trans form, and the symbol B will be added to indicate that the acid moiety is the d-cis form. Synthesis Example 9 d-trans-2 obtained in Synthesis Example 7,
4.2 g of 2-dimethyl-3-trifluoromethyl-3-ethoxycyclopropanecarboxylic acid was dissolved in 50 ml of methanol at 50°C, and 5.2 g of -(4-tolyl)-2-phenethylamine was dissolved in methanol.
Add the dissolved solution to 25ml to generate salt. Cool to room temperature, leave for 2 hours, and collect precipitated crystals. This crystal was further re-crystallized with methanol to give 3.2g
Obtain the crystals. After adding 20ml of 10% caustic soda aqueous solution to these crystals and suspending them, by ether extraction -
(4-Tolyl)-2-phenethylamine is recovered. The aqueous layer was acidified with hydrochloric acid, extracted with methylene chloride, and the solvent was distilled off to obtain 1.4 g of -trans-2,2-dimethyl-3-trifluoromethyl-3-ethoxycyclopropanecarboxylic acid. [α] ²⁰ _D -45° (Chloroform) Optical purity 93% 1.3 g of this carboxylic acid was reacted with 1.5 g of 3-phenoxy-α-cyanobenzyl bromide according to the method of Synthesis Example 1 to obtain 3'-phenoxy-α. ′-
Cyanobenzyl-trans-2,2-dimethyl-3-trifluoromethyl-3-ethoxycyclopropanecarboxylate 2.0 g (n ²⁰ _D
1.5374) was obtained. This compound exhibited approximately twice the insecticidal activity as compared to the d-trans ester. Hereinafter, add the symbol C after the compound number,
Indicates that the acid moiety is -trans form. Reference example 1 White kerosene was added to 0.2 parts of the present compound (1) and the whole
Obtain 0.2% oil solution as 100 parts. Reference Example 2 White kerosene is added to 0.2 parts of the compound of the present invention (2) and 0.8 parts of piperonyl butoxide to make a total of 100 parts to obtain an oil solution. Reference Example 3 To 20 parts of the compound of the present invention (4), 10 parts of Solpol SM-200 (trade name of Toho Chemical) and 70 parts of xylol were added and mixed and dissolved with stirring to obtain a 20% emulsion. Reference Example 4 0.4 parts of the present compound (10), 0.1 parts of resmethrin, and 1.5 parts of octachlorodipropyl ether were added to refined kerosene.
After dissolving the solution in 28 parts and filling it into an aerosol container and attaching a valve part, 70 parts of a propellant (liquefied petroleum gas) is pressurized and filled through the valve part to obtain an aerosol. Reference Example 5 0.5 parts of the compound of the present invention (17) and 0.5 g of BHT were added to a base material for mosquito coils such as pyrethrum extract powder, wood flour, starch powder, etc.99.0
g to obtain a mosquito coil by a known method. Reference Example 6 0.4 g of the compound (26) of the present invention and 1.0 g of MGK-5026 are uniformly mixed with 98.6 g of a mosquito coil base material to obtain a mosquito coil by a known method. Reference Example 7 3 parts of the compound (34) of the present invention and 97 parts of clay were thoroughly ground and mixed to obtain a 3% powder. Reference example 8 40 parts of the present compound (45), 35 parts of diatomaceous earth, 20 parts of clay
1 part, 3 parts of lauryl sulfonate, and 2 parts of carboxymethyl cellulose are ground and mixed to obtain a wettable powder. Test Example 4 Rice stems (about 12 cm in length) were immersed for 1 minute in a water dilution of an emulsion of the present invention compound and a control compound obtained according to Reference Example 3 at a predetermined concentration. After air-drying, rice stems were placed in test tubes and 10 adult brown planthoppers were released. After 1 day, they were examined for survival and death, and the relative insecticidal efficacy of the compound of the present invention relative to the control compound () was determined from the LC ₅₀ value (50% lethal concentration). The situation is as follows. Control compound ()... Compound of Reference 1 Control compound ()... Compound of Reference 2

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[Table] As a result of the test, the usefulness of the compound of the present invention having a halomethyl group at the 3-position of the cyclopropane ring was confirmed. Test Example 5 5 to 6 of a surface where a large number of green peach aphids appeared
Among the emulsions obtained in Reference Example 3 in the radish field at the leaf stage, compounds of the present invention (1), (4), (7), (12), (19), (23),
(28), (32), (37), (41), (8)-A, (14)-C, (29)
A 1000-fold dilution of each emulsion containing -B and (42)-B(44) with water was applied at a rate of 100/per plate.
Two days later, the parasitism rate was investigated and found that the density had decreased to less than 1/10 of the pre-spraying density in each plot. Test Example 6 Compound of the present invention among the emulsions obtained in Reference Example 3
(2), (4), (5), (10), (14), (17), (24), (29), (33)
，
(38), (42), (8)-A, (21)-C, (30)-B and (3
9) - A fresh leaf was immersed in the 2000 times diluted solution for about 5 seconds, and after the solution had dried, it was placed in a shear dish and 10 healthy larvae of armyworm were released. The test insects were released twice, once on the day of soaking the fresh leaves, and once 5 days later, and the mortality rate after 24 hours was determined.

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[Table] Test Example 7 One day before applying the insecticidal active ingredient to needle-planted fava beans, each tree was infested with approximately 200 aphids. Among the hydrating agents obtained by Reference Example 8
(3), (6), (9), (16), (20), (26), (31), (35), (3
9), (45) and (48) diluted 4000 times were sprayed on leaves infested with compressed air at 10 ml/pot, and the degree of damage was observed 2 days later. As a result, no increase in the degree of damage was observed in any of the cases. Test Example 8 (1), (5), (8), (12), (1) obtained by Reference Example 7
8), (22), (29), (34), (36), (41), and (47) were uniformly sprinkled on the bottom of a tall glass shear dish with a diameter of 14 cm at a rate of ² g/m2. , spread butter on the wall leaving about 1cm at the bottom. If adult German cockroaches were released into the container in groups of 10, and the cockroaches were left in contact for 30 minutes and then transferred to a new container, more than 80% of the cockroaches could be killed by either powder after three days. Test Example 9 1 for 4 leaves of potted green beans 5 days after sowing
Infested with 10 female adult spider mites per leaf.
Store in a constant temperature room at 27℃. After 6 days, compounds of the present invention (2), (4), (11), (18), (2) of the emulsion obtained in Reference Example 3 were added.
5), (30), (34), (39), (43), and (48) were diluted with water to 100 ppm of active ingredients, and 10 ml of each pot was sprayed on a turntable. After 10 days, the number of parasitized spider mites on the plants was less than 10 in all cases.

Claims (1)

[Claims] 1. General formula (In the formula, X represents O, S, or NH group, Y ₁ ,
Y ₂ and Y ₃ represent a hydrogen atom or a halogen atom. However, at least one of Y ₁ , Y ₂ and Y ₃ represents a halogen atom. R ₁ represents a lower alkyl group having 1 to 8 carbon atoms, a lower alkenyl group, a haloalkyl group, a haloalkenyl group, and a group represented by the general formula (), (), or (). [Formula] [Formula] Here, m is an integer of 1 to 3, n is an integer of 2 to 5, and R ₃ is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a haloalkyl group, or an alkoxyl group. R ₂ represents a hydrogen atom, a cyano group or a trifluoromethyl group. ) and its optical and geometric isomers. 2 General formula (In the formula, Y ₁ , Y ₂ , Y ₃ represent hydrogen atoms or halogen atoms. However, at least one of Y ₁ , Y ₂ , Y ₃
Each represents a halogen atom. R ₁ has 1 or more carbon atoms
8 lower alkyl group, lower alkenyl group, haloalkyl group, haloalkenyl group and general formula (),
Indicates a group represented by () or (). [Formula] [Formula] Here, m is an integer of 1 to 3, n is an integer of 2 to 5, and R ₁ is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a haloalkyl group, or an alkoxyl group. R ₂ represents a hydrogen atom, a cyano group or a trifluoromethyl group. ) and its optical and geometric isomers. 3 formulas The carboxylic acid ester derivative and optical and geometrical isomers thereof according to claim 2, which are compounds represented by the following. 4 formula The carboxylic acid ester derivative and optical and geometrical isomers thereof according to claim 2, which are compounds represented by the following. 5 formula The carboxylic acid ester derivative and optical and geometrical isomers thereof according to claim 2, which are compounds represented by the following. 6 formula The carboxylic acid ester derivative and optical and geometrical isomers thereof according to claim 2, which are compounds represented by the following. 7 General formula (In the formula, X represents O, S, or NH group, Y ₁ ,
Y ₂ and Y ₃ represent a hydrogen atom or a halogen atom. However, at least one of Y ₁ , Y ₂ and Y ₃ represents a halogen atom. R ₁ represents a lower alkyl group having 1 to 8 carbon atoms, a lower alkenyl group, a haloalkyl group, a haloalkenyl group, and a group represented by the general formula (), (), or (). [Formula] [Formula] Here, m is an integer of 1 to 3, n is an integer of 2 to 5, and R ₃ is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a haloalkyl group, or an alkoxyl group. ) or its reactive derivative and the general formula (Here, R ₂ represents a hydrogen atom, a cyano group, or a trifluoromethyl group.) A general formula characterized by reacting with an alcohol or a reactive derivative thereof. (Here, X, Y ₁ , Y ₂ , Y ₃ , R ₁ , and R ₂ have the same meanings as above.) A method for producing a carboxylic acid ester derivative and its optical and geometric isomers. 8 General formula (In the formula, X represents O, S, or NH group, Y ₁ ,
Y ₂ and Y ₃ represent a hydrogen atom or a halogen atom. However, at least one of Y ₁ , Y ₂ and Y ₃ represents a halogen atom. R ₁ represents a lower alkyl group having 1 to 8 carbon atoms, a lower alkenyl group, a haloalkyl group, a haloalkenyl group, and a group represented by the general formula (), (), or (). [Formula] [Formula] Here, m is an integer of 1 to 3, n is an integer of 2 to 5, and R ₃ is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a haloalkyl group, or an alkoxyl group. R ₂ represents a hydrogen atom, a cyano group or a trifluoromethyl group. ) and its optical and geometric isomers. 9 formula 9. The insecticide according to claim 8, which contains a carboxylic acid ester derivative represented by: and its optical and geometrical isomers. 10 formula 9. The insecticide according to claim 8, which contains a carboxylic acid ester derivative represented by: and its optical and geometrical isomers. 11 formula 9. The insecticide according to claim 8, which contains a carboxylic acid ester derivative represented by: and its optical and geometrical isomers. 12 formula 9. The insecticide according to claim 8, which contains a carboxylic acid ester derivative represented by: and its optical and geometrical isomers. 13. The insecticide according to claim 8, which contains a pyrethroid synergist as an adjuvant.