JPS5822149B2 - New carboxylic acid ester, its production method, and insecticides and acaricides containing it as an active ingredient - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a carboxylic acid ester represented by the following general a),
its production method and insecticides containing it as an active ingredient;
It concerns acaricides.

(In the formula, R1 is the following general formula (II) or Group represented by (III) and R2 is the general formula represents a group represented by

Here, X represents a fluorine atom, a chlorine atom or a bromine atom, and Y represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom or a bromine atom.

) Various types of cyclopropane carboxylic acid ester insecticides have been known so far, and several types exist among the pyrethrum components.

Among the many insecticides used today, these pyrethrum components have excellent insecticidal efficacy, as well as low toxicity to humans and livestock, fast-acting against pests, and difficulty in producing chemical resistance. Because of its superiority as an agent, it has been widely used to control sanitary pests and agricultural and horticultural pests.

However, on the other hand, it has drawbacks such as being expensive and limiting its applicability from an economical point of view, and many researchers have synthesized a large number of related compounds to date.

The present inventors have searched for a compound that has the above-mentioned advantages of the herethroid insecticide and is also excellent in economical efficiency, and as a result, the present compound represented by general gI) has properties that meet these objectives. It was found that

Next, the names of specific insect pests for which the compounds of the present invention are particularly effective will be listed.

I Hem1ptera (Hemiptera) 1, Delphacidae (planthoppers): for example, Sogatella furcifera 1), Ni1aparvata lugens
(Brown Planthopper), Laodelphax 5tr
iatellus 2, Del
tocephalidae (leafhoppers): e.g. N
ephotettix cincticeps (Tettigella viridis
(Giant leafhopper), Inazumadorsalis
(Inazuma leafhopper) 3, Aphididae
(Abrams): For example, Rhopalosiphu
m padi, Myzu
s persicae (green peach aphid) 4,
Pentatomidae: for example, Nezara antennata, Eysarcaris ventralis
(White stink bug) 2 Lepidoptera
(Lepidoptera): For example, Archips fumife
rana (suf c') lace bud worm) Chilo
5 uppressalis) Cua
pha 1 ocrocis mediinal is
(fufu'nmeiga) Galleria mel 1o
nel la (honey hemlock) Dendrol imu
s 5pectabi Iis Mal
acosoma neustria (obikareha) S
podoptera l1tura 3 Co1eoptera (Coleoptera): For example, T
ribolium castaneum (Oulema oryzae) Echinocnemus squameus
(rice weevil) 4 Diptera (Diptera)
:For example, Musca domestica (house fly) Aedes aegypti (necked fly) A
nopheles sp, Cul
ex pipiens pallens (Culex pipiens) Agromyza oryzae (Rice leafminer) 5 0rthhoptera (Orthoptera): For example, B
lattella germanica (German cockroach) Oxya yezoensis (Cockroach) 6 Acarina (Acarina): e.g. Tet
Tetranychus Urtica
e (two-spotted spider mite) 01igonychus hond
oensis Panonychus
The compound of the present invention represented by citri (citrus spider mite) general gI) is general m (wherein R1 has the same meaning as above).

) or a reactive derivative thereof and the general formula (wherein Z represents a hydroxyl group, a chlorine atom or a bromine atom, and R2 has the same meaning as above).

) or a method of reacting with an alcohol represented by the formula (2) or a reactive derivative thereof (wherein Q represents a chlorine atom or a bromine atom, and R1 has the same meaning as above).

) and the general formula ■ (wherein, R
2 has the same meaning as above.

) can be obtained in good yield by a method of reacting an aldehyde represented by the formula (gI) with an alkali metal cyanide, and when R1 in general gI) is a group represented by the above general gll), the general formula (g) (formula In the formula, X and R2 have the same meanings as above.

) can be obtained in good yield by brominating the carboxylic acid ester.

Examples of the reactive derivatives of carboxylic acids represented by m here include carboxylic acid halides, carboxylic acid anhydrides, salts of tertiary organic bases of carboxylic acids, and alkali metal salts of carboxylic acids.

Note that the compounds related to the present invention include optical isomers based on asymmetric carbon atoms of alcohol components and acid components, and all of them are included in the present invention.

The outline of the method for producing a carboxylic acid ester in the present invention is illustrated below.

(Synthesis method A) Method by reaction of alcohol and carboxylic acid halide General formula (to) (In the formula, R2 has the same meaning as above.

) and the general formula■ (In the formula, R1 and Q have the same meanings as above.

), preferably an acid chloride, in an inert solvent (e.g. benzene, toluene, ether, hexane, etc.) in the presence of a deoxidizing agent (e.g. pyridine, triethylamine, etc.) at an internal temperature of -30°C to 100°C. The desired ester is obtained by reacting for 30 minutes to 10 hours.

(Synthesis method B) Method by reaction of alcohol and carboxylic acid General formula (XD (wherein, horse has the same meaning as above).

) and the general formula (to) (In the formula, R1 has the same meaning as above.

) in the presence of a dehydration condensation agent (e.g. dicyclohexylcarbodiimide, etc.) in an inert solvent (e.g. benzene, toluene, xylene, etc.) at an internal temperature of 0°C to
The reaction is carried out at 150°C for 30 minutes to 10 hours to obtain the desired ester.

(Synthesis method C) Method by reaction of a halide with a salt of a tertiary organic base of a carboxylic acid General formula (a) (In the formula, Z' represents a chlorine atom or a bromine atom, and R2
has the same meaning as above.

) and the general formula (g) (In the formula, R1 has the same meaning as above.

) in an inert solvent (e.g., acetone, benzene, dioxane, etc.) in the presence of a tertiary organic base (e.g., triethylamine, trimethylamine, etc.) at an internal temperature of 0°C to 150°C for 30 minutes to 10 hours. React to obtain the desired ester.

(Synthesis method D) Method by reaction of a halide with an alkali metal salt of a carboxylic acid General formula (a) (In the formula, Z' and R2 have the same meanings as above.

) and the general formula (xi) (where M represents an alkali metal and R1 has the same meaning as above).

) and an alkali metal salt of a carboxylic acid represented by
In a phase system, in the presence of a phase transfer catalyst (e.g., tetra-n-butylammonium bromide, benzyltriethylammonium chloride, etc.) at an internal temperature of 0°C to 150°C for 30 minutes to
The desired ester is obtained by reacting for 10 hours.

(Synthesis method E) Method by reaction with aldehyde, alkali metal cyanide and acid halide <E-i> General I (wherein R2 has the same meaning as above).

), an aldehyde of an alkali metal cyanide, and the general formula (g) (wherein Q and R1 have the same meanings as above).

) in an inert solvent (e.g. benzene, toluene, etc.) using a phase transfer catalyst (e.g. dibenzo-18-crown-6, dicyclohexyl-18
-Crown-6, etc.) at an internal temperature of 0℃ to 150℃
The desired ester is obtained by reacting for 0 minutes to 20 hours.

(E-2) General I (In the formula, R2 has the same meaning as above.

), an aldehyde of an alkali metal cyanide, and the general formula (a) (wherein Q and R1 have the same meanings as above).

) with the carboxylic acid halide shown in water-inert solvent (
Reaction in a two-phase system of benzene, hexane, toluene, etc.) at an internal temperature of 0°C to 100°C for 30 minutes to 10 hours in the presence of a phase transfer catalyst (such as tetra-n-butylammonium bromide, benzyltriethylammonium chloride, etc.) to obtain the desired ester.

(Synthesis method F) Method using bromination reaction of ester General formula (
g) (wherein, X and R2 have the same meanings as above.

) and bromine are reacted in an inert solvent (e.g. carbon tetrachloride, methylene chloride, chlorobenzene, etc.) at an internal temperature of -30°C to 100°C for 30 minutes to 20 hours to obtain the desired ester. obtain.

The carboxylic acid ester of the present invention synthesized according to the above-mentioned synthesis method is shown below.

Next, the method for synthesizing the compound of the present invention will be explained in more detail with reference to the following examples.

Example 1 Synthesis of compound (2) 6-phenoxy-2-pyridyl-α-cyanemethanol 13.6 ? (6,0 mmoi), benzene 10
m1, g-cis to a solution consisting of 0.951 (12 mmol) of pyridine while stirring at an internal temperature of 5°C or less under water cooling,
trans-2,2dimethyl-3-(1,2-dibromo-
2,2-dichloroethyl)cyclo7'o/-e carboxylic acid chloride 2.33? (6,0 mmol)
Add a solution dissolved in 5 ml of benzene dropwise.

After completion of the dropwise addition, the mixture was stirred at room temperature overnight, and then water was added to the reaction mixture to separate the mixture.

The organic layer was washed with 5-hydrochloric acid, a saturated aqueous sodium carbonate solution, and a saturated saline solution, dried over anhydrous sodium sulfate, and then the solvent was distilled off. The residue was purified by column chromatography packed with silica gel. 6-phenoxy-2-pyridyl-α-cyanomethyl U-cis, trans-2,2-dimethyl-3-(1,2-dibromo-2,
2-di)chloroethyl)cyclopropanecarboxylate was obtained as a pale yellow liquid.

(Yield 95%) Example 2 Synthesis of compound starch 3) Sodium cyanide 0.37 f (7.5 mmol)
and 0.25 f (1.1 mmol) of benzyltriethylammonium chloride were dissolved in 5 m of water,
Here, 6-(4-fluorophenoxy) was added in a room under stirring.
-2-pyridinecarbaldehyde 1.09 f (5,
0 mmol) and dt-cis, trans 2,2-
Dimethyl-3-(1,2-dibromo-2,2-dichloroethyl)cyclopropanecarboxylic acid chloro.

Ride 2.03 f (5.25 mmol) toluene 10 m/.

Add the solution dissolved in the solution dropwise.

After completion of the dropwise addition, stirring was continued at the same temperature for 5 hours.

The resulting reaction solution was washed with saturated brine and dried over anhydrous sodium sulfate.

By distilling off the solvent, 2.92 f of 6-1 (4-
Fluorophenoxy)-2-pyridyl-α-cyanomethyl U-cis, trans-2゜2-dimethyl-3-(1,
2-Dibromo-2°2-dichloroethyl)cyclopropanecarboxylate was obtained as a pale yellow liquid.

(Yield: 98) Example 3 Synthesis of compound (1) 0.44 y (9.0 mmol) of sodium cyanide and benzo-18-crown-6,0,1f were suspended in 10 mt of benzene, and 6 at room temperature with stirring
-phenoxy-2-pyridinecarbaldehyde 1.20
? (6,0 mmol) and 2,2,33-tetramethylcyclopropanecarboxylic acid chloride 1. o
A solution prepared by dissolving 1 g (6.3 mm o I) in 10 mt of benzene is added dropwise.

After the addition is complete - continue stirring overnight.

The resulting reaction solution is washed with saturated brine and then concentrated.

The residue was purified by column chromatography packed with silica gel to obtain 2.0 Or of 6-phenoxy-2-pyridyl-α-cyanomethyl 2.2,3,3-tetramethylcyclopropanecarboxylate as a pale yellow liquid.

(Yield: 95) Example 4 Synthesis of compound (7) 1.73 f (6,01 of) 6-phenoxy-2-pyridyl-α-cyanmethyl bromide was dissolved in 1 toluene.
Sodium α-t-lance-2,
2-dimethyl-3-(1,2,2.

2-tetrabromoethyl)cyclopropanecarboxylate 3,461 (7,2 mmol) and tetra-n-
Butylammonium bromide 0.018mm 025mm
Add a solution of ol) dissolved in 10 mt of water and bring the internal temperature to 70-80.
Stir at ℃ for 5 hours.

The resulting reaction solution was washed with saturated brine and then diluted with anhydrous sulfuric acid.
Dry with IJum.

By distilling off the solvent, 3.801 6-phenoxy-2-pyridyl-α-cyanmethyl d-trans-2,
2-dimethyl-3-(1,2,2,2-tetrabromoethyl)cyclopropanecarboxylate was obtained as an orange liquid.

(Yield: 95) Example 5 Synthesis of compound (6) 6-phenoxy-2-pyridyl-α-cyanomethyl d-
Cis-2,2-dimethyl-3-(2゜2-dibromovinyl)cyclopropanecarboxylate 3.04 S'
(6,0 mmol) was dissolved in 20 ml of carbon tetrachloride, and 1.06 r (6,6 mmol) of bromine was dissolved at a stirrer internal temperature of 20°C.
1) dissolved in 5 mt of carbon tetrachloride is added dropwise.

After completion - continue stirring overnight. The resulting reaction solution was washed once with a 10% aqueous sodium sulfite solution and then with saturated brine, dried over anhydrous sodium sulfate, and concentrated.

The residue was purified by column chromatography packed with silica gel to give 3.841 6-phenoxy-2-pyridyl-α-cyanomethyl d-cis-2,2-dimethyl-3
-(1,2,2,2-tetrabromoethyl)cyclop0
/tan carboxylate was obtained as a pale yellow liquid.

(Yield: 96) When actually applying the compound of the present invention obtained in the above-mentioned example, it can be used alone without adding other ingredients, but in order to make it easier to use as a pesticidal agent, a carrier is added. It is common to mix them together to form a preparation, which is then diluted as necessary before application.

The preparation of formulations does not require any special conditions similar to general pesticides, and can be formulated using methods well known to those skilled in the art such as emulsions, irrigation agents, powders, granules, fine granules, oils, aerosols, thermal fumigants (mosquito It can be prepared into any dosage form such as incense coils, electric mosquito repellents, etc.), fumigants for fogging, non-heated fumigants, poison baits, etc., and can be used for various purposes depending on the purpose.

Furthermore, by combining two or more of these compounds,
It is also possible to express superior insecticidal power, and furthermore, α-(2-(2-butoxyethoxy)ethoxy)-4,5-methylenedioxy-2-propyltoluene ( piperonyl butoxide), 1゜2-methylenedioxy-4-(2-(octylsulfinyl)propyltorunzene (referred to as sulfoxide), 4-(3,4-methylenedioxyphenyl)- 5-Methyl-1,3-dioxane (referred to as safroxane), N-(2-ethylhexyl)-bicyclo[2,2,1]hebut-5-ene-2,3-dicarboxydomi (MGK-264) ), octachlorodipropyl ether (referred to as S-421), isopornyl thiocyanoacetate (referred to as Garnite), etc.
The insecticidal effect can also be enhanced by mixing with other known synergists effective against allethrin and pyrethrin.

In addition, unlike general chrysanthemum acid ester compounds, the compounds of the present invention are relatively stable against light, heat, oxidation, etc., but when particularly necessary under extremely oxidative conditions, antioxidants or ultraviolet absorbers may be added. For example, phenol derivatives such as BHT and BHA, his-phenol derivatives, and phenyl-
α-naphthylamine, phenyl-β-naphthylamine,
Arylamines such as condensates of phenetidine and acetone or benzophenone compounds are suitable as stabilizers.
By adding it, a composition with more stable effects can be obtained.

In addition, other physiologically active substances such as allethrin, N-(chrysansemoxymethyl)-3,4,5゜6-tetrahydrophthalimide (hereinafter referred to as tetramethrin), 5-
Benzyl-3-furylmethylchrysanthemate (hereinafter referred to as resmethrin), 3-phenoxybenzylchrysanthemate, 5-propargylfurfurylchrysanthemate, 2-methyl-5-propargyl-3-furylmethylchrysanthemate, and these d-4 lance chrysanthemum acid ester, d-cis, trans primary chrysanthemum ester or pyrethrum extract, d-1 lance chrysanthemum acid or d-cis, trans primary chrysanthemum ester of d-arethrolone, etc. In addition to known cyclopropane carboxylic acid esters,
0,0-dimethyl-〇-(3-methyl-4-nitrophenyl) phosphorothioate (referred to as fenitrothion), 0゜0-dimethyl-0-4-cyanophenyl phosphorothioate (referred to as cyanophos), 0.0-dimethyl- Organophosphorus insecticides such as 〇-(2,2-dichlorovinyl)-phosphate (referred to as dichlorovos), ■
-Naphthyl-N-methylcarbamate, 3,4-dimethylphenyl-N-methylcarbamate, meta-tolyl-
N-methylcarbamate 0-sec-butylphenyl-
Carbamate insecticides such as N-methylcarbamate, 0-iso-propoxyphenyl-N-methylcarbamate, other insecticides or fungicides, nematicides, acaricides, herbicides, plant growth regulators, fertilizers By mixing it with microbial pesticides such as , BT agents, BM agents, insect hormone agents, and other pesticides, it is possible to create multipurpose compositions with even better efficacy, and a synergistic effect of efficacy can be expected by combining them.

Next, we will give examples of formulations of insecticides and acaricides.

Formulation Example 1 Add 10 parts each of the compounds (1) to 01) of the present invention, 15 parts each of emulsifier (Tsurpol 3005X (registered trademark of Toho Chemical)), and 75 parts of Quijirol, stir well, mix and dissolve. Obtain each emulsion.

Formulation Example 2 PAP (
Add 0.3 parts of isopropyl acid phosphate, dissolve in 20 parts of acetone, and add 0.3 parts of isopropyl acid phosphate.
After stirring and mixing thoroughly in a crusher, the acetone is removed by evaporation to obtain each powder.

Formulation Example 3 0.2 parts of each of the compounds (1) to 01) of the present invention
- Add 2 parts of tolyl-N-methyl carbamate, further add 0.3 parts of each PAP (listed above), dissolve in 20 parts of acetone, add 97.5 parts of 300 mesh clay,
After thorough stirring and mixing in a crusher for 1°, acetone is removed by evaporation to obtain each powder.

Formulation Example 4 10 parts of the compounds (1) to (11) of the present invention were thoroughly mixed with 5 parts of an emulsifier (Tsurpol 5M-200 (registered trademark of Toho Chemical)), 85 parts of 300 Metsushukeisouji was added, and the mixture was crushed. A wettable powder is obtained by sufficiently stirring and mixing in a container.

Formulation Example 5 1-naphthyl-N to 10 parts of the compound of the present invention (υ~(11))
- Add 5 parts of methyl carbamate, mix well with 5 parts of emulsifier (Tsurpol 5M-200 (mentioned above)), process 80 parts of 300 mesh powder, stir thoroughly in a crusher, and each water Obtain Japanese medicine.

Formulation Example 6 Dissolve 0.5 part of each of the compounds of the present invention (1) to ←υ in white kerosene and make the total 100 parts to obtain each oil preparation. Formulation Example 7 Compound of the present invention (6) 0.4 part, Mix 0.2 parts of allethrin, 13.4 parts of deodorized kerosene, and 1 part of emulsifier (Atmos 300 (registered trademark of Atlas Chemical)), add 50 parts of pure water to emulsify, and then add 3 parts of deodorized butane and deodorized propane.
A water-based aerosol is obtained by filling an aerosol container with 35 parts of the :1 mixture.

Formulation Example 8 Compound (1) of the present invention 0.3 f and allethrin 0.32
was added, dissolved in 20 mt of methanol, and a carrier for incense sticks (mixed tab powder: lees powder: wood flour in the ratio of 3:5:1) 99.4
After uniformly stirring and mixing with y and evaporating methanol, 150 m7 of water was added and the mixture was thoroughly kneaded and molded and dried to obtain a mosquito coil.

Formulation Example 9 Compound of the present invention (1), o, 1f and allethrin d
-1-Lase tertiary chrysanthemum acid ester 0.022 B HT
Add 0.11 of O,0521 piperonyl butoxide,
Dissolve in appropriate amount of chloroform, 3.5cm x 1.5cr
The same highly heated fiber fumigation composition can be obtained by adsorbing it evenly onto the surface of asbestos with a rl thickness of 0.3Cn7.

As for the fibrous carrier, in addition to asbestos, materials having equivalent effects such as pulp board can be used.

The insecticidal effects of the composition of the present invention thus obtained are as follows.

Test Example 1 Insecticidal effect on house flies Place F paper of the same size on the bottom of a polyethylene cup with a diameter of 5.5 cm.

A 200-fold dilution of the emulsion obtained in Formulation Example 1 with water (5
00ppm equivalent) 0.7m/S is dropped onto P paper.

Place 3 ort of sucrose on the paper as bait.

, I released 10 houseflies into it, put a lid on it, and placed 4
After 8 hours, the insects were examined to see if they were alive or dead and the mortality rate was calculated.

(2 repetitions) Experimental example 2 Insecticidal efficacy against black leafhopper A 10% emulsion of the following invention compound obtained in Formulation Example 1 was diluted 1000 times with water (equivalent to 100 ppm), planted in 180 m plastic cuffs, sown 1 month. Spray 15 m 1/2 cup onto the rice on a turntable.

After air-drying, cover with a wire mesh cage and release about 15 adult carbamate-resistant leafhoppers.

After 24 hours, check whether they are alive or dead.

In addition, in order to examine the residual effect, adult insects appeared in the same manner 3 and 7 days after the spraying, and the survival and death were examined 24 hours after each application (two repetitions).

Test Example 3 Indigo leaves with insecticidal effect against Spodoptera spp.
It is immersed in a diluted solution of the following emulsion shown in Formulation Example 1 with water at a predetermined concentration for 1 minute and air-dried.

The treatment solution and 10 4th instar Spodoptera larvae were placed in a plastic cup with a diameter of 9 crr L 1 and a height of 4 (1:771), and the mixture was kept in a climate chamber at 26° C., and the survival or death was examined after 24 hours.

Test Example 4 Control effect against false red spider mites Four leaves of potted green beans 5 days after sowing are infested with 10 female adult false red spider mites per leaf and stored in a constant temperature room at 27°C.

After 6 days, a chemical solution prepared by diluting the following emulsion obtained in Formulation Example 1 with water to 500 ppm of active ingredient is sprayed on a turntable at 1 occ per pot.

Count the number of female adult spider mites on the 10-day diameter leaf transplant.

Criteria for determining effectiveness are ++ 0 to 9 adult female insects per leaf.

10 〃 10-30 animals 〃-
〃 31 or more animals〃

The result is as below.・Test Example 5 The powder shown in Formulation Example 3 was applied to rice in the 1/100,000th are planting in a Wagner pot using Pelger Duster.
Spray at a rate of 3:9 per 0a and cover each plant with a wire mesh cage.

Approximately 15 adult leafhoppers and adult leafhoppers are released in each cage.

The pots were kept in a greenhouse and the viability was observed after 24 hours, and both powders were able to kill too many pests of both species.

Test Example 6 Campbell's turn table method [Soap and Sanitary Chemicals vol. 14A6.

119 (1938)), one group of adult house flies
00 flies were sprayed with 5 mt of each oil agent obtained according to Formulation Example 6, and exposed to the descending spray for 10 minutes, it was possible to kill 100% of the flies using either oil agent.

Test Example 7 The insecticidal effect of the aerosol obtained in Formulation Example 7 on adult house flies was evaluated using an aerosol test method (C8MA method) using a beet grady chamber (6 feet cubic).
Tested by.

As a result, each aerosol was able to knock down more than 80% of the flies within 15 minutes after injection, and was able to kill more than 90% of flies after 24 hours.

Test Example 8 The following compounds of the present invention and a control compound were each adjusted to a predetermined concentration using deodorized kerosene.

Ten adult German cockroaches are placed in a glass petri dish with a diameter of 10 mm and the walls are lightly coated with Vaseline, and the lid is covered with 50 mesh nylon gauze.

0.6 ml of each oil agent in an atomizer at 50 CW
Spray from a distance of 1 and observe the number of insects knocked down over time.

KT5o (50% knockdown time) was determined from the results.

Claims (1)

[Claims] 1 General formula (wherein, R4 represents a group represented by the following general formula (n) or (I[), and R2 represents a group represented by the general formula. Here, X is fluorine a chlorine atom or a bromine atom, and Y represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom or a bromine atom). 2 A carboxylic acid represented by the general formula (wherein R1 represents a group represented by the following general formula (n) or (I), where X represents a fluorine atom, chlorine atom or bromine atom) or its Reactive derivatives and the general formula (wherein, Z represents a hydroxyl group, a chlorine atom or a bromine atom, and R2 represents a group represented by the general formula. Here, Y is a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom or a bromine atom) A method for producing a carboxylic acid ester represented by the patent (wherein R1 and R2 have the same meanings as above), characterized by reacting an alcohol represented by (representing an atom) or a reactive derivative thereof. (In the formula, Q represents a chlorine atom or a bromine atom, and R represents a group represented by the following general formula (llI). Here, X represents a fluorine atom, a chlorine atom, or a bromine atom.) Acid halides, aldehydes and alkali metals represented by the general formula (wherein, R2 represents a group represented by the general formula; Y represents a hydrogen atom, methyl group, fluorine atom, chlorine atom or bromine atom); A method for producing a carboxylic acid ester represented by the general formula (wherein R1 and R2 have the same meanings as above), which comprises reacting a cyanide salt. (In the formula, X represents a fluorine atom, a chlorine atom, or a bromine atom, and R2 represents a group represented by the general formula. Here, Y represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, or a bromine atom. ) A method for producing a carboxylic acid ester represented by the general formula (wherein X and R2 have the same meanings as above), which comprises brominating a carboxylic acid ester represented by the following. (In the formula, R1 represents a group represented by the following general formula (n) or (I'), and R2 represents a group represented by the general formula. Here, X represents a fluorine atom, a chlorine atom, or a bromine atom. , Y represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, or a bromine atom.