JPS6310945B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a carboxylic acid ester represented by the following general formula (), a method for producing the same, and an insecticide and acaricide containing the carboxylic acid ester as an active ingredient. [In the formula, R ₁ represents a methyl group or a hydrogen atom,
When R ₁ is a methyl group, R ₂ represents a hydrogen atom, a methyl group, or a chlorine atom; when R ₁ is a hydrogen atom, R ₂
represents a methyl group or a trifluoromethyl group. R ₃ represents a hydrogen atom, a cyano group or an ethynyl group, and R ₄ represents the general formula

[expression] or

Represents a group represented by the formula (where X represents a chlorine atom or a bromine atom). ] Insecticides and acaricides are essential production materials for maintaining agricultural production at a high level by eradicating various pests that damage agricultural crops. In addition, many infectious diseases are transmitted by insects, and exterminating them is very effective in preventing the spread of diseases, and the use of insecticides is the most effective way to achieve this goal. It is a practical means. In this way, pesticides play an extremely important role in maintaining the high standard of living that humanity has currently achieved and is expected to achieve in the future. In order to meet these objectives, many excellent insecticides have been created and used in the past, and have achieved results in various fields. However, organochlorine insecticides such as BHC and DDT are no longer used due to the emergence of pests that are resistant to them, as well as problems such as environmental pollution and toxicity to various organisms that are not targeted for extermination. severely restricted. Furthermore, there are signs that the problem of resistant insect pests is becoming more serious in various fields with regard to organic phosphate ester and carbamate insecticides, which should replace these insecticides. It's long awaited. If we think about the properties that a good insecticide should have, it goes without saying that it should have high insecticidal power, but today it is also important that it has low toxicity to non-target organisms such as humans and animals, is non-residual, and is environmentally friendly. Low contamination is strongly desired. Although natural pyrethrins have some of the properties required for insecticides as mentioned above, as they have low toxicity to humans and livestock and are easily decomposed under outdoor environmental conditions, they are relatively less toxic than organic phosphates and carbamates. Its use is limited to fields such as household insecticides because it has poor insecticidal power, decomposes too quickly, has little residual effect, and is expensive. In order to compensate for these shortcomings of natural pyrethrins, the present inventors conducted numerous studies and found that
The carboxylic acid ester represented by the general formula () has 1. extremely high insecticidal and acaricidal efficacy, and is fast-acting. 2.Although it has a long-lasting effect, it does not have the same environmental persistence as organic chlorine pesticides. 3.Low toxicity to humans and animals. Four.
It is also highly effective against pests that are resistant to organic phosphorus agents or carbamate agents. They discovered that it has excellent properties such as, and completed the present invention. Specific insect pests for which the compounds of the present invention are particularly effective include the following. 1 Hemiptera (1) Delphacidae: For example,
Sogatella furcifera,
Nilaparvata lugens
Laodelphax striatellus (2) Deltocephalidae: e.g.
Nephotettix cincticeps, Tettigella viridis,
Inazuma dorsalis (3) Aphididae: e.g.
Rhopalosiphum padi (4) Pentatomidae: e.g.
Nezara antennata,
Eysarcaris ventralis 2 Lepidoptera: for example Archips fumiferana Chilo suppressalis Cuapha locrocis medinalis Galleria mellonella Dendrolimus spectabilis Malacosoma neustria 3 Coleoptera (Coleoptera): For example, Onlema oryzae, Echinocnemus squameus 4 Diptera: For example, Aedes aegypti, Anopheles sp, Culex pipicns pallens, Agromyza oryzae, 5 Orthoptera: For example, Oxya yezoensis 6 Acarina: For example, Tetranychus cinnabarinus Tetranychus urticae Oligonychus hondoensis Panonychus citri The compound of the present invention has the general formula () [In the formula, R ₄ has the same meaning as above. ] Carboxylic acid represented by or its reactive derivative and general formula () [In the formula, R ₁ , R ₂ and R ₃ have the same meanings as above, and A represents a hydroxyl group or a halogen atom. ] By the method of reacting with the alcohol shown by or its reactive derivative, and when R ₃ represents a cyano group, the general formula () [In the formula, R ₁ and R ₂ have the same meanings as above. ] Aldehyde shown by and general formula () [In the formula, R ₄ has the same meaning as above, and Y represents a chlorine atom or a bromine atom. ] By the _method of reacting a carboxylic acid halide and an alkali metal cyanide _represented by

When a group represented by the formula (where X represents a chlorine atom or a bromine atom) is represented by the general formula () [In the formula, R ₁ , R ₂ and X have the same meanings as above. ] It can be obtained in good yield by the method of brominating the carboxylic acid ester shown below. Examples of the reactive derivatives of carboxylic acids represented by the general formula () herein 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 these 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 [In the formula, R ₁ , R ₂ and R ₃ have the same meanings as above. ] Alcohol and general formula shown by [In the formula, R ₄ and Y have the same meanings as above. ] A carboxylic acid halide, preferably an acid chloride, is heated at an internal temperature in an inert solvent (e.g., benzene, toluene, ether, hexane, etc.) in the presence of an acid-reducing agent (e.g., pyridine, triethylamine, etc.).
The desired ester is obtained by reacting at 30°C to 100°C for 30 minutes to 10 hours. (Synthesis method B) Method by reaction of alcohol and carboxylic acid anhydride General formula [In the formula, R ₁ , R ₂ and R ₃ have the same meanings as above. ] Alcohol and general formula shown by [In the formula, R ₄ has the same meaning as above. ] The desired ester is obtained by reacting the carboxylic acid anhydride represented by the following in an inert solvent (eg, benzene, toluene, hexane, acetone, etc.) at an internal temperature of -20°C to 100°C for 1 hour to 10 hours. (Synthesis method C) Method by reaction of alcohol and carboxylic acid General formula [In the formula, R ₁ , R ₂ and R ₃ have the same meanings as above. ] Alcohol and general formula shown by [In the formula, R ₄ 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 150°C for 30 minutes to 10 hours. to obtain the desired ester. (Synthesis method D) Method by reaction of a halide with a salt of a tertiary organic base of a carboxylic acid General formula [In the formula, Z represents a halogen atom, and R ₁ , R ₂ and R ₃ have the same meanings as above. ] Halide and general formula shown by [In the formula, R ₄ 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 E) Method by reaction of halide with alkali metal salt of carboxylic acid General formula [In the formula, R ₁ , R ₂ , R ₃ and Z have the same meanings as above. ] Halide and general formula shown by [In the formula, R ₄ has the same meaning as above, and M represents an alkali metal. ] An alkali metal salt of a carboxylic acid represented by
Phase transfer catalysts (e.g. tetra-
n-butylammonium bromide, benzyltriethylammonium chloride, etc.) at an internal temperature of 0°C to 150°C for 30 minutes to 10 hours to obtain the desired ester. (Synthesis method F) Method by reaction with aldehyde, alkali metal cyanide, and acid halide <F-1> General formula [In the formula, R ₁ and R ₂ have the same meanings as above. ] Aldehydes, alkali metal cyanates and general formulas shown by [In the formula, R ₄ and Y have the same meanings as above. ] in an inert solvent (e.g. benzene, toluene, etc.) in the presence of a phase transfer catalyst (e.g. benzo-18-crown-6, dicyclohexyl-18-crown-6, etc.) at an internal temperature of 0°C. The desired ester is obtained by reacting at ~150°C for 30 minutes to 20 hours. <F-2> General formula [In the formula, R ₁ and R ₂ have the same meanings as above. ] Aldehydes, alkali metal cyanates and general formulas shown by [In the formula, R ₄ and Y have the same meanings as above. ] The carboxylic acid halide represented by
n-butylammonium bromide, benzyltriethylammonium chloride, etc.) at an internal temperature of 0°C to 100°C for 30 minutes to 10 hours to obtain the desired ester. (Synthesis method G) Method by reaction of brominating ester General formula [In the formula, R ₁ , R ₂ and X have the same meanings as above. ] The carboxylic acid ester represented by and bromine are mixed 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 minutes.
The desired ester is obtained by reacting for a period of time. The carboxylic acid ester of the present invention synthesized according to the above-mentioned synthesis method is shown below.

【table】

【table】

[Table] The carboxylic acid ester obtained by the above method can be purified by means such as chromatography, if necessary. The raw material α-cyanobenzyl alcohol is “Preparative Organic” than aldehyde.
It can be easily obtained by the method described in "Chemistry" (C. Hilgetay et al.) p. 875, and halides can be easily obtained by the method described in Organic Synthesis Col vol.
It can be obtained by the method described on page 793. The carboxylic acid and carboxylic acid chloride used as raw materials are disclosed in JP-A-53-40743 and JP-A-53-101340.
The acid anhydride can be obtained by the method described in JP-A No. 53-40744, etc., and the acid anhydride can be obtained from these methods using "Synthetic Organic Chemistry" (RB
It can be obtained in good yield by the method described on page 558 of Wagner et al. In addition, the carboxylic acid ester used as a raw material is, for example,
Nature, 246 , 169−170 (1973), 248 , 710
(1974), (Elliott et al.), Japanese Patent Application Laid-Open No. 1983-95045,
JP-A-49-45039, JP-A-48-75550, Pestic.Sci, 5 791-799 (1974) (Elliott
et al.), Helv.Chem Acta, 7 390 (1924)
(Staudinger et al.). 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 (1) 2-fluoro-5-(4-chlorophenoxy)-
α-cyanobenzyl alcohol 1.67g (6.0m
mol), benzene 10ml, pyridine 0.95g (12m
dl-cis, trans-2,2-dimethyl-3-(1,2-dibromo-2,2-dichloroethyl)cyclopropanecarbonate while stirring at an internal temperature of 5°C or less under ice-cooling. acid chloride
A solution of 2.33 g (6.0 mmol) dissolved in 5 ml of benzene is added 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 saturated brine in this order, dried over anhydrous sodium sulfate, and then the solvent was distilled off. The residue was purified by column chromatography packed with silica gel to obtain 3.42 g of 2-fluoro-5-(4-chlorophenoxy)-α-cyanobenzyl dl-cis, trans-2,2-dimethyl-3-( 1,2-dibromo-2,2-dichloroethyl)cyclopropanecarboxylate was obtained as a pale yellow liquid. Example 2 Synthesis of compound (2) 3-(3-methylphenoxy)-4-fluoro-
α-cyanobenzyl bromide 1.92g (6.0m
mol) and dl-trans-2,2-dimethyl-
3-(1,2-dibromo-2,2-dichloroethyl)cyclopropanecarboxylic acid 2.66g (7.2m
mol) in 20 ml of acetone and heat it here at 15℃~
0.81g of triethylamine while stirring at 20℃
(8.0 mmol) dissolved in 5 ml of acetone is added dropwise. After the addition is complete, the mixture is heated under reflux for 2 hours and allowed to cool. Triethylamine bromate precipitated from the resulting reaction solution is filtered off and concentrated. The residue was purified by column chromatography packed with silica gel to give 3.14 g of 3-(3-methylphenoxy)-4-
Fluoro-α-cyanobenzyl dl-trans-
2,2-dimethyl-3-(1,2-dibromo-2,
2-dichloroethyl)cyclopropanecarboxylate was obtained as a pale yellow liquid. Example 3 Synthesis of compound (4) Sodium cyanide 0.37g (7.5mmol) and benzyltriethylammonium chloride 0.25g
(1.1 mmol) was dissolved in 5 ml of water, and 1.25 g (5.0 mmol) of 3-(4-chlorophenoxy)-4-fluorobenzaldehyde and dl
-cis,trans-2,2-dimethyl-3-(2,
1.19 g (5.25 mmol) of cyclopropanecarboxylic acid chloride (2-dichlorovinyl) in 10 ml of toluene
Drop into the solution dissolved in. After completion of the dropwise addition, stirring was continued at the same temperature for 5 hours. The resulting reaction solution is washed with saturated brine and then dried over anhydrous sodium sulfate. By distilling off the solvent, 1.83 g of 3-(4-chlorophenoxy)-4
-Fluoro-α-cyanobenzyl dl-cis, trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate was obtained as a pale yellow liquid. Example 4 Synthesis of compound (5) 2-fluoro-5-(3,4-dimethylphenoxy)-α-cyanobenzyl bromide 2.00 g
Sodium d-trans-2,2-dimethyl-3-
(1,2,2,2-tetrabromoethyl)cyclopropanecarboxylate 3.46g (7.2mmol) and tetra-n-butylammonium bromide
A solution of 0.081 g (0.25 mmol) dissolved in 10 ml of water is added and stirred at an internal temperature of 70 to 80°C for 4 hours. The resulting reaction solution is washed with saturated brine and then dried over anhydrous sodium sulfate. By distilling off the solvent, 3.40 g of 2-fluoro-5-(3,4-dimethylphenoxy)-α-cyanobenzyl d-trans-2,
2-Dimethyl-3-(1,2,2,2-tetrabromoethyl)cyclopropanecarboxylate was obtained as a yellow glassy liquid. Example 5 Synthesis of compound (2) 3-(3-methylphenoxy)-4-fluoro-
2.69 g (6.0 mmol) of α-cyanobenzyl dl-trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate was dissolved in 20 ml of carbon tetrachloride, and the bromine was dissolved at an internal temperature of 20°C under stirring.
A solution of 1.06 g (6.6 mmol) dissolved in 5 ml of carbon tetrachloride is added dropwise. After the addition is complete, stirring is continued overnight. The resulting reaction solution is washed 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 obtain 2.99 g of 3-(3-methylphenoxy)-4-fluoro-α-cyanobenzyl dl-trans-2,2-dimethyl-3-
(1,2-dibromo-2,2-dichloroethyl)
Cyclopropane carboxylate was obtained as a pale yellow glassy liquid. The compound of the present invention represented by the general formula () obtained as described above has low toxicity to humans and animals,
It has a wide range of uses, including for epidemic prevention purposes targeting flies, mosquitoes, and cockroaches, and for eliminating stored grain pests such as white mites, white-breasted grass moths, and brown elephants.
It is extremely effective in controlling agricultural, horticultural and forest pests such as aphids, caterpillars, spider mites, and chestnut beetles, as well as animal parasitic lice and mites, and can also control a wide variety of other pests. The compound of the present invention not only knocks down pests and kills them, but also has repellent properties and has the effect of repelling pests from hosts, and can be put to practical use in various dosage forms. The compound of the present invention represented by the general formula () is used to kill insects,
When preparing it as an acaricide, it can be prepared as an emulsion, wettable powder, powder, or granule by a method well known to those skilled in the art, using a dilution aid for general insecticides in the same way as conventional pyrethroids. , fine granules, oils, aerosols,
It can be prepared into any dosage form such as heating fumigants (mosquito coils, electric mosquito repellents, etc.), fumigants such as fogging, non-heating fumigants, poison baits, etc., and can be used for various purposes by using the form and carrier as required. It can be served. Furthermore, α-[2-
(2-butoxyethoxy)ethoxy]-4,5
- Mixed with other known synergists effective against allethrins and pyrethrins, such as methylenedioxy-2-propyltoluene {referred to as piperonyl butoxide}, octachlorodipropyl ether {referred to as S-421}, etc. Its use can also enhance its insecticidal effect. In general, chrysanthemum acid ester compounds are exposed to light, heat,
Since they tend to lack stability against oxidation, antioxidants or ultraviolet absorbers such as BHT and BHA are used.
Phenol derivatives such as bis. By adding an appropriate amount of phenol derivatives or arylamines such as phenyl-α-naphthylamine, phenyl-β-naphthylamine, condensates of phenetidine and acetone, or benzophenone compounds as stabilizers, compositions with more stable effects can be obtained. Obtainable. Also, 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-Phenoxybenzyl chrysansemate, 5-
Probargyl furfuryl chrysanthemate, and their d-trans primary chrysanthemum esters, d-
Cis-trans primary chrysanthemum ester or pyrethrum extract, d-trans primary chrysanthemum of d-arethrolone or d-cis. Trans primary chrysanthemum acid ester,
In addition to other known cyclopropane carboxylic acid esters, 0,0-dimethyl-0-(3-methyl-
4-nitrophenyl) phosphorothioate {referred to as phenitrothion}, 0,0-dimethyl-0
-4-cyanophenyl phosphorothioate {referred to as cyanophos}, 0,0-dimethyl-0
- Organophosphorus insecticides such as (2,2-dichlorovinyl)-phosphate {referred to as dichlorovos}, 1
-Naphthyl-N-methylcarbamate, 3,4-
Carbamate insecticides such as dimethylphenyl-N-methylcarbamate (referred to as MPMC), other insecticides, fungicides, nemicides, acaricides, herbicides, plant growth regulators, fertilizers,
By mixing it with microbial pesticides such as BT agents and BM agents, insect hormone agents, and other agricultural chemicals, it is possible to create multipurpose compositions with even better efficacy, and a synergistic effect of efficacy can be expected by combining these agents. Next, the preparation and effects of the insecticide and acaricide of the present invention will be explained using formulation examples and test examples. Formulation Example 1 An oil solution is obtained by dissolving 0.4 parts of the compound (2) of the present invention in white kerosene to make a total of 100 parts. Formulation Example 2 Add 2.0 parts of piperonyl butoxide to 0.4 parts each of the compounds (4) and (8) of the present invention, dissolve in white kerosene, and make the total 100 parts to obtain each oil solution. Formulation Example 3 10 parts each of the compounds (1) to (9) of the present invention, and
Add 15 parts of emulsifier {Solpol 3005X (registered trademark of Toho Chemical)} and 75 parts of xylol to each, and stir and mix these thoroughly to obtain each emulsion. Formulation Example 4 10 parts each of the compounds (2), (4), and (8) of the present invention, 20 parts each of S-421 (mentioned above), emulsifier {Solpol
3005X (mentioned above)} and 55 parts of xylene were added, and these were thoroughly stirred and mixed to obtain each emulsion. Formulation Example 5 Mix and dissolve 0.2 parts of the compound (4) of the present invention, 0.2 parts of tetramethrin (mentioned above), 7 parts of xylol, and 7.6 parts of deodorized kerosene, fill it into an aerosol container, and attach the valve part. An aerosol is obtained by filling 85 parts of propellant (liquefied petroleum gas) under pressure through the tank. Formulation Example 6 Mix and dissolve 0.2 parts of the compound (2) of the present invention, 0.2 parts of tetramethrin (mentioned above), 0.2 parts of resmethrin (mentioned above), 7 parts of xylol, and 7.4 parts of deodorized kerosene, fill it into an aerosol container, and apply it to the valve part. After installing the
Propellant (liquefied petroleum gas) 85 through the valve part
An aerosol can be obtained by filling a portion under pressure. Formulation Example 7 0.1 part of the compound (8) of the present invention, 0.2 part of the d-trans acid form of allethrin, 0.2 part of resmethrin (mentioned above),
Mix 11.5 parts of deodorized kerosene and 1 part of emulsifier {Atmos 300 (registered trademark name of Atlas Chemical Company)}, and add pure water.
Add 50 parts and emulsify it, then fill it into an aerosol container with 37 parts of a 3:1 mixture of deodorized butane and deodorized propane to create water. Get the base aerosol. Formulation Example 8 Add 0.3 g of allethrin d-trans primary chrysanthemum ester to 0.3 g each of the compounds (2) and (3) of the present invention, dissolve in 20 ml of methanol, and add 99.4 g of mosquito coil carrier (same as above). After stirring and mixing uniformly to evaporate the methanol, add 150 ml of water, mix thoroughly, and mold and dry to obtain each mosquito coil. Formulation Example 9 Add 5-propargylfurfuryl-dl-cis, 0.1 g of transchrysansemate, and 0.1 g of BHT to 0.1 g of each of the compounds (4) and (8) of the present invention, dissolve in an appropriate amount of chloroform, and form a 3.5 cm× Adsorb it evenly onto a 1.5cm, 0.3cm thick paper. A fiber fumigation composition heated on an electric heating plate is thus obtained. Formulation Example 10 To 20 parts each of the compounds (2), (3), and (8) of the present invention, 10 parts of fenitrothion (mentioned above) was added, and 5 parts of an emulsifier {Solpol 5029-0 (Toho Chemical registered trademark name)} was added. Mix, add 65 parts of 300 mesh diatomaceous earth, and thoroughly stir and mix in a grinder to obtain each wettable powder. Formulation Example 11 One part of each of the compounds (3), (4), and (9) of the present invention contains 1-
Add 2 parts of naphthyl-N-methyl carbamate,
Dissolve the mixture in 20 parts of acetone, add 97 parts of 300 ml of turquoise, mix well with stirring in a grinder, and remove the acetone by evaporation to obtain each powder. Formulation Example 12 To 5 parts each of the compounds of the present invention (1), (2), (4), (7), and (9), 5 parts each of Toyolignin CT (registered trademark name of Toyobo) and
GSM Clay (registered trademark name of Sieglite Machining Industry) 90
of the mixture and stir thoroughly in a crusher to mix. Next, water is added in an amount of 10% of the mixture, and the mixture is stirred and mixed, granulated using a granulator, and dried through ventilation to obtain each granule. Formulation Example 13 2 parts each of the compounds (3), (5), (6), and (8) of the present invention, 2 parts each of Cyanox (mentioned above), and Toyolignin CT
Add 91 parts of GSM clay (mentioned above) to 5 parts (mentioned above), and stir and mix thoroughly in a crusher. Next, water is added in an amount of 10% of the mixture, and the mixture is stirred and mixed, granulated using a granulator for fine granules, and dried through ventilation to obtain each fine granule. In order to make it clearer that the compounds of the present invention are excellent, experimental examples will be shown for representative examples, but other compounds represented by the general formula () also tend to have the same tendency. Experimental example 1 Place a piece of paper of the same size on the bottom of a polyethylene cup with a diameter of 5.5 cm. 0.7 ml of a 200-fold dilution (equivalent to 500 ppm) of the emulsion obtained in Formulation Example 3 with water is dropped onto paper, and 30 mg of sucrose is evenly added as bait. Ten female adult house flies were released into the container, the lid was closed, and 48 hours later, the mortality rate was determined (4 repetitions).

[Table] Experimental Example 2 30 ml of a 2,000-fold dilution (equivalent to 50 ppm) of the emulsion of the present invention compound and control compound below obtained in Formulation Example 3 with water is sprayed on potted Japanese orchid plants 30 days after sowing. After covering the cage with a cage, 10 4th instar larvae of Spodoptera were released, and 5 days later, whether they were alive or dead was examined (4 times).

[Table] Experimental Example 3 Compounds (2), (4), (6), and (8) of the present invention were diluted with acetone solution to a predetermined concentration, and the thoracic backs of susceptible adult female house flies (CSMA lineage) were tested 4 days after emergence. Apply topically to the board.
Food and water were placed in a plastic cup, and one day later, the animals were examined to see if they were alive or dead, and the LD ₅₀ value (50% lethal dose) was determined.

[Table] Experimental Example 4 The following compounds of the present invention and a control compound were each prepared into a 0.1% oil solution using deodorized kerosene. Ten adult German cockroaches are placed in a 10 cm diameter glass jar with a thin layer of Vaseline applied to the wall, and the lid is covered with 50 mesh nylon gauze. Spray 0.6 ml of each oil from a distance of 50 cm using a glass atomizer, and observe the number of knockdown insects over time. From the results, the KT ₅₀ value (50% knockdown time) and the mortality rate after 72 hours were determined.

[Table] Experimental Example 5 The emulsion obtained in Formulation Example 3 was diluted 10,000 times with water, and the solution 2 was placed in a styrene case of 23 x 30 cm and 6 cm deep, and the final instar larva of Culex pipiens was diluted with water.
If we released 100 insects, we were able to kill more than 90% of the last instar Culex mosquito larvae the next day. Experimental Example 6 Rice was grown 45 days after sowing in 1/10,000 Wagner pots, and the compounds (1), (2), (4), and (9) of the present invention obtained in Formulation Example 3 were grown. Spray a 200-fold dilution of each emulsion in water at a rate of 10 ml/pot. By covering it with a wire mesh and releasing about 30 adult black leafhoppers into it, they were able to kill more than 90% of the black leafhoppers within one day. Experimental Example 7 Place 10 3rd to 4th instar larvae of Spodoptera japonica in a waist-high glass jar with a diameter of 14 cm, and apply Formulation Example 4 using a scattering tower.
A 200-fold dilution with water of the emulsion obtained by
Spray ml. After that, if the emulsions were left in a high-height sieve containing feed in advance, more than 90% of the armyworms could be killed after two days using either emulsion. Experimental Example 8 Using Camper's turn table method [Soap and Sanitary Chemicals Vol. 14, No. 6, page 119 (1938)], a group of about 100 adult houseflies was used to prepare 50% of each oil solution obtained in Formulation Examples 1 and 2.
ml and exposed to the descending spray for 10 minutes, it was possible to kill more than 80% of the flies with either oil agent the next day. Test Example 9 The insecticidal efficacy of each of the aerosols obtained in Formulation Examples 5, 6, and 7 against adult house flies was evaluated using an aerosol test method using a peat gradient chamber (6 feet cubic) [Soap and Chemical].
The test was conducted according to the method described in Specialties Blue Book (1965). As a result, we were able to knock down more than 80% of flies within 15 minutes after spraying with either aerosol, and 70% of the flies could be knocked down the next day.
It was possible to kill more than % of flies. Experimental Example 10 Approximately 50 adult Culex mosquitoes were released into a glass box (70cm) ³ , and a small battery-powered electric fan (blade diameter 13cm) was placed inside the box and rotated. If you light one end of 0.1g of each mosquito coil obtained in Formulation Example 8 and place it in a glass box at the center bottom, each mosquito coil will produce 90% We were able to knock down over 80% of the Culex mosquitoes, and the next day we were able to kill over 80% of the Culex mosquitoes. Experimental Example 11 Approximately 50 adult house flies are released into a (70 cm) ³ glass box, and a small battery-powered electric fan (blade diameter 13 cm) is placed inside the chamber and rotated. When the composition for heat fumigation obtained in Formulation Example 9 was placed on an electric heating plate and heat fumigated in the chamber, more than 90% of the flies could be knocked down within 20 minutes. Experimental example 12 Approximately 20 rice seedlings per pot with 3 to 4 true leaves in a 3-inch flower pot.
Formulation example 10 grown in leaf stage and on turntable
Spray a 200-fold dilution of the wettable powder obtained by using water. After air-drying, the cage was covered with a wire mesh cage, and 20 to 30 adult brown planthoppers were released into the cage, and their survival and death were observed 24 hours later. The results showed a mortality rate of over 80%. Experimental Example 13 Each powder obtained in Formulation Example 11 was
Spread butter evenly at a rate of 2 g/m ² on the bottom of a waist-high glass cholera, and apply butter to the wall, leaving about 1 cm at the bottom. A group of 10 adult German cockroaches was released into the environment, and after 30 minutes of contact, more than 90% of the insects were killed on the third day.

Claims (1)

[Claims] 1. General formula [In the formula, R ₁ represents a methyl group or a hydrogen atom,
When R ₁ is a methyl group, R ₂ represents a hydrogen atom, a methyl group, or a chlorine atom; when R ₁ is a hydrogen atom, R ₂
represents a methyl group or a trifluoromethyl group. R ₃ represents a hydrogen atom, a cyano group or an ethynyl group, and R ₄ represents a group represented by the general formula [Formula] or [Formula] (wherein X represents a chlorine atom or a bromine atom). ] A carboxylic acid ester represented by 2 General formula [Wherein, R ₄ represents a group represented by the general formula [Formula] or [Formula] (wherein, X represents a chlorine atom or a bromine atom). ] Carboxylic acid or its reactive derivative and general formula [In the formula, R ₁ represents a methyl group or a hydrogen atom,
When R ₁ is a methyl group, R ₂ represents a hydrogen atom, a methyl group, or a chlorine atom; when R ₁ is a hydrogen atom, R ₂
represents a methyl group or a trifluoromethyl group. R ₃ represents a hydrogen atom, a cyano group or an ethynyl group, and A represents a hydroxyl group, a chlorine atom or a bromine atom. ] A general formula characterized by reacting with an alcohol or its reactive derivative represented by [In the formula, R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as above. ] A method for producing a carboxylic acid ester. 3 General formula [In the formula, R ₁ represents a methyl group or a hydrogen atom,
When R ₁ is a methyl group, R ₂ represents a hydrogen atom, a methyl group, or a chlorine atom; when R ₁ is a hydrogen atom, R ₂
represents a methyl group or a trifluoromethyl group. ] Aldehyde and general formula shown by [Wherein, R ₄ represents a group represented by the general formula [Formula] or [Formula] (where X represents a chlorine atom or a bromine atom), and Y represents a chlorine atom or a bromine atom. ] A general formula characterized by reacting a carboxylic acid halide and an alkali metal cyanide represented by [In the formula, R ₁ , R ₂ and R ₄ have the same meanings as above. ] A method for producing a carboxylic acid ester. 4 General formula [In the formula, R ₁ represents a methyl group or a hydrogen atom,
When R ₁ is a methyl group, R ₂ represents a hydrogen atom, a methyl group, or a chlorine atom; when R ₁ is a hydrogen atom, R ₂
represents a methyl group or a trifluoromethyl group, and X represents a chlorine atom or a bromine atom. ] A general formula characterized by brominating a carboxylic acid ester represented by [In the formula, R ₁ , R ₂ , R ₃ and X have the same meanings as above. ] A method for producing a carboxylic acid ester. 5 General formula [In the formula, R ₁ represents a methyl group or a hydrogen atom,
When R ₁ is a methyl group, R ₂ represents a hydrogen atom, a methyl group, or a chlorine atom; when R ₁ is a hydrogen atom, R ₂
represents a methyl group or a trifluoromethyl group. R ₃ represents a hydrogen atom, a cyano group or an ethynyl group, and R ₄ represents a group represented by the general formula [Formula] or [Formula] (wherein X represents a chlorine atom or a bromine atom). ] An insecticide and acaricide characterized by containing a carboxylic acid ester represented by the following as an active ingredient.