JPH0142242B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula (In the formula, R ₁ is a hydrogen atom, a cyano group, or an ethynyl group, and R ₂ is a lower alkoxyiminoalkyl group, a lower haloalkylcarbonyl group, or a lower alkoxyiminohaloalkyl group. n is 0 to 4
represents an integer. Further, R represents a group represented by formula (), () or (). Here, R ₃ and R ₄ are the same or different and are methyl groups,
Represents a halogen atom or halomethyl group, R ₅ ,
R ₆ and X represent a halogen atom. m is an integer of 1 to 2, and Y represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a lower haloalkyl group, or a lower haloalkoxy group. ) The present invention relates to an insecticide and acaricide characterized by containing a novel carboxylic acid ester derivative represented by the following formula, and a method for producing the same. Natural pyrethrins and chrysanthemum acid-based synthetic pyrethroids are excellent insecticides that are fast-acting against insects and have low toxicity to humans and livestock, but they are susceptible to oxidative decomposition by light, which has limited their use outdoors. On the other hand, the use of organochlorine pesticides such as BHC and DDT is prohibited due to problems such as environmental pollution and chronic toxicity, and organophosphate and carbamate pesticides that are related to these are also prohibited in various fields. The problem of resistant insect pests is showing signs of becoming more serious, and against this backdrop, the creation of new and better insecticides is eagerly awaited. As a result of repeated research, the inventors found that the above formula ()
The compound represented by (1) exhibits an extremely excellent insecticidal effect on various sanitary pests, agricultural and horticultural pests, mites, etc. (2) It is also highly effective against pests that are resistant to organic phosphorus agents or carbamate agents. (3) Low toxicity to warm-blooded animals. (4) Although it has a long-lasting effect, it does not cause the environmental pollution problems that organochlorine pesticides do. I learned that it has the following characteristics. By the way, various phenoxybenzyl alcohol-based synthetic pyrethroids developed in recent years are used as excellent insecticides for household use,
Practical application for agricultural use is being considered, but there are no published patent publications regarding benzyl alcohol esters substituted with alkylcarbonyl groups or alkoxycarbonyl groups.
55-111445. The compound of the present invention can be prepared by introducing a haloalkylcarbonyl group,
By changing the carbonyl group to oxime ether, the insecticidal and acaricidal efficacy was significantly enhanced, while the toxicity, especially fish toxicity, was greatly reduced. The present invention was completed based on the above findings. The compound represented by the above formula () used as an active ingredient in the present invention has the general formula R-COOH () according to the general method for ester production (wherein R is the formula (), () or ()). Indicates the group represented. Here, R ₃ and R ₄ are the same or different and are methyl groups,
Represents a halogen atom or halomethyl group, R ₅ ,
R ₆ and X represent a halogen atom. m is an integer of 1 to 2, and Y represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a lower haloalkyl group, or a lower haloalkoxy group. ) Carboxylic acid or its reactive derivative and general formula (In the formula, R is a hydrogen atom, a cyano group, or an ethynyl group, _R2 is a lower alkoxyiminoalkyl group,
Indicates a lower haloalkylcarbonyl group or a lower alkoxyiminohaloalkyl group. n represents an integer from 0 to 4. ) or a reactive derivative thereof. Examples of reactive derivatives of carboxylic acids include acid halides, acid anhydrides, carboxylic acid lower alkyl esters, alkali metal salts, and salts with organic tertiary bases. Examples of reactive derivatives of alcohol include chloride, bromide, p-
Examples include toluene sulfonic acid ester. 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. In addition, when the acid component of the general formula () is the formula () or (), cis and trans isomers arising from the substitution model of the cyclopropane ring can exist, and if R ₃ and R ₄ in () are not the same, the substitution E- and Z-isomers arising from the vinyl group can exist. Furthermore, the last two of the three carbon atoms of the cyclopropane can be present in either the R- or S-configuration. On the other hand, if the acid component is the formula (),
There is an asymmetric carbon at the α-position of the carboxyl group, and R ₁
-, S- both optical isomers exist. What is obtained by conventional synthetic methods is a mixture of these isomers, and each of these is of course included in the present invention.
The same applies when an asymmetric carbon is present in the alcohol component. Representative examples of the compound represented by the above formula () are as follows, but the present invention is of course not limited to these. 4'-trifluoromethylcarbonylbenzyl
2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate n ²⁰ _D
1.5480 2',3',5',6'-Tetrafluoro-4'-trifluoromethylcarbonylbenzyl 2,2-dimethyl-3-(2,2-dibromovinyl)cyclopropanecarboxylate n ²⁰ _D 1.5497 4'-trifluoromethylcarbonylbenzyl
2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxylate n ²⁰ _D 1.5485 4′-(β,β,β-trifluoroethylcarbonyl)-α′-cyanobenzyl 2,2-dimethyl-3-(2,2-dimethylvinyl)cyclopropanecarboxylate n ²⁰ _D 1.5471 2',4'-difluoro-5'-chloromethylcarbonyl-α'-ethynylbenzyl 2,2-dimethyl-3-(2-methyl-2-chlorovinyl)cyclopropanecarboxylate n ²⁰ _D 1.5504 2',6'-difluoro-4'-pentafluoroethylcarbonyl-α'-cyanobenzyl 2,2-
Dimethyl-3-(2,2-ditrifluoromethylvinyl)cyclopropanecarboxylate
n ²⁰ _D 1.5483 4'-trifluoromethylcarbonylbenzyl
α-(4-chlorophenyl)isovalerate
n ²⁰ _D 1.5512 2′,4′,5′,6′-tetrafluoro-3′-(γ-fluoropropylcarbonyl-α-cyanobenzyl α-(4-methoxyphenyl)isovalerate n ²⁰ _D 1.5527 2′,3′,5′,6′-tetrafluoro-4′-trifluoromethylcarbonylbenzyl α-(3,4
-dichlorophenyl)isovalerate n ²⁰ _D
1.5519 4′-Fluoromethylcarbonylbenzyl α-
(4-difluoromethoxyphenyl)isovalerate n ²⁰ _D 1.5505 4′-Fluoro-3′-(β,β,β-trichloroethylcarbonyl)-α′-ethynylbenzyl
α-(2-methyl-4-bromomethylphenyl)
Isovalerate n ²⁰ _D 1.5536 4'-(1-Methoxyimino-2,2,2-trifluoroethyl)benzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate n ²⁰ _D 1.5493 4'-(2-Methoxyiminopropyl)benzyl 2,2-dimethyl-3-(2,2-dibromovinyl)cyclopropanecarboxylate n ²⁰ _D
1.5508 2',3',5',6'-tetrafluoro-4'-(1-ethoxyimino-2,2,2-trifluoroethyl)benzyl2,2-dimethyl-3-(2-chloro-2- Trifluoromethylvinyl)cyclopropanecarboxylate n ²⁰ _D 1.5496 2',5'-difluoro-3'-(1-ethoxyiminoethyl)-α'-cyanobenzyl 2,2-dimethyl-3(2-fluoro-2-chlorodifluoromethylvinyl)cyclopropanecarboxylate n ²⁰ _D 1.5502 3′-Fluoro-4′-(1-methoxyimino-2
-fluoroethyl)-α′-ethynylbenzyl
2,2-dimethyl-3-(2,2-dimethylvinyl)cyclopropanecarboxylate n ²⁰ _D
1.5487 3'-isobutoxyiminomethyl-α'-cyanobenzyl 2,2-dimethyl-3-(2-methyl-2-trifluoromethylvinyl)cyclopropanecarboxylate n ²⁰ _D 1.5481 2′,3′,5′,6′-tetrafluoro-4′-methoxyiminoethylbenzyl α-(4-chlorophenyl)isovalerate n ²⁰ _D 1.5524 4'-(1-ethoxyimino-2,2,2-trifluoroethyl)benzyl α-(4-chlorophenyl)isovalerate n ²⁰ _D 1.5519 2',6'-difluoro-4'-(1-methoxyiminoethyl)-α'-cyanobenzyl α-(4-methylphenyl)isovalate n ²⁰ _D 1.5525 4'-(2-ethoxyimino-3-chloropropyl)-α'-ethynylbenzyl α-(3-isopropyl-4-trifluoromethylphenyl)isovalerate n ²⁰ _D 1.5539 2′,3′,5′,6′-tetrafluoro-4′-(1-methoxyimino-2,2,2-trifluoroethyl)benzyl α-(4-tert-butylphenyl)isovalate n ²⁰ _D 1.5528 2'-Fluoro-4'-(1-fluoro-2-ethoxyiminoethyl)-α'-cyanobenzyl α
-(2-ethoxy-4-bromophenyl)isovalerate n ²⁰ _D 1.5534 2′,3′,5′,6′-tetrafluoro-4′-trifluoromethylcarbonyl-α′-cyanobenzyl
2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate n ²⁰ _D
1.5491 4'-trifluoromethylcarbonylbenzyl
2,2-dimethyl-3-(1,2-dibromo-
2,2-dichloroethyl)cyclopropanecarboxylate n ²⁰ _D 1.5504 2',5'-difluoro-4'-bromomethylcarbonyl-α'-cyanobenzyl 2,2-dimethyl-3-(1,2-dichloro-2,2-dibromoethyl)cyclopropanecarboxylate
n ²⁰ _D 1.5528 3'-Fluoromethylcarbonyl-α'-ethynylbenzyl α-(2-fluoro-4-pentafluoroethoxyphenyl)isovalerate
n ²⁰ _D 1.5530 2',3',5',6'-tetrafluoro-4'-(2-methoxyimino-3,3,3-trifluoropropyl-α'-cyanobenzyl 2,2-dimethyl-3-(2, 2-dichlorovinyl)cyclopropanecarboxylate n ²⁰ _D 1.5503 4'-(1-Ethoxyimino-2,2,2-trifluoroethyl)benzyl 2,2-dimethyl-3-(2,2-dibromovinyl)cyclopropanecarboxylate n ²⁰ _D 1.5504 2',3',5',6'-tetrafluoro-4'-(1-methoxyimino-2,2,2-trifluoroethyl)benzyl2,2-dimethyl-3-(1,2
-dibromo-2,2-dichloroethyl)cyclopropanecarboxylate n ²⁰ _D 1.5534 4'-(2-propoxyimino-3,3,3-trifluoropropyl)-α'-cyanobenzyl
α-(4-Trifluoromethoxyphenyl)isovalerate n ²⁰ _D 1.5539 The compound of the active ingredient of the insecticide and acaricide of the present invention is a new compound, which is solid or liquid at room temperature and easily soluble in organic solvents in general. 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 a suitable organic solvent and soaking it in a mount, or dissolving it in a suitable solvent and heating and evaporating it with a suitable 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 insecticides and acaricides of the present invention can be used against sanitary pests such as flies, mosquitoes, and cockroaches, as well as organophosphorus agent- and carbamate-resistant black leafhoppers, planthoppers, stink bugs, armyworm moths, diamondback moths, tobacco moths, etc.
It is extremely useful for controlling agricultural pests such as bean weevils, nocturnal moths, cabbage weevils, chestnut beetles, leaf beetles, aphids, and scale insects, grain storage pests such as white snails, and mites. In addition, the insecticides and acaricides of the present invention include N-octylbicycloheptenedicarboximide (trade name MGK-264), a mixture of N-octylbicycloheptenedicarboximide and an arylsulfonate salt (tradename MGK-5026),
The insecticidal effect can be further enhanced by adding synergists such as cinepirin 500, octachlorodipropyl ether, and piperonyl butoxide.
In addition to the insecticides and acaricides of the present invention, other insecticides such as organic phosphorus agents such as fenitrothion, DDVP, diazinon, propaphos, and pyridafentione, carbamate agents such as NAC, MTMC, BPMC, and PHC, pyrethrin, allethrin, Conventional pyrethroid insecticides such as phthalthrin, flamethrin, phenothrin, permethrin, cypermethrin, decametrin, fuenvalerate, fuenpropanate, insecticides such as cartap, chlorphenamidine, methomil, or acaricides, fungicides, and fungicides. By mixing nematodes, herbicides, plant growth regulators, fertilizers, and other agricultural chemicals, highly effective multipurpose compositions can be obtained, and labor savings and synergistic effects among the drugs can be expected. It is. Next, examples of synthesizing compounds used as active ingredients in the present invention will be shown. The alcohol moiety constituting the ester is new; for example, trifluoromethylcarbonylbenzyl alcohol analogs can be easily obtained according to the synthetic route shown below. On the other hand, acid components are already known, and many documents regarding their synthesis are known. Synthesis Example 1 (A) Synthesis of 4-trifluoromethylcarbonylbenzyl alcohol 7.5 g of 4-bromobenzyl alcohol and 15 g of dihydropyran were mixed, and conc.HCl1
The mixture was added dropwise and stirred at room temperature for one day. After the reaction is completed 5
% aqueous sodium carbonate solution was added and the ether extraction was repeated, the collected ether portion was dried, and then the ether was distilled off. The residual oil was purified by flowing down an 80 g alumina column to obtain 11 g of pyranyl ether of 4-bromobenzyl alcohol. After suspending 1.2 g of magnesium in 20 ml of anhydrous ether and adding a small amount of ethyl iodide, 30 ml of a solution of 13.5 g of the above pyranyl ether in anhydrous ether was added dropwise at room temperature under a nitrogen stream. After heating to 30~40° to complete the reaction, add trifluoroacetic acid.
20 ml of an ether solution containing 1.9 g was added at below 35°C, and the mixture was further stirred at room temperature for 1 day. under ice cooling
After adding 15 ml of 6N-HCl and 20 ml of water to decompose the Grignard reagent, extract it twice with ether.
-3.0 g of pyranyl ether of trifluoromethylcarbonylbenzyl alcohol was obtained. Pyranyl ether is P- in 70% ethanol.
It was easily decomposed by refluxing for 2 hours in the presence of toluenesulfonic acid, and 1.9 g of 4-trifluoromethylcarbonylbenzyl alcohol was obtained from 2.9 g of the above pyranyl ether. Synthesis Example 2 (B) Ester synthesis by reaction of alcohol and carboxylic acid halide 2,2-dimethyl-3-(2-chloro-2-
(trifluoromethylvinyl) cyclopropanecarboxylic acid chloride 5.5g dried benzene 15ml
To this was added a solution of 4.2 g of 4-trifluoromethylcarbonylbenzyl alcohol dissolved in 20 ml of dry benzene, and then 3 ml of dry pyridine was added as a condensation aid to precipitate pyridine hydrochloride. After sealing the bottle and leaving it overnight at room temperature, the crystals of pyridine hydrochloride were separated, and the benzene solution was dried with sulfuric acid, and the benzene was distilled off under reduced pressure.
4'-trifluoromethylcarbonylbenzyl
7.5 g of 2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxylate was obtained. Synthesis Example 3 (C) Ester synthesis by reaction of alcohol and carboxylic acid 4.3 g of α-(4-methoxyphenyl)isovaleric acid and 2,4,5,6-tetrafluoro-3-(γ-fluoropropyl) carbonyl)-α
- 5.9 g of cyanobenzyl alcohol was dissolved in 50 ml of dry benzene, 6.2 g of dicyclohexylcarboimide 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 separated. The oily substance obtained by concentrating the filtrate is
2′, 4′,
5′,6′-tetrafluoro-3′-(γ-fluoropropylcarbonyl)-α-cyanobenzyl α
-(4-methoxyphenyl)isovalerate 8.0
I got g. Synthesis Example 4 (D) Ester synthesis by reaction of alcohol halide and alkali metal carboxylate 4.8 g of sodium salt of 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid and 4- (1-methoxyimino-2,
5.1 g of 2,2-trifluoroethyl)benzyl chloride was suspended in 50 ml of benzene and reacted under reflux in a nitrogen stream for 3 hours, then the reaction solution was cooled, the precipitated salt was filtered off, and then dissolved in brine. After washing thoroughly, drying with sulfur salt and distilling off the benzene under reduced pressure, 4'-(1-methoxyimino-2,2,2
-trifluoroethyl)benzyl 2,2-dimethyl-2-(2,2-dichlorovinyl)cyclopropanecarboxylate 7.1 g was obtained. Synthesis Example 5 (E) Ester synthesis by transesterification reaction of alcohol and lower alkyl ester of carboxylic acid 4.7 g of methyl ester of α-(4-chlorophenyl)isovaleric acid and 2,3,5,6-
5.1 g of tetrafluoro-4-methoxyiminoethylbenzyl alcohol is heated to 150°C. When the temperature reaches 50°C, add 0.25 g of sodium and start distilling off methanol. When the distillation of methanol has stopped, add another 0.25 g of sodium,
The temperature is maintained at around 150° C. and the above operation is repeated until the theoretical amount of methanol is obtained. The mixture was then cooled and dissolved in ether, and the ether solution was washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dried over nitric acid, and the ether was distilled off under reduced pressure to give 2', 3', 5',
7.8 g of 6'-tetrafluoro-4'-methoxyiminoethylbenzyl α-(4-chlorophenyl)isovalerate was obtained. Synthesis Example 6 (F) Ester synthesis by reaction of alcohol and carboxylic anhydride 14.2 g of 2,2-dimethyl-3-(1,2-dichloro-2,2-dibromoethyl)cyclopropanecarboxylic anhydride and 2,5-difluoro-
5.9 g of 4-bromomethylcarbonyl-α-cyanobenzyl alcohol was dissolved in 50 ml of dry pyridine and stirred overnight at room temperature. The next day, the reaction mixture was poured into 100 g of ice water and extracted three times with 20 ml of ether. The ether layers were combined and extracted twice with 20 ml of 5% aqueous sodium hydroxide solution to remove by-produced carboxylic acid. The ether layer was further washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dried over nitric acid, and the ether was removed under reduced pressure to obtain a crude ester, which was passed down a column containing 20 g of activated alumina to obtain 2', 5'- Difluoro-4'-bromomethylcarbonyl-α'-cyanobenzyl 2,2
-dimethyl-3-(1,2-dichloro-2,2
-dibromoethyl) cyclopropane carboxylate 10.8 g were obtained. Synthesis Example 7 (G) Ester synthesis by reaction of alcohol halide and organic tertiary base carboxylate 6.0 g of α-(3-isopropyl-4-trifluoromethylphenyl)isovaleric acid was dissolved in 50 ml of acetone. Dissolve and add 6.6 g of 4-(2-ethoxyimino-3-chloropropyl)-α-ethynylbenzyl bromide. Add 4 ml of triethylamine under stirring, react at 60 to 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. leave
9.6 g of 4'-(2-ethoxyimino-3-chloropropyl)-α'-ethynylbenzyl α-(3-isopropyl-4-trifluoromethylphenyl)isovalerate was obtained. Next, in order to make it clearer that the composition of the present invention is excellent, the results of test results will be shown. Test Example 1 Insecticidal test by spraying 0.2% of the compound used as an active ingredient in the present invention
White lamp solution (A), 0.2% and piperonyl butoxide 0.8
% white light solution (B), 0.1% white light solution of 0.1% and phthalthrin (C), and 0.2% white light solution of allethrin and phthalthrin, respectively. and further 24
The mortality rate after hours was determined as follows. The numbers in parentheses indicate the mortality rate after 24 hours.

【table】

[Table] Test Example 2 Insecticidal test by fumigation Mosquito coils containing 0.5% of insecticidal ingredients were made and tested for their effectiveness in causing adult Culex mosquitoes to fall and fall upside down. 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】

[Table] Test Example 3 Insecticidal test by microdropping method Control compound [4'-allylbenzyl 2,2-dimethyl-3-(2,2-dimethylvinyl)cyclopropanecarboxylate] and each of the compounds of the present invention and their Cinepirin 500 was added to twice the amount of each active ingredient and made into an acetone solution of a prescribed concentration, which was applied to the thoracic dorsal plate of adult house flies using a microsyringe, and the relative insecticidal efficacy against the control compound and Cinepirin were determined from the mortality rate after 24 hours. When we investigated the synergistic effect of 500, we found the following.

[Table] Examples of formulations are shown below, and formulations can be prepared by methods well known to those skilled in the art without requiring any special conditions in accordance with general agricultural chemicals. 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 present compound (4) 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 (9), 10 parts of Solpol SM-200 (registered trademark of Toho Chemical) and 70 parts of xylol were added and mixed and dissolved with stirring to obtain a 20% emulsion. Reference example 4 Compound of the present invention (13) 0.4 parts, resmethrin 0.1
After dissolving 1.5 parts of octachlorodipropyl ether in 28 parts of refined kerosene and filling it into an aerosol container and attaching a valve part, 70 parts of a propellant (liquefied petroleum gas) was pressurized and filled through the valve part to create an aerosol. obtain. Reference Example 5 0.5g of the compound (17) of the present invention and 0.5g of BHT were added to base material for mosquito coils such as pyrethrum extract lees powder, wood flour, starch powder, etc.
Mix 99.0g of the mixture uniformly and obtain a mosquito coil by a known method. Reference example 6 Compound of the present invention (21) 0.4g, MGK-5026 1.0g
The mixture was uniformly mixed with 98.6 g of a mosquito coil base material to obtain a mosquito coil by a known method. Reference Example 7 0.3 parts of the compound of the present invention (26) and 99.7 parts of clay are thoroughly ground and mixed to obtain a 0.3% powder. Reference Example 8 40 parts of the present compound (29), 35 parts of diatomaceous earth, clay
20 parts of laurin sulfonate, 3 parts of carboxymethyl cellulose, and 2 parts of carboxymethyl cellulose are ground and mixed to obtain a wettable powder. Test Example 4 5 to 5 on a surface where a large number of green peach aphids appeared
Among the emulsions obtained in Reference Example 3 in a radish field at the 6-leaf stage, compounds of the present invention (1), (5), (9), (14), (18),
A 1000-fold diluted solution of each emulsion containing (22), (27) and (30) with water was sprayed at 100 times per area.
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 5 Among the emulsions obtained in Reference Example 3, the compound of the present invention
(2), (6), (9), (12), (16), (21), (25) and (31)
Fresh leaves were immersed in a 2000-fold dilution of the chemical solution for about 5 seconds, and after the chemical solution had dried, they were placed in a shear dish and 10 healthy armyworm larvae 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.

[Table] Test Example 6 Approximately 200 aphids were infested on one tree one day before applying the insecticidal ingredient to potted fava beans. Among the hydrating agents obtained in Reference Example 8, (4)
(8), (11), (15), (17), (24), (26) and (2
9)
A 4000-fold dilution of the solution was sprayed on leaves infested with insects using a compressed air spray method (10 ml/pot), and the degree of damage was observed two days later. As a result, no increase in the degree of damage was observed in any of the cases. Test Example 7 (3), (7), (10), (13), obtained by Reference Example 7
Sprinkle each of the powders in (19), (23), (26) and (28) evenly on the bottom of a waist-high glass shear dish with a diameter of 14 cm at a ^rate of 2 g/m2, and apply butter to the wall surface, leaving about 1 cm at the bottom. . If a group of 10 adult German cockroaches were released into the container, and the cockroaches were left in contact for 30 minutes and transferred to a new container, more than 80% of the cockroaches could be killed by either powder after three days. . Test Example 8 1 for 4 leaves of potted green beans 5 days after sowing
Each leaf is infested with 10 female adult spider mites and stored in a constant temperature room at 27°C. After 6 days, emulsions (2), (5), (9), (13), (17), (21) obtained in Reference Example 3
,
A chemical solution prepared by diluting (24) and (30) with water to 100 ppm of active ingredients was sprayed on a turntable in an amount of 10 ml per pot. After 10 days, the number of parasitized spider mites on the plants was less than 10 for all drugs. Test Example 9 Carp was used as the subject, and the test was carried out in accordance with the toxicity test method for fish, Notification No. Agricultural Policy No. B 2735 (November 25, 1966), and the compounds of the present invention (1), (6), (10), (15 ),
TLm48 (ppm) of (19), (22), (25) and (31)
When calculated, it was 0.8 or higher in all cases.

Claims (1)

[Claims] 1. General formula (In the formula, R ₁ is a hydrogen atom, a cyano group, or an ethynyl group, and R ₂ is a lower alkoxyiminoalkyl group, a lower haloalkylcarbonyl group, or a lower alkoxyiminohaloalkyl group. n represents an integer from 0 to 4. Further, R represents a group represented by formula (), () or (). Here, R ₃ and R ₄ are the same or different and are methyl groups,
Represents a halogen atom or halomethyl group, R ₅ ,
R ₆ and X represent a halogen atom. m is an integer of 1 to 2, and Y represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a lower haloalkyl group, or a lower haloalkoxy group. ) An insecticide and acaricide characterized by containing a carboxylic acid ester derivative represented by: