JPS58116404A - Insecticide and acaricide containing novel carboxylic ester derivative and preparation thereof - Google Patents

Abstract

NEW MATERIAL:A carboxylic ester derivative of formulaI[R1 is H, cyano or ethynyl; R2 is lower alkoxyiminoalkyl, lower haloalkylcarbonyl or lower alkoxyiminohaloalkyl; n is an integer 0-4; R is formula II (R3 and R4 are methyl, halogen or halomethyl), formula III (X is halogen) or formula IV (Y is H, lower alkyl, halogen, etc.; m is an integer 1-2)]. EXAMPLE:4'-Trifluoromethylcarbonylbenzyl 2, 2-dimethyl-3-( 2, 2-dichlorovinyl ) cyclopropanecarboxylate. USE:An insecticide and acaricide, exhibiting a remarkable effect on injurious insects resistant to organophosphorus or carbamate chemicals, and having low toxicity without causing environmental pollution problems. PROCESS:A carboxylic acid of the formula R-COOH or a reactive derivative thereof is reacted with an alcohol of formula V or a reactive derivative thereof to give the compound of formulaI.

Description

Detailed Description of the Invention The present invention is based on the general formula (wherein W#IFi is a hydrogen atom, a cyano group, or an ethynyl group, and the island is a lower alkoxyiminoalkyl group, a lower haloalkylcarbonyl group, or a lower alkoxyiminohaloalkyl group). show.

ttFiO represents an integer of 4.

In addition, the wing represents a group represented by the formula (2), (to) or Fi (to), where the islands and ru are the same or different and represent a methyl group, a halogen atom, or a halomethyl group, and X is a halogen, Indicates an atom. -Fii-z is an integer! is a hydrogen atom,
It represents a lower alkyl group, a lower middle alkoxy group, a halogen atom, a lower haloalkyl group, or a lower haloalkoxy group. ) An insecticide characterized by containing a novel carboxylic acid ester derivative represented by
Concerning acaricides and their manufacturing methods.

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, B! The use of organochlorine insecticides such as IC and DDTE is prohibited by WiK due to environmental pollution and chronic toxicity, and even the organophosphate and carbamate insecticides that should replace these K have resistance in various fields. There are signs that the pest problem is 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 have found that the compound represented by the above formula (I): 1) exhibits an extremely excellent insecticidal effect against 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. 8) Low toxicity to warm-blooded animals.

4) It is rich in longevity, but on the other hand, it is environmentally polluted such as organochlorine insecticides 1! If not. I learned that it has the following characteristics. By the way, various phenoxybenzyl alcohol-based synthetic pyrethroids that have been developed in recent years are excellent insecticides, and their practical application for household and agricultural use is being considered. Published Patent Publication 55-
111445. In the compounds of the present invention, by introducing a haloalkylcarbonyl group or modifying the carbonyl group to an oxime ether, the insecticidal and acaricidal efficacy was significantly enhanced, while the toxicity, especially the toxicity to fish, was greatly reduced. The present invention was completed based on the above findings.

The compound represented by the above formula (I) used as an active ingredient in the present invention is prepared according to the general method for ester production using the general formula % formula % () (wherein R is the formula (ID, (to) or (3)). represents a halogen atom or a halomethyl group, X represents a halogen atom, - is an integer of 1-Pa, and ! represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a lower haloalkyl group, or a lower (in the formula, & is a hydrogen atom, a cyano group, or an ethynyl group), an island is a lower alkoxyiminoal+si group sta haloalkylcarbonyl group Indicates a lower alkoxyiminohaloalkyl group.

n represents an integer from 0 to 4. ) can be prepared by reacting an alcohol or a reactive derivative thereof. Examples of reactive derivatives of carboxylic acids include acid halides, acid anhydrides, carboxylic lower alkyl esters,
Examples include alkali metal salts or salts with organic octetary bases. Examples of reactive derivatives of alcohol include chloro2
Ide, bromide, p-toluenesulfonic acid ester, etc. The anti-IP5Fi reaction is carried out in a suitable solvent, optionally in the presence of an organic or inorganic base or a strong base as a deoxidizing agent or catalyst, and optionally with heating.

In addition, when the acid component of general formula (I) is formula (to), (to),
Cis and trans isomers resulting from the substitution model of the cyclopropane ring can exist, and when ``l'' and ``9'' in (2) are not the same, there can be cis- and 2-isomers resulting from the substituted vinyl group. Furthermore, two of the eight carbon atoms of cyclopropane can be present in either the R- or S-configuration. On the other hand, when the acid component is of formula (5), α of the carboxyl group
An asymmetric carbon exists at the position, and both X- and S- optical isomers exist. What is obtained by ordinary synthetic methods is a mixture of these isomers, and each of these is of course also included in Zero-Frequency 11.

The same applies when an asymmetric carbon is present in the alcohol component.

Typical examples of the compounds represented by the above formula (I) are as follows, and the present invention naturally applies to these 4'-trifluoromethylcarbonylbenzyl! 5J-dimethyl-8-
(gJ-dichlorovinyl)cyclo21', 8', 5',
6'-tetrafluoro-4'-trifluoromethylcarbonylbenzyl RJ-dimethyl-8-(g,s-dibromovinyl)cyclopropanecarphoki4'-)lifluoromethylcarbonylbenzyl 2,2-dimethyl-8-
(2-chloro-!-)lifluoromethylvinyl)cyclopropanecarboxylate 4'-(β,β,β-trifluoroethylcarbonyl)-α'-cyanobenzyl 2
,2-dimethyl-s-(g,g-dimethylvinyl)cyclopropanecarboxylate B',4'-9fluoro-
5'-Chloromethylcarponyl-ethynylpenzyl Z,'A-if-S-<S-methyl-3-licrovinyl)cyclopropanylporbonyl-α'-cyanobenzyl BJ-dimethyl-8-(g, g -ditrifluoromethylvinyl)cyclo(4-chlorophenyl)invalerate tropropylcarbonyl)-α-cyanobenzyl α-(4-methoxyphenyl)invalerate 0 ・nD L5! Ig7 g',8',5',6'-tetrafluoro-4'-trifluoromethylcarbonylbenzyl α-(8,'4-
Dichloro4'-fluoromethylcarbonylbenzyl α
-(4-difluoromethoxyphenyl)invaleratecarbonyl)-ethynylpenzyl α-CB-0 methyl-4-promomethylzenyl→invalereroethyl)benzyl 2,2-dimethyl-8-(gJ-dichloro・Vinyl)cyclopropanecarboxylate-O)
mm, 154
984'-(2-methoxyiminoprobyl)benzyl 2
．． 2-dimethyl-3-(2,2-dibromovinyl)cy2
1.31.5Z61-Tetrafluoro-4'-(1-ethoxyimino-2,2,2-trifluoromethyl)benzyl 2.2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclo Propane carboxylate 2
1.51-difluoro-3'-(1-ethoxyiminoethyl)-α'-cyanobenzyl 2,2-dimethyl-3
-(2-fluoro-2-chlorodifluoromethylvinyl)cyclopropanecarboxylate 1 m201.550
2 3'-Tsuruo W-4'-(1-methoxyimino-2-)
lleoloethyl)-α'-ethynylbenzyl 2.2-
Dimethyl-3-(2,2-dimethylvinyl)cyclopro3'-ingtoximinomethyl-α'-cyanobenzyl 2,2-dimethyl-3-(2-methyl-2-trifluoromethylvinyl)cyclopropanecarboxy 2 ′β
1,51.61-tetrafluoro-4'-methoxyiminomethylbenzyl α-(4-chlorophenyl)io sovalerate n, L552
44'-(1-ethoxyimino-2,2,2-trifluoroethyl)benzyl α-(4-chlorophenyl)ig', 6'-difluoro-4'-(1-methoxyiminoethyl)-α'- cyanobenzyl α-(4-methylfu&-ethynylbenzyl α-(8-impropyl-4-trif-7leolomethylphenyl) imparele g
',8',5',6'-tetrafluoro-4'-(1-
Methoxyimino-g,g,g-trifluoroethyl)benzyl α-(4-tertiaryptylfenino V)invaler, 0□5,28minoethyl)-cagedianobenzyl α-(2-ethoxy-4-bromo phenyl) invalerate! ', 8', 5
', 6'-tetrafluoro-4'-trifluoromethylcarbonyl-ga 1nopenzyl BJ-dimethyl-8-(g--dichlorovinyl)cyclopropanecarboxylate n'' L!14914I-tri7fluoromethylcarbonylpenzyl -cymethyl-s-
(t.g-dibromo-2,2-dichloroethyl)cyclopropanecarboxylate 2', 5'-difluoro-4'-bromomethylcarbonyl-7-cyanopenzyl 2,2-dimethyl-8-(1.

2-dichloro-2,3-dibromoethyl)cyclopro3
'-Fluoromethyl-tetrafluoro-4'-(g-fluoro-4-pentafluoroethoxyphenyl)invalerate g',8',5',6'-tetrafluoro-4'-(g
-methoxyimino-8.8.8-trifluoropropyl-gage anopenzyl 2,2-dimethyl-8-i,2
-dichlorovinyl)cyclopropanecarboxylate 4
'-(1-ethoxyimino-2.2.2-trifluoroethyl)benzyl 2,2-dimethyl-8-CB,Z-
dibromovinyl) cyclopropane carboxylate ff
i',8',5',6'-tetrafluoro-4'-(1
-methoxyimino-g,g,s-trifluoroethyl)
Benzyl S,S-dilfk-8-(1,B-sibu-a-mo2,B-dichloroethyl)cyclopropanecarboxylate O n n L5 B g 4 4'-(g-propoxyimino-s,21,s -trifluoropropyl)-gage anopendyl α-(4-)
Lifluoromethoxyphenyl)invalerate The compound of the active ingredient of the acaricide and acaricide of the present invention is a new compound, solid or liquid at room temperature, and generally easily soluble in organic solvents. Therefore, insecticides for spraying can be used as emulsions, oils, powders, wettable powders, aerosols, etc., and they can also be used as fumigation insecticides 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 has the same excellent effect as a mosquito coil. show. Chemical compound 11 of the present invention is more stable to light than conventional pyrethroids, has a broader insecticidal spectrum, has low toxicity, and is inexpensive, so it can be used as an alternative to conventional organophosphorus agents and organochlorine insecticides. It can be used as an agricultural and horticultural insecticide. The insecticides and acaricides of the present invention can be used to kill sanitary pests such as flies, mosquitoes, and cockroaches, and to kill organophosphorus agent- and carbamate-resistant leafhoppers, Clivias, Japanese stink bugs, stingworms, armyworms, armyworms, diamondback moths, tobacco moths, etc. It is extremely useful for controlling agricultural pests such as mezokumushi, nocturnal moth, cabbage beetle, chestnut beetle, leaf beetle, aphids, and scale insects, grain storage pests such as black elephant, mites, and the like. In addition, the insecticide and acaricide of the present invention include N-
Octylbicyclohebutene dicarboximide F (trade name MGK-264), a mixture of N-octylbicyclohebutene dicarboximide and arylsulfonic acid group (
The insecticidal effect can be further enhanced by adding synergists such as MG (trade name: -5026), cinepirin 500, octachlorodipropyl ether, and viberonyl ptoxide. In addition to the insecticide and acaricide of the present invention, other insecticides such as fenitrothion and DDVP may also be used.

Organic phosphorus agents such as diazinon, propafos, viridazenthion, etc., NAC, M''!MC%B'PMC.

Carbamate agents such as PHC, pyrethrin, allethrin, 7 tarthrin, 7 lametrin, phenothrin, permethrin, cypermethrin, decametrin, fenno (conventional birethroid such as relate, 7 enprobanate)'' series insecticides, cartap, chlor 7 enamidine, By mixing insecticides such as Menmyl, acaricides, fungicides, nematicides, herbicides, plant growth regulators, fertilizers, and other agricultural chemicals, a highly effective multipurpose composition can be obtained and save labor. We can also fully expect synergistic effects between these drugs.

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 analogues are known in many documents in the synthesis amounts shown below.

Synthesis Example 1.゛A) 4-) Synthesis of 4-bromobenzyl alcohol 7.5 g and dihydropicne 15 g, and e□nc, HCI 1
The mixture was added dropwise and stirred at room temperature for one day. After the reaction was completed, a 6% aqueous sodium carbonate solution was added, ether extraction was repeated, the collected ether portion was dried, and the ether was distilled off. The residual oil was purified by flowing down an 80 g alumina column to obtain pyranyl ether of 4-bromobenzyl afrecol. Anhydrous ether BOdK Magnesicum IJg was suspended and a small amount of ethyl iocodide was added thereto, and then an anhydrous ether solution Rod containing 5 g of the above pyranyl ether 13 was added dropwise at room temperature under a nitrogen stream. After completing the reaction by heating to 80-40°C, an ether solution f in which 19 g of trifluoroacetic acid was dissolved.
fiOm was added at a temperature below 85°C, and the mixture was further stirred at room temperature for 1 day. The Grignard reagent was decomposed by adding KIN-HCI 15d1 water zOd under water cooling, and then extracted twice with ether to obtain 4-triple olomethylbenzyl alcohol biranyl ether &Ogt*.

Pyranyl ether is easily decomposed by refluxing in 0% ethanol in the presence of P-toluenesulfonic acid for 2 hours, and from the above pyranyl ether &9g, 4-tri7fluoromethylcarponylpenzyl alcohol synthesis example & ) Ester synthesis by reaction of alcohol and carboxylic acid halide 5.5 g of 2,2-dimethyl-8-(2-chloro-2-trifluoromethiflevinyl)cyclopropanecarboxylic acid chloride was dissolved in 15 d of dry benzene. t'LK
A solution of 4 g of 4-trifluoromethylcarbonylbenzyl alcohol dissolved in 20 d of dry benzene is added, and then 8 g of dry pyridine is added as a KN coagulant to precipitate pyridine hydrochloride.

After sealing the cap and leaving it overnight at room temperature, the crystals of pyridine hydrochloride were separated by F, the benzene solution was dried with sulfuric acid, and the benzene was distilled off under reduced pressure to give 4'-triph7leolomethylcarbonylpencil 2J-dimethyl- 7.5 g of 8-CB-chloro-2-trifluoroethylvinyl)cyclopropanecarboxylate was obtained.

Synthesis Examples & C) Ester synthesis of alcohol and carboxylic acid by reaction α-(4-methoxyphenyl)invaleric acid 48g
and 9 g of 2,4,6.6-tetrafluoro8-(v-fluoropropylcarbonyl)-α-cyanobenzyl alcohol were dissolved in 50-g of dry benzene, and 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.
After cooling, precipitated dicyclohexyl urea was separated by F. The oily substance obtained by concentrating the filtrate was passed down a 1OOg silica gel column to obtain fi', 4', 5', 6
'-Tetrafluoro-81(r-fluoropropylcarbonyl)-α-cyanobenzyl α-(4-methoxyphenyl)invalerate 8.0 g was obtained.

Synthesis Example i D) Ester synthesis by reaction of alcohol halide with alkali metal carboxylate 48 g of sodium salt of 2,2-dimethyl-8-(Lg-dichlorovinyl)cyclopropanecarboxylic acid and 4-(1
-methoxyimino-gJ,! -) 1 g of benzyl black cucumber (lifluoroethyl) is suspended in 50 WIK of benzene,
After reacting under reflux for 3 hours in a nitrogen stream, the reaction solution was cooled, the precipitated salt was filtered off, thoroughly washed with brine, dried over sulfur, and benzene was distilled off under reduced pressure to give 4'- (1-
Methoxyimino-2.2.2-trifluoroethyl)benzyl 2,! ! -dimethyl-8-(2,2-dichlorovinyl)cyclopropanecarboxylate 7, 1g
I got it.

Synthesis Example E) Ester synthesis by transesterification reaction between alcohol and lower alkyl ester of carboxylic acid 47 g of methyl ester of α-(4-chlorophenyl)imparelianic acid
and 5.1 g of 2.8,5.6-tetrafluoro-4-methoxyiminoethylbenzyl alcohol are heated for 150'CK. When the temperature reaches 150°C, sodium 0.
Add f3ig and start distilling off methanol. When methanol distillation stops, more sodium OJJ! ; and the above operation is repeated, keeping the temperature around 150'C 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 sulfuric acid, and the ether was distilled off under reduced pressure to give y, Bp.

! ', 7.8 g of 6'-tetrafluoro-4'-methoxyiminoethylbenzyl α-(4-chlorophenyl)invalerate was obtained.

Synthesis Examples & F) Ester synthesis by reaction of alcohol and carboxylic anhydride 2,2-dimethyl-8-(IJ-dichloro-2,2-dibromoethyl)cyclopropanecarboxylic anhydride 144
g and 9 g of 8,5-Schiffleol-4-bromomethylcarbonyl-miscyanobenzyl alcohol in 50 liters.
1 was dissolved in dry pyridine and stirred at room temperature overnight. The next day, the reaction solution was pressurized into 100 g of ice water, and 20 d of ether was added.
Extracted 8 times using The ether layers were combined and extracted twice using 6% aqueous sodium hydroxide solution BO- to remove by-produced carboxylic acid. The ether layer was further washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dried over sulfur, and the ether was removed under reduced pressure to obtain a crude ester, which was added to 20 g of activated alumina.
g', 5'-difluoro-4
′-Bromomethylcarbonyl-α′-cyanobenzyl
BJ-dimethyl-8-(1,!-dichloro-2,2-diglomoethyl)cyclopropanecarboxylate Na8g
I got it.

Synthesis Example 7゜G) Ester synthesis by reaction of alcohol halide with carboxylic acid salt of organic 8th class base α-(8-inpropyl-4-trifluoromethylphenyl)invaleric acid &Og in acetone 50- 4-(2-
Add 6 g of ethoxyimino-8-lycloprovir)-α-ethynylbenzyl bromide a. Add 4d of triethylamine under stirring, react at 60 to 80°C for 3 hours, then dissolve in ether. Wash the ether solution thoroughly with diluted hydrochloric acid, aqueous sodium bicarbonate, and brine, dry with nitric acid, and remove the ether under reduced pressure. The residue was distilled off to obtain 9.6 g of 4'-(2-ethoxyimino-8-chloropropyl)-7-nitinylbenzyl α-(3-inpropyl-4-trifluoromethylphenyl)invalerate.

Next, in order to clarify the superiority of the composition of the present invention, test results of the effectiveness will be shown.

Test example 1. Insecticidal test with a cloth (A) 0.2% white light solution of the compound used as an active ingredient in the present invention (A), white light solution of α2% and piperonyl ptoxide α8% (B), α1% and 7-talusrin α1% white lamp solution (C) and each α2 of allethrin and phthalthrin
% of the white light solution was determined, the relative effectiveness of the test drug was calculated, and the mortality rate after 24 hours was determined as follows.

Values within 0 indicate the mortality rate after 24 hours.

Test example: Insecticidal test using smoked JEK Mosquito coils containing 5% of the insecticidal ingredient were made and tested for their effectiveness in making adult Culex mosquitoes fall and roll over. This experiment was carried out in accordance with the method of Insect Control Science Vol. 16 (1951), p. 176, Nagasha, Katsuta et al., and the relative effectiveness of the incense sticks was calculated as follows. The sample drug number is the same as that of the active ingredient example above.

Test Example & Insecticidal Test Control Compound [4'-allylbenzyl 2. B-dimethyl-8-(B,'B-dimethylvinyl.)cyclopropanecarboxylate] and the compound of the present invention, and cynevirin 50G was added thereto in an amount twice the amount of the active ingredient, respectively, to give a predetermined concentration of A7. A ton solution was applied to the thoracic dorsal plate of adult house flies using a microsyringe, and the relative insecticidal efficacy against the control compound and the synergistic effect with Cynevirin 500 were examined based on the mortality rate after 24 hours. For the sake of example, formulations can be prepared by methods familiar to those skilled in the art, without requiring any special conditions, in the same manner as general agricultural chemicals.

Reference Example 1゜ White kerosene was added to 8 parts α of the compound (1) of the present invention, and the total amount was 10 parts.
An α8% oil solution is obtained as 0 parts.

Reference Example & Invention Compound (4) α2 part and biperonyl ptoxide (
White kerosene was added to 18 parts to make a total of 100 parts to obtain an oil solution.

Reference example & Compound of the present invention (9) 20 parts Nlubol 8M-100
(Toho Chemical Registered Trademark) 10 parts and 70 parts of Kijirole were added and mixed and dissolved with stirring to obtain a 20% emulsion.

A propellant (liquefied petroleum gas) 7
0 part is filled under pressure to obtain an aerosol.

Reference Example 5g of the present compound Oetaa5g%BHte (L5g) was uniformly spread on 91LOg of a base material for mosquito coils such as pyrethrum extract lees powder, wood flour, starch powder, etc. to obtain a mosquito coil by a known method.

Reference Example & A mosquito coil was obtained by uniformly mixing 98.6 g of a mosquito coil base material with 98.6 g of the compound of the present invention 4 g% MGK-50261.0 g.

Reference Example 7 8 parts of the compound of the present invention-α and 99.7 parts of clay were thoroughly ground and mixed to obtain an a8% powder.

Reference Example 8 Compound of the present invention @40 parts, diatomaceous earth 85 parts, clay 20 parts,
A wettable powder is obtained by grinding and mixing 8 parts of lacryl sulfonate and 2 parts of carboxymethyl cellulose.

Among the emulsions obtained in Reference Example 8, compounds of the present invention (1), (5), (9), 04, etc. A 1000-fold dilution of each emulsion containing , Kan, Punishment, and - with water was made 10 times.
0// sprayed per counter.

Two days later, the parasitism rate was investigated and found that the density had decreased to less than 1/1O of the pre-spraying density in each plot.

Among the emulsions obtained in Reference Example 8, the compound of the present invention (2),
(6), (9), H, Hl (21), w and cIqo
The fish were immersed in the gooo double diluted solution for about 5 seconds, and after drying, they were placed in a petri dish and 10 healthy armyworm larvae were released. The test insects were released on the day of soaking the fresh leaves.
The test was carried out twice 5 days later to determine the mortality rate after 24 hours.

Test example & 1 day before applying insecticidal ingredients to potted fava beans! Approximately 20 aphids were infested on the tree. Reference example 8
(4), (8)% (!1) of the hydratactic agents obtained by
(＋＠、(1 屯臥翰 and 4) 4000-fold diluted solution was sprayed on the leaves infested with 10-rebot using a compressed air spray method, and the degree of damage was observed 2 days later.The results No increase in the degree of damage was found in either case.

Test Example 7゜Obtained according to Reference Example 7 (8 pieces (7), Koshikichi, Riki (
B), Kan and (Foundation) powders were uniformly sprinkled on the bottom of a 14 m+ diameter Gakusu Petri dish at a Bg/- ratio,
Apply the putter to the wall, leaving about 1 inch at the bottom. A group of 10 adult German cockroaches (T-1) was released into the cage, and 80
After 8 days, more than 80% of the cockroaches were killed by both powders after 8 days of contact with the cockroaches and transferred to a new container.

Test Example 8 5 days after sowing, four leaves of potted green beans are infested with 10 female adult spider mites per leaf and stored in a constant temperature room at 27°C. After 6 days, the emulsion obtained in Reference Example 8 (
A medicinal solution prepared by diluting 2), (5), (9), (In107L621), and - with water to an amount of 100,100 pp of the active ingredient was placed on a turntable for 1 Od per pot. 10
In the investigation of false red spider mites on plants, the number of parasitized spider mites was 10 or less 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 fishes, Notification No. 1182785 (November 25, 1966), and the compounds of the present invention (1), (6), and (l) were tested.
When the TU San 48 (ppm) of 1K4 and (31) was calculated, it was (L8 or higher) in both cases.

Procedural amendment 1.Display of the incident 1981 Patent Application No. 215714 Insects, acaricides and their manufacturing methods.

& person who makes corrections Address (residence) Kamikotoen, Nishinomiya City, Hyogo Prefecture Name (Name) @1) Jun representative agent & Correction target Full statement 7. Contents of correction Engraving of the statement (no changes to the contents)

Claims (1)

[Claims] (In the formula, R is a hydrogen atom, a cyano group, or an ethynyl group, and represents a lower alkoxyiminoalkyl group, a lower haloalkylcarbonyl group, or a lower alkoxyiminohaloalkyl group. n is from 0 to 4. Represents an integer.Also represents a group represented by the RFi formula (Ill, (to) or (5)). ■ Contains a carboxylic acid ester derivative represented by (Is an integer of Fif-1, and ! represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a lower haloalkyl group, or a lower haloalkoxy group.) Insecticide and acaricide characterized by (B) general formula % formula % (wherein R is a group represented by the formula (Ill, (to) or (2)), and -2- are the same or different; represents a methyl group, a halogen atom, or a halomethyl group, X represents a halogen atom, ■ is an integer of 1 to 2, and ! represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a lower haloalkyl group, or a lower represents a haloalkoxy group) or its reactive derivative (in the formula RI#
i is a hydrogen atom, a cyano group, or an ethynyl group, and a crow represents a lower alkoxyiminoalkyl group, a lower haloalkylcarbonyl group, or a lower alkoxyiminohaloalkyl group. n represents an integer from θ to 4. ) Contains a carboxylic acid ester derivative represented by the general formula (wherein R, RI, &, n represent the same meanings as above), which is characterized by reacting with an alcohol represented by () or a reactive derivative thereof. A manufacturing method for insecticides and acaricides. (8) Claim No. (1), characterized in that it contains a pyrethroid synergist as an auxiliary agent.