JPS60214760A - Antioxidative metabolic halogen-substituted cyclopropanecarboxylic acid ester derivative, its preparation and insecticidal and miticidal agent containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [A is group of formula II - formula IV (R6 and R7 are halogen or halomethyl; X is halogen; R8 is halogen or cyano; R9 is halogen, methyl, etc.); R1 is chlorine or methyl; R2 is H, cyano or ethynyl; R3 and R4 are H or F; B is O, S, methylene, etc.; R5 is H or halogen]. EXAMPLE:3'-( 4-Fluorophenoxy )-6'-fluoro-alpha'-cyanobenzyl 2,2'-dichloro-3-( 2,2-dichlorovinyl)cyclopropanecarboxylate. USE:An insecticidal and miticidal agent. PREPARATION:The compound of formula I can be prepared by reacting the cyclopropanecarboxylic acid of formula V or its reactive derivative with the alcohol of formula VI or its reactive derivative, if necessary in the presence of an acid acceptor and a catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION (wherein A represents a group represented by formula (2), 01) or (IV).

RI here 1. - are the same or different and represent a halogen atom or a halomethyl group, and X represents a halogen atom. & represents a halogen atom or a cyano group, l represents a halogen atom, methyl group, halomethyl group, or halomethoxy group, and l represents a chloro atom or a methyl group.

R is a hydrogen atom, a cyano group or an ethynyl group, R1,
R1 represents a hydrogen atom or a fluorine atom. B represents an oxygen atom, an iodine atom, a methylene group, an imino group or a methylimino group, and & represents a hydrogen atom or a halogen atom. )
The present invention relates to an antioxidant metabolic halogen-substituted cyclopropane carboxylic acid ester derivative represented by the following formula, a method for producing the same, and an insecticide or acaricide containing the same as an active ingredient.

) Currently, it is widely used as an insecticide for household use, epidemic prevention, and agriculture. By the way, the processes by which insecticides and acaricides decompose and lose their effectiveness include decomposition due to light and oxidation, and decomposition due to metabolism within the bodies of insects and mites. Chrysanthemum acid esters, represented by the general formula (@), have an isobutenyl group that is unstable to light in the acid moiety, and therefore their use outdoors has been restricted.Recently, research on acid moieties with high photostability has been active. As a result, the halogen-substituted chrysanthemum acid ester of the general formula (2) was invented, and its photostability was significantly improved and it met the requirements as an agricultural insecticide.Meanwhile, basic research on metabolic decomposition was also carried out. For example, in the general formula (to), the position marked with ■, that is, the methyl group at the trans position to the carboxyl group, the hydrogen atom at the 4th position of the phenoxy group, and the hydrogen atom at the 6th position of the benzyl group, It has become clear that they are susceptible to oxidative decomposition in the body.In addition, it has recently been reported that houseflies with slightly reduced susceptibility to pyrethroid drugs have appeared in actual use; Addition of piveronyl ptoxide, an inhibitor of pyrethroid oxidative metabolism, to pyrethroids was found to restore susceptibility.

One mechanism for the development of resistance to drugs is an increase in the activity of metabolic enzymes within the body of insects or ticks, and the above findings therefore suggest that modifying the structure of parts susceptible to oxidative metabolism can improve the ability of this species to develop resistance. This suggests that it may be possible to suppress the development of resistance.

Therefore, as a result of intensive research aimed at developing antioxidant metabolic pyrethroid, the present inventors discovered a cyclopropanecarboxylic acid ester derivative represented by the general formula (I), that is, a conventional A compound in which the methyl group of is converted to a chloro atom that is less susceptible to oxidative decomposition, and more preferably a halogen atom is introduced into the R1 and R1 positions, is also effective against insects and mites that have reduced sensitivity to pyrethroids. We have completed the present invention by discovering that the product exhibits insecticidal and acaricidal activity equivalent to that against the original susceptible strain without the addition of any agents.

Some of the compounds of general formula CI> are disclosed in JP-A No. 11858-799
It was disclosed in Publication No. 09, and although it is not necessarily a new compound in a broad sense, it is characterized by the introduction of the 0AtfJA molecule in the trans position relative to the carboxyl group, and it has reduced sensitivity to pyrethroids. It is unprecedented knowledge that it also exhibits high activity against insects and mites. Furthermore, in order to put pyrethroid agents, which are ideal insecticides and acaricides, into practical use in the future, the development of resistance must be avoided. provides an extremely useful means in that sense.

The compound of the present invention (general formula (I)) can be prepared using the general formula (wherein A represents a group represented by formula (II), (III), or (IV)) according to the general method for producing esters.

Here, Rt and Ry are the same or different and represent a halogen atom or a halomethyl group, or a halogen atom.

l is a halogen atom or a cyano group, l is a halogen atom,
It represents a methyl group, a halomethyl group or a halomethoxy group, and n represents a chloro atom or a methyl group. ) Cyclopropanecarboxylic acid or its reactive derivative represented by the general formula (wherein R is a hydrogen atom, a cyano group, or an ethynyl group, R1 and R1 represent a hydrogen atom or a fluorine atom, and B is oxygen represents an atom, an iodine atom, a methylene group, an imino group or a methylimino group, and & represents a hydrogen atom or a halogen atom.

) or a reactive derivative thereof.

Examples of the reactive i-conductor of cyclopropanecarboxylic acid include acid halides, acid anhydrides, lower alkyl esters, and alkali metal salts. Examples of reactive derivatives of alcohol include chloride, bromide, and p-toluenesulfonic acid ester.

The reaction is carried out in a suitable solvent in the presence of a deoxidizing agent or an organic or inorganic base or acid as a catalyst, if necessary under heating. The compounds of the invention of general formula (I) have two or more asymmetric carbon atoms. The compounds of the present invention include their optical isomers and racemic mixtures, but unless otherwise specified in the Examples and Compound Examples described later, the produced compounds are racemic mixtures. Next, representative examples of the compound represented by the above formula (I) will be shown, but the present invention is of course not limited to these.

3'-(4-fluorophenoxy)-6'-fluoro-
α'-Cyanobenzyl 2,2-dichloro-3-(2゜2-dichlorovinyl)cyclopropanecarboxylene 2〇1 n Dl-5721 3'-(4-chlorophenoxy)-α'-cyanobenzyl 2, 2-dichloro-3-(2,2-dibromovinyl)cyclopropanecarboxylate 3'-(4-fluoroanilino)-4'-fluoro-α
'-cyanopenzyl 2,2-dichloro-3-(2,2
-Dichlorovinyl)cyclopropanecarboxylate-
α′-cyanobenzyl 2,2-dichloro-3-(2,
2-dibromovinyl)cyclopropanecarboxylate)
n201.5790 3'-(4-7"lomobenzyl)-α'-cyanobenzyl 2,2-dichloro-3-(2,2-dichlorovinyl)
3'-(4-fluorobenzyl)-6'-fluoro-
α′-cyanobenzyl 2,2-dichloro-3-(2,
2-dibromovinyl)cyclopropanecarboxylate 3'-(4-fluorophenoxy)-α'-cyanobenzyl 2,2-dichloro-3-(1,2-dibromo-2
,2-dichloroethyl)cyclopropanecarboxy-cyanobenzyl 2,2-dichloro-3-(1,2-cyclo2,2-dibromoethyl)cyclopropane α'-
Cyanobenzyl 2,2-dichloro-3-(2-chloro-2-trifluoromethylvinyl)cyclopro-1 Nobenzyl 2,2-dichloro-3-(2-chloro-2-trifluoromethylvinyl)cyclopro3'-( 4-7'
lomopenzyl)benzyl 2-methyl-2-chloro-3
-(2-fluoro-2-difluorochloromethylvinyl)cyclopropanecarboxyCmi(h 3'-phenylthio-4'-fluoro-α'-ethynylbenzyl 2-methyl-2-chloro-3-(2,2- ditrifluoromethylvinyl)cyclopropanecardyl
2,2-dichloro-3-(2-chloro-2-(4-chlorophenyl)vinyl)cyclopropanecardianobenzyl 2,2-dichloro-3-(2-cyano-2-(4-
methylphenyl)vinyl)cycloprobaoloα'-cyanobenzyl 2-methyl-2-chloro-3-(2-promo2-(4-)lifluoromethylphenyl)vinyl1cyclopropanecarboxy0 rate n Dl-58' 33 2,2-dichloro-3-12-fluoro-2-(4
-difluoromethoxyphenyl)vinyl I cyclofluoroα'-ethynylbenzyl 2-methyl-2-rioo
-3-(2,2-dichlorovinyl)cyclop3'-(4
-chlorophenylthio)-6'-fluorobenzyl 2
,2-dichloro-3-(2,2-difluorovinyl)cyclopropanecarboxylate 0 n D 1-5762 3'-(4-bromoanilino)benzyl 2-methyl-
2-chloro-3-(1,2-dibromo-2,2-dichloroethyl)cyclopropanecarboxylate-ethynylpenzyl 2,2-dichloro-3-(1,2=cyclo2,2-',;fluoro ethyl) cyclopro3'-(
4-bromophenylthio) 41-fluoro-α'-cyanobenzyl 2-chloro-2-methyl-3-(1,2
,2,2-tetrabromoethyl)cyclopropa3'-(
4-Fluoro-N-methylanilino)benzyl 2,2
-dichloro-3-(1,2-difluoro-2,2-dichloroethyl)cyclopropanecarboxy-ethynylpenzyl 2-methyl-2-chloro-3-12-cyano-2
-(4-7'romophenyl)vinyllecropropanecarboxylate-cyfluoropenzyl 2-methyl-2-chloro-3-
12-Chloro-2-(4-)lifluoromethoxyphenyl)vinyl cyclopropanecarboxine 201 n D L5830 3'-(4-fluoro7zylthio), i/, 6/-
Difluoro-α'-ethynylbenzyl 2-methyl-2
-Chloro-3-(2-chloro-2-7'lomovinyl)3
'-(4-fluorophenoxy)benzyl 2,2-dichloro-3-(2,2-dichlorovinyl)cyclobucyanobenzyl 2,2-dichloro-3-(2-bromo2-fluorodichloromethylvinyl)cyclo3 '-(4
-bromophenyl)-4'-fluoro-α'-ethynylbenzyl 2-methyl-2-chloro-3-(2-fluoro-2-trifluoromethylvinyl)cyclopropanecarboxylate n 201.5725 monoethynylbenzyl 2- Methyl-2-chloro-3-(
2-Chloro-2-(4-fluorophenyl)vinyl 1cyclopropanecarboxyV-to3'-(4-chlorophenoxy)benzyl 2,2-cyclo3-(2-chloro-3-)'J fluoromef/ L/vinyl) cyclopropane carboxylate The compound used as an active ingredient in the present invention is solid or liquid at room temperature and is generally easily soluble in organic solvents. Therefore, insecticides and acaricides for killing insects can be used as emulsions, oils, powders, wettable powders, aerosols, etc., and they can also be mixed with wood flour or other suitable base materials to kill insects for fumigation such as mosquito coils. , can be used as an acaricide. Also, when used as a so-called electric mosquito repellent by dissolving this active ingredient in an appropriate organic solvent and soaking it in a mount, or dissolving it in an appropriate solvent and heating and evaporating it with an appropriate heating element, it is as good as a mosquito coil. Show effectiveness. Furthermore,
The compound of the present invention is more stable to light than conventional chrysanthemum acid ester-based pyrethroids, has a broader insecticidal and acaricidal spectrum, has low toxicity, and is inexpensive, so it It can be used as an agricultural and horticultural insecticide and acaricide instead of insecticides. The insecticides and acaricides of the present invention are extremely effective not only for insects and mites resistant to organophosphorus agents and carbamate agents, but also for insects and mites that have decreased susceptibility to conventional pyrethroid agents. Including sanitary pests such as flies, mosquitoes, and cockroaches.
・Ro h9− tsu −−ζ ノ v'y −= Suyu,
It is extremely useful for controlling agricultural pests such as stink bugs, armyworm moths, diamondback moths, tapako moths, bean beetles, noctuid moths, cabbage moths, chestnut beetles, leaf beetles, aphids, scale insects, grain storage pests such as kokuzoku, and mites. be.

In addition, the insecticide and acaricide of the present invention include N-octylbicyclohebutene dicarboximide (trade name MGK-264),
Mixture of N-octylbicyclohebutene dicarboximide and aryl sulfonate (trade name MGK-50
26) The insecticidal and acaricidal effects can be further enhanced by adding a synergist such as cinepirin 500° octachlorodipropyl ether or biperonyl ptoxide.

In addition, in addition to the insecticide and acaricide of the present invention, other insecticides, such as organic phosphorus agents such as fenitrothion, DDVP1 diazinon, propafos, and pyridafenthione, NAClMTM
Carbamate agents such as ClBPMC, PHC, conventional birethroid insecticides such as pyrethrin, allethrin, phenothrin, flamethrin, phenothrin, 7embererate, fenpropanate, acaricides, insecticides such as cartap, chlorzenamidine, menmyl, or Acaricides, fungicides, nematicides, herbicides, plant growth regulators,
By mixing fertilizers and other agricultural chemicals, a highly effective multipurpose composition can be obtained, and labor savings and synergistic effects between the chemicals can be fully expected.

Next, synthesis examples will be shown for representative examples, but other compounds of the present invention also show similar trends, and synthesis methods (5), (B), and (C)
, (9), (E), and (F) could be obtained in good yields by any method.

Synthesis Example 1 A) Method by reaction of alcohol with carboxylic acid halide 2. 6.3 g of 2-dichloro-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxylic acid chloride was added to dry benzene 15- 3-(
A solution of 5.4 g of (4-fluorophenoxy)-6-fluoro-α-cyanobenzyl alcohol dissolved in 20% of dry benzene is added, and then 3% of dry pyridine is added as a condensation aid to precipitate pyridine hydrochloride.

After sealing the cap and leaving it at room temperature overnight, the crystals of pyridine hydrochloride were dissolved in F.
After separation, the benzene solution was dried with sulfuric acid, and the benzene was distilled off under reduced pressure to obtain 3'-(4-fluorophenoxy)S/
-Fluoro-α'-cyanobenzyl 2.2-cyclo3-(2-chloro-2-)! 9.8 g of J fluoromethyl vinyl) cyclopropane carboxylate was obtained.

Synthesis Example 2 B) Method by reaction of alcohol and carboxylic acid 2-methyl-2-chloro-3-(1,2-dibromo-2
,2-dichloroethyl)cyclopropanecarboxylic acid8.
0g! : 5.7 g of 3-(4-7' lomoanilino)benzyl alcohol was dissolved in 50 me dry benzene, 6.2 g of dicyclohexyllupodiimide F 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 by F. 100g of oily substance obtained by condensing the filtrate
3'-(4-bromoanilino)benzyl 2-methyl-2-chloro-3-(1
, 2-dibromo-2,2-dichloroethyl)cyclopropane 1 carboxylate was obtained.

Synthesis Example 8 C) Method by reaction of alcohol halide with alkali metal carboxylate 2-methyl-2-chloro-3-12-cyano-2-(4
-7.3 g of sodium salt of 7'romophenyl)vinyl)cyclopropanecarboxylic acid and 6 of 3-(4-chlorobenzyl)-4-fluoro-α-ethynylbenzyl chloride
．． After suspending 0g in 50rnl of benzene and reacting under reflux in a nitrogen stream for 3 hours, the reaction solution was cooled, and the precipitated salt was filtered off, thoroughly washed with brine, and dried with sulfur sulfate. was distilled off under reduced pressure to obtain 3'-(4-chlorobenzyl)=4'-fluoroα'-ethynylbenzyl 2
-Methyl-2-chloro-3-f2-cyano-2-(4-
10.2 g of (bromophenyl)vinyl)cyclopropanecarboxylate) was obtained.

Synthesis Example 4゜D) Method by transesterification of alcohol and lower alkyl ester of carboxylic acid 2.2-dichloro-3-
Methyl ester of (2,2-difluorovinyl)cyclopropanecarboxylic acid 4.8 g (!:3-(4-chlorophenylthio)-6-:yfluorobenzyl alcohol5.
Heat 3g to 150'C.

When the temperature reached 150°C, 0.25 g of sodium was added and the distillation of methanol was started. When the distillation of methanol has stopped, 0.25 g of sodium is further added, and the above operation is repeated while keeping the temperature around 150°C until the theoretical amount of methanol is obtained. The mixture was then cooled, dissolved in ether, and the ether solution was washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dried over sulfur, and the ether was distilled off under reduced pressure.
8.0 g of '-(4-chlorophenylthio)-6'-fluorobenzyl 2,2-dichloro-3-(2,2-E; fluorovinyl)cyclopropanecarboxylate was obtained.

Synthesis Example 5゜E) Method by reaction of alcohol with carboxylic acid anhydride 2-Methyl-2-chloro-3-12-chloro-2-(4
14.0 g of cyclopropanecarboxylic anhydride and 6.5 g of 3-(4-promo N-methylanilino)-4,6-cyfluorobenzyl alcohol are dissolved in 50 rnl of dry pyridine. Stir overnight at room temperature. The next day, the reaction solution was poured into 100 g of ice water to give 201 nI of ether! Extracted three times using The ether layers were combined and extracted twice using 20 tne of IJ cum aqueous solution (5% hydroxide) to remove by-produced carboxylic acid. The ether layer was washed with dilute hydrochloric acid, sodium bicarbonate solution, and brine, dried over sulfuric 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 3'-( 4-promo N-methylanilino)-4',6'-dichloroopenzyl 2-methyl-2
11.4 g of -chloro-3-(2-chloro-2-(4-)!Jfluoromethoxyphenyl)vinyl 1 cyclopropanecarboxylate was obtained.

Synthesis Example 6 °F) Method by reaction of alcohol halide with carboxylic acid salt of organic tertiary base 2. 5.2 g of 2-dichloro-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid was aliquoted. 3-(4-fluorophenoxy)-6-,
Add 6.5 g of yluoro α-cyanobenzyl bromide. Add triethylamine 4- to 60-8
After reacting at 0°C for 3 hours, it was dissolved in ether, the ether solution was thoroughly washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dried over sulfur, and the ether was distilled off under reduced pressure to give 3'-(4- 8.9 g of fluorophenoxy)-6'-fluoro-α'-cyanobenzyl 2,2-dichloro-3-(2,2-dichlorovinyl)cyclopropanecarboxylate was obtained.

Next, in order to clearly demonstrate the superiority of the compounds of the present invention, the results of efficacy tests will be presented.

Test example 1. Insecticidal test by spraying 0.2% white light solution of the compound of the present invention, 0.2% and Cynevirin 500, 0.8% white light solution (B), 0.1% and 0.1% 7 tarsulin white light solution For solution (C), allethrin, and phthalthrin in an approximately 0.2% white light solution, the relative effectiveness of the test agent was calculated based on the falling and turning rate of susceptible house flies, and the mortality rate after 24 hours was determined. The situation is as follows.

Values within 0 indicate the mortality rate after 24 hours.

Test example 2. Insecticidal test using microdropping method Biperonyl ptoxide was added to each of the compounds of the present invention and conventional compounds in an amount twice the amount of the active ingredient to make an acetone solution of a predetermined concentration! It was applied to the thoracic dorsal plate of adult house flies using a microsyringe. House flies used were susceptible strains and field strains whose sensitivity to cypyrethroid drugs had decreased through successive rearing.

The relative insecticidal power of conventional compounds against susceptible strains and the synergistic effect of piperonyl ptoxide were investigated based on the insect mortality rate after 24 hours, and the results are as follows.

As a result of the test, the compound of the present invention showed high insecticidal efficacy against the low-susceptibility field strain of housefly, similar to that of the susceptible strain. On the other hand, the insecticidal activity of the control compounds CB>, (C), and (9) against the low-susceptibility field strain housefly was low, but the activity was restored by adding viberonyl ptoxide, which suppresses oxidative metabolism. In view of this, it is clear that the compounds of the present invention, which are structurally modified by introducing halogen atoms into sites susceptible to oxidative metabolism of conventional pyrethroids, are extremely effective in suppressing the development of resistance to pyrethroids. became.

Next, an example of formulation will be shown, and the formulation can be prepared by a method familiar to those skilled in the art without requiring any special conditions in accordance with general agricultural chemicals.

Reference Example 1゜Compound of the present invention (white kerosene was added to 210,2s and the whole was
Obtain 0.2% oil solution as part oo.

Reference Example 2 White kerosene was added to 610.2 parts of the compound of the present invention and 0.8 parts of biperonyl butoxide to make a total of 100 parts to obtain an oil solution.

Reference example 8゜Compound (II) of the present invention 0.4 part, Resmethrin 0.1
After dissolving 1.5 parts of Okuku chlorodiprobyl ether in 28 parts of refined kerosene and filling it into an aerosol container and attaching the pulp part, 70 parts of propellant (liquefied petroleum gas) was pressurized and filled through the valve part. Get an aerosol.

Reference Example 4゜Tsurpol 5M-200 was added to 20 parts of the compound (15) of the present invention.
(Toho Chemical registered trademark) and 70 parts of Kijirole were added and mixed and dissolved with stirring to obtain a 20% emulsion.

Reference Example 5 0.5 g of the present compound 0.0 g of camphor 1 0.5 g of BHT was added to a base material for mosquito coils such as pyrethrum extract lees powder, wood flour, starch powder, etc.99. Og
Mix K uniformly and obtain a mosquito coil by a known method.

Reference Example 6゜Compound of the present invention (2υ0.4g, MGK-50261.0
g 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 and 99.7 parts of clay were thoroughly ground and mixed to obtain a 0.3% powder.

Reference example 8゜Compound of the present invention - 40 parts, diatomaceous earth 35 parts, clay 20 parts,
Three parts of lacryl sulfonate and two parts of carboxymethyl cellulose are ground and mixed to obtain a wettable powder.

Test Example 3゜Among the emulsions obtained in Reference Example 4, compounds of the present invention (1), (4), (8), 02), (1 荀, (lL
1001 parts of a 1000-fold diluted solution of each emulsion containing E9 and Getsu with water was sprayed onto the surface.

Two days later, the parasitism rate was investigated and found to have decreased to less than 1/10 of the fine dissemination density in each plot.

Test Example 4 Among the emulsions obtained in Reference Example 4, compounds of the present invention (2), (
6), (9), (11), (I5), Dip fresh leaves in a 2000 times diluted solution of 幀, 翰 and 翰 for about 5 seconds, and after the liquid dries, put them in a petri dish to see if the young armyworms are healthy!
Ten It were released. The test insects were released twice, once on the day of immersion in the fresh leaves and 5 days later, and the mortality rate after 24 hours was determined.

Test Example 5 Approximately 200 aphids were infested on each tree one day before applying the insecticidal ingredient to potted broad beans. Reference example 8
Of the hydrating agents obtained by (3), (7), (10
), (141, (l?), @phantom, □□□ and evil 40
A 1:00 diluted solution was sprayed onto leaves infested with pests using a compressed air spray method, and the degree of damage was observed 2 days later. As a result, no increase in the degree of damage was observed in either case.

Test Example 6゜ (5), (9), ring, 06) obtained by Reference Example 7
11. Each powder of (goods), (b) and - has a diameter of 14
Spray eIn uniformly on the bottom of a tall glass petri dish at a rate of 2g/rrf, cut off 1G from the bottom, and apply butter to the wall. When adult German cockroaches were released into the container in groups of 10 and left in contact for 30 minutes and the cockroaches were transferred to a new container, more than 80% of the cockroaches could be killed by either powder after three days.

Test Example 7゜Five days after sowing, four leaves of potted green beans are infested with 10 adult female beetles per leaf and stored in a constant temperature room at 27°C. After 6 days, the emulsion obtained in Reference Example 4 (1
), (6), (10), (I), (1), (1), (2), and (2) were diluted with water to 1100 pp of active ingredients and sprayed on a turntable per pot. After 10 days, the number of parasitic mites on the plants was 10 or less for all drugs.

Procedural amendment (voluntary → 1.Display of the incident 1981 Patent Application No. 68818 B. Person who makes corrections 4. Agent 6. Subject of correction Full statement 7. Contents of correction Engraving of the statement (no changes to the contents)

Claims (2)

[Claims] (1) General Formula Here, Ry is the same or different and represents a halogen atom or a halomethyl group, and X represents a halogen atom. is a halogen atom or a cyano atom o−+4. ＋＋ρ＋＋bothヱ J 4. +-Sweet 1.5 It represents a notyl group or a halomethoxy group, and ru represents a chloro atom or a methyl group. & is a hydrogen atom, a cyano group, or an ethynyl group, R1,
R1 represents a hydrogen atom or a fluorine atom. B represents an oxygen atom, an iodine atom, a methylene group, an imino group or a methylimino group, and B represents a hydrogen atom or a halogen atom. )
An antioxidant metabolic halogen-substituted cyclopropane carboxylic acid ester derivative represented by (2) A group represented by the general formula (wherein A represents formulas (II) and (10)). 'qQc=(-H---(By) E where R+ and R+ are the same or different, and 7. Logon atom V represents halomethyl, and X represents a halogen atom. Ru represents a halogen atom or cyano group, negative is halogen atom,
It represents a methyl group, a halomethyl group or a halomethyl group, and ru represents a chloro atom or a methyl group. ) Cyclopropanecarboxylic acid or its reactive derivative represented by the general formula (wherein R is a hydrogen atom, a cyano group or an ethynyl group,
! l), R1 and R1 represent a hydrogen atom or a fluorine atom. B represents an oxygen atom, an iodine atom, a methylene group, an imino group or a methylimino group, and & represents a hydrogen atom or a halogen atom. ) or a reactive derivative thereof (where A, B, R7,
RI, R1, l, and RI have the same meanings as above. ) A method for producing an antioxidant metabolic halogen-substituted cyclopropane carboxylic acid ester derivative. (In the formula, Au formula (II), (III), (IV)?
Indicates the group represented. Kδ Here &, R1 are the same or different and represent a halogen atom or a halomethyl group, and X represents a halogen atom. R represents a halogen atom or a cyano group, R represents a halogen atom, methyl group, halomethyl group, or halomethoxy group, R represents a chloro atom or a methyl group. & is a hydrogen atom, a cyano group or an ethynyl group, Fb,
RI represents a hydrogen atom or a fluorine atom. B represents an oxygen atom, an iodine atom, a methylene group, an imino group or a methylimino group, and 9 represents a hydrogen atom or a halogen atom. )
An insecticide and acaricide characterized by containing an antioxidant metabolic halogen-substituted cyclopropane carboxylic acid ester derivative as an active ingredient.