JPS5879909A - Insecticidal and miticidal agent having low toxicity to fish, and its preparation - Google Patents

Abstract

PURPOSE:To provide an insecticidal and miticidal agent having low toxicity to fish, containing a specific mostly novel cyclopropanecarboxylic acid ester derivative wherein at least one of the two methyl groups of the cyclopropane ring is substituted with halogen to reduce the toxicity to fish. CONSTITUTION:The insecticidal and miticidal agent having low toxicity to fish and useful for the control of vermin in water, especially in paddy rice field, is obtained by using a compound of formulaI(R1 is group of formula R6R7C=CH, formula II, X3CCH2, or R8ON=NH; R2, X and Y are halogen; Y may be H; R3, R6 and R7 are halogen, CH3, or halomethyl; R6 and R7 may together form cyclopentylidene, etc.; R4 is H, CN, CH3 or C CH; R5 and R5' are H, halogen, CH3, CF3 or lower alkoxyl; R8 is 1-3C alkyl), as an active component. The compounds are novel excluding some of them (formula III and formula IV). The compound of formulaIcan be prepared by reacting the compound of formula V or its reactive derivative with the compound of formula VI or its reactive derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention represents a group represented by the general formula (wherein, R1(rI), (20), (V)).

XiCCHL-1-(pi) f? g0-N=CH
----m Here, R1 and Rt are the same or different and represent a methyl group, a halogen atom, or a halomethyl group.

It's okay.

Further, R1 is an alkyl group having 1 to 8 carbon atoms, X is a halogen atom, and Y is a hydrogen atom or a halogen atom.

represents a halogen atom, and the tortoise represents a halogen atom, a methyl group, or a halomethyl group.

Further, R represents a hydrogen atom, a cyano group, a methyl group, or an ethynyl group, and RI and R/ represent a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group, or a lower alkoxyl group. ) The present invention relates to a low-fish-toxic insecticide and acaricide characterized by containing a cyclopropanecarboxylic acid ester derivative represented by the following formula, and a method for producing the same.

Organophosphates, carbamate-based insecticides, and chlorine-based insecticides have become mainstream as agricultural chemicals and have contributed to increased production of agricultural products, but they have been considered unsafe due to concerns about environmental pollution and chronic toxicity. There is a strong need to search for new compounds. Natural pyrethrins are excellent insecticides that are fast-acting and have low toxicity to humans and livestock, but their use has been limited to household use because they are susceptible to oxidative decomposition outdoors. In recent years, research into its acid and alfur components has become active, and several compounds have been discovered that are more stable to light than conventional pyrethroids. For example, a compound in which RI and RI are both methyl groups in the general formula (1), that is, the general formula %) (where Ri, Ri, Rs', Ri,
Ry, R1, X and Y have the same meanings as above. ) The compounds shown in (1) have high insecticidal power and are fast-acting.

2. It has a long aftereffect, but does not persist in the environment.

3. Low toxicity to humans and livestock.

With these features, research is being conducted on its practical application as an alternative to conventional organic phosphorus and carbamate insecticides.

However, natural pyrethrins and other pyrethroid insecticides are known to be highly toxic to fish in general, and are used to exterminate aquatic pests such as rice paddies, ponds, and rivers, especially in rice areas such as Japan and Southeast Asia. It seems to be subject to temporary restrictions. In addition, it is natural for chemicals to flow into lakes, ponds, and rivers in areas where cotton, grain, and vegetables are cultivated in fields such as the United States and Europe, and therefore the development of pyrethroids with low toxicity to fish is an important issue.

It was revealed that this compound has high insecticidal efficacy and very low toxicity to humans and livestock.

(Japanese Patent Application Laid-Open No. 50-88529) The present inventors focused on fish toxicity, and as a result of further intensive research, the compound (XID, general formula (I) containing (l)
The fish toxicity of the compound group represented by the general formula (2), (1
) O, '(X), ( The finding that fish toxicity is significantly reduced and high insecticidal efficacy is maintained by replacing 2 with a halogen atom is an epoch-making finding that would be completely unexpected from the facts known before the filing of this application.Therefore, the general formula (I ) Zero Hatsu 1111 insecticide containing the compound shown as an active ingredient,
While acaricides have extremely high insecticidal efficacy and residual efficacy against various pests, they have extremely low toxicity against fish such as carp and Japanese medaka, and are even more effective against warm-blooded animals such as mice and rats. Since it also has low 11f characteristics, paddy fields,
It is particularly useful for exterminating pests that inhabit not only places with water systems such as mountains, lakes, rivers, and forests, but also agricultural fields that may contaminate water systems. The compound represented by the above formula (I) used as an active ingredient in the present invention is (where n is the formula (
Inc.), ([ID, (IV), ff+].

K, vCCHz ---(Iv)g, -Q-N=C)
(---(y) Coco K 9* M u The same or different may be a methyl group.

Further, R represents an alkyl group having 1 to 3 carbon atoms, X represents a halogen atom, and Y represents a hydrogen atom or a halogen atom.

R represents a halogen atom, and Ri represents a halogen atom, a methyl group, or a halomethyl group. ) Cyclopropanecarboxylic acid or its reactive derivative represented by the general formula (wherein R is a hydrogen atom, a cyano group, a methyl group, or an ethynyl group, and R5 and R1' are a hydrogen atom, a halogen atom,
Represents a methyl group, trifluoromethyl group or lower alkoxyl group. ) or a reactive derivative thereof. Examples of reactive derivatives of cyclopropanecarboxylic acid p-1 include acid halides, acid anhydrides, lower alkyl esters, and alkali metal salts.

Examples of reactive derivatives of alcohol include lylolite,
Examples include bromide and P-toluenesulfonic acid ester. The reaction is carried out in a suitable solvent in the presence of an optional deoxidizing agent and an organic or inorganic base or acid as a catalyst, optionally with heating. The compounds of the invention of general formula (I) have one or more asymmetric carbon atoms. The compounds of the present invention include their optical isomers and racemic mixtures; however, in the Examples and compound examples described below, unless otherwise specified, the compounds produced are racemic mixtures. Next, the above formula (I
), but the present invention is of course not limited to these.

3'-phenoxy-αI-cyanobenzyl 2,2-zig3'-phenoxy-α'-cyanobenzyl 2,2.
-dichloro-8(2,2-schif'lomopinyl)cyclof'lovancar repoxylate n201.5
8093'-7 enoxy α'-cyanobenzyl 2,
2-dichloro-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxylate n+%'
1.5702 3'-7 enoxy α'-cyanobenzyl 2,2-dichloro-8-(2-7' Romo 2-trifluoromethylvinyl 0 n 1., fi7 (J (I Roro 3 ( 2.2 - Silf Rubinyl Carpoxylate n 1.56813
'-Phenoxy-α-cyanobenzyl 2,2-dichloro-8-(1,2-dibromo-2,2-dichloroethyl)cyclopropanecarboxylate 0 1 1,5885 8'-phenoxy-α'-cyanobenzyl 2,2 -dichloro-8-(1,2-dichloro-2,2-dibromoethyl)cyclopropanecarboxylate 0 n 1.5877 3/-7 enoxy α'-cyanobenzyl 2,2-dichloro-3-( 2,2 .2-Trichloroethyl) cyclopropyloxylate 1 1.57543'-
Phenoxybenzyl 2.2-dichloro-3-cyclobentridenemethylcyclopropane lupogysylate
・20 1.56858'-
Phenoxybenzyl 2.2-dichloro-3-(2-oxothiolane-3-ylidenemethyl)cyclopropanecarboxylate n"1.57623'-7
Enoxy α'-cyanobenzyl 2,2-dichloro-
3-Methoxyiminomethyldicyclopropaneylpoxylate ・20 1.56483'-
7 Enoxy α'-methylbenzyl 2,2-cyclo3-ethoxyiminomethylcyclopropanolupoxylate 120 1.56708'-
Phenoxy-α'-cyanobenzyl 2-chloro-2-
Trifluoromethyl-3-(2,2-dichlorovinyl)
Cyclopropanecarboxylate 201.5706 3'-7 enoxy〇'-cyanobenzyl 2-chloro-2-trifluoromethyl-8-(2,2-dibromovinyl)cyclopropanecarboxylate 1.5
784 3'-7 Enoxy α'-cyanobenzyl 2-chloro-2-trifluoromethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxylate ・201.58733'
-7 enoxy α-cyanobenzyl 2-chloro-2-
1-Lifluoromethyl-3-<2-fluoro-2-tri7fluoromethylvinylruboxylate ・20 ], 56
193'-7 Enoxy U-cyanobenzyl 2-chloro-2-trifluoromethyl-8-(1,2-dibromo2,2:;chloroethyl)cyclopropanecarphoki3'
-(4-fluorophenoxy)-α'-cyanobenzyl 2-chloro-2-)lifluoromethyl-3-(1-chloro-2,2-dibromoethyl)cycloprobanca levoxylate ・20 1.58388'-
(8-trifluoromethylphenoxy)-(ν'.

5'-dimethylbenzyl 2-fluoro-2-bromomethyl-3-(2,2.2-)lifluoroethyl) Schiff
Lopropane lupoxylate n20 1.57
91 Methyl 2-bromo 2-methyl-8-profoxyiminomethylcyclopropane lupoxylate
1.5743 Methylbenzyl 2-fluoro-2-7'lomo8-(
2-oxooxolane-8-ylidenemethyl)cyclo7
・. Paaka 2, Poxito n” 1.57
828'-(2-)lifluoromethylphenoxy) -
5'-Ethoxy-α'-ethynylbenzyl-chlorodifluoromethyl-3-(2-oxopyrrolidin-3-ylidenemethyl)cyclopropanecarboxylate n20 1.5805
Zyl 2,2-dichloro-8-(2,2-dichlorovinyl)cyclopropanecarboxylate n 1.5720 Rho 2-trifluoromethyl-8-(2,2-dichlorovinyl)cyclopropanka! Levoxylate n” 1
．． 5605 3'-(4-bromophenoxy)-α'-cyanobenmethy 2,2-cycloro8 (2,2-cyclomopinyl)0 cyclopropanecarboxylate 1 1.588
03'-(4-Methoxyphenoxy)benzyl 2-lycoro-2-trifluoromethyl-3-(2,2-diglomopinyl)cyclopropanecarboxylate n
1.5744 3'-(4.-trifluoromethylphenoxy)-4
'-Fluoro-α'-ethynylbenzyl 2-7'Romo2-Flomolf) Roux 3 (2 7J RheoRo2
-talolopinyl) cyclopropanecarboxylate 201.5845 3'-(8-isopropoxyphenoxy)-α'-methylbenzyl 2-fluoro-2-methyl-3-(2-furomo 2-methylvinyl 0 boxylate n 1.5
8293'-7 Enogishibenzyl 2-chloro-2-1
-f-8-(2,2-dimethylvinyl)cyclopropanecarboxylate ・””
1.56288'-phenoxy-4'-methyl-α-ethynylbenzyl 2-promo2-chlorodifluoromethyl-3-(2-7'lomomethyl-2-talolofluoromethylpinyl)cyclopropanecarboxyroot 20
1.5861 Sil2'70Rho2-1-Lifluoromethyl-3-
Cyclopentylidenemethyl cyclopropane 8′
-phenoxy-α'-ethynylbenzyl 2-chloro-
2-) IJ Fluoromethyl-8-(2-F+
7thiolane-3-ylidenemethyl)cyclopropanecarboxylate 8'-(4-chlorophenoxy)-U-cyanobenzyl 2-chloro-2-trifluoromethyl-3-methoxyiminomethylcyclopropanecarboxylate
・20
1.56113'-(4-methylphenoxy)-6'
-methoxybenzyl 2,2-difluoro-3-(2,
2.2-)ribromoethyl) cyclopropanecarboxylate 3'-(4-7"lomophenoxy)-α'-ethynylbenzyl 2-chloro-2-trifluoromethyl-3-(2,2.2-trichloroethyl) Cyclopropanecarboxylate ・20 1
．． 57863'-(4.-methoxyphenoxy)-7-
Cyanobenzyl 2,2-dichloro-8-(1,2-dibromo-2,2-dichloroethyl)cyclopropanecarboxyroot 3'-(4-fluorophenoxy)-7-
Cyanobenzyl 2-10Rho2-ToIJ Fluoromethyl-8-(1,2-dibromo-2,2-dichloroethyl)cyclo8'-(8-trifluoromethylphenoxy)-5'-methyl-α'-ethynylbenzyl 2
-fluoro-2-fluorodichloromethyl-3-(1-
Promo 2,2-difluoroethyl root n20 1.5
7703'-7Enoxybimonomethylbenzyl 2-chloro-2-promo8-(1,2-dichloro-2,2-
ditrifluoromethylethyl) cyclopropane carboxylate ・201.5809
8'-(4-Flohoxyphenoxy)benzyl 2-chloro-2-trichloromethyl-8-(1-fluoroisobutyl)cyclopropanecarboxylate n201.5
71J6 3'-phenoxybenzyl 2,2-dibromo-8-(
2,2-dichlorovinyl)cyclopropanecarboxylate ・201.576
53'-(4-bromophenoxy)-α-cyanobenzyl 2-bromo-2-trifluoromethyl-8-(2
,2-dichlorovinyl) cycloprobanker 2
3- 8'-(4-1-lifluoromethylphenoxy) 6
1'-ethynylbenzyl 2-10rho2-zolomo3
-(2,2-dibromovinyl)cyclopropane carboxylate-1, n”01.5
812 Benzyl 2-fluoro-2-trifluoromethyl 8 (2,2-citrifluoromethylvinyllopropanecarboxylate n"0 1.56148'
-(3-methylphenoxy)nia-methylbenzyl 2
-chloro-2-methyl-3-(2-methyl-2-chlorodifluoromethylvinyl)cycloprobanca,,boxy L/-t n20 1.5650;3'-7 Enogycy α'-cyanobenzyl 2-chloro-2-
Fluoro-8-(1,2-dibromo-2,2-dichloroethyl)cyclopropanecarboxylate 3'-phenoxy-7-cyanobenzyl 2-fluoro-2-methyl-8-(2,2,2-trichloroethyl ) Cyclopropanecarboxylate 3'-phenoxy-α-cyanobenzyl 2-fluoro-2-methyl-8-(2,2-dibromovinyl) The compound of the present invention is a new compound that is solid or liquid at room temperature. It is generally easily soluble in organic solvents, so it can be used as an emulsion, oil, powder, wettable powder, aerosol, etc. as an insecticide for spraying. The insecticides and acaricides of the present invention can be used against sanitary pests such as flies, mosquitoes, and cockroaches, as well as against organic phosphorus agents, carbamate agent-resistant leafhoppers, Clivias, stink bugs, armyworm moths, diamondback moths, tapa moths, It is useful for controlling agricultural pests such as bean beetles, nocturnal moths, cabbage beetles, chestnut beetles, leaf beetles, aphids, and scale insects, grain storage pests such as black elephants, mites, and the like. The composition of the present invention has low fish toxicity, is inexpensive, and has a wide insecticidal spectrum, so it can be used as an agricultural and horticultural insecticide and acaricide to replace conventional organophosphorus agents and organochlorine insecticides. It can be expected to be widely used in exterminating resident pests.

In addition, the compounds of the present invention include N-octylbicyclohebutene dicarboximide (trade name MOK-264) and a mixture of N-octylbicyclohebutene dicarboximide and an arylsulfonate salt (trade name MC; Ni-5026).
The insecticidal and acaricidal effects can be further enhanced by adding a synergist such as , cinepirin 500, octachlorodibutyl ether, or piveronyl ptoxide. If necessary, the stability can be further enhanced by adding a stabilizer such as BHT or DBHQ or an antioxidant to the compound of the present invention. The compounds of the present invention may also contain other insecticides such as fenitrothion, DI) VP, diazinon, propafos, pyridafenthione, etc.
agent, NAC, MTMC.

Carbamate-L pyrethrins such as BPMCSPHC,
Allethrin, phenothrin, 7 lametrin, phenothrin, permethrin, cypermethrin, decametrin,
7. Conventional pyrethroid insecticides such as emvalerate and fenpropanate, insecticides and acaricides such as cartap, chlorzenamidine, and menmyl, fungicides, nematicides, herbicides, plant growth regulators, and fertilizers. By mixing other agricultural chemicals, a highly effective multipurpose H1 composition can be obtained, and labor savings and synergistic effects among 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, including synthesis methods (A), (B), TC),
fD), (E), fF) could be obtained in good yield by any method.

Synthesis Example I A) Method by Reaction of Alcohol with Carboxylic Acid Halide 2. 6.3 g of 2-dichloro-8-(2-chloro-2-tri7fluoromethylhydrochloride are dissolved in 15 me of dry benzene,
To this was added 4 g of 3-7 enogycy α-cyanobenzyl alcohol dissolved in 20 me of dry benzene,
Furthermore, when dry pyridine 8me is added as a condensation aid, pyridine hydrochloride is precipitated. After sealing the cap and leaving it overnight at room temperature, the crystals of pyridine hydrochloride were separated, the benzene solution was dried with borax, and the benzene was distilled off under reduced pressure to give 3'-phenoxy-α-cyanobenzyl 2,2-dichloro-3. -(2-
9.2 g of chloro-3-trifluoromethylvinyl xylate was obtained.

Synthesis Example 2.

B) Method by reaction of alcohol with carboxylic acid 2-fluoro-2-bromomethyl-3-(2,2
．． 5.7 g of 2-trifluoroethyl)cyclopropanecarboxylic acid and 6.7 g of 3-(3-trifluoromethylphenoxy)-α/, 5/-dimethylbenzyl alcohol.
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, and after cooling, the precipitated dicyclohexyl urea was distributed door to door. The oily substance obtained by concentrating the filtrate was passed down a 100 g silica gel column to obtain 8'-1-trifluoromethylphenoxy)-α',5'-dilf-rubenzyl 2-fluoro-2-bromomethyl-3-. (2,2.2-)lifluoroethyl)cyclopropanecarboxylate 9.4g
lJ7'c.

Synthesis Example 3.

C) Method by reaction of alcohol halide with alkali metal carboxylate 6.6 g of sodium salt of 2-chloro-2-trifluoromethyl-8-(2-oxothiolane-3-ylidenemethyl)cyclopropanecarboxylic acid and 3- Phenoxy-α-
5.1 g of ethynylbenzylchloride F and 50 m of benzene
After 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, dried over sulfate, and benzene was removed under reduced pressure. 8.2 g of 8'-phenoxyU-ethynylbenzyl 2-chloro-2-trifluoromethyl-3-(2-oxothiolane-3-ylidenemethyl)cyclopropanecarboxylate was obtained.

Synthesis Example Bundle D) Method by Transesterification of Flucol and Lower Alkyl Esters of Carboxylic Acid Methyl ester of 2-bromo-2-methyl-8-profoxyiminomethylcycloprobancarboxylic acid 5,7 g and 3-( 5.2 g of 4-methoxyphenoxy)-α-ethynylbenzyl alcohol are heated to 150°C. I7I
i 0.25g of sodium when the temperature reaches 150°C
was added to start distilling off methanol. When the distillation of methanol has stopped, an additional 0.25 g of sodium is added, and the above operation is repeated while keeping the temperature around 1508C until the theoretical sum of methanol is obtained. The mixture was then cooled and dissolved in ether, and the ether solution was washed with dilute hydrochloric acid, sodium hydroxide, and brine, dried over nitric acid, and the ether was distilled off under 1 pressure.
8.7 g of -(4-methoxyphenoxy)-α'-ethynylbenzyl-methyl-8-profoxyiminomethylcyclopropane lupoxylate was obtained.

Synthesis Example 5.

E) Method by reaction of alcohol and carboxylic anhydride 16.0 g of 2-chloro-2-trifluoromethyl-8-(1-chloro-2,2-dibromoethyl)cyclopropanecarboxylic anhydride and 8-( 4-fluorophenoxy)
-α-cyanobenzyl alcohol 4.9g and 50me
was dissolved in dry pyridine and stirred at room temperature overnight. the next day,
The reaction solution was poured into 100 g of ice water and extracted three times with ether 2'0-. The ether layers were combined and extracted twice using 5% aqueous sodium hydroxide solution 2'Ome to remove by-produced carboxylic acid. The ether layer was further washed with dilute hydrochloric acid, heavy water, and brine, dried over sulfur, 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 give 8'- -fluorophenoxy)-α'-E/7nobenzyl 2-chloro-2
- ) IJ fluoromethyl-3-(1-chloro-2
．． 10.6 g of 2-Schif'romoethyl)cyclopropanecarboxylate was obtained.

Synthesis Example 6.

F) Method 2 by reaction of alcohol halide with carboxylic acid salt of organic tertiary base, 6.9 g of 2-dibromo-8-(2,2-dichlorovinyl)cyclopropanecarboxylic acid is dissolved in 50 m/a of acetone. and 3-phenoxybenzyl bromide 5.
Add 3g. Add 4 m/s of triethylamine to the mixture and react at 60 to 80°C for 3 hours, then dissolve in ether, thoroughly wash the ether solution with diluted hydrochloric acid, heavy sodium water, and brine, dry with nitric acid, and remove the ether under reduced pressure. 3' phenoxybenzyl 2,2-dibromo-8-
9.2 g of (2,2-dichlorovinyl)cyclopropanecarboxylate was obtained.

Next, in order to make it clearer that the composition provided by the present invention is excellent, the results of testing the effectiveness will be shown.

Test example 1. Insecticidal test by spraying 0.2% white light solution of the compound of the present invention (A), 0.2% and white light solution CB) of cinepirin 5000.8%, 0.1%
7. The drop-upside-down rate of houseflies was calculated for a 0.1% white light solution of tarthrin and a white light solution of 0.2% each of allethrin and phthalthrin, and the relative effectiveness of the test drug was calculated. The mortality rate was calculated as follows.

Values within 0 indicate the mortality rate after 24 hours.

From the above results, the effect of the oil on house flies is comparable to or greater than that of the conventional pyrethroid phthalthrin.
10), and IvJ et al. showed that it has a much superior lethal efficacy compared to allethrin and 7tarsulin.

Sample False Example 2 Test Method (D Fish Toxicity Test - The test was conducted on goldfish in accordance with the method for testing the toxicity of pesticides on fish.

■Insecticidal test - A seven-ton solution of each compound was diluted with distilled water to a specified concentration and placed in a beaker, and 20
Release one.

50% lethal concentration (LC5o p
pm) was calculated.

Test results The fish toxicity and efficacy against Culex Culex larvae of each compound are shown in the table below.

*A Compound described in JP-A No. 49-47581 Based on the above results, all of the compounds used as active ingredients of the present invention have a fish toxicity of 1.8 ppm or more, and an LC5o against Culex mosquito larvae of 0. O1~0. The concentration difference was 30 to 400 times. On the other hand, the fish toxicity of compound A was less than α122m, and almost no difference was observed between it and the LC5o of Culex larvae. Therefore, when the present invention is used to control Culex Culex larvae, it can be said that it is extremely safe for fish living in the water system.

Next, an example of formulation will be shown, but the formulation does not require any special conditions similar to general agricultural chemicals, and can be prepared by a method well known to those skilled in the art.

Reference Example 1 Completed] White kerosene was added to 0.2 parts of Compound (1) to make the total 100 parts to obtain a 0.2% oil solution.

Reference Example 2゜ White kerosene was added to 0.2 parts of the present compound (4) and 0.8 parts of piperonyl ptoxide to make a total of 100 parts Reference Example 3゜ The present compound (9120 parts) was added with Tsurubol 5M-200 (
10 parts of Toho Chemical (registered trademark) and 70 parts of Kijirole were added and mixed and dissolved with stirring to obtain a 20% emulsion.

Reference 1 compound with no hair loss (+7) 0.4. part, resmethrin 0
．． 1 part of octachlorodipropyl ether, 1.581 dissolved in 28 parts of refined kerosene, filled into an aerosol type, and after storing the pulp part, 70 parts of propellant (liquefied petroleum gas) was pressurized through the pulp part. Fill it to get an aerosol.

Reference Example 5 0.3 parts of the compound of the present invention 121A and 99.7 parts of clay were thoroughly ground and mixed to obtain a 0.3% powder.

Reference Example 6 40 parts of the compound of the present invention (3(2), 35 parts of diatomaceous earth, 20 parts of clay, 3 parts of lacryl sulfonate, and 2 parts of carboxymethyl cellulose are ground and mixed to obtain a wettable powder.

Test Example 3 Compound examples (1), (4), (7) prepared as in Reference Example 3
), (9), (Otori (1'71, Haji J 姐@Hyo G Jisuzu 8),
←1) and (4η) as active ingredients in water at 200%
It was diluted to ppff+, and 20 drops per pot were sprayed on rice planted in Hugner pots with an area of 1/10,000. After air-drying, the pot was covered with a wire mesh, and 3,410 black-tailed snails were released into the wire mesh, and the mortality rate was investigated 24 hours later. Both drugs had a 100% mortality rate.

9 per leaf for 4 leaves of potted green beans 5 days after test seeding
It is infested with 10 false red spider mites and stored in a constant temperature room at 27°C. After 6 days, compound example (2) obtained in Reference Example 8, (
5), (9), (11), (16), (+8), (2 bottles, (sha), (31), (341, +3η, (4L (4)
A medicinal solution prepared by diluting an emulsion containing 菀 and 硛 as active ingredients with water to 500 ppm per pot on a turntable.
/li cloth.

After 10 days, the number of parasitized spider mites on the plants was 10 or less, and no damage Fi by spider mites was observed.

Test Example 5 Compound examples (3), (6), (8) obtained in Reference Example 6,
(1:l!, Q;+), Shil), Shi (he), (30),
(33), (3(2), (39), (42, (45)) and (400 ppm water phase agent with active ingredient)
The solution was diluted to 1/10,000 and sprayed at 20 vre per pot to cabbages planted in 1:10,000 Earl Wagner pots. After air-drying, the leaves were placed in a petri dish and 610 healthy armyworm larvae were released.
The mortality rate after 24 hours was investigated. Both drugs are 100
% mortality rate.

Test Example 6゜ Compound examples (1), (5), (10), (
14), (1 East (%), Kui, Shieta, Gentery, 0.2 g of powder containing 431 and 0 (2) as active ingredients was applied to rice seedlings using a Pelger duster (50 cmHg, 1 minute contact). The agents were sprayed on brown planthoppers, and the mortality rate was investigated 24 hours later.A 100% mortality rate was obtained for both agents.

Patent applicant 117fl-(] Pure part 'l',,
+ 1 Procedural amendment (method) Haruki Shimada, Commissioner of the Japan Patent Office 1, Indication of the case 1982 patent #J@No. 178587-=;

3. Relationship with the case of the person making the amendment Patent applicant 411 Agent 5, date of amendment order February 4, 1980 (Shipping date February 23, 1982)
0) 6. Subject to amendment” Details: A reprint of the detailed statement of the 7th amendment to the Rei-Kyu (no changes to the content) 76-

Claims (1)

[Scope of Claims] (In the formula, ichi represents a group represented by 徉, sui, (IV'), or m.) C'JC-CI''11 -- (IV') kl
z O'-N'''CH--(V) where R- and Fb are the same or different, and are a methyl group, or R is an alkyl group having 1 to 8 carbon atoms, and X is a halogen atom, Y represents a hydrogen atom or a V1 halogen atom. The mountain represents a halogen atom, and R+ represents a halogen atom, a methyl group, or a halomethyl group. Also, R represents a hydrogen atom, a cyano group, a methyl group, or vJ. An ethynyl group A low fish toxicity insecticide characterized by containing a cyclopropanecarboxylic acid ester visitant represented by the following formula: R+ and R/ represent a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group, or a lower alkoxyl group. , acaricide. (Wherein, n represents a group represented by formula (b), (IIDl(5), or (V). Xsc -C)(2----(IV) Vg-0-N
”'CH------ff) Here, Ra and RI are the same-
Alternatively, it may be a methyl group. Further, R represents an alkyl group having 1 to 3 carbon atoms, X represents a halogen atom, and Y represents a hydrogen atom or a halogen atom. The city represents a halogen atom, and the mountain represents a halogen atom, methyl group, or halomethyl group. ) Cyclopropanecarboxylic acid or its reactive derivative represented by the general formula (wherein, l is a hydrogen atom, a cyano group, a methyl group, or an ethynyl group, and l'h, R/ are hydrogen atoms, )\logen atom , represents a methyl group, a trifluoromethyl group or a lower alkoxyl group. ) or a reactive derivative thereof (herein, R1, RI, RI, R1, RI, R1/ have the same meanings as above). Process for producing a low-fish-toxic insecticide and acaricide containing propanecarboxylic acid ester 11 (1) (3) Claim No. (1) characterized in that it contains a pyrethroid synergist as an adjuvant. Low fish toxicity insecticides and acaricides listed in section.