JPH0240642B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula (In the formula, R ₁ represents a group represented by the formula (), (), (), ().

【formula】

_{[ Formula ] _ _}
Represents a halogen atom or halomethyl group, but R ₆ ,
R ₇ together

【formula】

【formula】

[Formula] or

It may form a ring of [Formula]. In addition, R ₈ and R ₉ are the same or different, and are methyl groups,
It represents a halogen atom or a halomethyl group, X represents a halogen atom, and Y represents a hydrogen atom or a halogen atom. R ₁₀ represents an alkyl group having 1 to 3 carbon atoms.
R ₂ represents a halogen atom, R ₃ represents a halogen atom,
Represents a methyl group or a halomethyl group. In addition, R ₄ represents a hydrogen atom, a cyano group, a methyl group, or an ethynyl group, but when R ₆ and R ₉ both represent a halogen atom, and R ₂ and R ₃ are chlorine atoms,
R ₄ represents only a cyano group, a methyl group, or an ethynyl group. R ₅ and R ₅ ' represent a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group or a lower alkoxy 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. Up until now, organic phosphorus agents, carbamate insecticides, and chlorine insecticides have been the mainstream agricultural chemicals and have contributed to increased production of agricultural products, but they have caused environmental pollution and
Alternatively, there is a strong desire to search for safer compounds from the standpoint of chronic toxicity and the like. 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 alcohol components has become active, and several compounds have been discovered that are more stable to light than conventional pyrethroids. For example, in the general formula (), R ₂ ,
Compounds in which both R ₃ are methyl groups, that is, the general formula (Here, R ₄ , R ₅ , R ₅ ′, R ₆ , R ₇ , R ₈ , X, and Y have the same meanings as above.) The compound represented by 1 has high insecticidal power and is fast-acting. . 2 Highly persistent, but not persistent in the environment. 3. Low toxicity to humans and animals. 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, especially in rice fields such as Japan and Southeast Asia.
It seems that there are considerable restrictions on the extermination of pests that live in water such as rivers. In addition, lakes, ponds,
It is natural for chemicals to flow into the river,
Therefore, the development of pyrethroids with low fish toxicity is a challenge. By the way, the inventors have applied for a patent first. It was revealed that this compound has high insecticidal efficacy and very low toxicity to humans and livestock. (Japanese Patent Application Laid-Open No. 50-89529) The inventors of the present invention focused on fish toxicity, and as a result of further intensive research, the fish toxicity of the compound group represented by the general formula () including compound (XII), () was found to be The inventors have found that this is extremely low compared to the compounds represented by the general formulas (), (), (), and (XI), leading to the completion of the present invention. There is no knowledge that by replacing at least one of the two methyl groups of the cyclopropane ring with a halogen atom in this way, fish toxicity is significantly reduced and high insecticidal efficacy is maintained, based on facts known before the filing of this application. This is a groundbreaking event that is difficult to predict. Therefore, the insecticide of the present invention containing the compound represented by the general formula () as an active ingredient,
While acaricides have extremely high insecticidal efficacy and residual efficacy against various pests, they are extremely toxic to fish such as carp and Japanese medaka, and are even more toxic to warm-blooded animals such as mice and rats. Because it has low toxicity, it is especially useful for exterminating pests that live in areas with water systems such as rice fields, ponds, lakes, rivers, and forests, as well as in agricultural fields that may contaminate water systems. The compound represented by the above formula () used as an active ingredient in the present invention can be prepared using the general formula (In the formula, R ₁ represents a group represented by the formula (), (), (), ().

【formula】

_{[ Formula ] _ _}
Represents a halogen atom or halomethyl group, but R ₆ ,
R ₇ together

【formula】

【formula】

[Formula] or

[Formula] may form a ring. In addition, R ₈ and R ₉ are the same or different, and are methyl groups,
It represents a halogen atom or a halomethyl group, X represents a halogen atom, and Y represents a hydrogen atom or a halogen atom. R ₁₀ represents an alkyl group having 1 to 3 carbon atoms. R ₂ represents a halogen atom, and R ₃ represents a halogen atom, a methyl group, or a halomethyl group. ) Cyclopropanecarboxylic acid or its reactive derivative and general formula (In the formula, R ₄ represents a hydrogen atom, a cyano group, a methyl group, or an ethynyl group, but when R ₆ and R ₇ both represent a halogen atom and R ₂ and R ₃ are chlorine atoms, R ₄ represents a cyano group. , methyl group, or ethynyl group; R ₅ , R ₅ ′ represents a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group, or a lower alkoxy group) or its reactive derivative. It can be prepared by letting. Examples of reactive derivatives 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, optionally in the presence of an organic or inorganic base or acid as a deoxidizer or catalyst, and optionally with heating. The compounds of the present invention of general formula () have one or more non-dispensable carbon atoms. The compounds of the present invention include optical isomers and racemic mixtures thereof;
In the Examples and Compound Examples described below, unless otherwise specified, the produced compounds are racemic mixtures. Next, representative examples of the compound represented by the above formula () will be shown, but the present invention is of course not limited to these. 3'-Phenoxy-α'-cyanobenzyl 2,2-
Dichloro-3-(2,2-dichlorovinyl)cyclopropanecarboxylate n ²⁰ _D 1.5734 3′-phenoxy-α′-cyanobenzyl 2,2,
-dichloro-3-(2,2-dibromovinyl)
Cyclopropane carboxylate n ²⁰ _D 1.5809 3'-Phenoxy-α'-cyanobenzyl 2,2-
Dichloro-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxylate n ²⁰ _D 1.5702 3'-Phenoxy-α'-cyanobenzyl 2,2-
Dichloro-3-(2-bromo-2-trifluoromethylvinyl)cyclopropanecarboxylate n ²⁰ _D 1.5760 3'-Phenoxy-α'-cyanobenzyl 2,2-
Dichloro-3-(2,2-dimethylvinyl)cyclopropanecarboxylate n ²⁰ _D 1.5681 3'-Phenoxy-α'-cyanobenzyl 2,2-
Dichloro-3-(1,2-dibromo-2,2-
dichloroethyl) cyclopropane carboxylate n ²⁰ _D 1.5885 3'-Phenoxy-α'-cyanobenzyl 2,2-
Dichloro-3-(1,2-dichloro-2,2-
dibromoethyl)cyclopropanecarboxylate n ²⁰ _D 1.5877 3'-Phenoxy-α'-cyanobenzyl 2,2-
Dichloro-3-(2,2,2-trichloroethyl)cyclopropanecarboxylate
n ²⁰ _D 1.5754 3'-Phenoxybenzyl 2,2-dichloro-3
-Cyclopentylidenemethylcyclopropanecarboxylate n ²⁰ _D 1.5685 3'-Phenoxybenzyl 2,2-dichloro-3
-(2-oxothiolane-3-ylidenemethyl)cyclopropanecarboxylate
n ²⁰ _D 1.5762 3'-Phenoxy-α'-cyanobenzyl 2,2-
Dichloro-3-methoxyiminomethylcyclopropanecarboxylate n ²⁰ _D 1.5648 3'-Phenoxy-α'-methylbenzyl 2,2-
Dichloro-3-ethoxyiminomethylcyclopropanecarboxylate n ²⁰ _D 1.5670 3'-Phenoxy-α'-cyanobenzyl 2-chloro-2-trifluoromethyl-3-(2,2-
dichlorovinyl) cyclopropane carboxylate n ²⁰ _D 1.5706 3'-Phenoxy-α'-cyanobenzyl 2-chloro-2-trifluoromethyl-3-(2,2-
dibromovinyl) cyclopropane carboxylate n ²⁰ _D 1.5784 3'-Phenoxy-α'-cyanobenzyl 2-chloro-2-trifluoromethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxylate n ²⁰ _D 1.5673 3'-Phenoxy-α'-cyanobenzyl 2-chloro-2-trifluoromethyl-3-(2-fluoro-2-trifluoromethylvinyl)cyclopropanecarboxylate n ²⁰ _D 1.5619 3'-Phenoxy-α'-cyanobenzyl 2-chloro-2-trifluoromethyl-3-(1,2-
Dibromo-2,2-dichloroethyl)cyclopropanecarboxylate n ²⁰ _D 1.5860 3'-(4-fluorophenoxy)-α'-cyanobenzyl 2-chloro-2-trifluoromethyl-3-(1-chloro-2,2-dibromoethyl)cyclopropanecarboxylate
n ²⁰ _D 1.5838 3′(3-trifluoromethylphenoxy)-α′,
5'-Dimethylbenzyl 2-fluoro-2-bromomethyl-3-(2,2,2-trifluoroethyl)cyclopropanecarboxylate
n ²⁰ _D 1.5791 3'-(4-Methoxyphenoxy)-α'-ethynylbenzyl 2-bromo-2-methyl-3-propoxyiminomethylcyclopropanecarboxylate n ²⁰ _D 1.5743 3′-(3-methylphenoxy)-4′-chloro-
α′-Methylbenzyl 2-fluoro-2-bromo-3-(2-oxooxolane-3-ylidenemethyl)cyclopropanecarboxylate
n ²⁰ _D 1.5782 3′-(2-trifluoromethylphenoxy)-
5'-Ethoxy-α'-ethynylbenzyl 2-chloro-2-chlorodifluoromethyl-3-(2-
Oxopyrrolidine-3-ylidenemethyl)cyclopropanecarboxylate n ²⁰ _D 1.5805 3'-(4-fluorophenoxy)-α'-cyanobenzyl 2,2-dichloro-3-(2,2-dichlorovinyl)cyclopropanecarboxylate n ²⁰ _D 1.5729 3'-(4-chlorophenoxy)benzyl 2-chloro-2-trifluoromethyl-3-(2,2
-dichlorovinyl)cyclopropanecarboxylate n ²⁰ _D 1.5695 3'-(4-bromophenoxy)-α'-cyanobenzyl 2,2-dichloro-3-(2,2-dibromovinyl)cyclopropanecarboxylate
n ²⁰ _D 1.5830 3′-(4-methoxyphenoxy)benzyl 2-
Chloro-2-trifluoromethyl-3-(2,
2-dibromovinyl)cyclopropanecarboxylate n ²⁰ _D 1.5744 3′-(4-trifluoromethylphenoxy)-
4'-Fluoro-α'-ethynylbenzyl 2-bromo-2-bromomethyl-3-(2-fluoro-
2-chlorovinyl)cyclopropanecarboxylate n ²⁰ _D 1.5845 3′-(3-isopropoxyphenoxy)-α′-
Methylbenzyl 2-fluoro-2-methyl-3
-(2-bromo-2-methylvinyl)cyclopropanecarboxylate n ²⁰ _D 1.5829 3'-Phenoxybenzyl 2-chloro-2-methyl-3-(2,2-dimethylvinyl)cyclopropanecarboxylate n ²⁰ _D 1.5623 3'-Phenoxy-4'-methyl-α'-ethynylbenzyl 2-bromo-2-chlorodifluoromethyl-3-(2-bromomethyl-2-chlorofluoromethylvinyl)cyclopropanecarboxylate n ²⁰ _D 1.5861 3'-(4-fluorophenoxy)-α'-cyanobenzyl 2-chloro-2-trifluoromethyl-3-cyclopentylidenemethyl cyclopropanecarboxylate n ²⁰ _D 1.5697 3'-Phenoxy-α'-ethynylbenzyl 2-chloro-2-trifluoromethyl-3-(2-oxothiolane-3-ylidenemethyl)cyclopropanecarboxylate n ²⁰ _D 1.5738 3'-(4-chlorophenoxy)-α'-cyanobenzyl 2-chloro-2-trifluoromethyl-
3-Methoxyiminomethylcyclopropanecarboxylate n ²⁰ _D 1.5611 3'-(4-methylphenoxy)-6'-methoxybenzyl 2,2-difluoro-3-(2,2,
2-Tribromoethyl)cyclopropanecarboxylate n ²⁰ _D 1.5897 3'-(4-bromophenoxy)-α'-ethynylbenzyl 2-chloro-2-trifluoromethyl-3-(2,2,2-trichloroethyl)cyclopropanecarboxylate n ²⁰ _D 1.5786 3'-(4-methoxyphenoxy)-α'-cyanobenzyl 2,2-dichloro-3-(1,2-dibromo-2,2-dichloroethyl)cyclopropanecarboxylate n ²⁰ _D 1.5885 3'-(4-fluorophenoxy)-α'-cyanobenzyl 2-chloro-2-trifluoromethyl-3-(1,2-dibromo-2,2-dichloroethyl)cyclopropanecarboxylate
n ²⁰ _D 1.5842 3′-(3-trifluoromethylphenoxy)-
5′-Methyl-α′-ethynylbenzyl 2-fluoro-2-fluorodichloromethyl-3-(1-
Bromo-2,2-difluoroethyl)cyclopropanecarboxylate n ²⁰ _D 1.5770 3'-Phenoxy-α'-methylbenzyl 2-chloro-2-bromo-3-(1,2-dichloro-
2,2-ditrifluoromethylethyl)cyclopropanecarboxylate n ²⁰ _D 1.5809 3′-(4-propoxyphenoxy)benzyl 2
-Chloro-2-trichloromethyl-3-(1-
Fluoroisobutyl) cyclopropane carboxylate n ²⁰ _D 1.5796 3'-Phenoxybenzyl 2,2-dibromo-3
-(2,2-dichlorovinyl)cyclopropanecarboxylate n ²⁰ _D 1.5765 3'-(4-bromophenoxy)-α'-cyanobenzyl 2-bromo-2-trifluoromethyl-
3-(2,2-dichlorovinyl)cyclopropanecarboxylate n ²⁰ _D 1.5781 3′-(4-trifluoromethylphenoxy)-
α′-Ethynylbenzyl 2-chloro-2-bromo-3-(2,2-dibromovinyl)cyclopropanecarboxylate n ²⁰ _D 1.5812 3'-(4-fluorophenoxy)-4'-fluorobenzyl 2-fluoro-2-trifluoromethyl-3-(2,2-ditrifluoromethylvinyl)cyclopropanecarboxylate
n ²⁰ _D 1.5614 3'-(3-methylphenoxy)-α'-methylbenzyl 2-chloro-2-methyl-3-(2-methyl-2-chlorodifluoromethylvinyl)cyclopropanecarboxylate n ²⁰ _D 1.5650 3'-Phenoxy-α'-cyanobenzyl 2-chloro-2-fluoro-3-(1,2-dibromo-
2,2-dichloroethyl)cyclopropanecarboxylate n ²⁰ _D 1.5823 3'-Phenoxy-α'-cyanobenzyl 2-fluoro-2-methyl-3-(2,2,2-trichloroethyl)cyclopropanecarboxylate
n ²⁰ _D 1.5687 3'-Phenoxy-α'-cyanobenzyl 2-fluoro-2-methyl-3-(2,2-dibromovinyl)cyclopropanecarboxylate
n ²⁰ _D 1.5749 3'-(4-methylphenoxy)benzyl 2,2
-Dichloro-3-(1-bromo-2,2-dichloro-3,3,3-trifluoropropyl)cyclopropanecarboxylate n ²⁰ _D 1.5785 3'-Phenoxy-α'-ethynylbenzyl 2-fluoro-2-methyl-3-(1-chloro-2-
Fluoro-2-methyl-3-bromopropyl)
Cyclopropane carboxylate n ²⁰ _D 1.5841 The compound of the present invention is a novel compound, is solid or liquid at room temperature, and is generally easily soluble in organic solvents.
Therefore, insecticides for spraying include emulsions, oils, powders,
It can be used as a hydrating agent, aerosol agent, etc. 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 and carbamate-resistant black leafhoppers.
It is useful for controlling agricultural pests such as planthoppers, stink bugs, armyworms, armyworm moths, diamondback moths, tobacco moths, bean weevils, nocturnal moths, cabbage moths, chestnut beetles, leafhoppers, aphids, and scale insects, grain storage pests such as brown 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 organophosphates and organochlorine insecticides, especially for aquatic habitats such as rice fields. It can be expected to be used in a wide range of ways to exterminate pests. In addition, the compound of the present invention has N
- Octylbicycloheptenedicarboximide (trade name MGK-264), mixture of N-octylbicycloheptenedicarboximide and arylsulfonate (tradename MGK-5026), Cinepirin 500, octachlorodipropyl ether,
The insecticidal and acaricidal effects can be further enhanced by adding a synergist such as piperonyl butoxide. If necessary, the compound of the present invention may include BHT or
Stability can be further increased by adding a stabilizer such as DBHQ or an antioxidant. The compound of the present invention may also contain other insecticides, such as organophosphorus agents such as fenitrothion, DDVP, diazinon, propaphos, and pyridafentione, NAC,
Carbamate agents such as MTMC, BPMC, PHC,
Pyrethrin, allethrin, phthalthrin, flamethrin, phenothrin, permethrin, cypermethrin, decamethrin, fuenvalerate,
Conventional pyrethroid insecticides such as fenpropanate, insecticides such as cartap, chlorphenamidine, and methomyl, or acaricides, fungicides, nematicides, herbicides, plant growth regulators, fertilizers, and other agricultural chemicals. By mixing, a multi-purpose composition with excellent effects can be obtained, labor saving, and synergistic effects between the drugs 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),
(C), (D), (E), and (F) could be obtained in good yields by any method. Synthesis Example 1 (A) Method by reaction of alcohol and carboxylic acid halide 2,2-dichloro-3-(2-chloro-2-
(trifluoromethylvinyl) cyclopropanecarboxylic acid chloride (6.3 g) to 15 ml of dry benzene
Dissolve 4.6 g of 3-phenoxy-α-cyanobenzyl alcohol in 20 ml of dry benzene.
When 3 ml of dry pyridine 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 sulfuric acid, and the benzene was distilled off under reduced pressure to give 3'-phenoxy-α'-cyanobenzyl 2,2-dichloro- 3-(2-chloro-3-trifluoromethylvinyl)cyclopropanecarboxylate
9.2g was obtained. Synthesis Example 2 (B) Method by reaction of alcohol and carboxylic acid 2-fluoro-2-bromomethyl-3-
Dissolve 5.7 g of (2,2,2-trifluoroethyl)cyclopropanecarboxylic acid and 6.0 g of 3-(3-trifluoromethylphenoxy)-α',5'-dimethylbenzyl alcohol in 50 ml of dry benzene. Then, 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 separated. The oily substance obtained by concentrating the filtrate was passed down a 100 g silica gel column to obtain 3'-(3-trifluoromethylphenoxy)-α',5'-dimethylbenzyl 2-fluoro-2-bromomethyl- 3-
9.4 g of (2,2,2-trifluoroethyl)cyclopropanecarboxylate was obtained. Synthesis Example 3 (C) Method by reaction of alcohol halide with alkali metal carboxylate 2-chloro-2-trifluoromethyl-3-
(2-oxothiolane-3-ylidenemethyl)
Sodium salt of cyclopropanecarboxylic acid 6.6
g and 5.1 g of 3-phenoxy-α-ethynylbenzyl cyclolide were suspended in 50 ml 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 nitric acid, and benzene was distilled off under reduced pressure. '-Phenoxy-α'-ethynylbenzyl 2-chloro-2-trifluoromethyl-3-(2-oxothiolane-3-ylidenemethyl)cyclopropanecarboxylate 8.2g
I got it. Synthesis Example 4 (D) Method using ester exchange reaction between alcohol and lower alkyl ester of carboxylic acid 5.7 g of methyl ester of 2-bromo-2-methyl-3-propoxyiminomethylcyclopropanecarboxylic acid and 3-(4 -Methoxyphenoxy)-α-ethynylbenzyl alcohol 5.2g
Heat to 150℃. When the temperature reaches 150°C, add 0.25 g of sodium and 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 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 sulfate, and the ether was distilled off under reduced pressure to give 3'-(4-methoxyphenoxy)-
8.7 g of α'-ethynylbenzyl 2-bromo-2-methyl-3-propoxyiminomethylcyclopropanecarboxylate was obtained. Synthesis Example 5 (E) Method by reaction of alcohol and carboxylic acid anhydride 2-chloro-2-trifluoromethyl-3-
(1-chloro-2,2-dibromoethyl)cyclopropanecarboxylic anhydride 16.0g and 3-(4
-fluorophenoxy)-α-cyanobenzyl alcohol (4.9 g) was dissolved in 50 ml of dry pyridine and stirred overnight at room temperature. The next day, the reaction solution
The 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 sulfur salt, and the ether was removed under reduced pressure to obtain a crude ester. -Fluorophenoxy)-
α′-cyanobenzyl 2-chloro-2-trifluoromethyl-3-(1-chloro-2,2-dibromoethyl)cyclopropanecarboxylate
10.6g was obtained. Synthesis Example 6 (F) Method by reaction of alcohol halide and organic tertiary base carboxylate 6.9 g of 2,2-dibromo-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid was added to 50 ml of acetone. and add 5.3 g of 3-phenoxybenzyl bromide. Add 4 ml of triethylamine with stirring and 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 sulfuric acid, and distill off the ether under reduced pressure. Leave 3′-
Phenoxybenzyl 2,2-dibromo-3-
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 cinepirin 500, 0.8% white light solution (B), 0.1% white light solution of 0.1% and phthalthrin, and allethrin, phthalthrin. The relative effectiveness of the test chemicals was calculated by determining the falling and turning rate of houseflies for each 0.2% white light solution, and the mortality rate after 24 hours was determined as follows.

【table】

[Table] From the above results, it is clear that the knockdown effect of the oil on house flies is comparable to or greater than that of phthalthrin, a conventional pyrethroid, and that its lethal efficacy is extremely superior to allethrin and phthalthrin. Ta. Test Example 2 Test Method Fish Toxicity Test - Conducted on goldfish in accordance with the toxicity test method for pesticides on fish. Insecticidal test - dilute an acetone solution of each compound with distilled water to a specified concentration, put it in a beaker, and release 20 Culex mosquito larvae. From the mortality rate after 24 hours
The 50% lethal concentration (LC ₅₀ ppm) was determined. Test Results The fish toxicity and efficacy against Culex Culex larvae of each compound are shown in the table below.

【table】

[Table] From the above results, all of the compounds used as active ingredients of the present invention have a fish toxicity of 1.3 ppm or more, and an LC ₅₀ against Culex larvae of 0.01 to 0.04 ppm, with a concentration difference of 30 to 400 times. Admitted.
On the other hand, the toxicity of compound A to fish is less than 0.1 ppm,
There was almost no difference between the LC ₅₀ and the Culex larvae. Therefore, when the present invention is used to control Culex mosquito 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 and can be prepared by a method well known to those skilled in the art, similar to 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 0.4 part of the present compound (17), 0.1 part of resmethrin,
Dissolve 1.5 parts of octachlorodipropyl ether in 28 parts of refined kerosene and fill it into an aerosol container.After attaching the valve part, 70 parts of propellant (liquefied petroleum gas) is charged under pressure through the valve part to create an aerosol. obtain. Reference Example 5 0.3 parts of the compound of the present invention (25) and 99.7 parts of clay are thoroughly ground and mixed to obtain a 0.3% powder. Reference example 6 40 parts of the present compound (36), 35 parts of diatomaceous earth, 20 parts of clay
1 part, 3 parts of lauryl 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), (12), (17), (20), (24), (29), (32), (38), (41
)
and (47) as active ingredients in water at 200ppm.
The solution was diluted to 1/10,000 are and 20 ml per pot was sprayed on rice planted in Wagner pots. After air-drying, the pots were covered with a wire mesh, 10 leafhoppers were released into the wire mesh, and the mortality rate was investigated 24 hours later. In both cases, a 100% insect mortality rate was obtained for each drug. Test Example 4 1 for 4 leaves of potted green beans 5 days after sowing
Each leaf is infested with 10 spider mites and stored in a constant temperature room at 27°C. 6 days later Compound examples (2), (5), (9), (11), (15), (18), (22), (26), (
3
1), (34), (37), (40), (44) and (46) as active ingredients were diluted with water to 500 ppm, and 10 ml of each was sprayed per pot on a turntable. After 10 days, the number of parasitized spider mites on the plants was less than 10, and no damage by spider mites was observed. Test Example 5 Compound examples (3), (6), (8), (1) obtained in Reference Example 6
3), (19), (21), (28), (30), (33), (36), (39), (4
A hydrating powder containing 2), (45) and (48) as active ingredients was diluted with water to 400 ppm, and 20 ml per pot was sprayed on cabbages planted in 1:10,000 RWagner pots. After air-drying, the leaves were placed in a jar, 10 healthy armyworm larvae were released, and the mortality rate was examined 20 hours later. Both drugs achieved a 100% mortality rate. Test Example 6 In Reference Example 5, compounds (1), (5), (10), (14), (16),
(23), (25), (27), (35), (43), (46), (49) and
(Five
0.2 g of a powder containing 0) as an active ingredient was applied to the brown planthoppers released on rice seedlings using a Belgear duster (50 cmHg, contact for 1 minute), and the mortality rate was investigated after 24 hours. Both drugs achieved a 100% mortality rate.

Claims (1)

[Claims] 1. General formula (In the formula, R ₁ represents a group represented by _the formula (), (), (), (). [ _Formula ] _[ Formula] ― …() Here, R ₆ and R ₇ are the same or different and are methyl groups,
Represents a halogen atom or halomethyl group, but R ₆ ,
R ₇ may be taken together to form a ring of [Formula] [Formula] [Formula] or [Formula]. In addition, R ₈ and R ₉ are the same or different, and are methyl groups,
It represents a halogen atom or a halomethyl group, X represents a halogen atom, and Y represents a hydrogen atom or a halogen atom. R ₁₀ represents an alkyl group having 1 to 3 carbon atoms.
R ₂ represents a halogen atom, R ₃ represents a halogen atom,
Represents a methyl group or a halomethyl group. In addition, R ₄ represents a hydrogen atom, a cyano group, a methyl group, or an ethynyl group, but when R ₆ and R ₇ both represent a halogen atom, and R ₂ and R ₃ are chlorine atoms,
R ₄ represents only a cyano group, a methyl group or an ethynyl group. R ₅ and R ₅ ' represent a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group or a lower alkoxy group. ) A low fish toxicity insecticide and acaricide characterized by containing a cyclopropanecarboxylic acid ester derivative represented by: