JPS5849523B2 - Pest control composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides compounds of the following general formula CI which are effective for controlling harmful arthropods.
The present invention relates to a pest control composition containing a substituted acetate ester shown in ) as an active ingredient, and a method for producing the composition.

[In the formula, R1 represents a hydrogen atom, a hydrogen atom, or a lower alkyl group, and A represents an oxygen atom or a sulfur atom.

X has the general formula CID, (I[) or CIV,1 (wherein,
R2 is an allyl group, a propargyl group, a benzyl group, a thenyl group, a furylmethyl group, a phenoxyl group, or a phenylthio group; R3 is a hydrogen atom, a methyl group, a trifluoromethyl group, or a norogen atom; and R2 and R3 are It also includes the case where they are bonded at the terminals to form a trimethylene chain or a tetramethylene chain.

R4 is a hydrogen atom, an ethynyl group, or a nitrile group, n is an integer of 1 to 2, and B is an oxygen atom, a sulfur atom, or a C
H=CH, R represents a phthalimide group, thiophthalimide group, di- or tetrahydro-phthalimide group, or dialkylmaleimide group, R6 represents an allyl group, propargyl group, benzyl group, or alkadienyl group. vR7
represents a hydrogen atom or a methyl group.

) represents a group represented by

Y represents a lower linear or branched alkyl group or alkenyl group.

] Since the discovery of BHC and DDT, the development of organic pesticides such as phosphors, carbamates, and pyrethroids has been remarkable, and they have flourished to the point where there is a strong correlation between the amount of pesticides used and crop yields. Accumulative and chronic poisons have become a problem, and have even encouraged the development of various resistant pests.

Therefore, it is most desirable that the substance has low toxicity, leaves little residue, decomposes quickly, and is incorporated into the ecosystem and rendered non-toxic.

Specially contains no heavy metal atoms or halogen atoms, and contains carbon, hydrogen,
Oxygen-based compounds are considered to be advantageous as pesticides.

Possible active groups of existing insecticides include organophosphorus, carbamate, chrysanthemum ester, and organochlorine, but those skilled in the art will know the advantages and shortcomings of each of these active groups. Currently, efforts are being made to discover new insecticides by understanding the long-term advantages of these derivatives and conducting searches through the synthesis of derivatives that selectively preserve only the advantages.

The inventors of the present invention believe that each of the above-mentioned active groups basically has a certain range of properties as an insecticide, and that it is difficult to go beyond that range and eliminate the drawbacks. While actively searching for an active group having a new skeleton, we discovered a substituted acetate ester represented by the general formula CI).

The compounds of the present invention have a very wide range of various advantages,
Its selectivity is strong, and depending on the compound, it is possible to create a structure that retains only its advantages as an agricultural chemical.

Traditionally, esters considered as insecticidal groups, such as phosphoric acid esters and chrysanthemum acid esters, are phosphoric acid and chrysanthemum ester, respectively.
It is thought that cyclopropanecarboxylic acid has a basic structure for its activity, with a double bond S(0) in pentavalent phosphorus being an essential structure, and chrysanthemum acid having a three-membered ring as an essential structure. As a nucleus, its activity waxes and wanes depending on changes in its surroundings.

The ester of the compound of the present invention represented by the general formula CI) is considered to have an important active basic skeleton on the acid side, and its essential structure is one hydrogen and a suitable substituent (Y) on the α-position carbon of the ester group,
It is established by having a substituted or unsubstituted furyl group or chenyl group, while the alcohol side is, as shown in the above general formula C■, l, (III), (IV),
It is an alcohol moiety of the ester group, which has been well known as a pyrethroid insecticide, and has the following general formula (V.
) We have discovered a compound that has a strong insecticidal effect when esterified with the acid represented by the following formula, and has a specific strong selectivity.

However, the order of activity in esters of existing alcohols with existing acids cannot be directly applied to the evaluation of the efficacy of the esters of the present invention, and exhibits completely different effects.

Therefore, esters obtained by combining the acid of the present invention with existing excellent alcohols do not necessarily exhibit excellent activity.

Furthermore, depending on the compatibility of the combination of the acid of the present invention with various alcohols, advantages such as rapid action, permeability, transferability to the plant body, residual effect, lethal effect, metamorphosis-disrupting property, infertility, and ability to suppress egg production can be freely obtained. It is thought that it is possible to make this possible.

In addition, regarding the spectrum of its insecticidal efficacy, the specific combination of acid and alcohol of the present invention can be selective for Coleoptera, Lepidoptera, Diptera, Orthoptera, Hemiptera, Homoptera, Acari, etc. Demonstrates non-selective efficacy.

It is also expected to be useful against pests such as nematodes.

Furthermore, because it differs from the basic structure of existing insecticides, it is of course effective against resistant insect pests, and its toxicity is generally low, as shown in the first experimental example.

To produce the substituted acetate ester represented by the general formula CI,1, use the general formula [V] Y R1+CH-COOH Cv] A [wherein R1, A and Y represent the same meanings as above.

] or its reactive derivative and the general formula CV
I,) X-OH [VI,1 [wherein, X represents the same meaning as above.

] or its halide or sulfoxylate.

The reactive derivatives of acids herein refer to acid halides, acid anhydrides, esters with low-boiling alcohols, alkali metal salts of acids, silver salts, and salts of organic tertiary bases.

In addition, the substituted acetate represented by the general formula CI) has α
Although it has optical isomers derived from the first carbon, it goes without saying that all of these esters are included in the present invention.

To describe in more detail the method for synthesizing the substituted acetate compound represented by the general formula [■], the reaction between an acid and an alcohol is carried out under appropriate dehydration conditions, such as dicyclohexyl luposiimide and an appropriate inert solvent at room temperature or This is achieved by reacting under heating.

When an acid halide is used as the reactive derivative, it is reacted with the alcohol using an organic tertiary base such as pyridine or triethylamine as a deoxidizing agent to obtain the desired ester in sufficient yield at room temperature.

Any acid chloride may be used within the scope of the present invention, but acid chloride is usually used.

Furthermore, although the presence of a solvent is not essential during the reaction, its use is desirable in order for the reaction to proceed smoothly, and an inert solvent such as benzene, toluene or petroleum benzine is usually used.

When esters of the aforementioned acids with low-boiling alcohols (e.g. methanol, ethanol, etc.) are used as reactive derivatives, they are treated in the presence of a suitable organic base catalyst, preferably an alkali metal alkoxide or sodium hydride of the corresponding low-boiling alcohol. The desired ester can be obtained in good yield by carrying out a heating reaction with the alcohol in an inert solvent such as toluene and removing the generated low-boiling alcohol from the reaction system using a rectification column.

Alternatively, when an acid anhydride is used as the reactive derivative, no reaction aid is particularly required, and the purpose can be achieved at room temperature with the alcohol.

At this time, heating and the presence of a solvent such as toluene or xylene are convenient for the reaction to proceed smoothly, but both are not essential.

When using halides or sulfoxylates of the alcohols, the acids are used as alkali metal salts, silver salts or salts of organic tertiary bases, which are formed by adding base and acid simultaneously to form during the reaction. It's okay.

During the reaction, the presence of a solvent such as benzene, acetone, dimethylformamide, etc. is desirable, and the reaction is preferably carried out by heating to the boiling point of the solvent or lower.

Chlorine and bromine atoms are often used as nitrogen atoms.

The method for producing the ester of the present invention will be explained in more detail with reference to Examples below.

Example 1 (2-7!J-3-methyl-2-cyclopentene-1
Example of production of -one-4-yl 2-(2-furyl)butyrate) 1.52 4-hydroxy-3-methyl-2-aryl-2-cyclopenten-1-one in 50 TLl of dry benzene
1 (0.01 mol) and pyridine 1.58P (0.02 mol) were dissolved.
1.73 P (0.01 mol) of monobutyryl chloride was added dropwise as a solution of 5 rILl of dry benzene over about 30 minutes.

After the dropwise addition was completed, the reaction was completed by stirring at room temperature for 3 hours.

The reaction solution was poured into 50 f of ice water to separate the benzene layer, and the aqueous layer was extracted twice with 20 r/'Ll of benzene.

The benzene layers were combined and washed with 5% aqueous hydrochloric acid, saturated aqueous sodium bicarbonate solution, and saturated brine in this order.

Benzene was distilled off under reduced pressure, and the resulting pale yellow oil was collected on silica gel 80? using benzene-n-hexane (1:3) as a developing solvent. It was purified by flowing down the column.

The desired ester 2.16f (75.0% of theoretical yield based on the carboxylic acid chloride used) was obtained as a colorless oil.

n”7 1.5 1 1 8 Example 2 (N-(3,4-dimethylmaleimido)monomethyl 2-
Production example of (5-methyl-3-furyl) monoisovalerate) 2-(5-methyl-3-furyl) monovaleric acid 9.1I
P (0.05 mol) and N-(3 4-dimethylmaleimide) monomethylol 7.76f (0.05 mol) were combined into 1
Dissolved in 00rfLl dry benzene, 1 6.5 1
P (0.08 mol) of dicyclohexyllupodiimide 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 dichlorohexyl urea was separated.

The viscous oil obtained by concentrating the filtrate was purified by flowing down a 36 oz silica gel column (developing solvent: chloroform ditetrachloride-carbon 3:1) to obtain the desired ester 9.
．． 235' (theoretical yield of 57 for the carboxylic acid used)
．． 8%) was obtained as a colorless viscous oil.

Story n 1.5747 Example 3 (4,5-tetramethylene-2-chenylmethyl 2-
(Production example of (4-methyl-2-furyl)-invalerate) 4,5-tetramethylene-2-chenylmethanol6.
73S' (0.04 mol) and ethyl 2-(4-methyl-2-furyl)monisovalerate6. 3 1 P (0.03
mol) in 100 ml of dry toluene, 0.12 ml of sodium hydride was added as a catalyst, and 50 cr.
It was attached to a rL Teflon rotating band rectification column and heated and stirred.

The reaction was completed in about 3 hours by removing the ethanol distilled azeotropically with toluene from the upper part of the rectification column.

After cooling, it was poured into 5 liters of cold water to separate the liquid.

Toluene was distilled off under reduced pressure to obtain 11.5'ft of crude ester.
I got it.

A silica gel 35010 column was flown with benzene-n-hexane (1:3) as a developing solvent to obtain the desired ester 7.03'i? (70.5% of the theoretical yield based on the ethyl ester used).

n2D' 1.5 4 8 9 Example 4 (Production example of 3-phenoxybenzyl 2-(5-chloro-2-chenyl) monoisovalerate) 3.95P (0.015 mol) m in 50rfLl of dimethylformamide
-7 enoxybenzyl bromide and 2-(5-chloro-2
-chenyl)mon-valeric acid 2.18y' (0.01 mol) and triethylamine 2.02P (0.02 mol) were added and stirred overnight at room temperature.

The reaction solution was poured into 50P ice water and extracted three times with 30ml of ether.

The ether layers were combined, washed successively with 5% aqueous hydrochloric acid, saturated aqueous sodium bicarbonate solution, and saturated brine, and then dried using anhydrous sodium sulfate.

The crude ester obtained by distilling off the ether under reduced pressure was
The target ester 3.15S' was purified as a colorless oil by flowing down a silica gel column (developing solvent: benzene-n-hexane (1:3)) (the theoretical yield for the carboxylic acid used). 78.5%).

n consideration 1, 5736 The compounds shown in the table below were obtained in the same manner as in Examples 1 to 4.

The substituted acetate compound represented by the general formula CI) of the present invention exhibits excellent insecticidal activity and is expected to have a repellent action against mites or a synergistic action with other biologically active compounds, and is useful in agriculture, horticulture, forestry, It can be provided widely and inexpensively as a composition for sanitary purposes and for controlling stored grain pests and mites.

In practice, when using these compounds, suitable solvents, fillers, diluents, activators, dispersants, surfactants, wetting agents,
By blending appropriate amounts of one or more of pressure agents, emulsifiers, and food attractants, you can create emulsions, wettable powders, powders, granules, fine granules, powders, liniments, oils, aerosols, and mosquito coils. , smoke agent, heating fumigant, electric mosquito repellent, bait, etc.

In order to make it clearer that the composition provided by the present invention is excellent, an experimental example of the effect will be shown below.

Example 1 An emulsion is prepared by blending 25% of each of the compounds (1) to (20) of the present invention, 50% of xylene, and 25% of Solpol SM-200 (registered trademark of Toho Chemical).

Rice is grown 45 days after sowing in a 1/5000a Wagner pot, and the emulsion obtained by the above formulation is diluted 400 times with water and sprayed at a rate of 10rrLl/pot.

If you cover it with a cylindrical wire mesh and release about 30 adult black leafhoppers into it, in either case, after one day, 8
It was possible to kill more than 0% of leafhoppers.

Experimental Example 2 Among the emulsions prepared in Experimental Example 1, compounds (1), (4), (5), (6), aυ, and (20) of the present invention were each diluted with water to ippm. ,3
A 200ml volume of the mixture was poured into a 00d glass beaker, and 30 Culex mosquito larvae were released into the beaker, and after being left for one day, survival or death was observed.

Experimental Example 3 Compounds of the present invention (1), (2), (4), (6), (7),
Dissolve (8), (9), αυ, (19) in acetone,
0.5 on the bottom of a waist-high glass petri dish with a diameter of 14 cIrL.
? (ai)/m'.

After the acetone was completely vaporized, 10 adult German cockroaches were released, and after 24 hours of contact, survival and death were examined.

As is clear from the above experimental examples, since the compound of the present invention exhibits excellent biological activity, the composition of the present invention can be used for planthoppers, blacktip reef sharks, armyworms, armyworms, etc.
It is extremely useful for controlling not only pesticide pests and forest pests such as the staghorn moth, cabbage moth, cabbage beetle, and forest insects, but also sanitary pests such as mosquitoes, fly cockroaches, grain storage pests such as the black elephant, and mites.

It is particularly excellent in that it can be freely used for crops before harvesting, home gardening, greenhouse cultivation, food-related packaging materials, etc. because it has low toxicity and is harmless when stored.

In preparing the composition of the present invention, it is possible to achieve a better control effect by combining two or more of the compounds of the present invention, and other insecticides such as DDT,
BHC, organic chlorine agents such as methoxychlor, Sumithion (registered trademark of Sumitomo Chemical), DDVP, diazinon,
Fenthion, Cyanox (registered trademark name of Sumitomo Chemical)
organic phosphors such as ■-naphthyl N-methyl carbamate, 3゜4-dimethylphenyl N-methyl carbamate, 3,5-dimethylphenyl N-methyl carbamate, carbamate agents such as pyrethrin, allethrin, neopinamine ( Sumitomo Chemical (registered trademark), Cryslon (Sumitomo Chemical (registered trademark)) and their respective geometric isomers, optically active forms, or other known cyclopropane carboxylic acid ester agents, and their synergist piperonyl butoxide , sulfoxide, safroxane, S-421, etc., and terephthalic acid, isophthalic acid, BHT when used as a heat fumigant, phenol derivatives as stabilizers, bis-phenol derivatives, phenyl α-naphthylamine, phenyl-β-naphthylamine, phenetidine, etc. Arylamines such as acetone condensates, other padan,
By mixing insecticides such as Galecron, acaricides, fungicides, nemicides, herbicides, fertilizers, and other agricultural chemicals, a multipurpose composition with excellent efficacy can be obtained, saving labor and reducing the need for chemicals. A synergistic effect can also be expected.

Next, the preparation and effects of the composition of the present invention will be explained using formulation examples and examples, but the scope of the present invention is of course not limited to the following examples.

Formulation example 1 Compounds of the present invention (1), (2), (6), (13), (
14), 20 parts of each of the decoys, 10 parts of Sumithion (same as above), 10 parts of Solpol SM-200 (same as above), and 60 parts of xylol, and stir well to mix and dissolve these to form an emulsion. get.

Formulation Example 2 2 parts each of the compounds of the present invention (2), (4), (13), and (20), 1 part each of 3,4-dimethylphenyl N-methyl carbamate, and 2 parts piperonyl butoxide. was added, dissolved in 20 parts of acetone, 95 parts of 300 mesh diatomaceous earth was added, filled in a shaker, stirred and mixed, and the acetone was removed by evaporation to obtain each powder.

Formulation Example 3 Each of the compounds of the present invention (1), (5), (6), (7), and (2) is dissolved in white kerosene in an amount of 0.5 parts to make the total 100 parts to obtain each oil solution.

Formulation Example 4 10 parts of 1-naphthyl-N methyl carbamate was added to 10 parts of the present compound (2), and Solpol SM-200 (
5 parts (same as above) were thoroughly mixed, 75 parts of 300 mesh talc were added, and the mixture was sufficiently stirred and mixed in a shaker to obtain a wettable powder.

Formulation Example 5 0.31 each of the compounds of the present invention 10), (15), and 08)
Add allethrin 0.3i to each, methanol 20rf
Dissolved in Ll, stirred and mixed uniformly with 99.4P of mosquito coil carrier (mixing tab powder: lees flour: wood flour in the ratio of 3:5:1), evaporated methanol, and added 150rrLl of water. In addition, each mosquito coil can be obtained by thoroughly kneading the mixture and molding and drying it.

Formulation example 6 Insecticidal active ingredients with the composition shown in the formulation table below are xylol,
Dissolve 15 parts in a 1:1 mixed solvent of refined kerosene, fill it into an aerosol container, attach a valve part, and pressurize 85 parts of a propellant (e.g. Freon, liquefied petroleum gas, etc.) through the valve part. If you fill it up, you get an aerosol.

Example 5 Each powder obtained according to Formulation Example 2 was made into a powder having a diameter of 14 crr.
Spread butter evenly at a rate of 21/m on the bottom of a L-sized glass petri dish, and apply butter to the wall, leaving about 1 crrL at the bottom.

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.

Example 6 Approximately 50 adult house flies were placed in a 70crrL cubic glass box.
Each of the oils obtained according to the free-for-all formulation example 3 had 0. 7
If you spray rul at a pressure of 1-5k9/crA,
After 10 minutes, more than 80% of the flies were able to fall and turn upside down.

Example 7 Approximately 5 adults of Achaie japonica were placed in a 70 cIrL cubic glass box.
0 mosquito coils were released, and 1 of each mosquito coil obtained according to Formulation Example 5.
By placing a stick with both ends lit at the center of the bottom of the glass box, more than 80% of the mosquitoes were able to fall and turn upside down after 20 minutes.

Example 8 A 200-fold diluted solution of each of the emulsions obtained in Formulation Example 1 of the compound of the present invention was sprayed at 100 liters/field onto a field of 5- to 6-leaf radish in which a large number of green peach aphids were infested.

A parasitic rate survey two days later showed that the density had decreased to less than 1/10 of the pre-spraying density in each plot.

Example 9 Each of the compounds (2) and (13) of the present invention and piperonyl phthoxide were added in an amount of 5 times the effective amount, and an acetone solution of a predetermined concentration was prepared. It was applied to adult house flies using a microinjector, and The synergistic effect of ronyl butoxide was observed.

As a result, the above-mentioned compounds of the present invention exhibited stronger insecticidal activity when piperonyl butoxide was added than when they were used alone.

Of course, piperonyl butoxide has no insecticidal effect on its own.

Claims (1)

[Scope of Claims] 1 General formula [wherein R1 represents a hydrogen atom, a halogen atom or a lower alkyl group, and A represents an oxygen atom or a sulfur atom. X is a general formula (wherein R2 is an allyl group, a propargyl group, a benzyl group, a thenyl group, a furylmethyl group, a phenoxyl group, or a phenylthio group, and R3 is a hydrogen atom, a methyl group, a trifluoromethyl group, or a halogen atom, It also includes a case where R2 and R3 are bonded at the terminal to form a trimethylene chain or a tetramethylene chain. R4 is a hydrogen atom, an ethynyl group, or a nitrile group, n is an integer of 1 to 2, and B is an oxygen atom. , sulfur atom or -C
H=CH, R5 is a phthalimide group, thiophthalimide group, di- or tetrahydrophthalimide group, or dialkylmaleimide group, R6 is an allyl group, propargyl group, benzyl group, or alkadienyl group, vR7 is a hydrogen atom or a methyl group. represent. ) represents a group represented by Y represents a lower linear or branched alkyl group or alkenyl group. ] A pest control composition comprising a substituted acetate as an active ingredient. 2 General Formula [In the formula, R1, A and Y each have the same meaning as stated in Claim 1. ] or its reactive derivative represented by the general formula [wherein, X has the same meaning as stated in claim 1]. A pest control composition characterized in that a substituted acetate represented by the general formula according to claim 1 is obtained by reacting an alcohol, a halide or a sulfoxylate thereof, which is reduced by Manufacturing method.