JPS596848B2 - Isovaleric acid ester derivative, method for producing isovaleric acid ester derivative, insecticide containing isovaleric acid ester derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula [wherein (1) A represents O or NH, R1 represents an alkyl group, alkenyl group, or alkynyl group, and R2 represents a hydrogen atom or a cyano group ( However, R
(2) A represents O or S, R1 represents a haloalkyl group, and R2 represents a hydrogen atom or a cyano group (except when 1 represents an alkynyl group and R2 represents a cyano group); (3) A is S
, R1 represents an alkyl group, R2 represents a hydrogen atom, cyano group or ethynyl group, or (4) A represents O or NH, R1 represents an alkenyl group or alkoxyalkyl R2 represents an ethynyl group (however, except when A is O and R1 represents an alkenyl group).

The present invention relates to isovaleric acid ester derivatives shown in ], their optical and geometrical isomers, and their production methods. Various alcohol components of cyclopropane carboxylic acid esters have been studied and put into practical use, but they are susceptible to oxidative decomposition by light, and their outdoor use has been restricted. Recently, research into acid components has become active, and a compound that is more stable to light than conventional pyrethroids by replacing the methyl group with a halogen atom has been discovered. However, when considering issues such as environmental pollution and chronic toxicity, compounds with structures similar to naturally occurring organic compounds, mainly consisting of carbon, hydrogen, oxygen, and nitrogen, are considered to be advantageous as insecticidal ingredients. . As a result of repeated research, the present inventor has found that the compound represented by the above formula (1) has an extremely excellent insecticidal effect as an insecticidal ingredient against various sanitary pests and agricultural and horticultural pests, while having extremely low toxicity to warm-blooded animals. We learned that it is much more stable against light than conventional pyrethroids. The present invention was completed based on the above findings.

The compound represented by the above formula (1) used as an active ingredient in the present invention can be prepared by the general formula 1 (
Here A is 0. S. NH, and R1 represents an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, or an alkoxyalkyl group.

) or its reactive derivative represented by the general formula (where R2 represents a hydrogen atom, a cyano group, or an ethynyl group).

) or a reactive derivative thereof. Examples of reactive derivatives of carboxylic acids include acid halides, anhydrides, lower alkyl esters, and alkali metal salts. Examples of reactive derivatives of alcohol include chloride. The reaction is carried out in a suitable solvent, optionally in the presence of an organic or inorganic base as a deoxidizing agent or catalyst, or an acid, and optionally with heating. Representative examples of the compound represented by the above formula (1) are as follows. 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, as an insecticide for spraying, it can be used as an emulsion, oil, powder, wettable powder, aerosol, etc. It can also be mixed with wood flour or other suitable base material and used as an insecticide for fumigation such as mosquito coils. can do. In addition, this active ingredient is dissolved in a suitable organic solvent and immersed in a mount, or adsorbed on a suitable filler and molded, or dissolved in a suitable solvent and heated and evaporated with a suitable heating element to be used as a so-called electric mosquito repellent. When using mosquito coils, it also shows excellent effects, just like mosquito coils. The compound of the present invention is more stable against light than conventional pyrethroids, and can also be used as an agricultural and horticultural insecticide. In addition, the compounds of the present invention include N-octylbicycloheptenedicarboximide (trade name MGK264), N-
Mixture of octylbicycloheptenedicarboximide and alkylaryl sulfonate (trade name MGK=5
026), octachlorodipropyl ether, piperonyl butoxide, etc., the insecticidal efficacy can be further enhanced.

Furthermore, the present invention can be improved by adding phenolic or amine antioxidants such as 2,6-ditertiarybutyl-4-methylphenol (BHT) and 2,6-ditertiarybutylphenol. The stability of the compound can be further improved. In addition, an even more effective insecticide can be obtained by using it in combination with conventional pyrethroids such as allethrin, starthrin, resmethrin, flamethrin, phenothrin, permethrin, sabermethrin, decametrin, fuenvalerate, etc. Next, the insecticidal test results of insecticides containing the compound of the present invention as an active ingredient will be shown.

Test Example 1 Insecticidal test by spraying 0.2% white light solution of the 23 compounds of the present invention of the above compound examples, 0.2% and piperonyl butoxide 0.8%
white light solution (B), 0.1% and phthalthrine 0.1%
For white light solutions (0 and 0.2% white light solutions of allethrin and phthalthrin), the falling and turning rate of house flies was determined using the spray drop method using house flies, and the relative effectiveness of the test drug was calculated. The mortality rate after hours was determined as follows.

Test Example 2 Insecticidal Test by Fumigation Mosquito coils containing 0.5% of insecticidal ingredients were prepared and tested for their effectiveness in causing adult Culex mosquitoes to fall and roll over.

In this experiment, the relative effectiveness of the incense sticks was calculated according to the method of Nagasawa, Katsuta, et al., Vol. 16 (1951), p. 176, and the results were as follows. The sample drug number is the same as that of the active ingredient example above. Examples of the present invention will be shown below.

The compound names are the same as those in the active ingredient examples above. Example 1 3.87 α-(1-methyl-propyloxy)-isovaleric acid chloride was dissolved in 15 ml of dry benzene, and 4.1 t of m-phenoxybenzyl alcohol was dissolved in 20 ml of dry benzene. In addition, when 3 ml of dry pyridine was further added as a condensation aid, crystals of pyridine hydrochloride were precipitated.

After sealing the cap and leaving it overnight at room temperature, the pyridine hydrochloride was removed, and the benzene solution was dried with sulfuric acid and concentrated at low temperature (bath temperature below 50°C) under reduced pressure in a nitrogen stream to obtain α-(1-methyl). -Propyloxy)-isovaleric acid d-phenoxybenzyl ester 6.2y was obtained. Example 2 3.47 ml of α-(1-methyl-allylamino)-isovaleric acid and 4.77 ml of α-cyano-m-phenoxybenzyl alcohol were dissolved in 150 ml of benzene, and while stirring the solution vigorously, 5 ml of concentrated sulfuric acid was added. Add.

Heat to reflux while stirring, and remove water produced by azeotropy using a dehydrating agent. Benzene was replenished from time to time and the reaction was carried out for about 4 hours. After washing the reaction solution with aqueous sodium bicarbonate and brine, benzene was distilled off under reduced pressure to obtain 6.97% of α7-cyano-d-phenoxybenzyl ester of α-(1-methyl-allylamino)-isovaleric acid. Obtained. Example 3 4.4f of the methyl ester of α-(1,2-dimethyl-propylthio)-isovaleric acid and 4.6y of α-ethyl-1m-phenoxybenzyl alcohol are heated to 150'C.

When the temperature reaches 150°C, 0.25y of sodium is added and the distillation of methanol is started. After the distillation of methanol has stopped, 0.257 ml of sodium is further added, the temperature is maintained at around 150° C., and the above operation is repeated 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 salt water, and the ether was distilled off under reduced pressure to obtain α.
α7-ethynyl-d-phenoxybenzyl ester of 1(1,2-dimethyl-propylthio)-isovaleric acid 7.1y was obtained. Example 4 Sodium salt of α-(1-ethylpropargyloxy)-isovaleric acid 4
．． 27 and 4.5 t of m-phenoxybenzyl chloride were dissolved in 50 ml of benzene and reacted under reflux in a nitrogen stream for 3 hours.The reaction solution was cooled and the precipitated salt was separated, and then dissolved in brine. After thorough washing, the residue was dried over nitric acid, and benzene was distilled off under reduced pressure to obtain 7.2y of M-phenoxybenzyl ester of α-(1-ethylpropargyloxy)-isovaleric acid.

Example 5 4.87 g of α-(1-methyl-2,2-dichloroethylthio)-isovaleric acid anhydride and 4.27 g of α-cyano-m-phenoxybenzyl alcohol were mixed, and 98 g. Gradually add 87% sulfuric acid to 80-10%
After reacting at 0°C for 3 hours, it was dissolved in ether, and the ether solution was thoroughly washed with a sodium bicarbonate solution and a saline solution, and then dried with salt solution.
The ether was distilled off under reduced pressure to give α-(1-methyl-2.2
-dichloroethylthio)-isovaleric acid α7-cyano d-phenoxybenzyl ester 7.07 was obtained.

Example 6 3.87 α-(1-ethoxy-propyloxy)-isovaleric acid was dissolved in 50 m
1 and add 5.97 g of α-1ethynyl-1m-phenoxybenzyl bromide.

Add 4 ml of triethylamine while stirring and heat to 60-80°C.
After reacting for 3 hours, the ether solution was thoroughly washed with aqueous sodium bicarbonate and brine, dried over nitric acid, and the ether was distilled off under reduced pressure to give α-(1-ethoxy-propyloxy)- 6.97% of α5-ethynyl-d-phenoxybenzyl ester of isovaleric acid was obtained. Reference Example 1 White kerosene was added to 0.2 parts of the compound (2) of the present invention, and the total amount was 1 part.
0.2% oil solution is obtained as 00 parts.

Reference Example 2 White kerosene is added to 0.2 parts of the compound (5) of the present invention and 0.8 parts of piperonyl butoxide to make a total of 100 parts to obtain an oil solution.

Reference Example 3 Solpol SM-200 (
10 parts of Toho Chemical (registered trademark) and 70 parts of xylene were added and mixed and dissolved with stirring to obtain a 20% emulsion.

Reference example 4 0.4 part of the present compound (9), 0.1 part of resmethrin,
Refined 1.5 parts of octachlorodiprobyl ether to 2 parts of kerosene
After dissolving the mixture in 8 parts and filling it into an aerosol container and attaching a valve part, 70 parts of a propellant (liquefied petroleum gas) is pressurized and filled through the valve part to obtain an aerosol.

Reference example? Compound (15) of the present invention 0.5y. BHT0.5y is used as a base material for mosquito coils such as pyrethrum extraction lees powder, wood flour, and marten powder.99.
07 to prepare a mosquito coil by a known method.

Reference Example 6 Compound (18) of the present invention 0.4y,. MGK-50261
.

Reference Example 7 3 parts of the compound (21) of the present invention and 97 parts of clay are thoroughly ground and mixed to obtain a 3% powder.

Reference Example 8 40 parts of the present compound (23), 35 parts of diatomaceous earth, clay 2
0 parts of lauryl sulfonate, and 2 parts of carboxymethyl cellulose are ground and mixed to obtain a wettable powder.

Test Example 3 Ten 3rd instar larvae of Spodoptera japonica were placed in a waist-high glass shear with a diameter of 14 (V7!), and among the emulsions obtained in Reference Example 3, compounds of the present invention (1), (3), and (6) were placed in a scattering tower. (
8) Spray 1 ml of a 200-fold diluted solution of each emulsion containing (10), (16), (19), and (22) with water, transfer to a waist-height petri dish containing feed in advance, and leave it for 2 days. We were able to kill more than 80% of the Spodoptera spp.

Test Example 4 Compounds of the present invention (2) (5) (7) (12) (14) of the emulsion obtained in Reference Example 3 were applied to a radish field at the 5-6 leaf stage where a large number of green peach aphids were infested. )(19)(2
A 200-fold dilution of each emulsion containing 3) with water was added to 10
01/Scattered per counter.

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.

Test Example 5 Rice was grown 45 days after sowing in a 1/50,000 Wagner Bottle, and among the wettable powders obtained in Reference Example 8, compounds of the present invention (1) (4) (9) ( 11)(13)(
18) Spray a 400-fold dilution of each wettable powder containing (20) with water at a rate of 10 ml/bottle.

Claims (1)

[Claims] 1. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
...(I) [In the formula, (1) A represents O or NH, R_1 represents an alkyl group, alkenyl group, or alkynyl group, and R_2 represents a hydrogen atom or a cyano group (provided that R_1 is (2) A represents O or S, R_1 represents a haloalkyl group, and R_2 represents a hydrogen atom or a cyano group (except when A is an alkynyl group and R_2 represents a cyano group);
(except when R_2 represents a hydrogen atom) or (3)A
represents S, R_1 represents an alkyl group, R_2 represents a hydrogen atom, a cyano group, or an ethynyl group, or (4) A represents O or NH, R_1 represents an alkenyl group or an alkoxyalkyl group, and R_2 represents an alkenyl group or an alkoxyalkyl group. Represents an ethynyl group (provided that A is O and R
(Except when _1 represents an alkenyl group). ] and its optical and geometric isomers. 2 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
......(II) (where R_1 represents an alkyl group, alkenyl group, alkynyl group, haloalkyl group, or alkoxyalkyl group, and R_2 represents a hydrogen atom, cyano group, or ethynyl group). The isovaleric acid ester derivative and stereoisomer thereof according to claim 1. 3 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
...(III) (where R_1 represents an alkyl group, alkenyl group, alkynyl group, haloalkyl group, or alkoxyalkyl group, and R_2 represents a hydrogen atom, a cyano group, or an ethynyl group). The isovaleric acid ester derivative and stereoisomer thereof according to claim 1. 4. The compound according to claim 2, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 5. The compound according to claim 2, which is a compound represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 6. The compound according to claim 2, which is a compound represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 7. The compound according to claim 2, which is a compound represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 8. The compound according to claim 3, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 9. The compound according to claim 3, which is a compound represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼. 10. The compound according to claim 3, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 11. The compound according to claim 3, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 12 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(IV) (Here, A and R_1 are the following general formula (I)
represents the meaning given by ) Carboxylic acids or their reactive derivatives and general formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼・・・・・・・・・
(V) (where R_2 represents the meaning given in the following general formula (I)) A general formula characterized by reacting with an alcohol or its reactive derivative ▲ Numerical formula, chemical formula, table, etc. ▼・・・・・・・・・・・・・・・(I) [In the formula, (1) A represents O or NH, R_1 represents an alkyl group, alkenyl group, or alkynyl group, and R_2 represents hydrogen (2) A represents O or S, R_1 represents a haloalkyl group, and R_2 represents a hydrogen atom or a cyano group; represents a group (where A is S)
(except when R_2 represents a hydrogen atom) or (3)A
represents S, R_1 represents an alkyl group, R_2 represents a hydrogen atom, cyano group, or ethynyl group, or (4) A represents O or NH, R_1 represents an alkenyl group or an alkoxyalkyl group, and R_2 represents an alkenyl group or an alkoxyalkyl group. Represents an ethynyl group (provided that A is O and R
(Except when _1 represents an alkenyl group). ] A method for producing an isovaleric acid ester derivative.