JPS5928538B2 - 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 (1): However, when considering problems such as environmental pollution and chronic toxicity, it is important to consider the following: Compounds having this structure are considered to be advantageous as future 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 (1) used as an active ingredient in the present invention is prepared by the general formula (): (wherein R1 represents the meaning given in the above general formula (1)) according to the general method for ester production.

) and a carboxylic acid represented by the general formula (V) (wherein R2 represents the meaning given in the general formula (1) above).

) or a reactive derivative thereof. Examples of reactive derivatives of carboxylic acids include acid halides, acid 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 or acid as a deoxidizer or catalyst, 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 new compound, which is solid or liquid at room temperature, and
It 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 can be dissolved in a suitable organic solvent and soaked in a mount, or adsorbed on a suitable filler and molded, or dissolved in a suitable solvent and heated and evaporated using a suitable heating element to make a so-called electric mosquito repellent. 11
ri heri-ko dohachi 1 Mi must white JZl mouth ↓≠) r1-”
−≠Fuda J indicates. 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. Moreover, the compound of the present invention has N-
octylbicycloheptene dicarboximide (trade name MGK264), a mixture of N-octylbicycloheptenedicarboximide and alkylaryl sulfonate (trade name MGK-5026), octachlorodipropyl ether, piperonyl butoxide, etc. The insecticidal efficacy can be further enhanced by adding a synergist.

Furthermore, the compounds of the present invention can be prepared by adding phenolic antioxidants such as 2,6-di-tert-butyl-4-methylphenol (BHT) and 2,6-ditertiary-butylphenol, or amine-based antioxidants. The stability of can be further increased. In addition, an even more effective insecticide can be obtained by using it in combination with conventional pyrethroids such as allethrin, phthalthrin, resmethrin, flamethrin, phenothrin, permethrin, sabermethrin, decametrin, and fuenvalerate. 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 1 test 0.2% white light solution (4) of the seven compounds of the present invention of the above compound examples, 0.2% and piperonyl butoxide 0.8
% white lamp solution (B), 0.1% and phthalthrine 0.1
% white light dissolution C) and 0.2% white light solutions of allethrin and phthalthrin, the spray drop method was followed using houseflies, and the drop-upside-down rate of the houseflies was determined to determine the relative effectiveness of the test drugs. After calculation, the mortality rate after 24 hours was determined as follows.

Test Example 2 Insecticidal test by fumigation Mosquito coils containing 0.5% of the insecticidal ingredient were prepared and tested for their effectiveness in making adult Culex mosquitoes fall and roll over.

This experiment was conducted according to the method of Nagasawa, Katsuta et al., Vol. 16 (1951), p. 176, and the relative effectiveness of the incense sticks was calculated 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 4.4 f of α-cyclohexyloxy-isovaleric acid chloride was dissolved in 15 ml of dry benzene, and d
-Cyano-m-phenoxybenzyl alcohol 4.7y
was dissolved in 20 ml of dry benzene, and then 3 ml of dry pyridine was added as a condensation aid to precipitate crystals of pyridine hydrochloride.

After sealing the cap and leaving it overnight at room temperature, the pyridine hydrochloride was removed, and the benzene solution was dried with borax and concentrated at low temperature (bath temperature below 50'C) under reduced pressure in a nitrogen stream to obtain α-cyclohexyloxy-iso. Valeric acid α1-cyano-ml
-Phenoxybenzyl ester 6.1y was obtained. Example 2 4.1 t of methyl ester of d-(1,1-ethylenedioxy-methyloxy)-isovaleric acid and 4.6 t of α-1-ethyl-1-m-phenoxybenzyl alcohol at 150 t
Heat to ℃.

When the temperature reaches 150°C, 0.25f of sodium is added and methanol distillation is started. When the distillation of methanol has stopped, an additional 0.25y of sodium is added, and the temperature is maintained at around 150°C until the theoretical amount of methanol is obtained, and the above operation is repeated. 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 borax, and the ether was distilled off under reduced pressure to give α-(1,1-ethylenedioxy- 6.97 of α(ethynyl (1 ml)-phenoxybenzyl ester of methyloxy)-isovaleric acid was obtained. Reference Example 1 White kerosene was added to 0.2 part of the compound of the present invention (2), and the total amount was 10
A 0.2% oil solution is obtained as 0 parts.

Reference Example 2 White kerosene is added to 0.2 parts of the present compound 0) and 0.8 parts of piperonyl butoxide to make a total of 100 parts to obtain an oil solution.

Reference Example 3 10 parts of Solpol SM2OO (registered trademark of Toho Chemical) and 70 parts of xylol were added to 20 parts of the compound (7) of the present invention, and the mixture was mixed and dissolved with stirring to obtain a 20% emulsion.

Reference Example 4 0.4 part of the compound of the present invention (4), 0.1 part of resmethrin, and 1.5 parts of octachlorodipropyl ether were mixed with 28 parts of refined kerosene.
After filling 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 5 Compound (7) of the present invention 0.57, BHTO. 5 tons of base material for mosquito coils such as pyrethrum extracted lees powder, wood flour, marten powder, etc.99.0
7 to obtain a mosquito coil by a known method.

Reference example 6 Compound of the present invention (7) 0.47, MGK-50261.0
7 is uniformly mixed into a mosquito coil base material 98.6y to obtain a mosquito coil by a known method.

Reference Example 7 3 parts of the compound (6) 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 (7), 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 1 Test Example 3 Ten 3rd instar larvae of Spodoptera japonica were placed in a waist-high glass jar with a diameter of 14c7n, and among the emulsions obtained in Reference Example 3, compounds of the present invention (1X3) (4) (6) were placed in a scattering tower.
Spray 1 ml of a 200-fold dilution of each emulsion with water, transfer to a waist-high petri dish containing feed, and leave to stand. After 2 days, 80
It was possible to kill more than % of insects.

Test example 4: 5 of a field where a large number of green peach aphids were infested
A 200-fold dilution with water of each of the emulsions containing the compounds (2), (4), and (7) of the present invention among the emulsions obtained in Reference Example 3 was sprayed on a radish field at the ~6-leaf stage at a rate of 1001/h. did.

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 (1), (5), and (6) of the present invention were used. Spray a 400-fold dilution of each hydrating agent contained in water at a rate of 10 ml/pot.

Claims (1)

[Claims] 1. General formula (I): ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 is a cycloalkyl group, a cycloalkenyl group, an indanyl group, a haloalkenyl group, an alkylcarbonyl group) ,
It represents a haloalkylcarbonyl group, an alkenylcarbonyl group, or a haloalkenylcarbonyl group, and R_2 represents a hydrogen atom or a cyano group. ) and its optical and geometric isomers. 2. The compound according to claim 1, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 3. The compound according to claim 1, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 4. The compound according to claim 1, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 5 General formula (IV): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(IV) (Here, R_1 represents the meaning given by the following general formula (I).) Carboxylic acid or its reactive derivative represented by the general formula (V): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ( Here, R_2 represents the meaning given by the following general formula (I). General formula (I) characterized by reacting with the alcohol shown in ) or its reactive derivative: ▲ Numerical formula, chemical formula, table, etc. ▼・・・・・・・・・(I) (In the formula, R_1 is a cycloalkyl group, a cycloalkenyl group, an indanyl group, a haloalkenyl group, an alkylcarbonyl group,
It represents a haloalkylcarbonyl group, an alkenylcarbonyl group, or a haloalkenylcarbonyl group, and R_2 represents a hydrogen atom or a cyano group. ) A method for producing an isovaleric acid ester derivative.