JPS6050777B2 - Isovaleric acid ester compound and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (wherein A is O or NH, and R represents a cyano group or an ethynyl group).

R1 is R is a cyano group, a cyclohexylmethyl group,
Represents a cyclohexylethyl group, (4-methyl-1-cyclohexenyl)isopropyl group or a morpholinoethyl group, and when R is an ethynyl group, a (1-cyclopentenyl)-methylethyl group, a 3-pyrrolidinyl-2-methylpropyl group or a morpholinoethyl group. Represents a peridinoisopropyl group.

), its optical and geometric isomers, and its production method. Various alcohol components of cyclopropanecarboxylic acid esters have been studied and put into practical use, but they are susceptible to oxidative decomposition by light and have been restricted in their use outdoors. Recently, research on acid components has become active,
A compound more stable to light than conventional pyrethroids was discovered by replacing the methyl group with a halogen atom. 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 future insecticidal ingredients. It will be done. As a result of repeated research, the present inventor has found that the compound represented by formula (1) above has an extremely excellent insecticidal effect on various sanitary pests and agricultural and horticultural pests as an insecticidal ingredient, 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 is prepared according to the general method for ester production using the general formula (where A is O or NH, and R1 is an alcohol moiety where R is a cyano group). , cyclohexylmethyl group, cyclohexylethyl group, (4-methyl-1-cyclohexenyl)isopropyl group or morpholinoethyl group, and when R is an ethynyl group, (1-cyclopentenyl)-methylethyl group, 3-pyrrolidinyl-2-methyl Represents a propyl group or a piperidinoisopropyl group.

) or its reactive derivative represented by the general formula (where R represents a cyano group or an ethynyl group).

) or its reactive derivative. 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, if necessary, in the presence of an organic or inorganic base as a deoxidizing agent or catalyst, or an acid, and if necessary, with heating. Representative examples of the compound represented by the above formula (1) are as follows. α′- of α-cyclohexylmethyloxyisovaleric acid
Cyano m-phenoxybenzyle*K STER NROl
．． 54O8 α-[2-(4'-Methyno-cyclohexenyl)-isopropyloxy]-isovaleric acid α'-
Cyano m-phenoxybenzyl ester 01.5673 α-(2-morpholinoethyloxy)-isovaleric acid α′-cyano m-phenoxypene, dyl ester n tongue 01.5714 α- Cyclohexylmethylamino-isovaleric acid α'-cyano m-phenoxybenzyle ☆A stern n
01.5590 α-[2-(4'-Methynocyclohexenyl)-isopropylamino]-α'- of isovaleric acid
Cyano m-phenoxybenzyl ester nji 01.5
846α-(2-morpholinoethylamino)-isovaleric acid α′-cyano m-phenoxypene**
Dyl ester 01.5872 α'-monoethynyl-m-phenonoxybenzyl ester of α-(2-piperidinoisopropylamino)-isoparelianic acid 01.5581 α-(2-methyl-3-pyrrolidinyl-propyloxy) )-α′-monoethynyl*1m-phenoxybenzyl ester of isovaleric acid nji 01.5430 α′-cyano m-phenoxybenzyl ester of α-(2-cyclohexyl-ethyloxy)-isovaleric acid nji 01 .5504 α'-monoethynyl-m-phenoxybenzyl ester of α-[2-(1-cyclopentenyl)-propylamino]-isovaleric acid. It is liquid and 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. I can do that. In addition, this active ingredient can be dissolved in an appropriate organic solvent and immersed in a mount, or adsorbed on an appropriate filler and molded, or dissolved in an appropriate solvent and heated and evaporated with an appropriate heating element to be used as a so-called electric mosquito repellent. When used, it is also as effective as mosquito coils.
The compound of the present invention is more stable to 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 MGK-264), N
-Mixture of octylbicycloheptenedicarboximide and alkylaryl sulfonate (trade name MGK-
5026), octachlorodipropyl ether, piperonyl butoxide, etc., the insecticidal efficacy can be further enhanced.

Furthermore, the compounds of the present invention can be improved by adding phenolic or amine antioxidants such as 2,6-ditertiarybutyl-4-methylphenol (BHT) and 2,6-ditertiarybutylphenol. Stability 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, cypermethrin, decametrin, and fuenvalerate.

Next, the performance of insecticidal tests 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 10 compounds of the present invention of the above compound examples, 0.2% white light solution (B) of 0.8% piperonyl butoxide, Using house flies, the falling and turning rates of house flies were determined according to the spray drop method using a white light solution (C) containing 0.1% phthalthrin and 0.1% phthalthrin, and 0.2% white light solutions of allethrin and phthalthrin. The relative effectiveness of the reagents was calculated, and the mortality rate after 24 hours was determined as follows.

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

This experiment was carried out in accordance with the method of Nagasawa, Katsuta et al., Vol. 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. ?
Qualitative test The test was conducted by spreading 10 mg of the sample thinly on a glass shear dish (36d), exposing it to sunlight outdoors on a sunny day in April, and quantifying the amount of the compound remaining after a certain period of time by gas chromatography.

The test drug numbers were the same as the compound example numbers of the present invention, and several recently developed pyrethroids were used as control drugs.

The test results showed that the compound of the present invention had extremely superior light resistance compared to the conventional pyrethroid as a control.

Example 1 4.7 q of α-cyclohexylmethyloxy-isovaleric acid chloride was dissolved in 15 ml of dry benzene, and 4.7 q of α-cyano m-phenoxybenzyl alcohol was dissolved in this.
．． Add 7y dissolved in 20ml of dry benzene,
Furthermore, when 3TI of dry pyridine is added as a condensation aid, crystals of pyridine hydrochloride are precipitated.

After sealing the cap and leaving it at room temperature overnight, the pyridine hydrochloride was removed, and the benzene solution was dried with nitric acid and concentrated under reduced pressure in a nitrogen stream at low temperature (bath temperature below 50°C) to give α-cyclohexylmethylene. Example 2 6.4q of α″-cyano-m-phenoxybenzyl ester of α-(2-piperidinoisopropylamino)-isovaleric acid was obtained. m-phenoxybenzyl alcohol 4.6y at 150℃
Heat to.

When the temperature reached 1500C, 0.25q of sodium was added and methanol distillation was started. After the distillation of methanol has stopped, 0.25 y of sodium is further added, and the above operation is repeated while maintaining the temperature at around 150° C. until the theoretical amount of methanol is obtained. Then, the mixture was 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-
(2-Piperidinoisopropylamino)-isovaleric acid α″ monoethynyl-m-phenoxybenzyl ester 7.1y was obtained. Example 3 α-[2-(4″-Methyl-’-cyclohexenyl)-
Isopropyloxy]-isovaleric acid anhydride 4.
9y and α-cyano m-phenoxybenzyl alcohol (4.61 g) were mixed, 8 g of 98% sulfuric acid was gradually added under stirring, the reaction was carried out at 80 to 100°C for 3 hours, and then dissolved in ether, and the ether solution was diluted with sodium bicarbonate solution. After thorough washing with brine and drying with salt water, the ether was distilled off under reduced pressure to obtain α-[2-
6.7y of α5-cyano m-phenoxybenzyl ester of (4-methyl-1″-cyclohexenyl)-isopropyloxy]-isovaleric acid was obtained.

Example 4 5.6y of α-(2-morpholinoethylamino)isovaleric acid was dissolved in 50 mL of dimethylformamide,
To this is added 5.7 y of α-cyano m-phenoxybenzyl bromide.

Add 4 ml of triethylamine while stirring and heat to 60-80°C.
After reacting for 3 hours, it was dissolved in ether, the ether solution was thoroughly washed with diluted hydrochloric acid and brine, dried over sulfuric acid, the ether was distilled off under reduced pressure, and α-(2-morpholinoethylamino)- 8.0y of α″-cyano m-phenoxybenzyl ester of isovaleric acid was obtained.Reference Example 1 White kerosene was added to 0.0% of the compound (2) of the present invention, and the total amount was 1 part, and 0.2% oil was added. obtain.

Reference Example 2 01 parts of the present compound (4) and 0 parts of piperonyl ptoxide
．． Add white kerosene to 8 parts and make 10 parts to obtain an oil solution.

Reference Example 3 To two parts of the compound (5) of the present invention, m 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 Compound (7) of the present invention 0.4 part, resmethrin 0
．． 1 part of octachlorodipropyl ether and 1.5 parts of refined kerosene are dissolved in 28 parts of refined kerosene, filled into an aerosol container, and after attaching the valve part, the propellant (
An aerosol is obtained by filling m parts of liquefied petroleum gas under pressure.

Reference Example 5 Compound (3) of the present invention 0.5y,. BHT0.5y is used as a base material for mosquito coils such as pyrethrum extract powder, wood flour, starch powder, etc.99.
0q to obtain a mosquito coil by a known method.

Reference Example 6 Compound (6) of the present invention 0.4y,. MGK-50261.
0y 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 (9) of the present invention and 97 parts of clay were thoroughly ground and mixed to obtain a 3% powder.

Reference Example 8 Compound of the present invention (10) Shunbu, 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: 3 pieces of Spodoptera on a 14cm diameter glass shear
Among the emulsions obtained in Reference Example 3 with 10 instar larvae added, compounds of the present invention (1), (3), (4),
Spray 20 Lml of each emulsion diluted with water containing (5), (7), (8), and (9), transfer to a waist-high chole dish containing feed in advance, and leave for 2 days. Later, they were able to kill more than 80% of the Spodoptera spp.

Reference Example 4: A 5- to 6-leaf stage radish field with a large number of green peach aphids. A 200-fold diluted solution of each of the emulsions containing the compounds of the present invention (2), (4), (5), (7), and (10) with water was sprayed at 100f/count. .

A parasitic rate survey two days later showed that the density had decreased to 1,110 or less than the pre-spraying density in each plot.

Next Test Example 5 Rice was grown 45 days after sowing in a 1/50,000 Wagner pot, and the rice was grown in Reference Example 8. Among the hydrating agents obtained by
Spray a 400 ff1 dilution of each hydrating powder containing 10) in water at a rate of 10 ml/pot.

Claims (1)

[Claims] 1 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, A is O or NH, and R represents a cyano group or an ethynyl group. R_1 is R When R is a cyano group, it represents a cyclohexylmethyl group, a cyclohexylethyl group, a (4-methyl-1-cyclohexenyl)isopropyl group, or a morpholinoethyl group, and when R is an ethynyl group, it represents a (1-cyclopentenyl)-methylethyl group. , 3-pyrrolidinyl-2-methylpropyl group or piperidino-isopropyl 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.▼. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ The compound according to claim 1, which is a compound represented by the following. 4. The compound according to claim 1, which is a compound represented by the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 5. The compound according to claim 1, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 6. The compound according to claim 1, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 7. The compound according to claim 1, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 8 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II)
(In the formula, A and R have the same meanings as stated in claim 1.) Carboxylic acid or its reactive derivative represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼... ...(III
) (wherein R represents the same meaning as stated in claim 1) General formula ▲ Numerical formula, chemical formula, table, characterized by reacting with alcohol or its reactive derivative etc. ▼・・・(I) Production method of isovaleric acid ester compound.