JPS5945665B2 - Isovaleric acid ester derivatives, their production methods, and insecticides containing the derivatives - Google Patents

Description

Detailed Description of the Invention The present invention relates to the general formula (1): [wherein, A represents 0, NH or S, and R represents the following formula () or (auxiliary: (where X is O or NH] and n represents an integer of O to 3.

R3 represents a lower alkyl group, lower alkenyl group, halogen atom or lower alkoxyl group, and R4 represents an alkylene group, alkenylene group, haloalkylene group or alkoxyalkylene group. ) represents a group represented by R
2 represents a hydrogen atom, a cyano group or an ethynyl group.

The present invention relates to a novel isovaleric acid ester derivative represented by the above formula, its optical and geometric isomers, a method for producing the same, and an insecticide characterized by containing this compound as an active ingredient.

Various alcohol components of cyclopropane carboxylic acid esters have been studied and put into practical use.
It is susceptible to oxidative decomposition by light, and its use outdoors 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 that are mainly composed of carbon, hydrogen, oxygen, and nitrogen and have structures similar to (1) naturally occurring organic compounds are advantageous as these insecticidal ingredients. it is conceivable that.

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 is prepared according to the general formula (V) according to the general method for producing esters.
:(In the formula, A and R1 represent the meanings given in the above formula (1).

) 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, 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 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. α1 [2 −(
d-cyano-d-fe(2)noxybenzyl ester of p-chlorophenoxy)monoethoxy]-isovaleric acid Nwl. 582l d-cyano-d-phenoki(3)sibenzyl ester of α-[1-p-methylphenyl)monoethoxy]-isovaleric acid nΥ1.5682 α-(1-chloro-2-anilino-ethylamino)-iso d-ethynyl-enoxybenzyl ester of valeric acid Nl. 55O7 d- of α-[1-methoxy-2-(p-isopropenylanilino)monoethylthio]-isovaleric acid
Ethynyl-digit-1 phenoxybenzyl ester Nwl. 5
96lα-[2-chloro-3-(3',5'-dimethylanilino)-propoxy]-isovaleric acid d-ethynyl-phenoxybenzyl ester n blue 1.5780α-[2,2-dichloro -3-(
Ifhenoxybenzyl ester of p-methylphenyl)-propylamino]-isovaleric acid n blue 1.
5692 α-[3-(p-Ethoxyphenoxy)-2-butenylthio]-isovaleric acid d-cyanoephenoxybenzyl ester NZBl. 5683 α-[2-ethoxy-3-(4'-methyl-3
',5'-dipromophenyl)-propoxy]-isobaric acid phenoxybenzyl ester NZB
l. 57l5α-[2-( p -isopropylanilino)-propylamino]-isovaleric acid d-jam-d-phenoxybenzyl ester NZBl. 59
25 α-[2-chloro-3-(4'-chloro-2'
,6'-dimethylphenyl)-propylthio]-isobareryl acid distillate-phenoxybenzyl ester Nwl
．． 58llα-[3-Methyl-4-(p-methoxyanilino)-2-butenyloxy]-isovaleric acid d-cyanoe phenoxybenzyl ester NW
l. α-[2-Methyl-3-(p-isoprobenylphenyl)-allylamino]-isovaleric acid phenoxybenzyl ester n blue 1.55901'α-[2-(2'-Methyl-4'-chlorophenoxy)monoethylthio]-isovaleric acid with d-ethynyl-phenoxybenzyl ester NZBl. 57
2d- of α-[2-methyl-2-(m-ethoxyphenoxy)-propylamino]-isovaleric acid
Ethynyl-distilled phenoxybenzyl ester NWl. 5
d-Phenoxybenzyl ester of 6Olaω α-(2-anilinomethyl-allylthio)-isovaleric acid Nwl.
5498 Decoy α-[1-chloro-2-(m-vinylphenoxy)monoethoxy]isovaleric acid d-cyanoephenoxybenzyl ester n crystal 1.5362 The compound of the present invention is a new compound and is solid at room temperature. Alternatively, it is a liquid and generally easily soluble in organic solvents.

Therefore, it can be used as an insecticide for spraying in the form of emulsions, oils, powders, wettable powders, aerosols, etc. It can also be used as an insecticide for fumigation such as mosquito coils by mixing with wood flour or other suitable base materials. can do. Also, when used as a so-called electric mosquito repellent by dissolving this active ingredient in an appropriate organic solvent and soaking it in a mount, or dissolving it in an appropriate solvent and heating and evaporating it with an appropriate heating element, it is as effective as a mosquito coil. shows. 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 compound of the present invention may include N-octylbicycloheptenedicarpoximide (trade name: NGK
-264), a mixture of N-octylbicycloheptenedicarboximide and alkylaryl sulfonate (
By adding synergists such as MGK-5026 (trade name), octachlorodipropyl ether, piperonyl butoxide, the insecticidal effect can be further enhanced.

Furthermore, the present invention can be improved by adding phenolic or amine antioxidants such as 2,5-ditertiarybutyl-4-methylphenol (BHT) and 2,6-ditertiarybutylphenol. The stability of the compound can be further increased. Furthermore, even more effective insecticides can be obtained by using conventional pyrethroids such as allethrin, starthrin, resmethrin, flamethrin, phenothrin, permethrin, 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 (4) of the 21 compounds of the present invention of the above compound examples, 0.2 (F6 and piperonyl butoxide 0
．． 8% white light solution 7V. (B) The fall-upside rate of house flies according to the spray drop method using white light solutions of 0.1% and phthalthrin (0.101) (0.1% and 0.201 of allethrin and phthalthrin, respectively). The relative efficacy of the test drug was calculated, and the mortality rate after 24 hours was determined as follows.

Test Example 2 Insecticidal test by fumigation A mosquito coil containing 0.596 as an insecticidal ingredient was made.
We tested the effect of forcing adult Culex mosquitoes to fall supine.

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 test drug numbers are the same as those in the active ingredient examples above. Examples of the compounds of the present invention are shown below.

The compound names are the same as those in the active ingredient examples above. Example 1 6.5 g of α-[1-methoxy-2-(p-isopropenylanilino)monoethylthio]-isovaleric acid and 4.69 g of α-1-ethynyl-1m-phenoxybenzyl alcohol
was dissolved in 150 ml of benzene, and 5 d of concentrated sulfuric acid was added while stirring the solution vigorously.

The mixture is heated to reflux with stirring, and the water produced by azeotropy is removed using a dehydrating agent. Benzene is replenished from time to time and the reaction is 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 d-[1-methoxy-2-(p-isopropenylanilino)-ethylthio]-isovaleric acid. 8.99% of ethynyl-d-phenoxybenzyl ester was obtained. Example 2α-[2,2-dichloro-
6.69% of the sodium salt of 3-(p-methylfuninyl)-propylamino]-isovaleric acid and 4.59% of m-phenoxybenzyl chloride were dissolved in 507n1 of benzene and reacted under reflux in a nitrogen stream for 3 hours. After that, the reaction solution was cooled and the precipitated common salt was separated in a furnace. After thoroughly washing with brine, it was dried over sulfuric acid, and the benzene was distilled off under reduced pressure.
-[-2,2-dichloro-3-(p-methylphenyl)
8.59 d-phenoxybenzyl ester of -propylamino]-isovaleric acid was obtained.

Example 3 5.39% of the methyl ester of α-(2-methyl-3-phenylallyluoquine)-isovaleric acid and 4.69% of α-ethynyl-m-phenoxybenzyl alcohol were dissolved in 150%
Heat to ℃.

When the temperature reaches 150° C., 0.25 g of sodium is added and methanol distillation is started. When the distillation of methanol has stopped, add another 0.259 g of sodium. Then, the temperature is maintained at around 150° C. and the above operation is repeated 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 nitric acid, and the ether was distilled off under reduced pressure to obtain α-
7.69 of d-ethynyl-m-phenoxybenzyl ester of (2-methyl-3-phenylallyloxy)-isovaleric acid was obtained. Example 4 5.39% of α-[2-(p-chlorophenoxy)monoethoxy]-isovaleric anhydride and 4.69% of α-cyano-phenoxybenzyl alcohol were mixed, and 98% of α-cyano-phenoxybenzyl alcohol was mixed with stirring. % sulfuric acid was gradually added, and after reacting at 80 to 100°C for 3 hours, it was dissolved in ether. The ether solution was thoroughly washed with aqueous sodium bicarbonate and brine, dried over sulfur sulfate, and the ether was distilled off under reduced pressure. Thus, 6.99 g of d-cyanoephe/xybenzyl ester of α-[2-(p-chlorophenoxy)monoethoxy]-isovaleric acid was obtained.

Reference Example 1 White kerosene was added to 0.2 parts of the compound of the present invention (2) to make the total 100 parts, and 0.20 parts! ) Obtain the oil solution.

Reference Example 2 White kerosene is added to 0.2 parts of the compound (4) 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 compound of the present invention (self), 0.1 part of resmethrin, 1.5 parts of octachlorodipropyl ether were dissolved in 28 parts of refined kerosene, filled into an aerosol container, and after attaching the valve part, The propellant (
70 parts of liquefied petroleum gas) is charged under pressure to obtain an aerosol.

Reference Example 5 Compound of the present invention CL7) 0.59, BHTO. 59 is used as a base material for mosquito coils such as pyrethrum extracted lees powder, wood flour, starch powder, etc.99.
09 to obtain a mosquito coil by a known method.

Reference Example 6 Compound (13) of the present invention 0.49, MGK-50261.
09 is uniformly mixed with a mosquito coil base material 98.69 to obtain a mosquito coil by a known method.

Reference Example 7 3 parts of the compound (16) 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 (20), 35 parts of diatomaceous earth, clay 2
Test example 3 of obtaining a wettable powder by crushing and mixing 0 parts of lauryl sulfonate, 3 parts of lauryl sulfonate, and 2 parts of carpoxymethyl cellulose.
Now, 10 larvae were added, and the back of the emulsion obtained in Reference Example 3 was mixed with compounds of the present invention (1), (2), and fu (3) in a scattering tower.
, (5), (8), (11), 04), 08), C! ．．
200-fold dilution with water of each emulsion containing D'g! Ll
ml was sprayed, transferred to a waist-high sieve containing feed in advance, and left to stand. After 2 days, more than 80% of the insects of Spodoptera were killed.

Test Example 4 Compounds of the present invention (1), (2), (3), (6 ), (9), 02)
A 200-fold diluted solution of each emulsion containing .

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 the compounds of the present invention (1), (2), (3) were added to the back of the wettable powder obtained in Reference Example 8. , (4), σ0)
, 04), (Own), C2O), and C2D, each of which was diluted 400 times with water, was sprayed at a rate of 10 ml/bottle.

Claims (1)

[Claims] 1 General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I
) [In the formula, A represents O, NH or S, and R_1 is the following formula (II) or (III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) or ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) (Here, X represents O or NH, n represents an integer of 0 to 3, R_3 is a lower alkyl group, a lower alkenyl group,
It represents a halogen atom or a lower alkoxy group, and R_4 represents an alkylene group, an alkenylene group, a haloalkylene group, or an alkoxyalkylene group. ), and R_2 represents a hydrogen atom, a cyano group, or an ethynyl group. ] Isovaleric acid ester derivatives and their optical and geometric isomers. 2 General formula (IV): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(IV)
[In the formula, R_1 is the following formula (II) or (III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II)
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) (Here, X represents O or NH, n represents an integer of 0 to 3, R_3 is a lower alkyl group, a lower alkenyl group,
Represents a halogen atom or lower alkoxyl group, R_4
represents an alkylene group, alkenylene group, haloalkylene group or alkoxyalkylene 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, characterized by the following: 3. The compound according to claim 2, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 4. The compound according to claim 2, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 5 General formula (V): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(V)
[In the formula, A represents O, NH or S, and R_1 is the following formula (II) or (III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II)
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) (where X represents O or NH, n represents an integer of 0 to 3, R_3 is a lower alkyl group, a lower alkynyl group,
Represents a halogen atom or lower alkoxyl group, R_4
represents an alkylene group, alkenylene group, haloalkylene group or alkoxyalkylene group. ) represents a group represented by ] Carboxylic acid or its reactive derivative and general formula (VI): ▲ mathematical formula, chemical formula,
There are tables, etc. ▼・・・・・・(VI) (Here, R_2 represents a hydrogen atom, a cyano group, or an ethynyl group.) A general product characterized by reacting with an alcohol or its reactive derivative Formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I) (here A
, R_1, and R_2 have the same meanings as above. ) A method for producing an isovaleric acid ester derivative. 6 General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I
) [In the formula, A represents O, NH or S, and R_1 is the following formula (II) or (III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II)
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) (Here, X represents O or NH, n represents an integer of 0 to 3, R_3 is a lower alkyl group, a lower alkenyl group,
Represents a halogen atom or lower alkoxyl group, R_4
is an alkylene group, an alkenylene group, a haloalkylene group,
Or represents an alkoxyalkylene group. ), and R_2 represents a hydrogen atom, a cyano group, or an ethynyl group. ] An insecticide characterized by containing an isovaleric acid ester derivative represented by the following. 7 Isovaleric acid ester derivative has general formula (IV)
:▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I
V) [In the formula, R_1 is the following formula (II) or (III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II)
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) (Here, X represents O or NH, n represents an integer of 0 to 3, R_3 is a lower alkyl group, a lower alkenyl group,
Represents a halogen atom or lower alkoxyl group, R_4
represents an alkylene group, alkenylene group, haloalkylene group or alkoxyalkylene group. ), and R_2 represents a hydrogen atom, a cyano group, or an ethynyl group. ] The insecticide according to claim 6. 8. The insecticide according to claim 7, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 9. The insecticide according to claim 7, which is a compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 10. The insecticide according to claim 6, which contains a pyrethroid synergist as an adjuvant.