JPS5839139B2 - Isovaleric acid ester derivative and method for producing isovaleric acid ester derivative - Google Patents

Description

Detailed Description of the Invention The present invention is based on the general formula (wherein A is 0, NH, CH2, and R1 is the general formula (
II), (m), (IV), and (V).

Here, X represents a methylene group or an ethylene group, and m represents an integer of 1 to 2.

R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R4 represents a hydrogen atom, a methyl group or a halogen atom.

Further, R2 represents a hydrogen atom, a cyano group or an ethynyl group.

), its optical and geometric isomers, and its production method.

Various alcohol components of cyclopropane carboxylic acid esters have been studied and put into practical use.
It is susceptible to oxidative decomposition due to light, which has limited its use outdoors.

Recently, research on acid components has become active, and a compound that is more stable to light than conventional pyrethroids has been invented by replacing the methyl group with a halogen atom.

However, when considering issues such as environmental pollution and chronic toxicity, compounds having a structure similar to naturally occurring organic compounds, mainly consisting of carbon, hydrogen, oxygen, and nitrogen, 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 (I) has an extremely excellent insecticidal effect as an insecticidal ingredient against various sanitary pests and agricultural and horticultural pests, and has extremely low toxicity to warm-blooded animals. I learned that it is much more stable against light than conventional pyrethroids.

This invention was completed based on the above findings.

The compound represented by the above formula (I) used as an active ingredient in the present invention can be prepared by the general formula (wherein A is O, NH, CH2, and Ro is the general formula (n), ( m), (IV), and (V).

Here, X represents a methylene group or an ethylene group, and m represents an integer of 1 to 2.

R3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R4 represents a hydrogen atom, a methyl group, or a halogen atom.

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

) or its reactive derivative.

Examples of reactive derivatives of carboxylic acids include acid halides,
Examples include acid anhydrides, lower alkyl esters, and alkali metal salts.

An example of a reactive derivative of alcohol is 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 (I) are as follows.

The compound of the present invention is a new 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. be able to.

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 using an appropriate heating element, 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 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-octylbicyclohebutene dicarboximide (trade name MGK-264) and a mixture of N-octylbicyclohebutene dicarboximide and alkylaryl sulfonate (trade name MGK-50).
26), the insecticidal efficacy can be further enhanced by adding a synergist such as octachlorociflovir ether or piperonyl ptoxide.

Furthermore, the stability of the compounds of the present invention can be further enhanced by adding antioxidants such as phenolic amines such as 2,6-ditertiary-**butyl-4-methylphenol (BHT) and 2,6-ditertiary-butylphenol. can be increased.

In addition, even more effective insecticides can be obtained by using in combination with conventional pyrethroids such as allethrin, phthalthrin, resmethrin, flamethrin, phenothrin, permethrin, cypermethrin, decametrin, fenvalerate, etc.

Next, 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 (A) of the 12 compounds of the present invention of the above compound examples, 0.2% and piperonyl butoxide 0
．． 8% white lamp solution), 0.1% and phthalthrine 0.
For a 1% white light solution Q and a 0.2% white light solution of allethrin and phthalthrin, the fall-upside-down rate of the housefly was determined by the spray drop method using house flies, and the relative effectiveness of the test drug was calculated. Furthermore, 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 carried out in Insect Control Science Volume 16 (1951 *year), No. 176.
The relative effectiveness of the incense stick was calculated according to the method of Page Nagahama, Katsuta et al., and the results were as follows.

The sample drug number is the same as that of the active ingredient example above.

Examples of the compounds of the present invention are shown below.

Note that the average temperature of compounding is the same as that of the above-mentioned active ingredient example.

The stability test was conducted by spreading sample 10 in a thin glass Petri dish (36 cd), 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 numbers for the compounds of the present invention, and several recently developed pyrethroids were used as control drugs.

Example 1 α-(2,5-methano-cyclohexyloxy)-isovaleric acid chloride 4.6? Dry benzene 15m
1, and add 4.7f of α-cyano-m-phenoxybenzyl alcohol to this. was dissolved in 207 d of dry benzene, and then 3 d of dry pyridine was added as a condensation aid.
When r/Ll is added, crystals of pyridine hydrochloride are precipitated.

After sealing the cap and leaving it overnight at room temperature, the pyridine hydrochloride was removed, the benzene solution was dried over 5 nitric nitrate, the benzene was distilled off under reduced pressure, and α(2,5-methano-cyclohexyloxy)- 7.4 tons of α'-cyano m-phenoxybenzyl ester of isovaleric acid was obtained.

Example 2 α-(5-methyl-1,2,3,4-tetrahydronaphthalene-2-amino)-isovaleric acid 5.3 F
and α-ethynyl-m-phenoxybenzyl alcohol 4
．． 6f? Dissolve 150FdK in benzene and add concentrated sulfuric acid 5rILl while stirring the solution vigorously.

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.

The reaction solution was then washed with an aqueous sodium bicarbonate solution and a saline solution, and then benzene was distilled off under reduced pressure to obtain 1 of α-(5-methyl-1,2,3,4-tetrahydronaphthalene-2-amino)-isovaleric acid. -Ethynyl-m-phenoxybenzyl ester 8.99% was obtained.

Example 3 Sodium salt of α-(3-isopropyl-2,5-ethano-cyclohexylamino)-isovaleric acid 5.7
y and m-phenoxybenzyl chloride 4.51 were dissolved in 50 ml of benzene and reacted under reflux in a nitrogen stream for 3 hours. The reaction solution was cooled and precipitated salt was separated, and then thoroughly washed with brine. After drying with salt water, benzene was distilled off under reduced pressure, and the m-
7.81 phenoxybenzyl ester was obtained.

Example 4 α-(3,4-)rimethylenecyclohexylmethyl)-
Mix 4.6 y of isovaleric acid anhydride and 4.7 t of α-Schiff/-m-phenoxybenzyl alcohol, gradually add 8 y of 98% sulfuric acid while stirring, react at 80 to 100°C for 3 hours, and then form ether. The ether solution was thoroughly washed with aqueous sodium bicarbonate and brine, dried over sulfate, and the ether was distilled off under reduced pressure to obtain α' of α-(3,4-trimethylenecyclohexylmethyl)-isovaleric acid. -cyano m
-Phenoxybenzyl ester 6.31 was obtained.

Example 5 α-(2,5-ethano-3-cyclohexenylmethoxy)-isovaleric acid 4.81? is dissolved in 50% of dimethylformamide, and 5.41% of m-phenoxybenzyl bromide is added thereto.

Triethylamine 4771A under stirring! Add 60~8
After reacting at 0°C for 3 hours, it was dissolved in ether, and the ether solution was thoroughly washed with aqueous sodium bicarbonate and brine, dried over salt water, and the ether was distilled off under reduced pressure to obtain α-(2,5-ethano-3). −
m of cyclohexenyl methoxy)-isovaleric acid
-Phenoxybenzyl ester 7.3i was obtained.

Reference Example 1 White kerosene was added to 0.2 parts of the compound (1) 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 (10) 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 To 20 parts of the compound (11) of the present invention was added Tsurupol 5M200 (
10 parts of Toho Chemical (registered trademark) and 70 parts of Kijirole were added and mixed and dissolved with stirring to obtain a 20% emulsion.

Reference Example 4 After dissolving 0.4 parts of the present compound (2), 0.1 part of resmethrin, and 1.5 parts of octachlorodipropyl ether in 28 parts of refined kerosene, filling it into an aerosol container and attaching the valve part. , 70 parts of propellant (liquefied petroleum gas) is pressurized and filled through the valve part to obtain an aerosol.

Reference Example 5 The present compound (3) 0.55', BHTo, 5ft was used as a substrate for mosquito coils such as pyrethrum extracted lees powder, wood flour, starch powder, etc.99
, and mix them uniformly to obtain a mosquito coil by a known method.

Reference example 6 Compound (4) of the present invention 0.4S', MGK-50261,
01 is uniformly mixed with 98.6 f of a mosquito coil base material 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 Compound of the present invention vA9) 40 parts, diatomaceous earth 35 parts, clay 20
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 Ten 3rd instar larvae of Spodoptera japonica were placed in a waist-high glass petri dish with a diameter of 14 crIL, and among the emulsion obtained in Reference Example 3, compounds of the present invention (1), (3), and (5) were placed in a scattering tower.
), (8), (9), 0]), (If you spray 1 ml of a 1000-fold dilution with water of each emulsion containing 1), transfer it to a waist-high petri dish containing feed in advance and leave it.
In both cases, more than 80% of the Spodoptera were able to be killed after two days.

Test Example 4 Among the emulsions obtained in Reference Example 3, compounds of the present invention (2), (4), (6), (7), (10), (1
1000 parts diluted with water of each emulsion containing 1)
001/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 pot, and among the wettable powders obtained in Reference Example 8, compounds of the present invention (2), (5), (6), (8), (9)
, (10), (Ll) with water.
Spray the 1:00 diluted solution at a rate of 10 rILl/pot.

If you cover it with a cylindrical wire mesh and scatter about 20 adult brown planthoppers in it, 80% of the insects will be removed after one day.
I was able to kill more than one insect.

Claims (1)

[Claims] 1 General formula (wherein A is 01 NH. CH2, R1 is the general formula where X is a methylene group or an ethylene group, and m is an integer from 1 to 2. R3 is hydrogen an atom or an alkyl group having 1 to 3 carbon atoms; R4 represents a hydrogen atom, a methyl group, or a halogen atom; and R2 represents a hydrogen atom, a cyano group, or an ethynyl group. Derivatives and their optical and geometric isomers. 2 general formula (wherein R1 represents a group represented by general formula (II), (m), or (V). (IV), where X is a methylene group or an ethylene group, and m is 1 to 2 Represents an integer. R3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R4 represents a hydrogen atom, a methyl group, or a halogen atom. R2 represents a hydrogen atom, a cyano group, or an ethynyl group.) The invaleric acid ester derivative and stereoisomer thereof according to claim 1, which are represented by: 3. The compound according to claim 2, which is a compound represented by formula 3. **4 The compound according to claim 2, which is a compound represented by the formula. [Stock] ■5 The compound according to claim 2, which is a compound represented by the formula. Sphere *6 The compound according to claim 2, which is a compound represented by the formula: 7 general formula (wherein A is O, NH, CH2, R□ is general formula (
n), (m), (IV), and (V). Here, X represents a methylene group or an ethylene group, and m represents an integer of 1 to 2. R3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R4 represents a hydrogen atom, a methyl group, or a halogen atom. ) or a reactive derivative thereof, and an alcohol represented by the general formula (where R3 represents a hydrogen atom, a cyan group, or an ethynyl group) or a reactive derivative thereof. A method for producing an invaleric acid ester derivative represented by 1,000 (herein, A, R1, and R2 have the same meanings as above).