JPS6117810B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula (): (In the formula, R ₁ is an alkynyl group, a haloalkyl group, an alkoxyalkyl group or the general formula (),
Indicates a group represented by () or (). Here, X is O or NH, and n represents an integer of 1 to 5. R ₃ represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom or a lower alkoxyl group, and R ₄ represents an alkenylene group, a haloalkylene group or an alkoxyalkylene group.
Further, R ₂ represents a hydrogen atom, a cyano group or an ethyl group. ), its optical and geometric isomers, its production method, 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, but they are susceptible to oxidative decomposition by light, and their 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 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. . As a result of repeated research, the inventor has determined that the above formula ()
The compound represented by 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 and being extremely stable against light compared to conventional pyrethroids. I learned. The present invention was completed based on the above findings. The compound represented by the above formula () used as an active ingredient in the present invention can be prepared using the general formula () according to the general method for producing esters: (In the formula, R ₁ is an alkynyl group, a haloalkynyl group, an alkoxyalkyl group or the general formula (),
() Indicates a group represented by (). Here, X is O or NH, and n represents an integer of 1 to 5. R ₃ represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom or a lower alkoxyl group, and R ₄ represents an alkenylene group, a haloalkylene group or an alkoxyalkylene group. ) or its reactive derivative and the general formula (): (Here, R ₂ represents a hydrogen atom, a cyano group, or an ethynyl group.) It can be prepared by reacting with an alcohol or a reactive derivative thereof. Examples of reactive derivatives of carboxylic acids include acid halides, acid anhydrides, lower alkyl esters,
Examples include 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 () are as follows. Note that compounds (3), (4), and (10) are shown at the same time as related compounds. α'-cyano-m'-phenoxybenzyl ester of α-isopropyl-ε-dichloro-hexanoic acid n ²⁰ _D 1.5208 Cyano-m'-phenoxybenzyl ester of α-(P-methylphenoxy-methyl)-isovaleric acid n ²⁰ _D 1.5730 α'-Cyano-m'-phenoxybenzyl ester of α-isopropyl-γ-(P-chloroanilino)-lactic acid n ²⁰ _D 1.5945 α'-cyano-m'-phenoxybenzyl ester of α-isopropyl-γ-(P-methylphenyl)-valeric acid n ²⁰ _D 1.5619 m-phenoxybenzyl ester of α-isopropyl-∂-hexic acid n ²⁰ _D 1.5064 m'-phenoxybenzyl ester of α-isopropyl-δ-(m'-methoxyphenyl)-γ-pentenoic acid n ²⁰ _D 1.5375 Cyano-m'-phenoxybenzyl ester of α-isopropyl-γ-methyl-δ-isopropoxy-valeric acid n ²⁰ _D 1.5283 α'-ethynyl-m'-phenoxybenzyl ester of α-(m'-allylanilino-methyl)-isovaleric acid n ²⁰ _D 1.5508 α'-ethynyl-m'-phenoxybenzyl ester of α-isopropyl-γ-bromo-δ-(P-vinylphenoxy)-valeric acid n ²⁰ _D 1.5647 α'-ethynyl-m'-phenoxybenzyl ester of α-isopropyl-γ-phenoxy-valeric acid n ²⁰ _D 1.5475 α-isopropyl-γ-methoxy-δ-(P-
α'-cyano-m'-phenoxybenzyl ester of fluoroanilino-valeric acid n ²⁰ _D 1.5250 α-isopropyl-γ-chloro-ε-methyl-
α'-ethynyl-m'-phenoxybenzyl ester of heptanoic acid n ²⁰ _D 1.5188 α'-cyano-m'-phenoxybenzyl ester of α(P-chlorophenoxymethyl)-isovaleric acid n ²⁰ _D 1.5464 m'-phenoxybenzyl ester of α-(3,5-dimethoxyanilinomethyl)-isovaleric acid n ²⁰ _D 1.5527 α-isopropyl-γ,δ-dichloro-δ-
α'-cyano-m'-phenoxybenzyl ester of 2,4,6-trimethylanilino-valeric acid n ²⁰ _D 1.5570 α'-cyano-m'-phenoxybenzyl ester of α-isopropyl-γ-methoxy-γ-phenyl-lactic acid n ²⁰ _D 1.5251 m'-phenoxybenzyl ester of α-isopropyl-δ-(P-promophenoxy)-γ-hexenoic acid n ²⁰ _D 1.5563 The compound of the present invention is a novel compound, which is solid or liquid at room temperature, and which can be used in organic solvents. It is generally easily soluble. 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. 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 has the same excellent effect 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, N-octylbicycloheptenedicarboximide (trade name MGK-
264), a mixture of N-octylbicycloheptenedicarboximide and alkylaryl sulfonate (trade name MGK-5026), octachlorodipropyl ether, piperonyl butoxide, and other synergists can be added to increase the effectiveness of the insects. The effect can be further enhanced. Also, 2,6-ditertiary-butyl-4
The stability of the compounds of the present invention can be further increased by adding phenolic or amine antioxidants such as -methylphenol (BHT) and 2,6-ditertiary-butylphenol. Furthermore, conventional pyrethroids such as allethrin,
Phthalthrin, resmethrin, flamethrin,
When used in combination with phenothrin, permethrin, etc., an even more effective insecticide can be obtained. 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 A 0.2% white light solution (A) of the 40 compounds of the present invention, a white light solution of 0.2% and 0.8% pipenyl ptoxide (B), 0.1% and phthalthrine 0.1 % white lamp solution (C), and 0.2% white lamp solution of allethrin and phthalthrin, respectively, using house flies, the falling and turning rate of house flies was determined according to the spray drop method, and the relative effectiveness of the test drug was calculated. Furthermore, the mortality rate after 24 hours was determined as follows.

[Table] Test Example 2 Insecticidal test by fumigation Mosquito coils containing 0.5% of insecticidal ingredients were made and tested for their effectiveness in causing adult Culex mosquitoes to fall and fall upside down. This experiment was published in Insect Control Science Volume 16 (1951).
The relative effectiveness of the incense sticks was calculated according to the method of Nagasawa, Katsuta et al. on page 176, and the results were as follows. The sample drug number is the same as that of the active ingredient example above.

【table】

[Table] 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 5.1 g of α-(3,5-dimethoxyanilinomethyl)-isovaleric acid was dissolved in 50 g of dimethylformamide.
ml and add 5.4 g of m-phenoxybenzyl bromide. After adding 4 ml of triethylamine with stirring and reacting at 60 to 80°C for 3 hours,
It was dissolved in ether, the ether solution was thoroughly washed with aqueous sodium bicarbonate and brine, and then dried over sulfuric acid. The ether was distilled off under reduced pressure to obtain m- of α-(3,5-dimethoxyanilinomethyl)-isovaleric acid. 8.0 g of phenoxybenzyl ester was obtained. Compounds (1) to (13), (15) in the same manner as above
~(17) was obtained. Reference example 1 White kerosene was added to 0.2 parts of the present compound (2) and the whole
Obtain 0.2% oil solution as 100 parts. Reference Example 2 White kerosene is added to 0.2 parts of the present compound (4) and 0.8 parts of piperonyl butoxide to make a total of 100 parts to obtain an oil agent. Reference Example 3 To 20 parts of the compound (8) of the present invention, 10 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 0.4 part of the present compound (12), 0.1 part of resmethrin, and 1.5 parts of octachlorodipropyl ether were added to refined kerosene 28
After filling 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 5 0.5g of the compound (17) of the present invention and 0.5g of BHT were added to base material for mosquito coils such as pyrethrum extract lees powder, wood flour, starch powder, etc.
Mix 99.0g of the mixture uniformly and obtain a mosquito coil by a known method. Reference example 6 Compound of the present invention (11) 0.4g, MGK-5026 1.0g
was uniformly mixed with 98.6 g of a mosquito coil base material to obtain a mosquito coil by a known method. Reference Example 7 3 parts of the compound (12) 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 (15), 35 parts of diatomaceous earth, clay
20 parts of lauryl sulfonate, 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 shear with a diameter of 14 cm, and among the emulsions obtained in Reference Example 3, compounds of the present invention (1)(2)(5)(6) were placed in a scattering tower. (9)
(10)(11)(13)(16) Each emulsion containing 200 ml of water
If you spray 1 ml of the diluted solution and transfer it to a waist-high chole dish with feed in advance, you can get 2.
After a few days, we were able to kill more than 80% of the armyworms. Test Example 4 5 to 5 on a surface where a large number of green peach aphids appeared
Each of the emulsions containing the compounds of the present invention (1)(4)(5)(7)(9)(11)(12)(14) obtained in Reference Example 3 was applied to a radish field at the 6-leaf stage. A 200-fold dilution of the emulsion with water was applied 100 times per roll. A parasitic rate survey 2 days later revealed that the pre-spray density was
The number decreased to less than 1/10 in each ward. 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 (3)(4)(5)(6) were grown. )(10)(11)(14)
Spray a 400-fold dilution of each hydrating powder containing (15) and (17) with water at a ratio of 10/bottle. By covering it with a cylindrical wire mesh and releasing about 20 adult brown planthoppers into it, we were able to kill more than 80% of the insects within one day.

Claims (1)

[Claims] 1 General formula (): (In the formula, R ₁ is an alkyl group, a haloalkyl group,
Alkoxyalkyl group or general formula (), (),
Indicates a group represented by (). Here, X is O or NH, and n represents an integer of 1 to 5. R ₃ represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom or a lower alkoxyl group, and R ₄ represents an alkenylene group, a haloalkylene group or an alkoxyalkylene group.
Further, R ₂ represents a hydrogen atom, a cyano group or an ethynyl group. ) and its optical and geometric isomers. 2 formulas The compound according to claim 1, which is a compound represented by: 3 formulas The compound according to claim 1, which is a compound represented by: 4 General formula (): (In the formula, R ₁ is an alkynyl group, a haloalkyl group, an alkoxyalkyl group or the general formula (),
Indicates a group represented by () or (). Here, X is O or NH, and n represents an integer of 1 to 5. R ₃ represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom or a lower alkoxyl group, and R ₄ represents an alkenylene group, a haloalkylene group or an alkoxyalkylene group. ) or its reactive derivative and the general formula (): (Here, R ₂ represents a hydrogen atom, a cyano group, or an ethynyl group.) General formula () characterized by reacting with an alcohol or a reactive derivative thereof: (R ₁ and R ₂ here have the same meaning as above.)
A method for producing an isovaleric acid ester derivative shown in 5 General formula (): (In the formula, R ₁ is an alkynyl group, a haloalkyl group, an alkoxyalkyl group or the general formula (),
Indicates a group represented by () or (). Here, X is O or NH, and n represents an integer of 1 to 5. R ₃ represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom or a lower alkoxyl group, and R ₄ represents an alkenylene group, a haloalkylene group or an alkoxyalkylene group.
Further, 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: 6 formula The insecticide according to claim 5, which is a compound represented by: 7 formula The insecticide according to claim 5, which is a compound represented by: 8. The insecticide according to claim 5, which contains a pyrethroid synergist as an adjuvant.