JPS61236741A - Benzyl ether derivative and insecticidal and miticidal agent containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R1 is lower alkyl, lower alkoxy, lower alkenyloxy, etc.; R2 is H or halogen; R3 and R4 are CH3 or R3 and R4 together form ethylene or 1,1-difluoroethylene; R5 is lower alkyl, lower alkenyl, lower alkynyl, etc.; R6 is H or F). EXAMPLE:4-Methyl-4-(4-ethoxyphenyl)-1-(3-phenoxyphenyl)penthyl ethyl ether. USE:Insecticidal and miticidal agent. It has no residual property in environment in contrast with organic chlorine insecticide and relatively low toxicity to man, animal and fish, and exhibits remarkable effect against vermin resistant to organo-phosphoric pesticides and carbamate pesticides. PREPARATION:The compound of formula I can be produced by converting the unsaturated carbinol of formula II to the compound of formula III by cata lytic reduction, and reacting the resultant compound with the compound of formula R5-X (X is halogen, tosyloxy or mesyloxy) in the presence of a base.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (1) [wherein R1 is a lower alkyl group, a lower alkoxyl group,
a lower alkenyloxy group, a lower halo7)l''r group, a halogen atom or a fluorine-substituted lower alkoxyl group, k represents a hydrogen atom or a halogen atom, and R1 and R8 together form a methylenedioxy group. R3 and R4 each represent a methyl group, or Rs
and R4 represent an ethylene group or a 1,1-difluoroethylene group. R6 represents a lower alkyl group, lower haloalkyl group, lower alkenyl group or lower alkynyl group, and Rs represents a hydrogen atom or a fluorine atom. ] The present invention relates to a benzyl ether derivative represented by the following and an insecticide and acaricide cage containing the benzyl ether derivative as an active ingredient.

As a result of repeated research aimed at developing a compound having excellent insecticidal and acaricidal activity, the present inventors found that the general formula (I
The compounds of the present invention shown in (1) have extremely high insecticidal efficacy. 2. It does not have environmental persistence like organochlorine pesticides.

81 Relatively low toxicity to humans, livestock and fish. 4. It is also highly effective against pests that are resistant to organic phosphorus agents or carbamate agents. 5. It can be manufactured relatively cheaply.

The present inventors have discovered that it has excellent properties such as, and have completed the present invention.

Specific pest insects for which the compounds of the present invention are particularly effective include Hemiptera such as planthoppers, leafhoppers, aphids, and stink bugs; Lepidoptera such as diamondback moths, Japanese mealybugs, and armyworms; and Diptera such as Culex mosquitoes and houseflies. , the German cockroach and other orders of the order Reticuloptera, Coleoptera, and Orthoptera, as well as spider mites such as the false red spider mite and the orange spider mite.

The compound of the present invention has the general formula <II) [wherein R1, R2, R1, R4 and R6 have the same meanings as above. ] By tangentially reducing the unsaturated carbinol represented by the general formula (2) [wherein, R1, R1, Rs, Ra and R6 have the same meanings as above. [In the formula, Rs has the same meaning as above, and X is a halogen atom, tosyloxy or mesyloxy group.

] It can be obtained by reacting with a compound shown in the following.

In the above production method, the catalytic reduction reaction is carried out in an inert solvent, and such solvents include hydrocarbon solvents such as hexane, toluene, and benzene, protic polar solvents such as acetic acid, methanol, and ethanol, and acetic acid. Examples include ester solvents such as ethyl. Typical examples of reduction catalysts include palladium-carbon and platinum oxide, and the amount of such reduction catalysts to be used is determined by the above general formula (]II
0.8 to 50% to the unsaturated carbinol shown by
The range of W/W is usually 0.5 to b. The reaction temperature ranges from 0 to 80°C, usually around 20°C, to achieve the purpose.

The reaction time may vary depending on the amount of catalyst used, but is usually 1 to 10 hours. Further, the reaction can be carried out either under pressure or normal pressure, but the purpose can be sufficiently achieved under normal pressure.

In addition, the amount of the compound represented by the general formula (Ko) used when etherifying the saturated carbinol represented by the general formula (III) obtained in this way is from 2.0 molar to 2.0 molar based on the carbinol. For example, sodium hydride is used as the base, and the amount thereof is 1.0 to 1.2 times the mole of the carbinol.In order to carry out the reaction more smoothly, it is usually Polar non-butylene τ such as dimethyl sulfoxide and dimethyl formamide
One ton of solvent is used. The reaction temperature is arbitrary within the range of 0 to 100°C, but the purpose is usually sufficiently achieved at 1'6 to 70°C, and the reaction time is usually 1 to 12 hours.

In addition, the unsaturated carbinol represented by the general formula (II) is
In the general formula (V), R1, R1, Rs and R4 have the same meanings as above. ] In the presence of a base, an acetylene compound represented by the general formula (4) [wherein R6 has the same meaning as above] is added. ] It can be obtained by reacting with an aldehyde represented by.

The reaction is usually carried out in the presence of an inert solvent, such as hydrocarbon solvents such as hexane, benzene and toluene, ether solvents such as tetrahydrofuran and dimethyl ether, dimethylformamide,
Examples include aprotic polar solvents such as dimethyl sulfoxide. The reaction temperature is arbitrary within the range of -78°C to 100°C, but is usually -40°C to 40°C. The base used in this reaction is typically n
-butyllithium, sodium hydride, potassium hydride, sodium, ethylmagnesiumlithium, etc.

Regarding the molar ratio of these reaction reagents, the acetylene compound is 0.6 to 1.5 times the mole of the aldehyde, usually 0.8 to 1.2 times the mole, and the base is the acetylene compound It is usually in the range of 0.9 to 1.1 times the mole.

Furthermore, the acetylene compound represented by the above general formula (V) is represented by the general formula (6) E in which R1, R1, R1) rJ: and R4g! It has the same meaning as above. ] From the aldehydes shown, for example, Tetrahedr
on Letters, 86, 8769 (1972)
It can be obtained by the method described in .

The first example of the compound of the present invention produced based on the above method was
Although shown in the table, the present invention is not limited to these examples.

Further, the compound of the present invention has an asymmetric carbon, and each optical isomer exists, and these optically active forms are also included in the present invention.

The present invention will be explained in more detail below using synthesis examples and reference examples.

Synthesis Example 1 4-Methyl-4-(4-ethoxyphenyl)-1-(8
Synthesis of -phenoxyphenyl)pentan-1-ol 4-methyl-4-(4-ethoxyphenyl)-1-(8
-Phenoxyphenylbento-2-yn-1-ol1. Vinegar f! ! After dissolving the mixture in 50++d and adding 200 μm of 5% palladium on carbon, a catalytic hydrogenation reaction was carried out at room temperature with shaking under normal pressure. After absorbing a theoretical amount of hydrogen (120sIt), the reaction solution was filtered, and the P solution was poured into water, followed by extraction with ethyl acetate. The extract was washed sequentially with water, sodium bicarbonate aqueous solution, and saline solution,
After drying over anhydrous magnesium sulfate, the solvent was distilled off. The residue was purified by silica gel column chromatography, and the
．． The target compound 721 was obtained as a pale yellow oil.

Refractive index 1.5752 (24°C) NMR (CDCtm, δ value) l. 4 (t, 8H), 1.5 (8,6H), 1
．． 7 (m, 4H), 4.0 (q, 2H), 4.5 (m
, 1) 1), 6.6-7.4 (m, 18H) Synthesis Example 2 4-Methyl-4-(4-ethoxyphenyl)-1-(8
Synthesis of -phenoxyphenyl)pentyl ethyl ether (compound (1)) 4-methyl-4-(4-ethoxyphenyl)-1-(8-phenoxyphenyl)pentane-1
-All 1. Of, sodium hydride 110119 (6
G%) and dimethylformamide 10- are placed in a reaction vessel, stirred at 20°C for 80 minutes, and then ethyl bromide 0.
3- was added and stirred at 50°C for 3 hours. The reaction solution was poured into 5-10% aqueous hydrochloric acid and extracted with ethyl acetate. Add the extract to water,
After sequentially washing with brine, it was dried over anhydrous sodium sulfate, and the solvent was distilled off. The residual liquid was purified by silica gel column chromatography to obtain 0.92f of the desired product.

Refractive index 1.5522 (28.5°C) NMR (CDCts, δ value) 1.28 (s, 6H), 1.28 (t, 8H), 1.5
(m, 4H), 8.8 (dd, IH), 4.0 (q
, 2) 1, 6.7 to 7.4 (18H) When the compound of the present invention is used as an active ingredient of an insecticide or acaricide, it may be used as it is without adding any other ingredients, but usually teeth,
It can be mixed with solid carriers, liquid carriers, gaseous carriers, surfactants, other formulation auxiliaries, baits, etc., or impregnated into base materials such as incense sticks and mats to form emulsions, wettable powders, powders, and granules. , oil solutions, aerosols, heating fumigants such as mosquito coils and electric mosquito repellent mats, fogging agents such as fogging, non-heating fumigants, poison baits, etc.

The content of the taste invention compound as an active ingredient in these preparations is 0.01% to 95% by weight.

Solid carriers include kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite,
Fine powders or granules such as talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, M7 ammonium sulfate, and synthetic hydrated silicon oxide may be mentioned, and the liquid carrier may include:
Aliphatic hydrocarbons such as kerosene and kerosene; aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene;
Halogenated hydrocarbons such as dichloroethane, trichloroethylene, carbon tetrachloride, alcohols such as methanol, ethanol, isopropanol, ethylene glycol, cellosolve, ketones such as acetone, methyl ethyl ketone, cyclohexanone, isophorone, diethyl ether, dioxane, tetrahydrofuran, etc. X-f) I/% Vinegar Ml
Examples include esters such as ethyl, nitrites such as acetonitrile and isobutyronitrile, acid amides such as dimethylformamide and dimethylacetamide, dimethyl sulfoxide, vegetable oils such as soybean oil, and cottonseed oil. As a gaseous carrier, fluorocarbon gas, LPG (liquefied petroleum gas)
, dimethyl ether and the like. Surfactants used for emulsification, dispersion, wetting, etc. include alkyl sulfate ester salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, naphthalene sulfone. Examples include anionic surfactants such as acid-formalin condensates, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Examples of formulation aids such as fixing agents and dispersants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, molasses, casein, gelatin, CMC (+ carboxymethylcellulose), pine oil, agar, etc. Stabilizers include PAP (isopropyl acid phosphate), T
Alkyl phosphate such as cp (tricresyl phosphate), vegetable oil, niboxylated moiety, the above surfactant, B) iT, BH
Examples include antioxidants such as A, fatty acid salts such as sodium oleate and calcium stearate, and fatty acid esters such as methyl oleate and methyl stearate.

Examples of formulations are shown below. The compounds of the present invention are indicated by compound numbers in Table 1. Parts are parts by weight.

Formulation Example 1 0.2 parts of each of the compounds (1) to (17) of the present invention, 2 parts of xylene and 97.8 parts of white kerosene are mixed to obtain an oil solution.

Formulation Example 2 10 parts each of the compounds (1) to (17) of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 70 parts of xylene
Mix well to obtain an emulsion.

Formulation Example 8 20 parts of the present compound (1), 10 parts of fenitrothion,
8 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 65 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 4 1 part of the compound of the present invention (2), 2 parts of carbaryl, 87 parts of kaolin clay, and 1 G part of talc are thoroughly ground and mixed to obtain a powder.

Formulation Example 5 5 parts of the compound of the present invention (8), 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignosulfonate, 80 parts of bentonite, and 62 parts of kaolin clay were thoroughly ground and mixed, and water was added and kneaded thoroughly. Granulate and dry to obtain granules.

Formulation Example 6 Compound of the present invention (4) 0.05 part, tetramethrin 0.2
1 part, Resmethrin 0.05 parts, xylene 7 parts, and deodorized kerosene 82.7 parts are mixed and dissolved, filled into an aerosol container, and a valve part is attached. Then, 60 parts of propellant (PgL petroleum gas) is poured through the valve part. If it is filled under pressure, an aerosol can be obtained.

Formulation Example 7 Compound (5) of the present invention 0.8 f and d - of allethrin
Add 0.8 g of trans primary chrysanthemum acid ester, dissolve it in 20-methanol, and stir and mix uniformly with 99.4F carrier for mosquito coils (mixing tab powder, lees powder, and wood flour in a ratio of AI5:t). After evaporating the methanol, add 150 m of water, mix well, mold and dry to obtain a mosquito coil.

These preparations are used as they are or diluted with water. In addition, other insecticides, acaricides, nematicides, fungicides,
It can also be used in combination with herbicides, plant growth regulators, fertilizers, soil conditioners, etc.

When the compound of the present invention is used as an insecticide, insecticide, or acaricide, the application amount is usually 6 g to 50 ON per 10 ares, and when applying the emulsion, wettable powder, etc. diluted with water, the application concentration is is 10 ppm to 1000 ppm,
Powders, granules, oils, aerosols, etc. are applied as a preparation without any dilution.

Next, a test example is shown. The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 2.

Table 2 Compound Symbol Structural Formula Name Test Example 1 A 200-fold dilution (corresponding to 500 ppm) of an emulsion of the compound of the present invention below with water obtained according to Formulation Example 2 was added to 12
Soaked in artificial bait for Spodoptera M, diameter 11
cIII polyethylene cup. Ten 4th instar Spodoptera larvae were released into the larvae, and 6 days later, they were examined for survival and mortality to determine the mortality rate (2 repetitions).

The results are shown in Table 8.

Table 8 Test Example 2 Place two pieces of paper of the same size on the bottom of a polyethylene cup with a diameter of 5.5G, and dilute the following emulsions of the present invention compound and control compound prepared according to Formulation Example 2 with water to a predetermined concentration H.0. ,7
- was dropped onto - paper, and 80m+9 of white sugar was added uniformly as bait.

Release 10 female adult house flies into the container, put the lid on, and
Check whether it is alive or dead after an hour and check the LCso value (60% lethality)
was calculated (2 repetitions).

The results are shown in Table 4.

Table 4 Test Example 8 Rice stalks (about 12 cm in length) were immersed for 1 minute in a water dilution of an emulsion of the present invention compound and a control compound prepared according to Preparation Example 2 at a predetermined concentration. After air-drying, put the rice stems in a test tube and incubate 10 resistant leafhopper adults.
The head was released, and one day later, it was examined whether it was alive or dead, and the LC5 (l value (60%
(lethal concentration) was determined (two replicates).

The results are shown in Table 5.

Table 5 Test Example 4 -
10 adult female spider mites per leaf, 2
It was stored in a constant temperature room at 5°C. After 6 days, a drug solution prepared by diluting an emulsion of the present compound and a control compound below with water to 500 ppm of the active ingredient, prepared according to Formulation Example 2, was sprayed on a turntable at 15% per pot, and at the same time, the same wave 2- was applied. soil j
14 notes. Eight days later, the degree of damage caused by spider mites to each plant was investigated.

The effectiveness criteria are m: Almost no damage was observed.

+: Slight damage is observed.

-1+: The same damage as in the untreated area is observed.

And so. The results are shown in Table 6.

Table 6

Claims (1)

[Claims] (1) General formula ▲ Numerical formulas, chemical formulas, tables, etc. It represents an alkoxyl group, R_2 represents a hydrogen atom or a halogen atom, and R_1 and R_2 together represent a methylenedioxy group. R_3 and R_4 each represent a methyl group, or R_3 and R_4 together represent an ethylene group or a 1,1-difluoroethylene group. R_5 is a lower alkyl group, a lower haloalkyl group,
It represents a lower alkenyl group or a lower alkynyl group, and R_6 represents a hydrogen atom or a fluorine atom. ] A benzyl ether derivative represented by (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_5 represents a methyl group or an ethyl group,
_6 represents a hydrogen atom or a fluorine atom. ] The benzyl ether derivative according to claim 1. (8) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_5 represents a methyl group or an ethyl group,
_6 represents a hydrogen atom or a fluorine atom. ] The benzyl ether derivative according to claim 1. (4) General formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 represents a lower alkyl group, lower alkoxyl group, lower alkenyloxy group, lower haloalkyl group, halogen atom or fluorine-substituted lower alkoxyl group, R_2 represents a hydrogen atom or a halogen atom, and R_1 and R_2 together represent a methylenedioxy group. R_3 and R_4 each represent a methyl group, or R_3 and R_4 together represent an ethylene group or a 1,1-difluoroethylene group. R_5 is a lower alkyl group, a lower haloalkyl group,
It represents a lower alkenyl group or a lower alkynyl group, and R_6 represents a hydrogen atom or a fluorine atom. ] An insecticide and acaricide containing the benzyl ether derivative shown as an active ingredient.