JPH0422903B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an oxime derivative represented by the following general formula () and an insecticide or acaricide containing the same as an active ingredient. [In the formula, R ₁ is an alkyl group having 2 to 8 carbon atoms, a cycloalkylalkyl group having 4 or 5 carbon atoms,
Represents a haloalkyl group having 2 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a haloalkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms,
R ₂ represents a hydrogen atom or a lower alkyl group,
R ₃ and R ₄ are the same or different and represent a methyl group or an ethyl group, or R ₃ and R ₄ combined at the terminals represent an ethylene group. Y is the formula or general formula a _group represented _by represents a sulfur atom, imino group or methylene group). ] The present inventors have conducted numerous studies to develop excellent insecticides and acaricides, and as a result, the oxime derivatives represented by the above general formula () (hereinafter referred to as the compounds of the present invention), in particular, The substituent R ₁ is an alkyl group having 2 to 5 carbon atoms, a haloalkyl group having 2 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms.
The compound of the present invention, which represents a haloalkenyl group of 5 or an alkynyl group having 2 to 5 carbon atoms, and in which R ₂ is a hydrogen atom or a methyl group, has 1. High insecticidal and acaricidal efficacy and is fast-acting. 2.Excellent effectiveness against pests that are resistant to organic phosphorus agents or carbamate agents. 3.Can be manufactured relatively cheaply. They discovered that it has excellent properties such as, and 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 Orthoptera such as the Japanese cockroach, other Coleoptera, Orthoptera, and spider mites include the red-throated spider mite, the orange spider mite, and the like. The compound of the present invention represented by the general formula () can be produced by the following method. (Manufacturing method A) General formula () R ₁ -O-NH ₂ () [In the formula, R ₁ represents the same meaning as above. ] A compound represented by or a reactive derivative thereof,
General formula () [In the formula, R ₂ , R ₃ , R ₄ and Y have the same meanings as above. ] A method of reacting with a carbonyl compound represented by or a reactive derivative thereof. Here, examples of the reactive derivative of the amine compound represented by the general formula () include mineral acid salts such as hydrochloride and sulfate, and organic acid salts, and
Examples of reactive derivatives of the carbonyl compound represented by the general formula () include derivatives such as acetals and ketals. In this production method, the reaction can be carried out in the presence or absence of an inert solvent, and in the presence or absence of an acid or alkali. Suitable solvents include water, benzene, toluene, carbon tetrachloride, chloroform, ethylene chloride, methylene chloride, and mixed solvents of two or more thereof. Suitable acids include hydrochloric acid, sulfuric acid, and p-toluenesulfonic acid, and suitable alkalis include inorganic bases such as sodium hydroxide, potassium hydroxide, and potassium carbonate, and organic bases such as triethylamine and pyridine. Although the reaction temperature is not particularly limited, it is usually carried out at a temperature of -30°C to the boiling point of the reaction mixture, more generally at a temperature of room temperature to 100°C. Also,
The reaction is usually completed in 0.5 to 24 hours. The molar ratio of the compound represented by the general formula () or its reactive derivative to the compound represented by the general formula () or its reactive derivative is usually 1:0.1 to
2, more generally 1:0.8 to 1.0. In this production method, the amine compound represented by the general formula () is a known compound or a J.Org.
Chem., 36 3835 (1971). Furthermore, the carbonyl compound represented by the general formula () is a new compound, for example or [In the formula, R ₃ , R ₄ , Y and A ₃ have the same meanings as above. ] The aldehyde compound represented by the general formula (') can be obtained by the following route, or a substituent can be added to the aldehyde compound by, for example, a Grignard reaction.
It can be produced, for example, by introducing R ₂ and then oxidizing it. (Manufacturing method B) General formula () R ₁ -A ₁ () [In the formula, R ₁ represents the same meaning as above, and A ₁ represents a halogen atom, a tosyloxy group or a mesyloxy group. ] Compounds shown by and general formula () [In the formula, R ₂ , R ₃ , R ₄ and Y have the same meanings as above. ] A method of reacting the compound shown in the following in the presence of a deoxidizing agent. (Manufacturing method C) General formula () [In the formula, R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as above, and A ₂ represents a halogen atom, a tosyloxy group or a mesyloxy group. ] A compound represented by the general formula () H-O-CH ₂ -Y () [wherein, Y represents the same meaning as above. ] A method of reacting the compound shown in the following in the presence of a deoxidizing agent. (Manufacturing method D) General formula () [In the formula, R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as above. ] A compound represented by the general formula (XI) A ₃ -CH ₂ -Y (XI) [wherein Y represents the same meaning as above, and A ₃ represents a halogen atom, a tosyloxy group or a mesyloxy group. ] A method of reacting the compound shown in the following in the presence of a deoxidizing agent. In the above production methods B, C, and D, the deoxidizing agent includes alkali metals such as sodium and potassium, alkali metal hydrides such as sodium hydride, alkali metal amides such as sodium amide, sodium hydroxide, potassium hydroxide, etc. Examples include alkali metal hydroxides, alkali metal carbonates such as potassium carbonate, and organic bases such as pyridine and triethylamine. In addition, in these production methods, it is convenient to use an inert solvent to allow the reaction to proceed smoothly, and such solvents include dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, dimethoxyethane, toluene, etc. For example, a mixed solvent of two or more of the following solvents may be used. In addition, when a phase transfer catalyst such as benzyltriethylammonium chloride or tetra n-butylammonium bromide is used in this reaction, water can also be used as the solvent. In these production methods, the reaction temperature is not particularly limited, but is usually in the range of -80°C to the boiling point of the reaction mixture, more generally room temperature to
The temperature range is 100°C, and the reaction is usually completed in 0.5 to 24 hours. Compounds represented by general formula () and general formula ()
The molar ratio with the compound represented by is usually 1:0.1 to
1.2, preferably 1:0.8 to 1.0. Further, the molar ratio of the compound represented by the general formula () and the compound represented by the general formula () is usually 1:
The ratio is in the range of 1 to 10, preferably 1:1.0 to 1.2.
Furthermore, the molar ratio of the compound represented by the general formula () and the compound represented by the general formula (XI) is usually 1:
The ratio is in the range of 1 to 10, preferably 1:1.0 to 1.2. In the above production method B, the compound represented by the general formula () is a publicly known product or a J.Org.
Chem., 9 , 238 (1944). In addition, the compound represented by the general formula () is a new compound, and from the carbonyl compound represented by the general formula (), Org.syn., Coll.Vol., 313
(1943). In the above production method C, the compound represented by the general formula () is, for example, Org.syn., Coll.Vol., 313
(1943), general formula [In the formula, R ₃ and R ₄ have the same meanings as above. ] The aldehyde compound represented by is reacted with the amine compound represented by the general formula () to form the general formula [In the formula, R ₁ , R ₃ and R ₄ have the same meanings as above. ] It can be produced by obtaining an alcohol compound represented by the following and reacting the alcohol compound with a halogenating agent such as thionyl chloride or phosphorus tribromide, p-toluenesulfonic acid chloride, or mesyl chloride. In addition, in production method D, the compound represented by the general formula () is manufactured by Org.syn.Coll.Vol., 313 (1943)
According to the method described in the general formula [In the formula, R ₂ , R ₃ and R ₄ have the same meanings as above. ] It can be produced by reacting the carbonyl compound represented by the above with the amine compound represented by the general formula (). The compounds of the present invention obtained by the above production methods A to D can be purified by means such as column chromatography and distillation, if necessary. The compound of the present invention includes geometric isomers based on the unsaturated bond of oxime and optical isomers based on R ₃ and R ₄ , and all of these are included in the present invention. Next, the method for producing the compound of the present invention will be explained in detail using production examples. Production Example 1 Production of compound (27) by Production Method A 3,3-dimethyl-4-(3-phenoxybenzyloxy)-2-butanone 1.00g (3.35mmol)
0.654 g (6.70 mmol) of O-ethylhydroxylamine hydrochloride in 10 ml of pyridine solution of 5 to 10
℃ and was added dropwise with stirring over a period of 10 minutes. After stirring at room temperature overnight, the mixture was poured into 100 ml of water, extracted twice with 30 ml of toluene, washed with water, dried over anhydrous sodium sulfate, and the toluene was distilled off under reduced pressure.
The obtained oil was purified by column chromatography using silica gel to obtain 0.97 g of 2-ethoxyimino-3,3-dimethyl-4-(3-phenoxybenzyloxy)butane as a colorless liquid. . n ^24.5 _D 1.5377 Production Example 2 Production of Compound (2) by Production Method B 2. ,2-
Dimethyl-3-(3-phenoxybenzyloxy)
A solution of 0.299 g (1.0 mmol) of propionaldoxime in anhydrous dimethyl sulfoxide (5 ml) was added dropwise over 10 minutes with stirring. After stirring at room temperature for 1 hour, n-propyl iodide 0.204
g (1.2 mmol) in anhydrous dimethyl sulfoxide was added dropwise over 10 minutes with stirring. After stirring at room temperature overnight, the mixture was poured into 100 ml of water, extracted twice with 30 ml of toluene, washed with water, dried over anhydrous sodium sulfate, and the toluene was distilled off under reduced pressure. The obtained oil was purified by column chromatography using silica gel to obtain 0.28 g of O-n-propyl-2,2-dimethyl-3-(3-phenoxybenzyloxy)propional aldoxime. Obtained as a liquid. n ^25.0 _D 1.5310 Production Example 3 Production of compound (6) by Production Method C 0.19 g of sodium hydride (62% oil suspension) in 10 ml of anhydrous dimethyl sulfoxide
(5.0 mmol) was added thereto, and then 5 ml of a solution of 1.00 g (5.0 mmol) of 3-phenoxybenzyl alcohol in anhydrous dimethyl sulfoxide was added, followed by stirring at 65 to 70°C for 1 hour. After cooling to room temperature, 5 ml of a solution of 1.64 g (5.0 mmol) of O-sec-butyl-2,2-dimethyl-3-tosyloxypropionaldoxime in anhydrous dimethyl sulfoxide was added dropwise over 10 minutes, and the mixture was stirred at 100°C for 24 hours. did. After cooling to room temperature,
Pour the reaction mixture into 100 ml of water and dilute with 30 ml of toluene.
Extracted twice, washed with water, dried over anhydrous sodium sulfate, distilled off toluene, purified by column chromatography using silica gel, 0.113g
O-sec-butyl-2,2-dimethyl-3-(3
-Phenoxybenzyloxy)propional aldoxime was obtained as a colorless liquid. n ^28.5 _D 1.5207 Production Example 4 Production of compound (46) by Production Method D 0.19 g of sodium hydride (62% oil suspension) in 10 ml of anhydrous dimethyl sulfoxide
(5.0 mmol) and then O-n-propyl-
After dropping 5 ml of a solution of 0.80 g (5.0 mmol) of 2,2-dimethyl-3-hydroxypropionaldoxime in anhydrous dimethyl sulfoxide over 10 minutes,
The mixture was stirred at 70°C for 1 hour. After cooling to room temperature, 1.41 g of 3-phenoxy-4-fluorobenzyl bromide
(5.0 mmol) in anhydrous dimethyl sulfoxide solution 5
ml was added dropwise over 10 minutes, and the mixture was stirred overnight at room temperature. Pour the reaction mixture into 100ml of water and 30ml of toluene.
After washing with water and drying with anhydrous sodium sulfate, toluene was distilled off and purified by column chromatography using silica gel to obtain 1.55 g of O-n-propyl-2,2-dimethyl-3. −(3
-Phenoxy-4-fluorobenzyloxy)propionaldoxime was obtained as a colorless liquid. n ^25.5 _D 1.5205 Next, Table 1 shows some of the compounds of the present invention produced according to these production examples.

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[Table] 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 it is usually used as a solid carrier, liquid carrier,
It can be mixed with gaseous carriers, surfactants, other formulation auxiliaries, baits, etc., or impregnated into base materials such as incense sticks and mats to produce emulsions, wettable powders, powders, granules, oils, aerosols, and mosquitoes. It is formulated into heating fumigants such as incense coils and electric mosquito repellents, fogging agents such as fogging, non-heating fumigants, poison baits, etc. These preparations contain 0.01% to 95% by weight of the compound of the present invention as an active ingredient. Solid carriers include kaolin clay, attapalgite clay, bentonite, acid clay, pyrophyllite,
Talc, diatomaceous earth, calcite, corn cob flour,
There are fine powders or granules such as walnut flour, urea, ammonium sulfate, and synthetic hydrous silicon oxide, and liquid carriers include aliphatic hydrocarbons such as kerosene and kerosene,
Aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene, halogenated hydrocarbons such as dichloroethane, trichloroethylene, and carbon tetrachloride, alcohols such as methanol, ethanol, isopropanol, ethylene glycol, and cellosolve, acetone, methyl ethyl ketone, cyclohexanone, and isophorone. Ketones such as diethyl ether, dioxane, tetrahydrofuran and other ethers, esters such as ethyl acetate, nitriles such as acetonitrile and isobutyronitrile, acid amides such as dimethylformamide and dimethylacetamide, dimethyl sulfoxide, vegetable oils such as soybean oil and cottonseed oil. etc. Gaseous carriers include fluorocarbon gas,
Examples include LPG (liquefied petroleum gas) and dimethyl ether. Surfactants used for emulsification, dispersion, wetting, etc. include alkyl sulfate ester salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, and naphthalene sulfone. Examples include anionic surfactants such as acid formalin condensates, and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. 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 for,
Alkyl phosphates such as PAP (isopropyl acid phosphate) and TCP (trecresyl phosphate), vegetable oils, epoxidized oils, surfactants mentioned above, antioxidants such as BHT and BHA, fatty acids such as sodium oleate and calcium stearate. salt, methyl oleate,
Examples include fatty acid esters such as methyl stearate. Next, a formulation example will be shown. It should be noted that the compound of the present invention is
Indicated by compound number in the table. Parts are parts by weight. Formulation example 1 0.2 parts of the compound of the present invention (1), 2 parts of xylene, white kerosene
Mix 97.8 parts to obtain an oil solution. Formulation Example 2 10 parts of the compounds (1) to (59) of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 70 parts of xylene are thoroughly mixed to obtain an emulsion. Formulation Example 3 20 parts of the compound of the present invention (46), 10 parts of fenitrothion
3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 65 parts of synthetic hydrated silicon oxide.
Thoroughly grind and mix the two parts to obtain a wettable powder. Formulation Example 4 1 part of the compound of the present invention (49), 2 parts of carbaryl,
87 parts of kaolin clay and 10 parts of talc are thoroughly ground and mixed to obtain a powder. Formulation Example 5 5 parts of the compound of the present invention (53), 1 part of synthetic hydrous silicon oxide
1 part, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and 62 parts of kaolin clay are thoroughly ground and mixed, water is added and the mixture is thoroughly kneaded, followed by granulation and drying to obtain granules. Formulation example 6 0.05 part of the compound of the present invention (14), tetramethrin
Mix and dissolve 0.2 parts of Resmethrin, 0.05 parts of xylene, and 32.7 parts of deodorized kerosene, fill it into an aerosol container, attach the valve part, and then pressurize and fill 60 parts of propellant (liquefied petroleum gas) through the valve part. Then you get an aerosol. Formulation Example 7 Allethrin d-
Add 0.3 g of trans primary chrysanthemum acid ester, dissolve in 20 ml of methanol, and stir and mix uniformly with 99.4 g of carrier for mosquito coils (mixing tab powder, lees powder, and wood flour in the ratio of 3:5:1). , after evaporating methanol, water
Add 150ml, mix well, mold and dry to obtain each mosquito coil. These preparations are used as they are or diluted with water. In addition, other insecticides, acaricides, nematicides, fungicides, herbicides, plant growth regulators, fertilizers,
It can also be used in combination with soil conditioners and the like. When the compound of the present invention is used as an insecticide or acaricide, the application amount is usually 5 g to 10 are.
500g, and when applying emulsions, wettable powders, etc. diluted with water, the application concentration is 10ppm to 1000ppm.
Powders, granules, oils, aerosols, etc. are applied in their original form without any dilution. Next, a test example is shown. Note that the compound of the present invention has the first
The compounds used for comparison are indicated by the compound numbers in the table, and the compounds used for comparison are indicated by the compound symbols in Table 2.

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[Table] Test Example 1 Place a piece of paper of the same size on the bottom of a polyethylene cup with a diameter of 5.5 cm. A 200-fold dilution of the emulsion of the following compound prepared according to Formulation Example 2 with water (equivalent to 500 ppm)
Drop 0.7ml onto paper and evenly add 20mg of sucrose as bait. Ten female adult house flies were released into the container, the lid was closed, and 24 hours later, the survival rate was determined to determine the mortality rate (repeat twice).

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[Table] Test Example 2 A 200-fold dilution of the emulsion of the compound of the present invention below with water (equivalent to 500 ppm) 1 prepared according to Formulation Example 2
ml is soaked into 5 g of artificial feed for snailfish prepared in a polyethylene cup with a diameter of 5.5 cm. They released 10 10-day-old nymph moth larvae into it.
After 8 days, viability was examined (2 replicates).

[Table] Test Example 3 A rice stem (about 12 cm in length) is immersed for 1 minute in a water dilution of an emulsion of the present invention compound and a control compound obtained according to Formulation Example 2 at a predetermined concentration. After air-drying, rice stems were placed in a test tube and 10 adult leafhoppers of a resistant strain were released, and one day later, the viability was examined and the LC ₅₀ value (50% lethal concentration) was determined (2 repetitions).

[Table] Test Example 4 Ten female adult spider mites per leaf are infested on a potted green bean (initial leaf stage) 7 days after sowing, and stored in a constant temperature room at 25°C. 6 days later,
An emulsion of the following inventive compound and control compound prepared according to Formulation Example 2 was diluted with water to 500 ppm of active ingredient.
ml of the solution, and at the same time, irrigate the soil with 2 ml of the same solution. Eight days later, each plant was examined for damage caused by spider mites. The effectiveness criteria are -: Almost no damage observed. +: Slight damage is observed. : The same damage as in the untreated area is observed. And so.

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Claims (1)

[Claims] 1. General formula [In the formula, R ₁ is an alkyl group having 2 to 8 carbon atoms, a cycloalkylalkyl group having 4 or 5 carbon atoms,
Represents a haloalkyl group having 2 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a haloalkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms,
R ₂ represents a hydrogen atom or a lower alkyl group,
R ₃ and R ₄ are the same or different and represent a methyl group or an ethyl group, or R ₃ and R ₄ combined at the terminals represent an ethylene group. Y is the formula or general formula A group represented by (where R ₅ represents a hydrogen atom or a fluorine atom, R ₆ represents a hydrogen atom, a halogen atom or a lower alkyl group, Q represents a nitrogen atom or a methine group, and Z represents an oxygen atom) , a sulfur atom, an imino group or a methylene group). ] An oxime derivative represented by 2 General formula [In the formula, R ₁ is an alkyl group having 2 to 8 carbon atoms, a cycloalkylalkyl group having 4 or 5 carbon atoms,
Represents a haloalkyl group having 2 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a haloalkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms,
R ₂ represents a hydrogen atom or a lower alkyl group,
R ₃ and R ₄ are the same or different and represent a methyl group or an ethyl group, or R ₃ and R ₄ combined at the terminals represent an ethylene group. Y is the formula or general formula A group represented by (where R ₅ represents a hydrogen atom or a fluorine atom, R ₆ represents a hydrogen atom, a halogen atom or a lower alkyl group, Q represents a nitrogen atom or a methyl group, and Z represents an oxygen atom) , a sulfur atom, an imino group or a methylene group). ] An insecticide and acaricide characterized by containing an oxime derivative shown by the following as an active ingredient.