JPH0471062B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel hydrocarbon compound represented by the following general formula (), a method for producing the same, and an insecticide and acaricide containing the compound as an active ingredient. [In the formula, R ₁ is a halogen atom, a lower alkyl group,
It represents a lower alkoxyl group or a lower haloalkoxyl group, and R ₂ and R ₃ each represent a methyl group, or R ₂ and R ₃ combine to represent an ethylene group.
R ₄ represents a hydrogen atom or a fluorine atom, and R ₅ represents a hydrogen atom or a halogen atom. ] As a result of repeated research aimed at developing a compound with excellent insecticidal and acaricidal activity, the present inventors found that
The compound of the present invention represented by the general formula () is 1
It has extremely high insecticidal and acaricidal efficacy and is fast-acting. 2. It is also highly effective against pests that are resistant to organic phosphorus agents or gerbamate agents. 3. Can be manufactured relatively cheaply. The present invention was completed based on the discovery that the present invention has the following characteristics. 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 Reticiptera, Coleoptera, and Orthoptera, and the spider mites include the false red spider mite, the orange spider mite, and the like. The compound of the present invention can be produced, for example, by the following method. <Manufacturing method (A)> General formula () [In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ have the same meanings as above. ] The carbonyl group of the compound represented by is converted into hydrazone by adding hydrazine hydrate in an inert solvent such as diethylene glycol or triethylene glycol under a nitrogen atmosphere, and then adding potassium hydroxide or sodium hydroxide, etc. Add base to 180
℃ ~ 220℃, continuing heating for 2 hours to 2 days (J.Chem.
Soc., 4202 (1958), J.Amer.Chem.Soc., 86 ,
2909 (1964)) to convert it into a methylene group, a compound represented by the general formula () can be obtained. In this method, examples of the compound represented by the general formula () used as a raw material include the following compounds. 2-Methyl-2-(4-ethoxyphenyl)-5
-(3-anilinophenyl)-3-pentanone 2-methyl-2-(4-ethoxyphenyl)-5
-(3-anilino-4-fluorophenyl)-3-
Pentanone 1-(4-ethoxyphenyl)-1-[3-(3-
Anilinophenyl)-1-propanoyl]cyclopropane 1-(4-ethoxyphenyl)-1-[3-(3-
Anilino-4-fluorophenyl)-1-propanoyl]cyclopropane 2-methyl-2-(4-chlorophenyl)-5-
(3-anilino-4-fluorophenyl)-3-pentanone <Production method (B)> General formula () [In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ have the same meanings as above. ] The carbonyl group of the compound represented by the above manufacturing method (A)
By converting into a methylene group in the same manner as above, a compound represented by the general formula () can be obtained. In this method, examples of the compound represented by the general formula () used as a raw material include the following compounds. 2-Methyl-2-(4-ethoxyphenyl)-5
-(3-anilinophenyl)-5-pentanone 2-methyl-2-(4-ethoxyphenyl)-5
-(3-anilino-4-fluorophenyl)-5-
Pentanone 1-(4-ethoxyphenyl)-1-[3-(3-
Anilinophenyl)-3-propanoyl]cyclopropane 1-(4-ethoxyphenyl)-1-[3-(3-
Anilino-4-fluorophenyl)-3-propanoyl]cyclopropane 2-methyl-2-(4-chlorophenyl)-5-
(3-anilino-4-fluorophenyl)-5-pentanone <Production method (C)> General formula () [In the formula, R ₁ ' represents a lower alkyl group or a lower alkoxyl group, and R ₂ , R ₃ and R ₄ have the same meanings as above. ] Compounds shown by and general formula () [In the formula, R ₅ represents the same meaning as above. ] In an inert solvent (e.g. dimethylformamide, dimethylacetamide, pyridine, etc.), a base (e.g. potassium carbonate, soda carbonate, etc.) and copper or a copper compound (e.g. cuprous chloride, copper powder, etc.) are added. 120℃~ under nitrogen flow in the presence of
By reacting at 150℃ for 10 to 60 hours,
General formula () [In the formula, R ₁ ′, R ₂ , R ₃ , R ₄ and R ₅ have the same meanings as above. ] A compound represented by the following is obtained. <Manufacturing method (D)> Compound represented by the above general formula () and general formula [In the formula, R ₅ has the same meaning as above. ] The compound represented by is mixed in an inert solvent (for example,
dimethylformamide, dimethylacetamide,
pyridine, etc.) in the presence of a base (e.g., potassium carbonate, soda carbonate, etc.) and copper or a copper compound (e.g., cuprous chloride, copper powder, etc.) in a nitrogen stream.
After reacting for 10 to 60 hours at ℃ to 150℃, the above-mentioned general A compound represented by formula () is obtained. Examples of the compounds represented by the above general formula () that serve as raw materials in the above production methods (C) and (D) include the following compounds. 2-Methyl-2-(4-ethoxyphenyl)-5
-(3-bromo-4-fluorophenyl)pentane 1-(4-ethoxyphenyl)-1-[3-(3-
Bromo-4-fluorophenyl)propyl]cyclopropane 2-methyl-2-(4-ethoxyphenyl)-5
-(3-bromophenyl)pentane 1-(4-ethoxyphenyl)-1-[3-(3-
Bromophenyl)propyl]cyclopropane 2-methyl-2-(4-methylphenyl)-5-
(3-bromophenyl)pentane 2-methyl-2-(4-methylphenyl)-5-
(3-bromo-4-fluorophenyl)pentane 2-methyl-2-(4-methoxyphenyl)-5
-(3-bromo-4-fluorophenyl)pentane 1-(4-methoxyphenyl)-1-[3-(3-
Bromo-4-fluorophenyl)propyl]cyclopropane Compounds represented by the general formula () include aniline, p-chloroaniline, p-fluoroaniline, etc.; , acetanilide, p-chloroacetanide, p-fluoroacetaniline, and the like. In addition, in the above manufacturing methods (A), (B), (C) and (D),
Compounds of general formulas (), () and () can be produced, for example, by the routes shown below. [In the formula, R represents an alkyl group having 1 to 2 carbon atoms, and R ₁ , R ₁ ', R ₂ , R ₃ , R ₄ and R ₅ have the same meanings as above. Furthermore, examples of the compounds of the present invention produced based on the above production method are shown in the table below, but of course the compounds of the present invention are not limited to these examples.

[Table] The compounds of the present invention will be explained in more detail with reference to Examples below. Example 1 Production of compound (4) by production method (A) 1-(p-ethoxyphenyl)-1-[3-(m-
Add 0.47 g of hydrazine hydrate to 1.2 g of (anilinophenyl)-1-oxopropyl]cyclopropane, add 30 ml of diethylene glycol, and add 80
Heat to 100°C. Then potassium hydroxide
0.47g was added and the reaction was carried out at 200°C to 210°C for 5 hours. The reaction solution was cooled to room temperature, water and ether were added to separate the layers, the aqueous layer was extracted twice with ether, the ether layers were combined and washed twice with saturated brine, dried over anhydrous magnesium sulfate, and then dried under reduced pressure. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 0.58 g of the desired product as a pale yellow oil. Example 2 Synthesis of compound (1) by production method (C) 2-methyl-2-(4-ethoxyphenyl)-5
2.2 g of -(3-bromo-4-fluorophenyl)pentane are dissolved in 50 ml of dry dimethylformamide. Add 0.96 g of potassium carbonate, 0.65 g of aniline, and 0.3 g of cuprous chloride to this, and heat to 140 ~
Heated to 150°C and continued for 36 hours. After the reaction was completed, the mixture was cooled to room temperature, poured into ice water, and extracted with ethyl acetate.
The aqueous layer was extracted once with ethyl acetate, the ethyl acetate layers were combined, washed twice with saturated brine, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography. 0.31 g of the target product was obtained. When the compound of the present invention is used as an active ingredient of an insecticide or acaricide, it is usually used as a solid carrier, liquid carrier, gaseous carrier, or other formulation auxiliary agent (e.g., surfactant, dispersant, wetting agent, stabilizer). etc.) to produce various preparations such as emulsions, wettable powders, powders, granules, oils, aerosols, heated smoke agents (mosquito coils, electric mosquito repellents, etc.), fogging agents such as fogging, non-heated Use as fumigant, poisonous bait, etc. The active ingredient content during their manufacture is 0.01-95%. Solid carriers include clays (e.g. kaolin, bentonite, acid clay, pyrophyllite, sericite), talcs, and other inorganic minerals (e.g.
Examples include fine powders or powders such as hydrated silicon dioxide, pumice, diatomaceous earth, sulfur powder, and activated carbon. Liquid carriers include alcohols (e.g. methyl alcohol, ethyl alcohol, ketones (e.g. acetone, methyl ethyl ketone), ethers (e.g. ethyl ether, dioxane, cellosolve, tetrahydrofuran), aromatic hydrocarbons (e.g. benzene, toluene, xylene, methylnaphthalene), aliphatic hydrocarbons (e.g. kerosene, kerosene), esters, nitriles, acid amides (e.g. dimethylformamide, dimethylacetamide), halogenated hydrocarbons (e.g. dichloroethane, trichloroethylene, carbon tetroxide)
etc. are mentioned. Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, polyethylene glycol ethers, polyhydric alcohol esters, and the like. Furthermore, the fixing agents and dispersants that can be used include:
Stabilizers include casein, gelatin, starch powder, CMC, gum arabic, alginic acid, lignin sulfonate, bentonite, molasses, polyvinyl alcohol, pine oil, and agar.
For example, PAP (isopropyl phosphate), TCP (tricresyl phosphate), tall oil, epoxidized oil,
Examples include various surfactants, various fatty acids or esters thereof, and the like. Examples of formulations are shown below. Formulation Example 1 By dissolving 0.2 parts of each of the compounds (1) to (4) of the present invention in white kerosene to make a total of 100 parts, an oil solution is obtained. Formulation Example 2 10 parts each of the compounds (1) to (4) of the present invention, and
Add 15 parts of an emulsifier (Solpol 3005X (trade name of Toho Chemical Records)) and 75 parts of xylene, and stir and mix these to obtain each emulsion. Formulation Example 3 0.2 part of the compound of the present invention (3), 0.2 part of tetramethrin ,
7 parts of xylene and 32.6 parts of deodorized kerosene are mixed and dissolved, filled into an aerosol container, a valve part is attached, and 60 parts of a propellant (liquefied petroleum gas) is charged under pressure through the valve part to obtain an aerosol. Formulation Example 4 Add 0.3 g of allethrin d-trans monochrylate to 0.3 g of the compound (3) of the present invention, and add methanol 20 g.
ml and stirred and mixed uniformly with 99.4 g of mosquito coil carrier (Tab powder: lees powder: wood flour mixed at a ratio of 3:5:1). After evaporating the methanol, add 150 ml of water and mix thoroughly. Mosquito coils are obtained by molding and drying the mixture. Formulation Example 5 10 parts of fenitrothion was added to 20 parts each of the compounds (1) to (4) of the present invention, and emulsifier {Solpol 5029-0
(Toho Chemical registered trademark name) Mix 5 parts well and add 300
Add 65 parts of mesh diatomaceous earth and thoroughly stir and mix in a crusher to obtain each wettable powder. Formulation Example 6 2 parts of naphthyl-N-methyl carbamate was added to 1 part of each of the compounds (1) to (4) of the present invention, dissolved in an appropriate amount of acetone, 97 parts of 300 ml of turquoise was added, and the mixture was placed in a grater. After thorough stirring and mixing, the acetone is removed by evaporation to obtain each powder. Formulation Example 7 To 5 parts each of the compounds (1) to (4) of the present invention, 5 parts of Toyolignin CT (registered trademark of Toyobo) and 90 parts of GSM clay (registered trademark of Zieglite Co., Ltd.) were added, and the mixture was placed in a crusher. Stir thoroughly to mix. Next, water is added in an amount of 10% of the mixture, and the mixture is stirred and mixed, granulated using a granulator, and dried through ventilation to obtain each granule. The compound of the present invention is widely used as an agricultural and horticultural insecticide and acaricide in rice fields, fields, orchards, tea gardens, mulberry gardens, lawns, etc.
In addition to being used in pastures and forests, it can also be used as an insecticide and acaricide for epidemic prevention. Next, test examples will be used to demonstrate that the compounds of the present invention are useful as active ingredients for insecticides and acaricides. The compounds of the present invention have compound numbers in Table 1, and
Compounds used as comparison controls are indicated by the following compound codes.

【table】

[Table] Test Example 1 2 ml of a 200-fold dilution of the emulsion of the compound of the present invention obtained in Formulation Example 2 with water (equivalent to 500 ppm)
Soak it in 13g of artificial food for Spodoptera japonica and place it in a polyethylene cup with a diameter of 11cm. Ten 3rd instar Spodoptera larvae were released into the larvae, and 6 days later, their survival and death were examined (2 repetitions).

[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. Release 10 10-day-old nymph moth larvae into it.
After 8 days, viability was examined (2 replicates). The results are shown in the table below.

【table】

[Table] Test Example 3 Compounds (1), (3) of the present invention and a control compound were diluted with acetone to a predetermined concentration, and adult male cockroaches
Apply topically to the ventral thorax of 10 animals. After treatment, the animals were kept together with food and water in polyethylene cups, and 3 days later, they were examined for survival and the LD ₅₀ value (50% lethal dose) was determined.
(3 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,
A drug solution prepared by diluting an emulsion of the compound of the present invention and a control compound below with water to 500 ppm of active ingredient, prepared according to Formulation Example 2, was added to 10 ml per pot on a turntable.
Spray and at the same time irrigate the soil with 2 ml of the same solution. After 8 days, spider mites were counted on each plant. Effect evaluation criteria: -: Almost no damage observed. +: Slight damage is observed. : The same damage as in the untreated area is observed. And so. The results are shown in the table below.

【table】

Claims (1)

[Claims] 1. General formula [In the formula, R ₁ is a halogen atom, a lower alkyl group,
It represents a lower alkoxyl group or a lower haloalkoxyl group, and R ₂ and R ₃ each represent a methyl group, or R ₂ and R ₃ combine to represent an ethylene group. _R4
represents a hydrogen atom or a fluorine atom, and R ₅ represents a hydrogen atom or a halogen atom. ] A hydrocarbon compound represented by 2 General formula [In the formula, R ₁ is a halogen atom, a lower alkyl group,
It represents a lower alkoxyl group or a lower haloalkoxyl group, and R ₂ and R ₃ each represent a methyl group, or R ₂ and R ₃ combine to represent an ethylene group.
R ₄ represents a hydrogen atom or a fluorine atom, and R ₅ represents a hydrogen atom or a halogen atom. ] General formula characterized by reducing the carbonyl group of the compound represented by [In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ have the same meanings as above. ] A method for producing a hydrocarbon compound shown in 3 General formula [In the formula, R ₁ is a halogen atom, a lower alkyl group,
It represents a lower alkoxyl group or a lower haloalkoxyl group, and R ₂ and R ₃ each represent a methyl group, or R ₂ and R ₃ combine to represent an ethylene group.
R ₄ represents a hydrogen atom or a fluorine atom, and R ₅ represents a hydrogen atom or a halogen atom. ] General formula characterized by reducing the carbonyl group of the compound represented by [In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ have the same meanings as above. ] A method for producing a hydrocarbon compound shown in 4 General formula [In the formula, R ₁ ' represents a lower alkyl group or a lower alkoxyl group, R ₂ and R ₃ each represent a methyl group, or R ₂ and R ₃ combine to represent an ethylene group, and R ₄ Represents a hydrogen atom or a fluorine atom. ] The compound represented by and the general formula [In the formula, R ₅ represents a hydrogen atom or a halogen atom. ] A general formula characterized by reacting a compound represented by the above in the presence of a base and copper or a copper compound. [In the formula, R ₁ ', R ₂ , R ₃ , R ₄ and R ₅ have the same meanings as above. ] A method for producing a hydrocarbon compound shown in 5 General formula [In the formula, R ₁ ' represents a lower alkyl group or a lower alkoxyl group, R ₂ and R ₃ each represent a methyl group, or R ₂ and R ₃ combine to represent an ethylene group, and R ₄ represents hydrogen Represents an atom or a fluorine atom. ] The compound represented by and the general formula [In the formula, R ₅ represents a hydrogen atom or a halogen atom. ] A general formula characterized in that the compound represented by is reacted with a base in the presence of copper or a copper compound, and then deacetylated. [In the formula, R′ ₁ , R ₂ , R ₃ , R ₄ and R ₅ have the same meanings as above. ] A method for producing a hydrocarbon compound shown in 6 General formula [In the formula, R ₁ is a halogen atom, a lower alkyl group,
It represents a lower alkoxyl group or a lower haloalkoxyl group, and R ₂ and R ₃ each represent a methyl group, or R ₂ and R ₃ combine to represent an ethylene group.
R ₄ represents a hydrogen atom or a fluorine atom, and R ₅ represents a hydrogen atom or a halogen atom. ] An insecticide and acaricide characterized by containing a hydrocarbon compound represented by the following as an active ingredient.