JPH03261737A - Hydrocarbon compound and insecticide containing thereof as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R1 is halogen, lower alkyl, lower alkoxyl or fluorine-substituted lower alkoxyl; R2 is n or F). EXAMPLE:1-(4-Ethoxyphenyl)-1-{3-(3-phenoxyphenyl)-1-propenyl} cyclopropane. USE:Used as an insecticide having characteristics such as extremely high insecticidal effect, also exhibiting excellent effect to harmful insect resistant to an organic phosphorus agent or a carbamate agent with producible in a relatively low cost and having a low toxicity to hematherm. PREPARATION:A compound expressed by formula II is reacted with a base such as n-butyllithium in a solvent such as tetrahydrofuran in a nitrogen atmosphere at a temperature of from -78 deg.C to 30 deg.C and resultant reacted solution is treated with diluted hydrochloric acid, etc., at a temperature of from -78 deg.C to 10 deg.C, or a compound expressed by formula III is reacted with said base, etc., in a solvent such as dried ether at a temperature from -78 deg.C to 20 deg.C to afford the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel hydrocarbon compound represented by the following general formula (I) and an insecticide containing the compound as an active ingredient.

[In the formula, R1 represents a halogen atom, a lower alkyl group, a lower alkoxyl group, or a fluorine-substituted lower alkoxyl group. R2 represents a hydrogen atom or a fluorine atom. ] As a result of repeated research for the purpose of developing a compound having excellent insecticidal activity, the present inventors found that the compound of the present invention represented by the above general formula (1) has 1. Extremely high insecticidal efficacy. 2. It is also highly effective against pests that are resistant to organic phosphorus agents or carbamate agents. 3. It can be manufactured relatively cheaply. 4. Low toxicity to warm-blooded animals. The present inventors have discovered that it has the following characteristics, 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, stink bugs, and whiteflies; Lepidoptera such as diamondback moths, Japanese mealybugs, brown borers, and armyworms; Culex mosquitoes; and houseflies. Examples include Diptera, such as the German cockroach, Reciptera, Coleoptera, and Orthoptera.

The compound of the present invention can be produced, for example, by the following method.

<Production method A> 2 (II) [In the formula, R1 and Rt have the same meanings as above. ] A base such as n-butyllithium or 5ec-butyllithium is added to the compound represented by - in a solvent such as diethyl ether or tetrahydrofuran under a nitrogen atmosphere.
By reacting at 78°C to 30°C for 2 to 24 hours, and then treating the reaction solution with a mineral acid such as dilute hydrochloric acid, ammonium chloride, or an aqueous solution thereof at -78°C to -10°C, the desired book can be obtained. The invention compound is obtained.

In this method, examples of the compound represented by the general formula (n) used as a raw material include the following compounds.

1-(4-ethoxyphenyl)-1-(3-(3-phenoxyphenyl)-2-propenyl)cyclopropane 1-(4-ethoxyphenyl)-1-(3-(3-phenoxy-4-fluorophenyl) -2-propenyl)cyclopropane 1-(4-methoxyphenyl)-1-(3-(3-phenoxyphenyl)-2-propenyl)cyclopropane ■-(4-methoxyphenyl)-1-(3-(3 -phenoxy-4-fluorophenyl)-2-propenyl)cyclopropane!-(4-n-propyloxyphenyl)-1-(3-
(3-phenoxyphenyl)-2-propenyl)cyclopropane 1-(4-ethylphenyl)-1-(3-(3-phenoxyphenyl)-2-propenyl)cyclopropane 1-(4-methylphenyl)-1 -(3-(3-phenoxy-4-fluorophenyl)-2-propenyl)cyclopropane1-(4-chlorophenyl")-1-(3-(3phenoxy-4-fluorophenyl)-2-propenyl)cyclo Propane 1-(4-trifluoromethoxyphenyl)-1-(3
-(3-phenoxyphenyl)-2-propenyl)cyclopropane 1-(4-iso-propoxyphenyl)-1(3-(
3-phenoxyphenyl)-2-propenyl)cyclopropane 1-(4-t-butylphenyl')-1-(3-(3-
phenoxyphenyl)-2-propenyl)cyclopropane 1-(4-fluorophenyl")-1"-(3-(3-
Phenoxyphenyl)-2-propenyl)cyclopropane Production Method B> General Formula (III) [In the formula, R1 and R1 have the same meanings as above. ] Add 2 equivalents of a base such as n-butyllithium, se C-butyllithium, or potassium hydroxide to the hydrazone represented by 0.5 in a solvent such as dry ether or dry tetrahydrofuran at -78 to 20°C. The compound of the present invention can be obtained by reacting for ~24 hours.

In the shark method, the above-general formula (I
Examples of the hydrazone represented by II) include the following.

1-(4-ethoxyphenyl)-1-(3-(3-phenoxyphenyl)-1-oxopropyl)cyclopropantosylhydrazone 1-(4-ethoxyphenyl)-1-(3-(3-phenoxy- 4-fluorophenyl)-1-oxopropyl)cyclopropantosylhydrazone 1-(4-methoxyphenyl')-1-(3-(3-
Phenoxyphenyl)-1-oxopropyl)cyclopropane tosylhydrazone! -(4-Methoxyphenyl')-1-(3-(3-phenoxy-4-fluorophenyl)-1-oxobrobyl)cyclopropantosylhydrazone 1-(4-iso-propyloxyphenyl)-1-(
3-(3-phenoxyphenyl)-1-oxopropyl)cyclopropantosylhydrazone 1-(4-ethylphenyl)-1-(3-(3-phenoxyphenyl)-1-oxopropyl)cyclopropantosylhydrazone 1- (4-methylphenyl)-1-(3-(3-phenoxy-4-fluorophenyl)-1-oxopropyl)
Cyclopropantosylhydrazone! -(4-fluorophenyl)-1-(3-(3-phenoxyphenyl)-1
-oxopropyl)cyclopropantosylhydramono In the above production method A, the compound represented by the general formula CI[) used as a raw material can be produced, for example, by the synthetic route shown below.

Method 1 Method 2 2 [In the formula, R and R1 have the same meanings as above, X represents a halogen atom, and R1 represents a lower alkyne group. ] Furthermore, in production method B, hydrazone used as a raw material can be produced by the following route.

[In the formula, RI and R3 have the same meanings as above. ] Next, some of the compounds of the present invention produced based on the above production method are illustrated in the table below, but the present invention is not limited thereto.

(Note) Contents of each substituent in the compound represented by the above general formula (I).

The method for producing the compound of the present invention will be explained in more detail in the following Production Examples.

Production example 1-(4-ethoxyphenyl)-1-(3-(3-phenoxyphenyl)-2-propenyl)cyclopropane 2
．． 0 g was dissolved in dry tetrahydrofuran, and to this was added 4.8 mm of a solution of n-butyllithium in n-hexane (1.35 molar solution) at -50° C. under a nitrogen atmosphere. After continuing the reaction at the same temperature for 1 hour, the reaction was continued for 24 hours while gradually raising the temperature of the reaction solution to room temperature. Next, the reaction solution was cooled to -50°C, 30% of 10% hydrochloric acid solution was added thereto, and then extracted with ethyl acetate. The ethyl acetate solution was washed twice with saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: n-beef san: ethyl acetate = 10
1-(4-ethoxyphenyl)-1-(3-(3-phenoxyphenyl)-1-
propenyl) cyclopropane (compound (1)) 400
I got ■.

Refractive index: 1.5774 (23.0°C) When the compound of the present invention is used as an active ingredient of an insecticide, it may be used as it is without adding any other ingredients, but it is usually used with a solid carrier,
It can be mixed with liquid carriers, 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, etc. It is formulated into aerosols, heating fumigants such as mosquito coils and electric mosquito mats, fogging agents such as Foraking, 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 fine powders or granules such as kaolin clay, attapulgite clay 1, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. 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, methanol, Alcohols such as ethanol, isopropanol, ethylene glycol, and cellosolve; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and isophorone;
These include ethers such as diethyl ether, dioxane, and tetrahydrofuran, esters such as ethyl acetate, nitrites such as acetonitrile and isobutyronitrile, acid amides such as dimethylformamide and dimethylacetamide, and vegetable oils such as dimethyl sulfoxide, soybean oil, and cottonseed oil. . Gaseous carriers include chlorofluorocarbon 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, and naphthalene sulfone. Examples include anionic surfactants such as acid formalin condensates, and nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Formulation aids such as fixing agents and dispersants include genin sulfonate, alginate, polyvinyl alcohol, gum arabic, 11 casein, gelatin, CMC (carboxymethyl cellulose), pine oil, and agar.Stabilizers include ,
Alkyl phosphates such as PAP (isopropyl acid phosphate) and TCP (tricresyl phosphate), vegetable oil, epoxidized moieties, surfactants mentioned above, antioxidants such as BHT and BHA, fatty acids such as sodium oleate and calcium stearate. These include salts, 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 Compounds of the present invention (1) to (410, 1 part, xylene 2 parts,
Mix 97.9 parts of white kerosene to obtain an oil solution.

Formulation Example 2 0 parts of the compounds (1) to (4) of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 70 parts of xylene are thoroughly mixed to obtain an emulsion.

Formulation Example 3 Compound of the present invention (1120 parts, 10 parts of fenitrothion,
3 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 (1) of the present invention, 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 (1), 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignosulfonate, 30 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 (210.05 parts, tetramethrin 0.2
1 part, Resmethrin 0.05 parts, xylene 7 parts, and deodorized kerosene 32.7 parts are mixed and dissolved, filled into an aerosol container, and after the valve part is attached, 60 parts of propellant (liquefied petroleum gas) is injected through the bulk valve part. If it is filled under pressure, an aerosol can be obtained.

Formulation Example 7 To 410.3 g of the compound of the present invention, 0.3 g of d-1 lance chrysanthemum acid ester of allethrin was added, and methanol 20-
Dissolve in a carrier for mosquito coils (3 parts: tab powder: lees powder: wood powder).
(mixed at a ratio of 5:1) with 99.4 g, and after evaporating the methanol, 150 g of water was added, and the thoroughly kneaded mixture was molded and dried to obtain each 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 promoters, fertilizers, soil conditioners, etc.

When the compound of the present invention is used as an insecticide, the application amount is usually 5 g to 500 g per 1O are, emulsion,
When applying wettable powders etc. after diluting them with water, the application concentration is 5 ppa+ to 1000 ppm, and powders, granules, oils, aerosols, etc. should be applied as they are without any dilution. .

Next, a test example is shown.

Test Example 1 Place a filter paper of the same size at the bottom of a polyethylene cup with a diameter of 5.5 an. A 200-fold dilution of an emulsion of the following compound prepared according to Formulation Example 2 with water (equivalent to 500 ppm) 0.7-
was dropped onto the filter paper, and 20 μm of sucrose was evenly added as bait. Ten female adult house flies were released into the chamber, the lid was closed, and 48 hours later, the survival rate was determined (2 repetitions).
.

Test Example 2 Rice stems (about 12 cm in length) are 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 test tubes and 10 adult leafhoppers of a resistant strain were released, and one day later, the survival and death of L.
The Clo value (50% lethal concentration) was determined (2 replicates).

Test Example 3 A 200-fold diluted solution (equivalent 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 13
Soaked in artificial feed for Spodoptera g, diameter 11
Pour into a polyethylene cup. Fourth-instar larvae of Spodoptera japonica were released into the 101F, and 6 days later, their survival and death were examined (2 repetitions).

CH.

Test Example 4 Rice stems (length: about 120 mm) are 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, put the rice stem into a test tube and add one adult brown planthopper.
0 animals were released, and one day later, they were examined to see if they were alive or dead.

The value (50% lethal concentration) was determined (2 replicates).

Test Example 5 A 200-fold dilution of an emulsion of the compound of the present invention below with water (equivalent to 500 ppm) 1ff7 prepared according to Formulation Example 2
Soak into 5 g of artificial feed for snailfish prepared in a polyethylene cup with a diameter of 5.5011 mm. 10 larvae of the 10-day-old Japanese borer moth were released into the larvae, and 8 days later, the survival and death of the larvae was examined (2 repetitions).

Claims (2)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R_1 represents a halogen atom, a lower alkyl group, a lower alkoxyl group, or a fluorine-substituted lower alkoxyl group. R_2 represents a hydrogen atom or a fluorine atom. ] A hydrocarbon compound represented by (2) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R_1 represents a halogen atom, a lower alkyl group, a lower alkoxyl group, or a fluorine-substituted lower alkoxyl group. R_2 represents a hydrogen atom or a fluorine atom. ] An insecticide characterized by containing a hydrocarbon compound represented by the following as an active ingredient.