JPH1171317A - Phenylcyclopropane derivative and insecticide containing the derivative as active component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject new compound having excellent insecticidal activity. SOLUTION: This compound is expressed by the formula I (A is methylene or carbonyl; X is H, cyano or ethynyl; Y is H, a halogen or a lower alkyl; Z is H or F; W is H or a halogen), e.g. 2-methyl-3-phenylcyclopropylmethyl (3-phenoxybenzyl) ether. The compound of the formula I wherein A is methylene can be produced e.g. by reducing an ester compound of the formula II (R is a 1-4C lower alkyl) to obtain an alcohol compound of the formula III and reacting the compound with a benzyl halide compound of the formula IV (L1 is a halogen) preferably in the presence of a base (e.g. an inorganic base such as potassium carbonate or an organic base such as pyridine) in a solvent (e.g. a polar solvent such as N,N-dimethylformamide or a hydrocarbon such as toluene) at a temperature between -5 deg.C and the boiling point of the solvent or 100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to 2-methyl-3-
The present invention relates to a phenylcyclopropane derivative and an insecticide containing the same as an active ingredient.

2. Description of the Related Art Conventionally, 2, such as natural pyrethrin,
2-dimethyl-3-substituted cyclopropanecarboxyle-
Is known to exhibit insecticidal activity.

However, these compounds are not always satisfactory as insecticidal compounds.

[0002]

Means for Solving the Problems The present inventors have found that a 2-methyl-3-phenylcyclopropane derivative represented by the following general formula (2) has excellent insecticidal activity, and reached the present invention. That is, the present invention provides a compound represented by the general formula:

Embedded image [In the formula, A represents a methylene group or a carbonyl group,
X represents a hydrogen atom, a cyano group or an ethynyl group. Y
Represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxyl group, a lower haloalkyl group or a lower haloalkoxyl group, Z represents a hydrogen atom or a fluorine atom, and W represents a hydrogen atom or a halogen atom. A 2-methyl-3-phenylcyclopropane derivative (hereinafter, referred to as the compound of the present invention) and an insecticide characterized by containing the compound as an active ingredient. In the compound of the present invention, from the viewpoint of insecticidal activity, a compound in which A is a methylene group, X is a hydrogen atom and a compound in which A is a carbonyl group and X is a hydrogen atom, a cyano group or an ethynyl group are preferable, and , Y
Is preferably a hydrogen atom or a substituent at the 4-position.
The compounds of the present invention include 2- and 3-positions on the cyclopropane ring.
There are geometric isomers derived from the position (cis, trans) and optical isomers derived from the asymmetric carbon atom, and the present invention includes each stereoisomer having insecticidal activity and a mixture in any ratio thereof. In particular, (1S, 2)
The stereoisomer (S, 3S) is preferred.

[0003]

BEST MODE FOR CARRYING OUT THE INVENTION In the compound of the present invention, the substituent Y
Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom, examples of the lower alkyl group include a C1-C4 alkyl group such as a methyl group and an ethyl group, and examples of the lower alkoxyl group include A C1-C4 alkoxy group such as a methoxy group and an ethoxy group is exemplified, and a lower haloalkyl group is, for example, a C1-C2 haloalkyl group such as a trifluoromethyl group, and a lower haloalkoxyl group is, for example, a trifluoromethoxy group And C1-C2 haloalkoxy groups such as difluoromethoxy group, bromodifluoromethoxy group and the like. Examples of the halogen atom as the substituent W include a chlorine atom.

In the compound of the present invention, when A is a methylene group, for example,

Embedded image (Wherein, Y represents the same meaning as described above, and R represents C1 to C4
Represents a lower alkyl group. A) a compound represented by the general formula:

Embedded image (Wherein, Y represents the same meaning as described above) and a compound represented by the general formula

Embedded image (Wherein, Z and W have the same meanings as described above, and L ₁ represents a halogen atom (for example, a chlorine atom, a bromine atom, etc.)). . The reaction is preferably performed in a solvent in the presence of a base. Examples of the base used include inorganic bases such as potassium carbonate and sodium hydroxide, and organic bases such as pyridine and triethylamine. The solvent used may vary depending on the base used. For example, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DM
Polar solvents such as SO), hydrocarbons such as toluene, hexane and benzene, 1,2-dimethoxyethane (DME),
Ethers such as tetrahydrofuran (THF) can be used alone or as a mixture. The reaction temperature is usually
It can range from 20 ° C to the boiling point of the solvent used for the reaction or 100 ° C, but more preferably from -5 ° C to the boiling point of the solvent used for the reaction or 100 ° C.
The molar ratio of the alcohol compound represented by the general formula 4 to the benzyl halide compound represented by the general formula 5 can be arbitrarily set, but it is advantageous to carry out the reaction at an equimolar ratio or a ratio close thereto. The base can be used in an equimolar amount to an excess amount with respect to 1 mol of the alcohol compound of the general formula 4, but is preferably in an equimolar to 2 mol ratio. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent, concentration, etc., to isolate the target compound of the present invention. If necessary, it can be further purified by a usual operation such as chromatography and distillation.

When A is a carbonyl group, for example, a carboxylic acid obtained by hydrolyzing an ester compound represented by the general formula (3) and a reactive derivative compound thereof are used.

Embedded image (Wherein, Y represents the same meaning as described above, and L ₂ represents a hydroxyl group or a halogen atom (eg, a chlorine atom, a bromine atom, etc.)).

Embedded image (Wherein, X, Z and W have the same meanings as described above;
₃ represents a hydroxyl group or a halogen atom (eg, a chlorine atom, a bromine atom, etc.). ) To react with the compound represented by the formula (1). The reaction is preferably performed in an inert solvent in the presence of a suitable condensing agent or a base, if necessary. As the condensing agent used,
For example, dicyclohexylcarbodiimide (DCC)
Or 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC). As the base used, for example, triethylamine, pyridine, 4-dimethylaminopyridine,
Organic bases such as diisopropylethylamine are exemplified. Examples of usable inert solvents include hydrocarbons such as benzene, toluene and hexane; ethers such as diethyl ether and tetrahydrofuran; dichloromethane;
And halogenated hydrocarbons such as 2-dichloroethane. The range of the reaction time is usually from 5 minutes to 72 hours. The reaction temperature can be generally in the range of -20 ° C to the boiling point of the solvent used in the reaction or 100 ° C.
Temperatures from 0 ° C to the boiling point of the solvent used in the reaction or up to 100 ° C are more desirable. The molar ratio of the compound represented by the general formula (7) to the carboxylic acid represented by the general formula (6) or a reactive derivative thereof can be arbitrarily set, but it is advantageous to carry out the reaction in an equimolar or close ratio. The condensing agent or base used as needed can be used in an equimolar amount to an excess amount relative to 1 mol of the compound represented by the general formula 7, but is preferably in an equimolar to 5 mol ratio. After completion of the reaction, the compound of the present invention can be obtained by performing ordinary post-treatments such as extraction with an organic solvent and concentration. The compound can be purified by an operation such as chromatography and distillation.

[0006] Examples of the compounds of the present invention are shown in Table 1. (Indicated by the content of each substituent in the 2-methyl-3-phenylcyclopropane derivative represented by the general formula (2).)

[Table 1] In Table 1 above, Me represents a methyl group.

The ester compound represented by the general formula 3 is, for example, a compound represented by the general formula 8

Embedded image (Wherein, Y represents the same meaning as described above) and a 1-phenyl-1-propene derivative represented by the following general formula:

Reacting a diazoacetic acid ester represented by N ₂ CHCO ₂ R (where R represents a C1-C4 alkyl group) in the presence of a copper catalyst (copper powder, cupric chloride, etc.) Can be manufactured.

Examples of pests against which the compound of the present invention exerts control effects include the following. Hemiptera pests Planthoppers such as brown planthoppers, brown planthoppers and brown planthoppers, leafhoppers such as black leafhopper, locust leafhopper, leafhopper leafhopper, aphids, stinkbugs, whiteflies, scale insects, and scale insects ), Scabbard worms, such as Scutellaria japonica, Spodoptera litura, Spodoptera litura, armyworm such as Spodoptera litura, white butterflies such as cabbage beetle, scuttlefish such as stag beetle,
Agrotis spp., Heliothis spp., And Helicoverpa spp.
overupa spp.), moth moth, moss, moth, etc. Diptera pests Culex mosquitoes such as Culex pipiens, Culex pipiens, Aedes such as Aedes aegypti, Aedes albopictus, Anopheles such as Chinese anopheles, Musca domestica, Musca domestica and Musca domestica, Musca domestica Coleoptera, Phylliidae, Flies, Onions and other flies, fruit flies, Drosophila, Drosophila, Flies, Black flies, etc. Coleoptera pests Western cornworms, Southern cornflowers Worms such as corn worms such as corn worms, beetles such as dung beetles and corn beetles, weevil such as weevil, rice weevil, etc .; Genus (Henosu epiracuna)
epilacha spp.), Flying beetles, Long-spotted beetles, Longhorn beetles, etc. Eye pests Ants, wasps, wasps, and wasps such as wasps, etc. Orthoptera pests Insects, grasshoppers, etc. Insect pests, human fleas, etc. Lice pests, human lice, white lice, etc. Insects Soil nematodes Neksare nematodes, cyst nematodes, root-knot nematodes, etc.Nematodes, pine wood nematodes, singare nematodes, etc.In addition, it is effective against pests that have developed resistance to existing insecticides It is.

When the compound of the present invention is used as an active ingredient of an insecticide, it is generally used as a solid carrier, a liquid carrier, a gaseous carrier,
Mix with feed, or impregnate into base materials such as mosquito coils and mats, and add surfactants and other formulation auxiliaries as needed, oils, emulsions, wettable powders, suspensions in water・ Floables such as underwater emulsions, granules, powders, aerosols, mosquito coils, electric mosquito coils, heated smokers such as mats, self-combustion smokers, and chemically reactive smokers Formulations are used as heating agents, non-heating evaporating agents such as resin evaporating agents and impregnated paper evaporating agents, fogging agents and the like, ULV agents, poison baits and the like. These preparations contain the compound of the present invention as an active ingredient in an amount of usually 0.01 to 9 by weight.
Contains 5%. Examples of the solid carrier used in the formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasamikure, acid clay, etc.), talcs, ceramics, and other inorganic minerals (sericite, quartz) , Sulfur, activated carbon, calcium carbonate, hydrated silica, etc.) and fine powders or granules such as chemical fertilizers (ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, salt ammonium, etc.). Examples of the liquid carrier include water, Alcohols (methanol,
Ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methyl naphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, gas oil, etc.), Esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.),
Acid amides (N, N-dimethylformamide, N, N-
Dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, vegetable oils such as soybean oil, cottonseed oil and the like. Examples of the gaseous carrier, that is, propellant, for example, chlorofluorocarbon gas, butane gas , LPG (liquefied petroleum gas),
Examples include dimethyl ether and carbon dioxide.

As the surfactant, for example, alkyl sulfates, alkyl sulfonates, alkyl allys
Sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives and the like. Pharmaceutical adjuvants such as fixatives and dispersants include, for example, casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers ( Polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids, etc.). Examples of the stabilizer include PAP (acidic isopropyl phosphate), BH
T (2,6-di-tert-butyl-4-methylpheno-
), BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil, surfactant, fatty acid or ester thereof and the like. can give. The base material of the mosquito coil includes, for example, a mixture of a raw plant powder such as wood flour or lees flour and a binder such as tub flour, starch or glutein. Examples of the base material of the electric mosquito collecting mat include a plate obtained by hardening fibrils of cotton linter or a mixture of cotton linter and pulp. As the base material of the self-burning type smoke agent, for example, nitrate, nitrite, guanidine salt, potassium chlorate, nitrocellulose
, Ethylcellulose, wood flour, etc., combustion exothermic agents, alkali metal salts, alkaline earth metal salts, bichromates, chromate and other thermal decomposition stimulants, oxygen supply agents such as potassium nitrate, melamine, wheat starch And the like, a bulking agent such as diatomaceous earth, a binder such as synthetic paste, and the like. Examples of the base material of the chemical reaction type smoke agent include exothermic agents such as sulfides, polysulfides, hydrosulfides, hydrated salts and calcium oxide of alkali metals, and catalyst agents such as carbonaceous materials, iron carbide and activated clay. And organic foaming agents such as azodicarbonamide, benzenesulfonylhydrazide, dinitrosopentamethylenetetramine, polystyrene and polyurethane, and fillers such as natural fiber fragments and synthetic fiber fragments. Examples of the base material of the non-heated evaporant include a thermoplastic resin, filter paper, and Japanese paper. Examples of the bait bait include bait components such as cereal flour, vegetable oil, sugar, and crystalline cellulose; antioxidants such as dibutylhydroxytoluene and nordihydroguaseletic acid; preservatives such as dehydroacetic acid; and pepper powder. Erroneous eating preventives, cheese flavors, onion flavors, and attractants such as peanut oil. Formulations of flowables (water suspensions or emulsions) generally contain 1-75% of the compound as a 0.5-15% dispersant, 0.1-10% a suspending aid (e.g., a protective agent). A compound which imparts a colloid or thixotropic property), 0 to 10% of an appropriate auxiliary agent (for example, an antifoaming agent, a rust inhibitor, a stabilizer, a spreading agent, a penetration aid, an antifreezing agent, a bactericide) , Micro fungicides, etc.). It is also possible to use an oil in which the compound hardly dissolves in place of water and use it as a suspension in oil. As protective colloids, for example, gelatin,
Casein, gums, cellulose ether, polyvinyl alcohol and the like are used. Examples of the compound imparting thixotropic properties include bentonite, aluminum magnesium silicate, xanthan gum, polyacrylic acid and the like.

The preparation thus obtained is used as it is or after dilution with water or the like. Also other pesticides,
It can be used in combination with or without mixing with miticides, nematicides, soil pest control agents, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners.

When the compound of the present invention is used as an active ingredient of an agricultural pesticide, its application rate is usually 1 to 10 al.
When the emulsion, wettable powder, flowable and the like are diluted with water and applied, the application concentration is 1 to 2000 pp.
m, and granules, powders, etc. are applied as they are without dilution. When used as an active ingredient of an insecticide for home and epidemic control, emulsions, wettable powders, flowables and the like are diluted with water to 1 to 10,000 ppm and applied.
, Fumigants, fumigation agents, transpiration agents, aerosols, ULV agents, bait etc. are applied as they are. These application rates and application concentrations vary depending on the type of preparation, application time, application place, application method, type of pest, degree of damage, etc., and can be increased or decreased without being affected by the above range. Or you can.

[0013]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Production Examples, Preparation Examples, Test Examples, and the like, but the present invention is not limited to these Examples. First, Production Examples of the compound of the present invention will be shown. The ¹ H-NMR spectrum was measured using tetramethylsilane (TMS) as an internal standard. Production Example 1 29 mg (1.2 mmol) of sodium hydride (60
% Oil) was suspended in 1.0 ml of DMF, and 162 mg (1.0 mmol) of 2-methyl-3-phenylcyclopropyl methanol (synthesized by the method described in Reference Production Example 1 described below) was suspended therein while stirring. ) And 316 mg (1.2
mmol) of 3-phenoxybenzyl bromide in DMF
1.0 ml of the solution was added, and the mixture was stirred at room temperature for 2 hours. Water was poured into the reaction solution and extracted with ether. The ether layer was washed successively with water and saturated saline, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel chromatography (developing solvent: hexane / ethyl acetate =
20: 1) to give 241 mg (70% yield) of the desired 2-methyl-3-phenylcyclopropylmethyl = (3-phenoxybenzyl) ether (compound (12)) as a colorless liquid. . ¹ H-NMR (400 MHz) δ 1.19 (3H, d, J = 6.1 H
z), 1.24-1.36 (1H, m), 1.45 (1H, dd,
Jtrans = 5.1 Hz, Jtrans = 5.1 Hz), 1.46-1.55
(1H, m), 3.46 (1H, d, J = 8.5 Hz, Jgem
= 10.2 Hz), 3.75 (1H, dd, J = 5.9 Hz, Jgem
= 10.2 Hz), 4.49 (1H, d, Jgem = 12.2Hz), 4.5
5 (1H, d, Jgem = 12.2 Hz), 6.90-7.38 (14
H, m); IR (neat) 2866, 1586, 1487 cm ^-1 .

Production Example 2 92 mg (0.52 mmol) of 2-methyl-3-phenylcyclopropanecarboxylic acid (synthesized by the method described in Reference Production Example 2) and 150 mg (0.52 mmol) of bromo (3-phenoxy) A solution of phenyl) acetonitrile in acetone (1.0 ml) was added with stirring.
mg (0.57 mmol) of triethylamine,
Stirred at room temperature for 2 hours. A 1 molar hydrochloric acid solution was poured into the reaction solution and extracted with ether. The ether layer was washed successively with water and saturated saline, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel chromatography (developing solvent: hexane / ethyl acetate = 1).
2: 1), and 139 mg (70% yield) of the desired cyano (3-phenoxyphenyl) methyl 2-methyl-3-phenylcyclopropanecarboxylate (compound (2)) as a yellow liquid Obtained. ¹ H-NMR (400 MHz) δ 1.31 (3H x 1/2, d, J =
6.1 Hz), 1.39 (3Hx1 / 2, d, J = 6.4 Hz), 1.75
-1.90 (1H, m), 2.08 (1H x1 / 2, dd, Jtra
ns = 4.4 Hz, Jcis = 9.3 Hz), 2.08 (1H x1 / 2, d
d, Jtrans = 4.6 Hz, Jcis = 9.0 Hz), 2.47 (1H
x1 / 2, dd, Jtrans = 4.9 Hz, Jtrans = 6.8 H
z), 2.51 (1H x1 / 2, dd, Jtrans = 4.9 Hz, J
trans = 6.8 Hz), 6.40 (1H x1 / 2, s), 6.43 (1
H x1 / 2, s), 7.00-7.43 (14H, m); IR (ne
at) 2359, 1740, 1588 cm ^-1 .

Next, an ester compound represented by the general formula (3), an alcohol compound represented by the general formula (4) and a compound represented by the general formula (4), which are intermediates for producing the compound of the present invention,
1 shows a production example of a carboxylic acid obtained by hydrolyzing an ester compound represented by Reference Production Example 1 Ethyl 2-methyl-3-phenylcyclopropanecarboxylate 5.39 g (46 mmol) of E-1-phenyl-1-
While stirring propene and a small amount of copper powder, a 1 molar solution of ethyldiazoacetate in dichloromethane was added.
1.0 ml (11 mmol, 60-65 ° C) was added, and the mixture was stirred at the same temperature for 2 hours. After the reaction solution was filtered through filter paper, the residue was subjected to silica gel chromatography (developing solvent: hexane / ether = 20: 1), and the target ethyl = 2
-Methyl-3-phenylcyclopropanecarboxyla-
987 mg (44% yield) were obtained as a colorless liquid. ¹ H-NMR (400 MHz) δ 1.28 (3H, t, J = 7.2H)
z), 1.35 (3H, d, J = 6.1 Hz), 1.63-1.73 (1
H, m) 2.02 (1H, dd, Jtrans = 4.9 Hz, Jcis
= 9.3 Hz), 2.41 (1H, dd, Jtrans = 5.0 Hz,
Jtrans = 6.5 Hz), 4.17 (2H, q, J = 7.2 Hz),
7.06-7.11 (2H, m), 7.14-7.22 (1H, m), 7.
24-7.35 (2H, m).

Reference Production Example 2 2-methyl-3-phenylcyclopropyl methanol 57 mg (1.49 mmol) of LiAlH ₄ was added to 1.0
suspended in 2,000 ml of THF, and 262 m
g (1.49 mmol) of a solution of ethyl 2-methyl-3-phenylcyclopropanecarboxylate (synthesized by the method described in Reference Production Example 1) in THF (1.0 ml) (0 to 5 ° C.). In addition, the mixture was stirred at the same temperature for 1 hour. A saturated aqueous sodium sulfate solution was poured into the reaction solution, and the mixture was filtered through celite using ether. The ether layer was washed successively with water and saturated saline, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. Silica gel chromatography of the residue
(Developing solvent: hexane / ethyl acetate = 3: 1),
241 mg (yield 70%) of the desired 2-methyl-3-phenylcyclopropyl methanol was obtained as a colorless liquid. ¹ H-NMR (400 MHz) δ 1.27 (3H, d, J = 5.9 H
z), 1.26-1.38 (1H, m), 1.47-1.57 (2H,
m), 1.50-1.77 (1H, br, OH), 3.54-3.72
(1H, m), 3.87-3.93 (1H, m), 7.00-7.36
(5H, m).

Reference Production Example 3 0.50 g (2.43 mmol) of 2-methyl-3-phenylcyclopropylcarboxylic acid in ethyl 2-methyl-3-phenylcyclopropanecarboxylate (described in Reference Synthesis Example 1 above) 1.37 g (2
(4.4 mmol) of potassium hydroxide was stirred at room temperature for 3 hours in a water / methanol (1: 2) mixture. Methano
After the solvent was distilled off, a 4 molar hydrochloric acid solution was added to adjust the pH of the reaction solution to 2.0. This reaction solution was extracted with ether. The ether layer was washed successively with water and a saturated saline solution, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 400 mg of the desired 2-methyl-3-phenylcyclopropylcarboxylic acid (yield 93). %) As colorless crystals (melting point 66-68 ° C). ¹ H-NMR (400 MHz) δ1.40 (3H, d, J = 6.3H
z), 1.78-1.83 (1H, m), 2.03 (1H, dd, J
trans = 5.0 Hz, Jcis = 9.1 Hz), 2.47 (1H, d
d, Jtrans = 5.0 Hz, Jtrans = 6.8 Hz), 7.06-7.
11 (2H, m), 7.16-7.23 (1H, m), 7.24-7.32
(2H, m).

Next, preparation examples are shown. Parts represent parts by weight, and the compound of the present invention is represented by the aforementioned compound number. Formulation Example 1 Emulsion 10 parts of each of the compounds (1) to (20) of the present invention are dissolved in 35 parts of xylene and 35 parts of dimethylformamide, and polyoxyethylenestyrylphenyl ether 14 is added thereto.
Parts and 6 parts of calcium dodecylbenzenesulfonate were added and mixed well with stirring to obtain 10% emulsions of each. Formulation Example 2 wettable powder 20 parts of each of the compounds of the present invention (1) to (20) were mixed with 4 parts of sodium lauryl sulfate, 2 parts of calcium ligninsulfonate, 20 parts of synthetic hydrous silicon oxide fine powder and silicon earth 54.
The parts were mixed and stirred with a Juice mixer to obtain each 20% wettable powder. Formulation Example 3 Granules To 5 parts of each of the compounds (1) to (20) of the present invention, 5 parts of synthetic hydrous silicon oxide fine powder, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 55 parts of clay are added and sufficiently stirred. Mix. Then, an appropriate amount of water is added to the mixture, and the mixture is further stirred, granulated by a granulator, and dried by ventilation to obtain 5% granules of each. Formulation Example 4 Dust One part of each of the present compounds (1) to (20) is dissolved in an appropriate amount of acetone, and 5 parts of synthetic hydrous silicon oxide fine powder is added thereto.
Add 0.3 part of PAP and 93.7 parts of Cle, and add
Stir and mix with a mixer and evaporate off acetone to obtain 1% powder of each. Formulation Example 5 Flowable agent 20 parts of each of the present compounds (1) to (20) and 1.5 parts of sorbitan trioleate are mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, After finely pulverizing with a grinder (having a particle size of 3 μm or less), 40 parts of an aqueous solution containing 0.05 parts of xanthan gum and 0.1 parts of aluminum magnesium silicate are added thereto, and 10 parts of propylene glycol are further added. In addition, agitate and mix to obtain each 20% suspension in water.

Formulation Example 6 Oil Preparation 0.1 parts of each of the compounds (1) to (20) of the present invention are dissolved in 5 parts of xylene and 5 parts of trichloroethane, and the mixture is mixed with 89.9 parts of deodorized kerosene to give 0 parts of each. 1% oil is obtained. Formulation Example 7 Oily azole 0.1 part of each of the present compounds (1) to (20), 0.2 part of tetramethrin, 0.1 part of d-phenothrin, 10 parts of trichloroethane and 59.6 parts of deodorized kerosene are mixed. After dissolving, filling into an aerosol container and attaching a valve portion, a propellant (liquefied petroleum gas) 30 is passed through the valve portion.
The parts are filled under pressure to obtain the respective oily aerosols. Formulation Example 8 aqueous azole 0.2 part of each of the present compounds (1) to (20), 0.2 part of d-aresulin, 0.2 part of d-phenothrin, 5 parts of xylene, 3.4 parts of deodorized kerosene And emulsifier @ Atmos 30
0 (registered trademark of Atlas Chemical Co., Ltd.) # 1 part was mixed and dissolved, and 50 parts of pure water were filled in an aerosol container.
A valve portion is attached, and 40 parts of a propellant (liquefied petroleum gas) is charged under pressure through the valve portion to obtain each aqueous aerosol. Formulation Example 9 Mosquito coil incense 0.3 g of each of the compounds (1) to (20) of the present invention was added with 0.3 g of d-arrestrin and dissolved in 20 ml of acetone. The powder was mixed in a ratio of 4: 3: 3) and mixed uniformly with 99.4 g.
Then, the mixture is molded and dried to obtain each mosquito coil. Formulation Example 10 Electric Mosquito Cat Mat 0.4 g of each of the compounds of the present invention (1) to (20), 0.4 g of d-aresulin and 0.4 g of pipenyl butoxide
And add acetone to make 10 ml with total.
0.5 ml of this solution is uniformly impregnated into a 2.5 cm × 1.5 cm, 0.3 cm thick electric mat substrate (a fibril of a mixture of cotton linter and pulp solidified into a plate). Obtain each electric mosquito repellent matting agent. Formulation Example 11 Heat-smoking agent 100 mg of each of the present compounds (1) to (20) is dissolved in an appropriate amount of acetone, and 4.0 cm × 4.0 cm, thickness 1.
Each heated smoke is obtained by impregnating a 2 cm porous ceramic plate. Formulation Example 12 Poison bait 10 mg of each of the compounds of the present invention (1) to (20) is dissolved in 0.5 ml of acetone, and this solution is used as solid feed powder for animals (solid feed powder for breeding and breeding, CE-2, CLEA Japan) Treat to 5 g and mix uniformly. Then, the acetone is air-dried to obtain each 0.5% bait.

Next, Test Examples show that the compound of the present invention is useful as an active ingredient of an insecticide. Test Example 1 Insecticidal Test Against Larvae of Spodoptera litura The dilutions of each emulsion of compounds (2) and (12) of the present invention obtained according to Formulation Example 1 with water (500 pp)
m) 2 ml were impregnated with 13 g of artificial feed for the cutworm armyworm prepared in a polyethylene cup having a diameter of 11 cm. In it, 10 larvae of the fourth cutworm, Spodoptera litura, are released,
Six days later, their survival was examined, and the mortality was determined. As a result, all showed 100% mortality.

Test Example 2 Insecticidal Test Against Culex pipiens According to Formulation Example 1, the compounds of the present invention (2) and (12) were each made into an emulsion, which was diluted with water, and 0.7 ml of the solution was added to 100 ml of ion-exchanged water. Added (active ingredient concentration 3.5
ppm). Release 20 larvae of Culex pipiens into it,
The mortality after 6 days was investigated. The effect criteria were: a: mortality of 90% or more, b: mortality of 10% or more and less than 90% c: mortality of less than 10%. As a result, all showed the effect of the judgment a.

The compounds of the present invention have excellent insecticidal activity.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 255/38 A01N 53/00 508D

Claims (4)

[Claims] 1. A compound represented by the general formula: [In the formula, A represents a methylene group or a carbonyl group,
X represents a hydrogen atom, a cyano group or an ethynyl group. Y
Represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxyl group, a lower haloalkyl group or a lower haloalkoxyl group, Z represents a hydrogen atom or a fluorine atom, and W represents a hydrogen atom or a halogen atom. A 2-methyl-3-phenylcyclopropane derivative represented by the formula: 2. In the above general formula 1, a 2-methyl-3-phenylcyclopropane derivative wherein A is a methylene group and X is a hydrogen atom, or A is a carbonyl group, X is a hydrogen atom, A 2-methyl-3-phenylcyclopropane derivative which is a cyano group or an ethynyl group. 3. An insecticide comprising the 2-methyl-3-phenylcyclopropane derivative according to claim 1 as an active ingredient. 4. An insecticide comprising the 2-methyl-3-phenylcyclopropane derivative according to claim 2 as an active ingredient.