JP3051967B2 - Benzohydroxymoylazole derivatives and insecticides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a benzohydroxymoylazole derivative and an insecticide containing the same as an active ingredient.

[0002]

2. Description of the Related Art The present inventors have previously described Japanese Patent Application Laid-Open No. 1-30826.
No. 0 discovered that benzohydroxymoylazole derivatives have excellent insecticidal activity. However, the activities of the compounds specifically described in the specification tend not to be sufficient yet.

[0003] Agricultural crops are seriously damaged by insect pests, and various insecticides such as organochlorine, organophosphorus and carbamate are used for controlling these insects.
However, in recent years, the use of these insecticides has been restricted due to problems such as residue, accumulation, and environmental pollution, and resistant insects have been generated by long-term use, and some of them have become less effective. Therefore, development of an insecticide which shows a high controlling effect even at a low dose, is excellent in safety and is effective against resistant pests is desired.

[0004]

SUMMARY OF THE INVENTION The present invention provides a further improved benzohydroxymoylazole derivative.

[0005]

Means for Solving the Problems The present inventors have synthesized various benzohydroxymoylazole derivatives and studied the physiological activities thereof. As a result, they have found that the compound of the present invention has extremely excellent insecticidal activity against various harmful insects, and completed the present invention.

That is, the present invention provides a compound represented by the general formula (I)

[0007]

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(Wherein X is an alkenyl group, an alkynyl group, an alkenyloxy group optionally substituted with a halogen atom, an alkynyloxy group, a cycloalkylidenealkyl group optionally substituted with an alkyl group, Alkyloxyalkyl group, alkyloxyalkyloxy group, halogen atom, alkyl group,
Or Y represents an alkyl group, Z represents a nitrogen atom or a methine group, and n represents an integer of 1 or 2. However, when X represents a halogen atom or an alkyl group, n represents an integer of 2, and the other substituent does not represent a halogen atom or an alkyl group. ) And an insecticide containing the same as an active ingredient.

[0009]

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(Wherein, R ¹ represents a hydrogen atom or an alkyl group, R ² represents a cycloalkyl group, a cycloalkenyl group or a chemical formula 8 which may be substituted with a halogen atom or an alkyl group, and m represents 0 to 3) Represents an integer.)

[0011]

Embedded image

(Wherein, R ³ represents a cycloalkyl group, an alkylamino group, an alkylthio group, a phenyl group or a chemical formula 8 which may be substituted with a halogen atom or an alkyl group, and R ¹ and m have the same meanings as described above.) Is shown.)

[0013]

Embedded image

(In the formula, R ⁴ , R ⁵ and R ⁶ independently represent an alkyl group, an alkenyl group or a phenyl group which may be substituted with a halogen atom.)

The following terms used in the present invention have the following meanings unless otherwise specified.

That is, the term halogen atom means each atom of chlorine, bromine, fluorine and iodine.

The term alkyl is a straight-chain or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, 1,1,
It means 1,2-trimethylpropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group and the like.

The term alkenyl is an aliphatic hydrocarbon group in which a part of an alkyl group having 2 to 6 carbon atoms has a double bond,
For example, ethenyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 3-methyl-1-butenyl group, 3
-Methyl-2-butenyl group, 3,3-dimethyl-1-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-
It means a hexenyl group or the like.

The term alkynyl is an aliphatic hydrocarbon group in which part of an alkyl group having 2 to 6 carbon atoms has a triple bond,
For example, it means an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 3-methyl-1-butynyl group, a 3,3-dimethyl-1-butynyl group, or the like.

The term cycloalkyl has 3 to 7 carbon atoms.
Alicyclic hydrocarbon group, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group.

The term cycloalkenyl means an alicyclic hydrocarbon group in which a part of the above cycloalkyl has a double bond.

The terms alkyloxy, alkenyloxy, alkynyloxy, alkylthio, alkylamino mean that the terminal of the above alkyl, alkenyl or alkynyl is bonded to an oxygen, sulfur or nitrogen atom.

In the compounds of the present invention represented by the general formula (I), X represents an alkenyl group, an alkynyl group, an alkenyloxy group optionally substituted with a halogen atom, and an alkyloxyalkyl optionally substituted with a halogen atom. A benzohydroxymoylazole derivative in which Y represents an alkyl group having 1 to 4 carbon atoms, Z represents a nitrogen atom or a methine group, and n represents 1 is a preferred compound. Here, as Chemical Formula 2, R ¹ represents a hydrogen atom or a methyl group, R ² represents a cycloalkyl group, a cycloalkenyl group or a Chemical Formula 4 which may be substituted with a chlorine atom or a methyl group, and m represents 0 or The compound of the formula (1) is preferred, and as the chemical formula (3), R ¹ represents a hydrogen atom or a methyl group, and R ³ is a cycloalkyl group, an alkylthio group, a phenyl group or a chemical formula (4) which may be substituted with a chlorine atom or a methyl group. And a compound wherein m is an integer of 0 to 2 is preferred. Further, as Chemical Formula ⁴ , a compound in which R ⁴ , R ⁵ and R ⁶ independently represent an alkyl group which may be substituted with a halogen atom or an alkenyl group having 2 or 3 carbon atoms is preferable.

In the compound of the present invention represented by the general formula (I), X is an alkenyl group having 3 to 6 carbon atoms, an alkynyl group, or a C 1 to C 6 optionally substituted by a halogen atom.
Represents an alkyloxy group having 1 to 3 carbon atoms, or a chemical formula 2 or 3, wherein Y represents an alkyl group having 1 to 4 carbon atoms,
Benzohydroxymoylazole derivatives in which Z represents a nitrogen atom or a methine group and n represents 1 are more preferred compounds. Here, as Chemical Formula 2, R ¹ represents a hydrogen atom or a methyl group, R ² represents a cycloalkyl group having 5 or 6 carbon atoms which may be substituted with a chlorine atom or a methyl group or Chemical Formula 4, and m represents Compounds representing 0 or 1 are preferable, and as Chemical formula 3, R ¹ represents a hydrogen atom or a methyl group, and R ³ represents a cycloalkyl group having 5 or 6 carbon atoms which may be substituted with a chlorine atom or a methyl group; An alkylthio group, a phenyl group or a chemical formula 4 of the formulas 3 to 6,
Compounds showing an integer of from 2 to 2 are preferred. Further, as Chemical Formula 4, a compound in which R ⁴ , R ⁵ and R ⁶ independently represent a C 2 or C 3 alkyl group or a C 2 or C 3 alkenyl group which may be substituted with a halogen atom is preferable. .

The compound of the present invention represented by the general formula (I)
Although there are two types of stereoisomers, a syn-form and an anti-form, the present invention also includes these isomers and mixtures of these isomers in any ratio.

In the general formula (I), when X has a saturated or unsaturated alicyclic hydrocarbon group or an aliphatic hydrocarbon group having a double bond as a substituent in the substituent, two or more kinds thereof may be used. The present invention also encompasses these isomers and mixtures of these isomers in any ratio.

The compound of the present invention represented by the general formula (I) can be produced by the following reaction formulas 1 to 4.

[0028]

[Reaction formula 1]

(In the formula, A represents a halogen atom or a paratoluenesulfonyl group, and X, Y, Z and n have the same meanings as described above.)

That is, the compound of the present invention represented by the general formula (I) comprises a benzohydroxymoylazole compound represented by the general formula (II) and a halogen compound or a sulfonate compound represented by the general formula (III). The reaction can be carried out in the presence of

In this reaction, the halogen compound or the sulfonic acid ester compound can be used in an equivalent amount or more. Examples of the base that can be used include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, carbonates of alkali metals such as sodium carbonate and potassium carbonate, sodium hydrogencarbonate and potassium hydrogencarbonate. Inorganic bases such as alkali metal bicarbonates, metal hydrides such as sodium hydride, etc. or triethylamine, N, N-dimethylaniline, pyridine, 1,8
Organic bases such as -diazabicyclo [5,4,0] unde-7-cene.

The reaction can be carried out, if necessary, in the presence of a suitable diluent. The diluent that can be used is water or an inert organic solvent, for example, ketones such as acetone and butanone, aromatic hydrocarbons which may be halogenated such as benzene, toluene, xylene, chlorobenzene, petroleum ether, ligroin, etc. Aliphatic hydrocarbons, diethyl ether, tetrahydrofuran (hereinafter referred to as THF), ethers such as dioxane, acetonitrile,
Nitriles such as propionitrile or N, N-dimethylformamide (hereinafter referred to as DMF), N, N-dimethylacetamide (hereinafter referred to as DMAC), N-
Amides such as methylpyrrolidone are exemplified.

The reaction temperature is any temperature from 0 ° C. to the reflux temperature in the reaction system, preferably from 40 ° C. to 100 ° C.
° C. The reaction time varies depending on the compound, but the reaction may be carried out for 1 to 6 hours.

[0034]

[Reaction formula 2]

(Wherein B represents a halogen atom, X,
Y, Z and n have the same meaning as described above. )

That is, the compound of the present invention represented by the general formula (I) is reacted with a benzohydroxymoyl halide compound represented by the formula (IV) and an azole or triazole compound represented by the formula (V) in the presence of a base. Can be manufactured. In this reaction, the azole or triazole compound can also be used in an equivalent amount or more as a base. As the base, the same base as that used in Reaction Scheme 1 can be used.

The reaction can be carried out, if necessary, in the presence of a suitable diluent. Reaction formula 1 can be used as diluent
The same diluents as used in the above can be mentioned.

The reaction temperature is an arbitrary temperature from room temperature to the reflux temperature in the reaction system, preferably 80 to 130 ° C.
It is. The reaction time varies depending on the compound, but if the reaction is carried out for 2 to 5 hours, the desired product can be produced in good yield.

[0039]

[Reaction formula 3]

(Wherein E is a tri-substituted silylalkyl group, a trialkyl-substituted silyl group, an alkynyl group, or a halogen atom optionally selected from an alkyl group or an alkenyl group or a phenyl group which may be substituted with a halogen atom. Represents an optionally substituted alkenyl group, a cycloalkyl group optionally substituted with a halogen atom or an alkyl group, a cycloalkylalkyl group optionally substituted with a halogen atom or an alkyl group, a cycloalkenyl group, and D represents a halogen atom or an alkyl group. Represents a group, q represents an integer of 0 or 1, and Y, Z and A have the same meaning as described above.)

That is, the compound of the present invention represented by the general formula (VIII) comprises a compound having a hydroxyl group on a benzene ring represented by the formula (VI) and a halogen compound or a sulfonate compound represented by the formula (VII). And / or if necessary, a reaction in the presence of a catalytic amount of potassium iodide.

In this reaction, the halogen compound or sulfonic acid ester compound can be used in an equivalent amount or more. As the base, the same base as that used in Reaction Scheme 1 can be used.

The reaction can be carried out in the presence of a suitable diluent if necessary. Reaction formula 1 can be used as diluent
The same diluents as used in the above can be mentioned. The reaction temperature is any temperature from 0 ° C. to the reflux temperature in the reaction system, and is preferably from 40 to 120 ° C. The reaction time varies depending on the compound, but the reaction may be carried out for 1 to 8 hours.

[0044]

[Reaction formula 4]

(Wherein F is a trisubstituted silylalkyl group, alkynyl group, or alkenyl group optionally substituted with a halogen atom, which is arbitrarily selected from an alkyl group or alkenyl group optionally substituted with a halogen atom or a phenyl group) , A cycloalkyl group optionally substituted with a halogen atom or an alkyl group, a cycloalkylalkyl group optionally substituted with a halogen atom or an alkyl group, and a cycloalkenyl group, wherein D, Y, Z and q are as defined above. Is shown.)

That is, the compound of the present invention represented by the general formula (X) comprises a compound having a hydroxyl group on a benzene ring represented by the formula (VI) and an alcoholic compound represented by the formula (IX). It can be produced by reacting in the presence of diethyl dicarboxylate.

In this reaction, the alcoholic compound is
Equivalent or more can be used. The reaction can be carried out in the presence of a suitable diluent, if necessary. Examples of the diluent that can be used include the same diluents used in Reaction Scheme 1. Among them, acetonitrile or THF is preferred. The reaction temperature is any temperature from 0 ° C. to the reflux temperature in the reaction system, and is preferably 30 to
120 ° C. The reaction time varies depending on the compound, but it is 0.1.
The reaction may be performed for 5 to 72 hours.

The starting materials represented by the general formulas (II), (IV) and (V)
The compound represented by I) can be produced by the methods of Reaction Schemes 5 to 9 shown below.

[0049]

[Reaction formula 5]

(Wherein, X, Z, B and n have the same meaning as described above)

That is, the benzohydroxymoylazole compound represented by the general formula (II) can be prepared by converting the benzohydroxymoyl halide compound represented by the formula (XI) in a solvent such as acetonitrile in the presence of a base such as potassium carbonate. In the above, it can be produced by reacting with an azole or triazole compound represented by the formula (V). The reaction temperature is any temperature from 0 ° C. to the reflux temperature in the reaction system, and is preferably from 50 to 80 ° C. The reaction time is
The reaction may be performed for 1 to 6 hours, depending on the compound.

The compound represented by the general formula (XI) is prepared by reacting a corresponding benzaldehyde compound with hydroxyamine hydrochloride by a known method to obtain a corresponding benzaldoxime, which is then reacted with N-bromosuccinimide (hereinafter referred to as N-bromosuccinimide).
Called NBS. ), N-chlorosuccinimide (hereinafter referred to as
Called NCS. ) Or a halogenating agent such as chlorine.

[0053]

[Reaction formula 6] (In the formula, X, Y, B and n have the same meaning as described above.)

That is, the benzohydroxymoyl halide compound represented by the general formula (IV) can be obtained by converting a benzamide compound represented by the formula (XII) to an aromatic hydrocarbon such as benzene or toluene, or a halogen such as chloroform or carbon tetrachloride. Reaction with a halogenating agent such as phosphorus pentachloride or thionyl chloride in the presence or absence of an inert solvent such as fluorinated hydrocarbons, or nitriles such as acetonitrile and propionitrile or benzene and chlorobenzene. It can be produced by reacting with a halogenating agent consisting of triphenylphosphine and carbon tetrachloride or triphenylphosphine and carbon tetrabromide in the presence of an inert solvent such as aromatic hydrocarbons. In this case, carbon tetrachloride and carbon tetrabromide can also serve as a solvent. The reaction temperature is
The temperature is any temperature from 0 ° C. to the reflux temperature in the reaction system, and is preferably 50 to 80 ° C. The reaction time varies depending on the compound, but the reaction may be carried out for 1 to 6 hours.

The compound represented by the general formula (XII) can be produced by converting a benzoic acid derivative into a benzoic acid halide or imidazole by a known method, and reacting the resulting product with an alkoxyamine.

[0056]

[Reaction formula 7]

(In the formula, D, Y, Z and q have the same meanings as described above.)

That is, the compound represented by the general formula (VI)
The corresponding benzyloxy compound (XIII) is converted into an inert solvent such as water, acetic acid, alcohols, acetates, aprotic polar solvents such as DMAC and DMF,
Hydrocracking using palladium carbon as a catalyst, or converting the corresponding benzyloxy compound (XIII) into aromatic hydrocarbons such as benzene and chlorobenzene or dichloromethane,
It can be produced by reacting with boron tribromide or boron trichloride in an inert solvent such as halogenated hydrocarbons such as 1,2-dichloroethane and debenzylating. The reaction temperature is from -60C to 40C, preferably from -30C to room temperature. The reaction time varies depending on the compound, but the reaction may be carried out for 1 to 8 hours.

The benzyloxy compound represented by the general formula (XIII) is obtained by benzylating a hydroxybenzoic acid derivative, converting it into a benzoic acid halide by a known method, and reacting it with alkoxyamine. After halogenation according to the above, the compound can be produced according to the reaction formula 2.

[0060]

[Reaction formula 8]

(Wherein, X, Z and n have the same meanings as described above)

That is, the compound represented by the general formula (II) is
The corresponding benzyloxy compound (XIV) is reacted with an aprotic polar solvent such as water, acetic acid, alcohols, acetates, DMAC, DMF, etc.
Hydrogenolysis using palladium carbon as a catalyst or the corresponding benzyloxy compound (XIV) is performed using aromatic hydrocarbons such as benzene and chlorobenzene or dichloromethane,
It can be produced by reacting with boron tribromide or boron trichloride in an inert solvent such as halogenated hydrocarbons such as 1,2-dichloroethane and debenzylating. The reaction temperature is from -60C to 40C, preferably from -30C to room temperature. The reaction time is
The reaction may be performed for 1 to 8 hours, depending on the compound.

The compound represented by the general formula (XIV) was prepared by reacting a corresponding benzaldehyde compound with hydroxyamine hydrochloride by a known method to form a corresponding benzaldoxime, which was then reacted with benzyl halide. Thereafter, a benzohydroxymoyl halide compound is reacted with a halogenating agent such as NBS, NCS or chlorine to produce a benzohydroxymoyl halide compound, and then an azole or triazole compound is reacted according to Reaction Formula 5 to produce the compound.

[0064]

[Reaction formula 9]

(Wherein, X, Z and n have the same meaning as described above)

That is, the compound represented by the general formula (II) is
The corresponding t-butyloxy compound (XV) is converted to an aromatic hydrocarbon such as benzene or chlorobenzene, dichloromethane,
Halogenated hydrocarbons such as 1,2-dichloroethane, T
It can be produced by reacting with a boron trifluoride ether complex in an aprotic polar solvent such as HF, ether or acetonitrile or a polar solvent such as DMAC, DMF or dimethyl sulfoxide. The reaction temperature is -1
The temperature is any temperature from 0 ° C. to the reflux temperature in the reaction system, and is preferably room temperature to 80 ° C. The reaction time varies depending on the compound, but the reaction may be performed for 2 to 12 hours.

[0067]

EXAMPLES The production method of the compound of the present invention will be specifically described below with reference to examples. Incidentally, the refractive index is Na− at 20 ° C.
The measured value at line D is shown.

Example 1 Synthesis of 1- (O-ethyl-3-trimethylsilylmethoxybenzohydroxymoyl) -1H-1,2,4-triazole (Compound No. 13) 1- (3-Trimethylsilylmethoxybenzohydroxymoyl)- 1.5 g of 1H-1,2,4-triazole was dissolved in a mixed solvent of 50 ml of dried THF and 50 ml of DMF, 0.15 g of sodium hydride was added, and the mixture was stirred at room temperature for 10 minutes. Then, at room temperature, ethyl iodide 2.0 g
Was added dropwise over 15 minutes to a THF solution in which
The reaction was further performed at 50 ° C. for 3 hours. The reaction solution was concentrated to about half under reduced pressure, allowed to cool, poured into a large amount of water, and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography (eluted with hexane: ethyl acetate = 4: 1) to give a refractive index of 1. Object showing 5385 1.
2 g (75% yield) was obtained as a viscous liquid.

Example 2 Synthesis of 1- (O-isopropyl-3-cyclohexylbenzohydroxymoyl) -1H-1,2,4-triazole (Compound No. 24) O-isopropyl-3-cyclohexylbenzohydroxymoyl chloride 3. 3 g, 1.6 g of 1,2,4-triazole and 3.3 g of potassium carbonate in 100 ml of DMAC
And stirred under heating at 130 ° C. for 2 hours. The reaction solution was allowed to cool and then poured into water, extracted with ethyl acetate, and the organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography (eluted with hexane: ethyl acetate = 4: 1) to obtain 3.1 g of the desired product having a melting point of 49 to 51 ° C. (84% yield) as a white solid.

Example 3 1- [O-isopropyl- {3- (1,1,1,3,3,3
-Hexafluoro-2-methyl-2-propoxy) methyl {benzohydroxymoyl] -1H-1,2,4-triazole (Compound No. 45) O-isopropyl-3- {3- (1,1,1,3) .3,3-hexafluoro-2-methyl-2-propoxy) methyl {benzohydroxymoyl chloride 1.2 g, 1,2,4-
DMA of 0.4 g of triazole and 0.9 g of potassium carbonate
C., and reacted at 130 ° C. for 3 hours with stirring. The reaction solution was allowed to cool, poured into water, extracted with ethyl acetate, and the organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography (eluted with hexane: ethyl acetate = 4: 1) to give 0.9 g of the target compound having a refractive index of 1.4821 ( (69% yield) as a clear viscous liquid.

Example 4 Synthesis of 1- (O-isopropyl-3-trimethylsilylmethoxybenzohydroxymoyl) -1H-1,2,4 triazole (Compound No. 5) 1- (O-isopropyl-3-hydroxybenzohydroxymoyl) ) -1H-1,2,4-triazole 2.7
g, 1.5 g of chloromethyltrimethylsilane, 1.8 g of potassium carbonate and a catalytic amount of potassium iodide in DMF 10
The mixture was added to 0 ml and stirred at 90 ° C. for 2 hours. The reaction solution was allowed to cool, poured into water, extracted with ethyl acetate, and the organic layer was dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography (eluted with hexane: ethyl acetate = 4: 1) to give 3.2 g of the desired product having a refractive index of 1.5310 ( (89% yield) as a clear viscous liquid.

Example 5 Synthesis of 1- (O-isopropyl-3-cyclohexyloxybenzohydroxymoyl) -1H-1,2,4-triazole (Compound No. 33) 1- (O-isopropyl-3-hydroxybenzohydroxy Moyl) -1H-1,2,4-triazole 2.0
g, 1.6 g of cyclohexanol and 4.3 g of triphenylphosphine were dissolved in 100 ml of THF and kept at about 5 ° C. To this solution, 10 ml of a THF solution in which 2.8 g of diethyl azodicarboxylate was dissolved was added dropwise over 30 minutes, and the mixture was further reacted at room temperature for 8 hours. The reaction solution was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluted with hexane: ethyl acetate = 4: 1) to obtain 2.1 g of the target product having a refractive index of 1.5490 (yield). 78%) as a clear viscous liquid.

The compounds of the present invention produced according to the above production methods are shown in Tables 1A to 1F. The compound numbers will be referred to in the following description.

[0074]

[Table 1A]

[0075]

[Table 1B]

[0076]

[Table 1C]

[0077]

[Table 1D]

[0078]

[Table 1E]

[0079]

[Table 1F]

[0080]

[Table 1G]

The insecticide of the present invention comprises a benzohydroxymoylazole derivative represented by the general formula (I) as an active ingredient. To use the compound of the present invention as an insecticide,
The compound of the present invention may be used as it is, but a carrier, a surfactant, a dispersant or an auxiliary agent generally used in formulating a pesticide is blended, and a powder, a wettable powder, an emulsion, a fine granule or It is preferable to use the composition in the form of granules or the like.

The carriers used in the formulation are as follows:
Examples include solid carriers such as ziglite, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea, and liquid carriers such as isopropyl alcohol, xylene, cyclohexane, and methylnaphthalene. Examples of the surfactant and dispersant include metal salts of alkyl benzene sulfonic acid, metal salts of dinaphthyl methane disulfonic acid, alcohol sulfates, alkyl aryl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, and polyoxyethylene alkyl aryls. Ether and polyoxyethylene sorbitan monoalkylate. Examples of the auxiliary include carboxymethylcellulose, polyethylene glycol, gum arabic and the like. Upon use, these preparations are diluted to an appropriate concentration and sprayed or applied directly.

The insecticide of the present invention can be used by foliage application, soil application, nursery box application or water surface application. The compounding ratio of the active ingredient is appropriately selected according to need, but in the case of a powder or granule, it is suitably selected from the range of 0.05 to 20% (weight), preferably 0.1% to 10% (weight) Good to choose. 0.1 when used as an emulsion or wettable powder.
5-80% (weight) is suitable. Preferably 1 to 60
% (Weight).

Next, the present invention will be described specifically with reference to examples. The types and compounding ratios of the compounds and additives are not limited to these and can be changed in a wide range. In the following description, “%” indicates weight percentage.

Example 6 Emulsion 30% of compound (5), 20% of cyclohexanone, 11% of polyoxyethylene alkylaryl ether, 4% of calcium alkylbenzenesulfonate and 35% of methylnaphthalene were uniformly dissolved to form an emulsion.

Example 7 Water-dispersible compound (23) 40%, diatomaceous earth 15%, clay 15%,
25% white carbon, 2% sodium dinaphthylmethanedisulfonate and 3% sodium ligninsulfonate
% Was uniformly mixed and pulverized to obtain a wettable powder.

Example 8 Dust A powder (2%) of compound (66), 5% of diatomaceous earth and 93% of clay were uniformly mixed and ground.

Example 9 Granules Compound (60) 5%, lauryl alcohol sulfate sodium salt 2%, lignin sulfonate sodium 5
%, Carboxymethylcellulose 2% and clay 86%
Is uniformly mixed and pulverized. 100 parts by weight of this mixture is mixed with water 2
0 parts by weight, kneaded, and extruded using an extrusion granulator.
After processing into a 32 mesh granule, it was dried to obtain a granule.

The application rate of the insecticide of the present invention varies depending on the kind of the compound used, the target pest, the tendency of occurrence, the degree of damage, the environmental conditions, the dosage form to be used, etc. If you do, 10
0.05 g to 5 kg per are, preferably 0.1 g to 1
It is better to select from the range of kg as appropriate. When used in a liquid form such as an emulsion and a wettable powder, 0.1 to 0.1
It is appropriate to appropriately select from the range of 5,000 ppm, preferably 1 to 1,000 ppm. Furthermore, the insecticide of the present invention can be used by mixing other insecticides and fungicides.

Next, the effects of the compound of the present invention will be described with reference to Test Examples.

Test Example 1 Insecticidal Test of Brown Planthopper Incorporation of 500 ppm of wettable powder prepared according to Example 7 and 1
Diluted with water to a concentration of 00 ppm. Rice stems and leaves were immersed in the medicinal solution, air-dried, and left still in a test tube. 10 brown hopper larvae were released into the larva, and the larva was plugged with absorbent cotton. afterwards,
It was placed in a constant temperature room at 25 ° C., and after 6 days, the number of dead insects was examined, and the mortality was calculated. The test was performed in a two-part system.

As a result, Compound Nos. 3, 5, 6, 8 to 3
0, 32-65, 68-75, 78 and 83-93 are 1
At a treatment dose of 00 ppm, the mortality was 100%. Compound Nos. 7, 31, 66 and 67 were 500 ppm
A mortality rate of 100% was shown at the treatment dose of.

Test Example 2 Insecticidal Test of Leafhopper Leafhopper The wettable powder prepared according to Example 7 was diluted with water to a concentration of 500 ppm. Soak the rice stalks and leaves in the solution, air-dry,
It was left in a test tube. Five larvae of the black leafhopper larva were released into it and plugged with absorbent cotton. Then, it was placed in a constant temperature room at 25 ° C., and after 6 days, the number of dead insects was examined, and the mortality was calculated. The test was performed in a two-part system.

As a result, Compound Nos. 3, 5 to 22, 24 to
30, 32-40, 42-49, 51-54, 56-6
1, 63, 65, 67-75, 78 and 83-93 showed 100% mortality. Compound Nos. 23 and 31,
41, 50, 55, 64 and 66 showed mortality of 80% or more.

Test Example 3 Cotton Aphid Insecticide Test A wettable powder prepared according to Example 7 was diluted with water to a concentration of 100 ppm. Cucumber seedlings were immersed in the chemical solution, air-dried, and then placed in a 55 mm diameter polyethylene cup. Ten cotton aphid larvae were released on the leaves. Then 2
It was placed in a thermostat at 5 ° C., and after 3 days, the number of dead insects was examined, and the mortality was calculated. The test was performed in a two-part system.

As a result, Compound Nos. 3, 5, 6, 8 and 2
9, 32 to 36, 38 to 40, 42, 43, 45 to 5
0, 52, 53, 55 to 59, 61, 63 to 65, 6
7, 68, 71 to 75, 78 and 83 to 93 indicate mortality of 1
00%. Compound numbers 30, 41, 44,
60 and 70 showed a mortality of 90% or more.

[0097]

The benzohydroxymoylazole derivatives of the present invention include planthoppers such as brown planthopper, brown planthopper and brown planthopper, leafhoppers such as leafhopper leafhopper and green leafhopper, aphids such as cotton aphid, peach aphid, radish aphid, and aphid whitefly. Hemiptera pests such as whiteflies such as whiteflies, stink bugs such as stag beetles, and stink bugs such as spider bugs; It is effective for controlling Coleoptera pests, such as sea urchin beetles, Orthoptera pests, such as German cockroaches, and spider mites, such as spider mites and orange mites. Further, the compound of the present invention also has bactericidal activity, rice blast, rice sheath blight, cucumber downy mildew, cucumber gray mold,
Cucumber powdery mildew, cucumber spot bacterial disease and Komatsuna black spot can be effectively controlled.

[Table 1H]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07F 7/08 C07F 7/08 R (72) Inventor Tomonori Shimazu 6-10-48 Sanarudai, Hamamatsu-shi, Shizuoka Examiner Shunichi Yokoo (56 References JP-A-3-68559 (JP, A) JP-A-1-308260 (JP, A) JP-A-61-68461 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) C07D 233/61 C07D 249/08 C07F 7/08 A01N 43/50 A01N 43/653 A01N 55/00 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A compound of the general formula (I) (In the formula, X is an alkenyl group, an alkynyl group, an alkenyloxy group optionally substituted with a halogen atom, an alkynyloxy group, a cycloalkylidenealkyl group optionally substituted with an alkyl group, an alkyl optionally substituted with a halogen atom. An oxyalkyl group, an alkyloxyalkyloxy group, a halogen atom, an alkyl group, or a chemical formula 2 or 3, Y represents an alkyl group, Z represents a nitrogen atom or a methine group, and n represents an integer of 1 or 2 However, when X represents a halogen atom or an alkyl group, n represents an integer of 2, and the other substituent does not represent a halogen atom or an alkyl group.) Derivatives. Embedded image (Wherein, R ¹ represents a hydrogen atom or an alkyl group; R ² represents a cycloalkyl group, a cycloalkenyl group, or a chemical formula 4 which may be substituted with a halogen atom or an alkyl group;
m shows the integer of 0-3. ) (Wherein, R ³ represents a cycloalkyl group, an alkylamino group, an alkylthio group, a phenyl group or a phenyl group which may be substituted with a halogen atom or an alkyl group, and R ¹ and m
Has the same meaning as described above. ) (In the formula, R ⁴ , R ⁵ and R ⁶ independently represent an alkyl group, an alkenyl group or a phenyl group which may be substituted with a halogen atom.) 2. An insecticide comprising the benzohydroxymoylazole derivative according to claim 1 as an active ingredient.