JP3248003B2 - Hydrazine derivatives and agricultural and horticultural insecticides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a compound of the formula (I)

Embedded image Wherein R ¹ represents a hydrogen atom or a lower alkyl group;
² and R ³ may be the same or different and represent a hydrogen atom, a hydroxyl group or a lower alkyl group, Ar ¹ and Ar ² may be the same or different, and may be a phenyl group or 1 to 3 identical or different An oxygen atom, a heterocyclic group having 3 to 6 carbon atoms having a heteroatom selected from a nitrogen atom or a sulfur atom, and when the heteroatom on the heterocyclic group is a nitrogen atom, the nitrogen atom is oxidized. The phenyl group or the heterocyclic group may be the same selected from a halogen atom, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group or a lower alkoxycarbonyl group. Or it may have one or more substituents which may be different. A is

Embedded image (Wherein, R ⁴ represents a hydrogen atom or a lower alkyl group;
⁵ represents a hydrogen atom, a lower alkylcarbonyl group, a lower haloalkylcarbonyl group, a cycloalkylcarbonyl group or a lower alkoxycarbonyl group, R ⁶ represents a hydrogen atom or a lower alkyl group, Ar ³ represents a phenyl group or 1 to
3 represents a heterocyclic group having 3 to 6 carbon atoms having a heteroatom selected from the same or different oxygen atoms, nitrogen atoms or sulfur atoms, wherein the heteroatom on the heterocyclic group is a nitrogen atom In this case, the nitrogen atom may be oxidized, and the phenyl group or the heterocyclic group may be a halogen atom, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group or a lower alkoxycarbonyl group. And may have one or more substituents which may be the same or different and are selected from ), And W represents an oxygen atom or a sulfur atom. However, Ar ¹ , Ar ² and A
r ³ does not simultaneously represent a phenyl group or a phenyl group having a substituent. Hydrazine derivatives represented by the formula
It relates to the fine agricultural horticultural insecticide.

The hydrazine derivatives represented by the general formula (I) of the present invention include the E- and Z-isomers of the hydrazine derivatives represented by the general formulas (I-1) and (I-3). The present invention also encompasses these E-forms, Z-forms or mixtures containing E-forms and Z-forms in an arbitrary ratio. The hydrazine derivatives represented by the general formula (I) include R-forms and R-forms. It may have an S-isomer or a combination of these stereoisomers (diastereomers), and also includes an R-isomer, an S-isomer, and a mixture thereof.

[0003]

2. Description of the Related Art Semicarbazides are disclosed as insecticides in JP-A-48-91223.
Japanese Patent Application Laid-open No. 63-93761 discloses thiosemicarbazones as agricultural and horticultural disease controlling agents, and Japanese Patent Application Laid-Open No. 63-93761 discloses substituted hydrazones as pest controlling agents.

[0004]

The present inventors have conducted intensive studies to create a novel insecticide. As a result, hydrazine derivatives represented by the general formula (I) are described in the above-mentioned prior art documents and the like. The present invention has been found to be a novel compound that has not been suggested nor described in the literature and has an excellent insecticidal effect at a lower dose than in the prior art, and has completed the present invention.

[0005]

As a typical method for producing the hydrazine derivative represented by the general formula (I) of the present invention, the hydrazine derivative can be produced, for example, by the following production method. Manufacturing method A.

Embedded image [Wherein, R ¹ , R ² , R ³ , R ⁴ , Ar ¹ , Ar ² , A
r ³ and W are the same as above. The compound represented by the general formula (I-1) is reacted with a compound represented by the general formula (XI) and a compound represented by the general formula (VIII) in the presence of an inert solvent and in the presence or absence of a catalyst. )) Can be produced.

The inert solvent which can be used in this reaction includes:
Any substance that does not significantly inhibit the progress of this reaction may be used, for example, methanol, ethanol, propanol, butanol.
Alcohols such as toluene, dichloromethane, chloroform,
Halogenated hydrocarbons such as carbon tetrachloride; aromatic hydrocarbons such as benzene, toluene and xylene; nitriles such as acetonitrile and benzonitrile; ethers such as methyl cellosolve, diethyl ether, diglyme, dioxane and tetrahydrofuran And carboxylic acids such as acetic acid, dimethylacetamide, dimethylsulfoxide, water and the like. These inert solvents may be used alone or as a mixture.

As the catalyst used in this reaction, for example, an inorganic acid such as hydrochloric acid or sulfuric acid or an organic acid such as paratoluenesulfonic acid can be used. The catalyst may be used in an amount of 0.001% by weight to 10% by weight based on the compound represented by the general formula (XI) in the reaction system. Since this reaction is an equimolar reaction, each reactant may be used in an equimolar amount, but any of the reactants may be used in excess. The reaction temperature may be appropriately selected from the range of room temperature to the boiling point range of the inert solvent to be used.
It is good to perform in the range of ° C. The reaction time is not fixed depending on the reaction amount, the reaction temperature and the like, but may be selected from a range of several minutes to 48 hours. After completion of the reaction, the target product can be produced from the reaction solution containing the target product by a conventional method, for example, solvent distillation, solvent extraction, etc., and if necessary, purification by recrystallization, column chromatography, or the like. it can.

The compound represented by the general formula (I-1) or (I-
The compound represented by the general formula (XI) or the compound represented by the general formula (VIII), which is a raw material compound for producing the hydrazine derivative represented by 2 ′), is produced by, for example, a production method illustrated below. can do.

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , Ar ¹ , Ar ² , A
r ³ and W are the same as described above, R ⁸ represents a lower alkyl group, and V represents a leaving group such as a halogen atom or a lower alkoxy group or an imidazole group. )

That is, the compound represented by the general formula (XI) is prepared by converting an aromatic carboxylic acid represented by the general formula (XIII) and a compound represented by the general formula (XII) in the presence of an inert solvent and a base. Wherein the compound represented by the general formula (VIII) is a compound represented by the general formula (XV) or (XIV) and a hydrazine represented by the general formula (X) Can be produced by reacting the compound with

Process B (when R ¹ is a hydrogen atom).

Embedded image [Wherein, R ¹ , R ² , R ³ , R ⁴ , Ar ¹ , Ar ² , A
r ³ and W are the same as above. However, R ¹ excludes a lower alkyl group. The compound represented by the general formula (I) is reacted with a hydrazine represented by the general formula (X) in the presence of an inert solvent and in the presence or absence of a catalyst.
X) wherein the compound (IX) is isolated or not isolated in the presence of a compound represented by the general formula (VII) and an inert solvent and in the presence or absence of a catalyst. To produce a hydrazine derivative represented by the general formula (I-1).

B-1 . Formula (XI) → Formula (I
X) As the inert solvent that can be used in this reaction, the inert solvents exemplified in Production Method A can be used. The catalyst used in this reaction and the amount used may be the same as in Production Method A. The hydrazines represented by the general formula (X) used in this reaction may be used in the form of various salts, or may be used in the form of an aqueous solution having an appropriate concentration. The amount of the hydrazine represented by the general formula (X) can be used in an equimolar amount or in excess with respect to the compound represented by the general formula (XI), and is preferably 2 to 2.
It is preferable to use a 10-fold molar amount appropriately selected.
The reaction temperature may be appropriately selected from the range of room temperature to the boiling point range of the inert solvent used, and is preferably from 70 ° C to 80 ° C.
It is better to do within the range. The reaction time is not fixed depending on the reaction amount, the reaction temperature and the like, but may be selected from a range of several minutes to 48 hours. After completion of the reaction, the target product can be produced from the reaction solution containing the target product by a conventional method, for example, solvent distillation, solvent extraction, etc., and if necessary, purification by recrystallization, column chromatography, or the like. it can. The compound represented by the general formula (IX) obtained by this reaction may be isolated and purified by the above-mentioned method and used for the next reaction, or the next reaction can be carried out without isolation.

B-2 . General formula 1 (IX) → General formula (I-1) As an inert solvent that can be used in this reaction, for example, the production method A
Among the inert solvents that can be used in the above, in addition to the inert solvents except alcohols, carboxylic acids and water, esters such as ethyl acetate and pyridines can also be used. As the catalyst that can be used in this reaction, for example, amines such as triethylamine can be used, and the amount of the amine is appropriately selected from the range of the amount of the catalyst or the molar excess with respect to the compound represented by the general formula (IX). You can use it. Since this reaction is an equimolar reaction, each reactant may be used in an equimolar amount, but any of the reactants may be used in excess. The reaction temperature may be appropriately selected from the range of -20 ° C to the boiling point range of the inert solvent used, and preferably -1.
It is in the range of 0 ° C. to room temperature. The reaction time is not fixed depending on the reaction scale, the reaction temperature and the like, but may be selected from a range of several minutes to 48 hours. After completion of the reaction, the target product can be produced by treating in the same manner as in B-1.

The typical compounds of the hydrazine derivatives represented by the general formula (I-1) of the present invention, which are produced by the production methods A and B, are shown in Table 1.

[Table 1]

[0014]

[Table 2]

[0015]

[Table 3]

[0016]

[Table 4]

[0017]

[Table 5]

[0018]

[Table 6]

In Table 1, ¹ H-NMR data of glassy substances and paste-like substances are shown in Table 2.

[Table 7]

Production Method C

Embedded image [Wherein, R ¹ , R ² , R ³ , R ⁴ , Ar ¹ , Ar ² , A
r and W are the same as above. The hydrazine derivative represented by the general formula (I-2) is produced by reducing or catalyzing the hydrazine derivative represented by the general formula (I-1) in the presence or absence of an inert solvent. can do. This reduction reaction can be carried out by catalytic reduction in the presence of a suitable reducing agent or a catalyst. Examples of the reducing agent include LiAlH ₄ , NaBH ₃ C
N, a metal hydride such as LiBH ₃ CN, and a reducing agent such as NaHSO ₃ can be used. The amount of the reducing agent is based on the hydrazine derivative represented by the general formula (I-1). The amount may be selected from the range of equimolar to excess mole in terms of moles and used. The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, and includes, for example, methanol, ethanol, and propanol.
Alcohols such as toluene and butanol, diethyl ether,
Aids such as diglyme, dioxane, tetrahydrofuran, etc.
Examples thereof include cellosolves such as ters and methyl cellosolve, dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, water and the like. These inert solvents may be used alone or as a mixture.

This reaction is carried out under acidic or neutral conditions at pH 1 to
The reaction is carried out in the range of 7, preferably in the range of pH 4 to 6, and may be adjusted by adding hydrogen chloride, hydrogen bromide or the like to the reaction system. The reaction temperature may be appropriately selected from the range of −20 ° C. to the boiling point range of the inert solvent used. The reaction time is not fixed depending on the reaction scale, the reaction temperature and the like, but is in the range of several minutes to 48 hours. After completion of the reaction, the reaction solution containing the target compound is subjected to a conventional method, for example, solvent distillation, solvent extraction, and the like,
If necessary, the desired product can be produced by purification by a recrystallization method, a column chromatography method or the like. Next, in the case of performing catalytic reduction as a reduction reaction, it may be carried out according to a conventional method described in, for example, "Shin Jikken Kagaku Koza" (Vol. 15-II: Maruzen). Examples of usable inert solvents include, for example, methanol , Ethanol, propano
Alcohols such as toluene and butanol, cellosolves such as methyl cellosolve, ethers such as diethyl ether, diglyme, dioxane and tetrahydrofuran, hydrocarbons such as hexane and cyclohexane, acetic acid, ethyl acetate and the like. Fatty acids or esters thereof, dimethylformamide, dimethylacetamide, amides such as N-methylpyrrolidone, dimethylimidazoline, ureas such as tetramethylurea can be exemplified, and these inert solvents may be used alone. Good, they can be mixed and used. As a catalyst used in this reaction, for example, a typical catalytic reduction catalyst such as palladium carbon, palladium black, platinum dioxide, and Raney nickel can be used, and the amount of use is represented by the general formula (I). It may be appropriately selected from the range of 0.0001% to 20% by weight based on the hydrazinecarboxamides to be used. The hydrogen pressure in this reaction can be selected from the range of normal pressure to 300 atm, and is preferably in the range of normal pressure to 50 atm. After completion of the reaction, the target product can be produced from the reaction solution containing the target product in the same manner as when a reducing agent is used.

Manufacturing method D.

Embedded image [Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , Ar ¹ , Ar
^2, Ar ³ and W are the same comb in the, Z is a halogen atom or a -N = C = O. However, R ⁵ except a hydrogen atom. The hydrazine derivative represented by the general formula (I-2 ′) is reacted with the compound represented by the general formula (VI) in the presence of an inert solvent and a base to obtain a compound represented by the general formula (I-2)
The hydrazine derivative represented by these can be manufactured.

The inert solvent which can be used in the present reaction may be any solvent which does not hinder the progress of the present reaction. Examples of the inert solvent include halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, and benzene, toluene and xylene. Examples include aromatic hydrocarbons, esters such as ethyl acetate, nitriles such as acetonitrile and benzonitrile, ethers such as methyl cellosolve, diethyl ether, diglyme, dioxane and tetrahydrofuran, sulfolane and dimethyl sulfoxide. These inert solvents may be used alone or as a mixture. As the base that can be used in this reaction, an inorganic base or an organic base can be used.Examples of the inorganic base include hydroxides, carbonates, and the like of alkali metals or alkaline earth metals such as sodium, potassium, magnesium, and calcium. Examples of alcoholates and organic bases include, for example, triethylamine and pyridine. Since this reaction is an equimolar reaction, each reactant may be used in an equimolar amount, but any one of them may be used in excess. The reaction temperature may be selected from the range of 0 ° C. to the boiling point range of the inert solvent to be used. The reaction time is not fixed depending on the reaction scale, the reaction temperature, etc.
You can choose from a range of time. After completion of the reaction, the desired product can be produced by isolating the reaction product from the reaction solution containing the desired product by a conventional method, and purifying the product by a recrystallization method, a column chromatography method or the like as necessary.

Table 3 shows representative compounds of the hydrazine derivatives represented by the general formula (I-2) of the present invention produced by the production methods C and D.

[Table 8]

[0025]

[Table 9]

In Table 3, ¹ H-NMR data of glassy and paste-like substances are shown in Table 4.

[Table 10]

Process E.

Embedded image [Wherein R ¹ , R ² , R ³ , R ⁶ , R ⁷ , Ar ¹ , Ar
² , Ar ³ and W are the same as before. ]

The compound represented by the general formula (V) is reacted with the aniline represented by the general formula (III) in the presence of an inert solvent, in the presence or absence of a base and / or a condensing agent. Or a compound represented by the general formula (I-3) by reacting a compound represented by the general formula (IV) with a halide represented by the general formula (II) in the presence of an inert solvent and a base. Hydrazine derivatives can be produced. E-1 . General formula (V) → General formula (I-3) As the inert solvent that can be used in the present reaction, any solvent that does not significantly inhibit the progress of the present reaction may be used. For example, halogenation of dichloromethane, chloroform, carbon tetrachloride, etc. Hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene; nitriles such as acetonitrile and benzonitrile; and chain ethers such as methyl cellosolve and diethyl ether.
Cyclic ethers such as ters, dioxane, tetrahydrofuran, etc.
Ketones such as ters, acetone, methyl ethyl ketone,
Esters such as ethyl acetate, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO),
Pyridine and the like can be exemplified, and these inert solvents may be used alone or in combination.

As the base used in the present reaction, an organic base or an inorganic base can be used.
For example, alkali metals such as sodium and potassium, hydroxides and carbonates of alkaline earth metals such as calcium and magnesium, hydrides of alkali metals such as sodium hydride, and triethylamine and pyridine as organic bases.
N, N-dimethylaniline, 2,6-dimethylpyridine, 4-N, N-dimethylaminopyridine, and the like can be used in an amount of from a catalytic amount to a compound represented by the general formula (V). And can be selected from the range of equimolar to excess molar. As the condensing agent, for example, carbodiimidazole, dicyclohexylcarbodiimide, 2-chloro-1-methylpyridinium iodide and the like can be used. The amount of the condensing agent is based on the compound represented by the general formula (V). It may be used by selecting from an equimolar to excess molar range. Since this reaction is an equimolar reaction, each reactant may be used in an equimolar amount, but an aniline may be used in excess. The reaction temperature may be appropriately selected from the range of room temperature to the boiling point range of the inert solvent to be used, and the reaction is preferably carried out under heating. The reaction time is not fixed depending on the reaction amount, the reaction temperature and the like, but may be selected from a range of several minutes to 48 hours. After completion of the reaction, the target product can be produced from the reaction solution containing the target product by a conventional method, for example, solvent distillation, solvent extraction, etc., and if necessary, purification by recrystallization, column chromatography, or the like. it can.

E-2 . General formula (IV) → General formula (I
-3) a compound represented by the general formula (I-3) by reacting a compound represented by the general formula (IV) with a halide represented by the general formula (II) in the presence of an inert solvent and a base. Hydrazone derivatives can be produced. The inert solvent that can be used in this reaction may be any solvent that does not significantly inhibit the progress of this reaction, such as methanol, ethanol,
Alcohols such as propanol, halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; aromatic hydrocarbons such as benzene, toluene and xylene; nitriles such as acetonitrile and benzonitrile; methylcellosolve; Examples thereof include chain ethers such as diethyl ether, cyclic ethers such as dioxane and tetrahydrofuran, ketones such as acetone, esters such as ethyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide, and water. These inert solvents may be used alone or as a mixture. As the base used in this reaction, an organic base or an inorganic base can be used. Examples of the inorganic base include hydroxides or carbonates of alkali metals such as sodium and potassium, and alkaline earth metals such as calcium and magnesium. Hydrides of alkali metals such as sodium hydride, and alkali metal alcoholates such as sodium methoxide and potassium t-butoxide as organic bases;
Aminated compounds of alkali metals such as sodium amine, tertiary alkylamines such as triethylamine, pyridine,
-N, N-dimethylaminopyridine and the like can be used. The amount of the base used may be selected from the range of equimolar to excess molar with respect to the compound represented by formula (IV).

Since this reaction is an equimolar reaction, each reactant may be used in an equimolar amount. However, an excess of the halide represented by the general formula (II) may be used. The reaction temperature may be appropriately selected from the range from room temperature to the boiling point range of the inert solvent used. The reaction time is not fixed depending on the reaction amount, the reaction temperature and the like, but may be selected from a range of several minutes to 48 hours. After completion of the reaction, the target product can be produced in the same manner as in the above reaction. The general formula (I-) of the present invention
The compound represented by the general formula (V), which is a raw material compound for producing the hydrazone derivative represented by 3), is disclosed in
Nos. 223169 and 64-70462; Or
g. Chem. 417 (1941), Ber. 56B,
1060-1065 (1923). Compounds represented by the general formula (IV) are described in Collection Czech. Chem.
Communs. , 25, 2651-2667 (196)
0) and the like.

The typical compounds of the hydrazine derivative represented by the general formula (I-3) produced by the production methods E-1 and E-2 are shown in Table 5 below.

[Table 11]

Manufacturing method F.

Embedded image [Wherein, R ¹ , R ² , R ³ , R ⁶ , Ar ¹ , Ar ² , A
r ³ and W are the same as above. The hydrazine derivative represented by the general formula (I-4 ′) can be produced by carrying out the reaction in the same manner as in Production Method C.

Manufacturing method G.

Embedded image [Wherein, R ¹ , R ² , R ³ , R ⁵ , R ⁶ , Ar ¹ , Ar
^2, Ar ³ and W are the same comb in the, Z is a halogen atom or a -N = C = O. However, R ⁵ except a hydrogen atom. The hydrazine derivative represented by the general formula (I-4) can be produced by carrying out the reaction in the same manner as in Production Method D. Table 6 below shows typical compounds prepared by the methods for producing F and G.

[0035]

[Table 12]

The following are typical examples of the present invention, but the present invention is not limited to these examples. Example 1 N- (4-chlorophenyl) -2- [1,
Production of 2-di (pyridin-2-yl) -2-hydroxyethylidene] hydrazinecarboxamide (Compound No. 9)

Embedded image 5.0 g (23 mmol) of pyridoin are dissolved in 30 ml of ethanol and 12 g (240 mmol) of 100
% Hydrazine hydrate and 2 drops of concentrated sulfuric acid were added, and the mixture was refluxed for 2 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure and extracted and concentrated with ethyl acetate to obtain 3.0 g of a paste-like pyridoinhydrazone (yield 57%). 1.3 g (5.7 mmol) of the obtained pyridoinhydrazone was dissolved in 40 ml of dry tetrahydrofuran, and 0.85 g (5.6 mmol) of 4-chlorophenyl isocyanate was added, followed by a reaction at room temperature for 2 hours. Was. After completion of the reaction, the reaction solution containing the desired product was allowed to cool, the reaction solvent was distilled off under reduced pressure, and the precipitated crystals were collected by filtration and washed with a small amount of toluene to obtain 0.40 g of the desired product. Properties mp 145 ° C Yield 19%

Embodiment 2 2-1. Production of (4-cyanobenzyl) (pyridin-4-yl) ketone

Embedded image 13.8 g (360 mmol) of 60% oily sodium hydride are suspended in 150 ml of dry dimethylformamide and, with stirring at room temperature, 21.1 g (180 mmol) of 4-tolunitrile and 25.0 g (180 mmol) The mixture of methyl isonicotinate was added dropwise at 40 ° C.
For 5 hours. After completion of the reaction, the reaction solution was poured into ice water, neutralized with 15% hydrochloric acid, and the precipitated crystals were collected by filtration and washed with a small amount of ethanol to obtain 30.4 g of the desired product. Physical properties mp 65 ° C Yield 79%

2-2. 2- [2- (4-cyanobenzyl) -1- (pyridin-4-yl) ethylidene] -N-
Production of [4- (1,1,2,2-tetrafluoroethoxy) phenyl] hydrazinecarboxamide (Compound No. 2
5)

Embedded image 5.0 g (22 mmol) of (4-cyanobenzyl)
(Pyridin-4-yl) ketone was dissolved in 30 ml of ethanol, 5.5 g (110 mmol) of 100% hydrazine hydrate and 2 drops of concentrated sulfuric acid were added, and the mixture was heated under reflux for 4 hours. After completion of the reaction, the reaction solution was allowed to cool, the reaction solution was distilled off under reduced pressure, and the precipitated crystals were collected by filtration and recrystallized from ethanol to give (4-cyanobenzyl) (pyridin-4-yl) ketone hydrazone. 4.4 g were obtained. Physical properties mp 145 ° C Yield 85% obtained (4-cyanobenzyl) (pyridin-4-yl)
0.78 g (3.3 mmol) of ketone hydrazone was added to 10
Then, 0.78 g (3.3 mmol) of 4- (1,1,2,2-tetrafluoroethoxy) phenyl isocyanate dissolved in 5 ml of tetrahydrofuran and dissolved in 5 ml of tetrahydrofuran was added dropwise, and the mixture was left overnight. . After completion of the reaction, the reaction solution was distilled off under reduced pressure, and the resulting oil was purified by silica gel column chromatography to obtain 0.80 g of the desired product. Physical properties mp 201 ° C Yield 51%

Embodiment 3 3-1. Production of phenyl (pyridin-4-yl) ketone

Embedded image 8.5 g (210 mmol) of 60% oily sodium hydride are suspended in 50 ml of dry dimethylformamide and a mixture of 10.0 g (108 mmol) of 4-picoline and 13.5 g (108 mmol) of methyl benzoate Was added dropwise at room temperature, and after the completion of the addition, the reaction was carried out at 50 ° C. for 16 hours. After completion of the reaction, the reaction solution was poured into ice water, the pH was adjusted to about 7 with concentrated hydrochloric acid, and the precipitated crystals were collected by filtration and a small amount of air was added.
The residue was washed with tel to obtain 14.1 g of the desired product. 70% yield

3-2. Production of 2- [1-phenyl-2- (pyridin-4-yl) ethylidene] -N- (4-trifluoromethoxyphenyl) hydrazinecarboxamide (Compound No. 39)

Embedded image 0.50 g (2.6 mmol) of phenyl (pyridine-
4-ylmethyl) ketone was dissolved in 30 ml of ethanol, 3 g (60 mmol) of 100% hydrazine hydrate and one drop of concentrated sulfuric acid were added, and the mixture was heated under reflux for 2 hours. After the completion of the reaction, the reaction solution was allowed to cool, concentrated under reduced pressure, extracted with ethyl acetate and concentrated to obtain oily phenyl (pyridine-
0.45 g of 4-ylmethyl) ketone hydrazone was obtained. Yield 84% 0.45 g (2.2 mmol) of the obtained phenyl (pyridin-4-ylmethyl) ketone hydrazone was dissolved in 20 ml of dry tetrahydrofuran, and 20 ml of dry pyridine was added. .2 mmol) of 4-trifluoromethoxyphenyl isocyanate was added dropwise, and allowed to stand overnight after completion of the addition. After completion of the reaction, the reaction solvent was distilled off under reduced pressure, and the precipitated crystals were collected by filtration and washed with ether to obtain 0.82 g of the desired product. Physical properties mp 151 ° C Yield 92%

Example 4 2- [1-phenyl-2-
Production of (pyridin-4-yl) ethyl] -N- (4-trifluoromethoxyphenyl) hydrazinecarboxamide (Compound No. 66)

Embedded image 0.44 g (1.1 mmol) of 2- [1-phenyl-
2- (pyridin-4-yl) ethylidene] -N- (4-
Trifluoromethoxyphenyl) hydrazinecarboxamide was dissolved in a mixed solvent of 10 ml of tetrahydrofuran and 10 ml of methanol, and 0.13 g (2.1 mmol) of sodium cyanoborohydride was added thereto. Of the solution was added dropwise, and the reaction was carried out at room temperature for 1 hour. After completion of the reaction, the reaction solution was concentrated under reduced pressure, ethyl acetate was added to the concentrated solution, and the organic layer was washed with an aqueous sodium bicarbonate solution and distilled under reduced pressure to obtain 0.35 g of a glassy target product. Was. Physical properties Glassy substance Yield 80% NMR (CDCl ₃ / TMS, δ value, ppm) 2.97-3.15 (m, 2H), 4.01-4.11
(M, 2H), 5.80 (s, 1H), 7.07-7.
46 (m.11H), 7.76 (s, 1H), 8.52
-8.56 (m, 2H).

Example 5 2- [2- (1-oxopyridin-4-yl) -1-phenylethylidene] -N-
Production of (4-trifluoromethoxyphenyl) hydrazinecarboxamide (Compound No. 40)

Embedded image 0.38 g of 2- [1-phenyl-2- (pyridine-4)
-Yl) ethylidene] -N- (4-trifluoromethoxyphenyl) hydrazinecarboxamide was dissolved in 40 ml of chloroform, and 0.18 g (1.1 mmol) of 3-chloroperbenzoic acid was added, followed by 3 hours at room temperature. The reaction was performed. After completion of the reaction, the reaction solution was washed with an aqueous solution of sodium bicarbonate and water in that order, dried, and the solvent was distilled off under reduced pressure to obtain 0.28 g of the desired product. Physical properties mp 208 ° C (decomposition) Yield 71%

Embodiment 6 6-1. 2- [2- (3-fluorophenyl) -2-
Production of [hydroxyvinyl] pyridine-5-carbonitrile

Embedded image 1.4 g (3.4 mmol) of 60% oily sodium hydride are suspended in 50 ml of dry dimethylformamide, 2.6 g (1.7 mmol) of methyl 3-fluorobenzoate and 2.0 g (1. 7 mmol) 5-cyano-
A mixture of 2-methylpyridine was added dropwise at room temperature, and after completion of the addition, the mixture was reacted at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into ice water, the pH was adjusted to about 7 with concentrated hydrochloric acid, and the precipitated crystals were collected by filtration and washed with a mixed solution of ether-n-hexane (1: 1). 2.4 g of the product were obtained. Yield 59%

6-2. Production of 2- [2- (5-cyanopyridin-2-yl) -1- (3-trifluorophenyl) ethylidene] -N- (4-trifluoromethoxyphenyl) hydrazinecarboxamide (Compound No. 44)

Embedded image 2.0 g (8.8 mmol) of 2- [2- (3-fluorophenyl) -2-hydroxyvinyl] pyridine-5-
Carbonitrile is suspended in 30 ml of methanol,
4.4 g (88 mmol) of hydrazine hydrate and one drop of concentrated sulfuric acid were added, and the mixture was reacted under reflux for 4 hours. After completion of the reaction, the reaction solution was allowed to cool, concentrated under reduced pressure, extracted by adding ethyl acetate, and the extract was dried and concentrated to obtain a paper.
(5-cyanopyridin-2-ylmethyl) (3
2.0 g of (-fluorophenyl) ketone hydrazone was obtained (89% yield). The resulting (5-cyanopyridine-2-
1.6 g (6.3 mmol) of ylmethyl) (3-fluorophenyl) ketone hydrazone was dissolved in 30 ml of tetrahydrofuran, 1 ml of pyridine was added, and then 1.15 g dissolved in 20 ml of dry tetrahydrofuran
(5.7 mmol) of 4-trifluoromethoxyphenyl isocyanate was added dropwise at room temperature, and after completion of the addition, the reaction was carried out at room temperature for 3 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and the precipitated crystals were collected by filtration and washed with a mixed solution of ether-n-hexane (1: 1) to obtain the desired product 2.
65 g were obtained. Physical properties mp 176 ° C Yield 95%

Example 7 Preparation of 2- [2- (5-cyanopyridin-2-yl) -1- (3-fluorophenyl) ethyl] -N- (4-trifluoromethoxyphenylhydrazinecarboxamide (Compound No. 68)

Embedded image 1.2 g (2.7 mmol) of 2- [2- (5-cyanopyridin-2-yl) -1- (3-fluorophenyl)
[Ethylidene] -N- (4-trifluoromethoxyphenyl) hydrazinecarboxamide was suspended in 30 ml of methanol, 1.7 g (27 mmol) of sodium borohydride was added, and a saturated methanol solution of hydrogen chloride was gradually added. In addition, the reaction was carried out at room temperature for 7 hours while adjusting the pH to 3-4. After completion of the reaction, the reaction solution was concentrated under reduced pressure, ethyl acetate was added, the organic layer was washed with sodium bicarbonate and dried, and the solvent was distilled off under reduced pressure. Ethyl: n-
Hexane = 1: 1) to give the desired product 0.1
0 g was obtained. Physical properties mp 160 ° C Yield 8%

Embodiment 8 8-1. Production of 2- [2-hydroxy-2- (3-trifluoromethylphenyl) vinyl] pyrazine-5-carbonitrile

Embedded image 1.0 g (25 mmol) of 60% oily sodium hydride are suspended in 40 ml of dry dimethylformamide,
A mixture of 3.4 g (17 mmol) of methyl 3-trifluoromethylbenzoate and 2.0 g (17 mmol) of 2-methylpyrazine-5-carbonitrile was added dropwise at room temperature at room temperature. The reaction was performed at the temperature for 2 hours. After completion of the reaction, the reaction solution was poured into ice water, the pH was adjusted to about 7 with hydrochloric acid, the precipitated crystals were collected by filtration, and the mixed solution of ether-n-hexane (1: 1) was washed to obtain the objective. 3.4 g of product were obtained. 70% yield

8-2. 2- [2-cyanopyridine-5
-Yl) -1- (3-trifluoromethylphenyl) ethylidene] -N- (4-trifluoromethoxyphenyl) hydrazinecarboxamide (Compound No. 56)

Embedded image 0.9 g (3.1 mmol) of 2- [2-hydroxy-
2- (3-trifluoromethylphenyl) vinyl] pyrazine-5-carbonitrile and 0.73 g (3.1 mmol) of N- (4-trifluoromethoxyphenyl) hydrazinecarboxamide were dissolved in 80 ml of ethanol. Then, 10 mg of 4-toluenesulfonic acid was added and reacted at room temperature for 4 hours. After completion of the reaction, the reaction solution is concentrated under reduced pressure, ethyl acetate is added to extract the desired product, washed with sodium bicarbonate and water in that order, dried, and the solvent is distilled off under reduced pressure. Purification by silica gel column chromatography (ethyl acetate: n-hexane = 1: 2) gave 0.30 g of the desired product. Physical properties mp 175 ° C Yield 20%

Example 9 2- [1- (3-chlorophenyl) -2- (4-cyanophenyl) ethylidene]-
Production of N- (pyridin-3-yl) hydrazinecarbothioamide (Compound No. 58)

Embedded image 1.0 g (3.7 mmol) of (3-chlorophenyl)
(4-Cyanobenzyl) ketone hydrazone was dissolved in 10 ml of dry tetrahydrofuran, 1 ml of pyridine and 0.5 g (3.7 mmol) of 3-pyridyl isothiocyanate were added, and 1.0 g (3.7 mmol) of (3 mmol) was added. -Chlorophenyl) (4-cyanobenzyl) ketone hydrazone was dissolved in 10 ml of dry tetrahydrofuran, 1 ml of pyridine and 0.5 g (3.7 mmol) of 3-pyridyl isothiocyanate were added, and the reaction was carried out by heating under reflux for 1 hour. Was. After completion of the reaction, the reaction solvent was distilled off under reduced pressure, and the precipitated crystals were collected by filtration and toluene-n-hexane (1: 1).
By washing with a mixed solution of the above, 1.0 g of the desired product was obtained. mp 177 ° C Yield 67%

Example 10 2- [N- (5-cyano-
2-pyridylmethyl) -N- (3-chlorophenyl)]
Production of hydrazono-4-trifluoromethoxyacetanilide (Compound No. 80)

Embedded image 0.80 g (2.2 mmol) of 3-chlorophenylhydrazono-4-trifluoromethoxyacetanilide was added to 2
Dissolve in 0 ml of dimethylformamide, and add
% Sodium hydride 0.10 g (2.5 mmol) and 2-bromomethyl-5-cyanopyridine 0.50 g
(2.5 mmol) was added thereto, and the mixture was reacted at room temperature for 5 hours with stirring. After completion of the reaction, 80 ml of ice water was added to the reaction solution, and the desired product was extracted with ethyl acetate (100 ml × 2). The organic layer was washed with water, dried (anhydrous sodium sulfate) and concentrated under reduced pressure, and the residue obtained was silica gel. Purification by column chromatography (n-hexane-ethyl acetate) gave 0.82 g of the desired product. Physical properties mp 154.5-156.2 ° C Yield
78.7%

Example 11 2- [N- (5-cyano-
2-pyridylmethyl) -N- (3-chlorophenyl)]
Production of hydrazono-4-trifluoromethoxyacetanilide (Compound No 83)

Embedded image 2- [N- (5-cyano-2-pyridylmethyl) -N-
(3-Chlorophenyl)] hydrazono-4-trifluoromethoxyacetanilide 0.5 g (1.1 mmol)
Was dissolved in a mixed solvent of 2 ml of tetrahydrofuran and 5 ml of methanol, and 0.30 g (4.4 mmol) of sodium cyanoborohydride was added thereto.
ml of saturated hydrogen chloride methanol was added dropwise.
The reaction was performed at room temperature for hours. After completion of the reaction, the solvent is distilled off, ethyl acetate is added, the mixture is neutralized with an aqueous sodium hydrogen carbonate solution, and the organic layer is separated and dried. The organic layer is dried over anhydrous sodium sulfate and concentrated under reduced pressure. Was purified by silica gel column chromatography (n-hexane-ethyl acetate) to obtain 0.08 g of the desired product. Physical properties mp 64-67 ° C Yield 15.3%

The agricultural and horticultural insecticides containing the hydrazine derivative represented by the general formula (I) of the present invention as an active ingredient include rice,
It is suitable for various agriculture and forestry, horticulture, storage pests, sanitary pests, nematodes, and other pests that injure vegetables, fruit trees, other crops and flowers.
hyes orana fasciata)
oxophyes sp.), apple hog squid (Grapholita inopi)
nata), Nashihime Shingua (Grapholita mlesta),
Mameshin iga (Leguminivora glycinivorel-la), Kuwahamaki (Olethreutes mori), Canohosoga (Calopt)
ilia thevivor-a), apple hosoga (Caloptilia zachr)
ysa), Kingmon Hosoga (Phyllonoryc-ter ringoniell)
a), Psychonid moth (Spulerina astaurota), cabbage butterfly (Pieris rapae crucivora), giant tobacco (Heliothis sp.), codling moth (Laspeyresia pomone)
lla), Japanese moth (Plutella xylostella), apple squirrel (Argyresthia conjugella), peach moth (Carposina niponensis), squid (Chilo suppre)
ssalis) and Coleoptera (Cnaphalocrocis medina-lis)
), Ephestia elutella, Glyphodespyloalis, and Scir (Scir)
pophaga incertulas), Parnara gu
ttata), armyworm (Pseudaletia separata), rice armyworm (Ses-amia inferens), lotus armyworm (Spod)
optera litura), Spodoptera litura (Spodoptera)
exigua) and other lepidopteran pests, Leafhopper leafhopper (Macros)
telesfascifrons), leafhopper (Nephotettix)
cincticeps), brown planthopper (Nilaparvata lugen)
s), White-spotted planthopper (Sogatella furcifera), orange lice (Diaphorina citri), grape whitefly (Al)
eurolobus taonabae, tobacco whitefly (Bemisia ta)
baci), Whitefly (Trialeurodes vapo-rari)
orum) and the radish aphid (Lipaphis erysim)
i), peach aphid (Myzus persicae), horned beetle (Ceroplastes ceriferus), citrus stag beetle (Pulvinaria aurantii), citrus stalk beetle (Pseudaoni-dia duplex), pear stalk beetle (Comstockaspis perniciosa), and lynosperm Hemiptera pests, such as the Japanese beetle (Anomalarufocuprea) and the beetle (Popillia japon)
ica), tobacco bug (Las-ioderma serricorn)
e), Flying bark beetle (Lyctus brunneus), Papilio periwinkle (Epilachna vigintioctopunctata)
), Adzuki beetle (Callosobr-uchus chinensis)
), Weevil (Listroderes costirostris),
Black elephant (Sitophilus zeamais), Cotton weevil (An
thonomus grandis grandis), rice weevil (Liss
orhoptrus oryzophilus), turtle beetle (Aulacophora)
f-emoralis), rice beetle (Oulema oryzae),
Leaf beetle (Phyll-otreta striolata), pine bark beetle (Tomicus piniperda), colorado potato bite (Leptinotarsa decemlineata), Mexican beetle (Epi-lachna varivestis), corn-
Coleopteran pests such as worms (Diabrotica sp.), Sea flies (Dacus (Zeugodacus) cucurbitae), citrus fruit flies (Dacus- (Bactrocera) dorsalis), rice leaf flies (Agromyza oryzae), and onion flies (Delia anti)
qua), fly (Delia platura), soybean fly (Asphondylia sp.), housefly (Musca domestic)
a), dipteran pests such as Culex pip-iens pipiens, and the nematode (Pratylenchus sp.),
Southern nematode (Pratylenchus coffeae),
Potato cyst nematode (Globodera rostochiensi
s), root-knot nematodes (Meloidogyne sp.), tangerine nematodes (Tylenchulus semipenetrans), moss root nematodes (Aphelenchus avenae), and nematode (Aphelenchoides ritzemabosi), and other insecticidal effects. Especially Lepidoptera,
It has a remarkable effect on pests such as Coleoptera. The scientific names and the like are based on the 1987 Agricultural and Forestry Pest and Animal Directory, edited by the Japan Society of Applied Animal Entomology.

The agricultural and horticultural insecticide of the present invention has a remarkable insecticidal effect on the above-mentioned pests or sanitary pests that infect paddy fields, fruit trees, vegetables, other crops, flowers and the like. Before and after the occurrence of the pests is confirmed, the paddy fields, fruit trees, vegetables, other crops, paddy water such as flowers, foliage or soil, etc. The intended effect of the insecticide of the present invention can be obtained by treating the inside of a house or a ditch around a house where the occurrence of the above-mentioned pests or the occurrence of the above-mentioned pests is predicted.

However, the present invention is not limited to only these embodiments. When the hydrazine derivative represented by the general formula (I) of the present invention is used as an agricultural and horticultural insecticide, it is generally used by formulating it into a convenient form according to a conventional method for agricultural chemical formulation. It is. That is, the hydrazine derivatives represented by the general formula (I) of the present invention can be dissolved, separated, blended in a suitable ratio with an appropriate inert carrier or, if necessary, with an auxiliary. It may be suspended, mixed, impregnated, adsorbed or adhered and formulated into an appropriate dosage form, for example, a suspension, emulsion, solution, wettable powder, granule, powder, tablet or the like. The inert carrier that can be used in the present invention may be either solid or liquid. Examples of the material that can be a solid carrier include soybean flour, cereal flour, wood flour, bark flour, saw flour, and tobacco stem flour. , Walnut shell powder, bran,
Cellulose powder, residue after extraction of plant extract, synthetic polymer such as pulverized synthetic resin, clays (eg, kaolin, bentonite, acid clay), talcs (eg, talc, pyrophyllide, etc.), silicas (eg, diatomaceous earth, silica sand) , Mica, white carbon [Synthetic high-dispersion silicic acid, also known as hydrous fine silicon powder and hydrous silicic acid, some of which contain calcium silicate as a main component.]), Activated carbon, sulfur powder, pumice, calcined diatomaceous earth, brick crushing Thing, fly ash, sand,
Inorganic mineral powders such as calcium carbonate and calcium phosphate,
Examples include chemical fertilizers such as ammonium sulfate, phosphorous ammonium, ammonium nitrate, urea, and salt ammonium, and compost, and these are used alone or in the form of a mixture of two or more.

The material that can be a liquid carrier is selected from those having a solvent function per se and those capable of dispersing the active ingredient compound with the aid of an adjuvant even without the solvent function. The following carriers can be exemplified as typical examples. These can be used alone or in the form of a mixture of two or more. Examples thereof include water, alcohols (eg, methanol, ethanol, isopropanol, butanol). , Ethylene glycol and the like), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Diisobutyl ketone, cyclohexanone, etc.), ethers (eg, ethyl ether, dioxane, cellosolve,
Dipropyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbons (eg, kerosene, mineral oil, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, solvent naphtha, alkylnaphthalene, etc.), halogenated hydrocarbons (eg, dichloroethane) , Chloroform, carbon tetrachloride, chlorinated benzene, etc.), esters (eg, ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctophthalate), amides (eg, dimethylformamide, diethylformamide, dimethylacetamide) Etc.), nitriles (eg, acetonitrile, etc.), dimethyl sulfoxides and the like. Examples of the other adjuvants include the following representative adjuvants. These adjuvants are used according to the purpose, and may be used alone or in combination of two or more kinds. In some cases, it is possible to use no auxiliaries at all.

Surfactants are used for the purpose of emulsifying, dispersing, solubilizing and / or wetting the active ingredient compound, such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene, and the like. Ethylene higher fatty acid ester, polyoxyethylene resin acid ester, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkyl aryl sulfonate, naphthalene sulfonic acid condensate,
Surfactants such as lignin sulfonate and higher alcohol sulfate can be exemplified. For the purpose of stabilizing the dispersion of the active ingredient compound, adhering and / or binding, the following auxiliaries can be used. For example, casein, gelatin, starch, methylcellulose, carboxymethylcellulose can be used. Auxiliaries such as gum arabic, polyvinyl alcohol, pine oil, bran oil, bentonite, and lignin sulfonate can also be used. The following auxiliaries can be used to improve the flowability of the solid product. For example, auxiliaries such as wax, stearate, alkyl phosphate and the like can be used. As peptizers for suspension products, auxiliary agents such as, for example, naphthalenesulfonic acid condensates, condensed phosphates and the like can also be used. As an antifoaming agent, for example, an auxiliary agent such as silicone oil can be used.

The compounding ratio of the active ingredient compound can be adjusted as required. For example, 0.01 to 50% by weight in the case of powder or granules, and 0.1% in the case of emulsion or wettable powder. A suitable amount is from 01 to 50% by weight. The agricultural and horticultural insecticide containing the hydrazine derivative represented by the general formula (I) of the present invention as an active ingredient is useful for controlling various pests.
An amount effective for controlling pests may be used as it is, or appropriately diluted or suspended with water or the like, and applied to the pests, or applied to places where the generation or growth of the pests is not preferred. The amount of the agricultural and horticultural insecticide containing the hydrazine derivative represented by the general formula (I) of the present invention as an active ingredient depends on various factors, for example, the purpose, the target pest, the growth status of the crop, the tendency of the pest to develop, and the weather. Although it varies depending on environmental conditions, dosage form, application method, application place, application time, etc., the active ingredient compound may be appropriately selected from the range of 0.1 g to 5 kg per 10 ales according to the purpose. The insecticide for agricultural use comprising the hydrazine derivative represented by the general formula (I) of the present invention as an active ingredient is further added to other insect pests for the purpose of controlling pests, extending the suitable period of control, or reducing the amount of drugs. It is also possible to use a mixture with an agent or a bactericide. Hereinafter, typical formulation examples and test examples of the present invention are shown, but the present invention is not limited thereto. In the formula examples, “parts” means “parts by weight”.

Formulation Example 1 Compound of the present invention 50 parts Xylene 40 parts Mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate 10 parts The above are uniformly mixed and dissolved to form an emulsion. Formulation Example 2 Compound of the present invention 3 parts Clay powder 82 parts Diatomaceous earth powder 15 parts The above are uniformly mixed and pulverized to give a powder. Formulation Example 3 Compound of the present invention 5 parts Mixed powder of bentonite and clay 90 parts Calcium ligninsulfonate 5 parts The above components were uniformly mixed, kneaded by adding an appropriate amount of water, and granulated.
Dry to granules. Formulation Example 4 Compound of the present invention 20 parts Kaolin and synthetic highly dispersed silicic acid 75 parts Mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate 5 parts The above are uniformly mixed and pulverized to obtain a wettable powder.

Test Example 1 Lotus armyworm ( Spodoptera)
Insecticidal test on litura ) Cabbage leaf pieces (variety: four seasons harvest) were immersed for about 30 seconds in a drug solution prepared by diluting a drug containing the compound of the present invention as an active ingredient to 500 ppm. After air-drying, it was placed in a plastic dish having a diameter of 9 cm, inoculated with the second instar larvae of Spodoptera litura, covered, and allowed to stand in a 25 ° C constant temperature room. Eight days after the inoculation, the number of live and dead insects was investigated, the mortality was calculated by the following formula, and judgment was made according to the following criteria. Judgment criteria. A: 100% mortality B: 99% to 90% mortality C: 89% to 80% mortality D: 79% to 50% mortality Table 7 shows the results. Shown in

[0059]

[Table 13]

[0060]

[Table 14]

Test Example 2 Sitophilus zeam
a ) Insecticidal test against adult insects Brown rice was immersed for about 30 seconds in a drug solution obtained by diluting a drug containing the compound of the present invention as an active ingredient to 200 ppm. Diameter 4 after air drying
After placing in a glass dish of cm and inoculating adult black elephants, it was covered and left to stand in a constant temperature room at 25 ° C. Eight days after the inoculation, the number of live and dead insects was investigated, the mortality was calculated according to Test Example 1, and the judgment was made according to the criteria of Test Example 1. 10 units per ward in three wards. The results are shown in Table 8.

[0062]

[Table 15]

[0063]

[Table 16]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07D 213/38 C07D 213/38 213/53 213/53 213/57 213/57 213/89 213/89 241/24 241/24 (72) Inventor Watuji Ando 7-2-804 Shinkitajima, Suminoe-ku, Osaka-shi, Osaka (72) Inventor Hiroshi Hamaguchi 10-1, Fukakusa-Horita-cho, Fushimi-ku, Kyoto, Kyoto, A804 (56) Reference Europe Patent application publication 462456 (EP, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. A compound of the general formula (I) Wherein R ¹ represents a hydrogen atom or a lower alkyl group;
² and R ³ may be the same or different and represent a hydrogen atom, a hydroxyl group or a lower alkyl group, Ar ¹ and Ar ² may be the same or different, and may be a phenyl group or 1 to 3 identical or different An oxygen atom, a heterocyclic group having 3 to 6 carbon atoms having a heteroatom selected from a nitrogen atom or a sulfur atom, and when the heteroatom on the heterocyclic group is a nitrogen atom, the nitrogen atom is oxidized. The phenyl group or the heterocyclic group may be the same selected from a halogen atom, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group or a lower alkoxycarbonyl group. Or it may have one or more substituents which may be different. A is (Wherein, R ⁴ represents a hydrogen atom or a lower alkyl group;
⁵ represents a hydrogen atom, a lower alkylcarbonyl group, a lower haloalkylcarbonyl group, a cycloalkylcarbonyl group or a lower alkoxycarbonyl group, R ⁶ represents a hydrogen atom or a lower alkyl group, Ar ³ represents a phenyl group or 1 to
3 represents a heterocyclic group having 3 to 6 carbon atoms having a heteroatom selected from the same or different oxygen atoms, nitrogen atoms or sulfur atoms, wherein the heteroatom on the heterocyclic group is a nitrogen atom In this case, the nitrogen atom may be oxidized, and the phenyl group or the heterocyclic group may be a halogen atom, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group or a lower alkoxycarbonyl group. And may have one or more substituents which may be the same or different and are selected from ), And W represents an oxygen atom or a sulfur atom. However, Ar ¹ , Ar ² and A
r ³ does not simultaneously represent a phenyl group or a phenyl group having a substituent. ] Hydrazine derivatives represented by the formula: 2. A compound of the general formula (I-1) [Wherein, R ¹ , R ² , R ³ , R ⁴ , Ar ¹ , Ar ² , A
r ³ and W are the same as above. However, Ar ¹ , Ar ² and A
r ³ does not simultaneously represent a phenyl group or a phenyl group having a substituent. The hydrazine derivative according to claim 1, which is represented by the formula: 3. A compound of the general formula (I-2) [Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , Ar ¹ , Ar
² , Ar ³ and W are the same as above. However, Ar ¹ , Ar ²
And Ar ³ do not simultaneously represent a phenyl group or a phenyl group having a substituent. The hydrazine derivative according to claim 1, which is represented by the formula: 4. A compound of the general formula (I-3) [Wherein, R ¹ , R ² , R ³ , R ⁶ , Ar ¹ , Ar ² , A
r ³ and W are the same as above. However, Ar ¹ , Ar ² and A
r ³ does not simultaneously represent a phenyl group or a phenyl group having a substituent. The hydrazine derivative according to claim 1, which is represented by the formula: 5. A compound of the formula (I-4) [Wherein, R ¹ , R ² , R ³ , R ⁵ , R ⁶ , Ar ¹ , Ar
² , Ar ³ and W are the same as above. However, Ar ¹ , Ar ²
And Ar ³ do not simultaneously represent a phenyl group or a phenyl group having a substituent. The hydrazine derivative according to claim 1, which is represented by the formula: 6. A compound of the general formula (I) Wherein R ¹ represents a hydrogen atom or a lower alkyl group;
² and R ³ may be the same or different and represent a hydrogen atom, a hydroxyl group or a lower alkyl group, Ar ¹ and Ar ² may be the same or different, and may be a phenyl group or 1 to 3 identical or different An oxygen atom, a heterocyclic group having 3 to 6 carbon atoms having a heteroatom selected from a nitrogen atom or a sulfur atom, and when the heteroatom on the heterocyclic group is a nitrogen atom, the nitrogen atom is oxidized. The phenyl group or the heterocyclic group may be the same selected from a halogen atom, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group or a lower alkoxycarbonyl group. Or it may have one or more substituents which may be different. A is (Wherein, R ⁴ represents a hydrogen atom or a lower alkyl group;
⁵ represents a hydrogen atom, a lower alkylcarbonyl group, a lower haloalkylcarbonyl group, a cycloalkylcarbonyl group or a lower alkoxycarbonyl group, R ⁶ represents a hydrogen atom or a lower alkyl group, Ar ³ represents a phenyl group or 1 to
3 represents a heterocyclic group having 3 to 6 carbon atoms having a heteroatom selected from the same or different oxygen atoms, nitrogen atoms or sulfur atoms, wherein the heteroatom on the heterocyclic group is a nitrogen atom In this case, the nitrogen atom may be oxidized, and the phenyl group or the heterocyclic group may be a halogen atom, a cyano group, a nitro group, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group or a lower alkoxycarbonyl group. And may have one or more substituents which may be the same or different and are selected from ), And W represents an oxygen atom or a sulfur atom. However, Ar ¹ , Ar ² and A
r ³ does not simultaneously represent a phenyl group or a phenyl group having a substituent. Agricultural and horticultural insecticide characterized by containing hydrazine derivatives as an active component represented by].