JP3330155B2 - Hydrazone-based compounds, methods for their production, intermediates for their production, and pesticides containing them - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hydrazone compound represented by the following general formula (I), a method for producing them, an intermediate for producing them, and a hydrazone compound represented by the following general formula (IX). The present invention relates to a pesticidal agent and a pesticidal method for applying an effective amount thereof.

[0002]

2. Description of the Related Art Hydrazone compounds are disclosed in, for example,
No. 0-16410, JP-A-5-122261, JP-A-56
-45452, 63-93761, JP-A-2-138
246 publications. However, there is no disclosure of the compound of the present invention represented by the following general formula (I).

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a compound of the general formula (I):

[0004]

Embedded image (Wherein R ¹ , R ² and R ⁴ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a trialkylsilyl group, an optionally substituted alkyl group, or an optionally substituted R ³ is a cycloalkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted carboxyl group, an optionally substituted aryl group or an optionally substituted aryloxy group; Hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, optionally substituted alkyl group, optionally substituted cycloalkyl group, optionally substituted alkoxy group, optionally substituted alkylthio group, substituted Carboxyl group, X ¹ SO ₂ NH— group, X ² CO ₂ — group, X ³
An SO— group, an X ⁴ SO ₂ — group, an X ⁵ SO ₃ — group, or (X
⁶ Y ¹ ) ₂ P (＝ Y ² ) Y ³ —, and R ⁵ and R ⁶
Are each independently a hydrogen atom, an alkyl group which may be substituted, an X ⁷ CO- group, an X ⁸ OCO- group, an X ⁹ SO ₂ -group,
An optionally substituted carbamoyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted heteroaryl group, or R ⁵ and R ⁶
May together form a = CR ⁷ R ⁸ group,
¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁸ and X ⁹ are each independently an alkyl group which may be substituted, an alkoxy group which may be substituted, an alkenyl group which may be substituted or substituted. X ⁶ is an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group, and X ⁷ is a hydrogen atom, an optionally substituted alkyl group. Group, an optionally substituted alkenyl group or an optionally substituted aryl group, Y ¹ , Y ²
And Y ³ are each independently an oxygen atom or a sulfur atom;
R ⁷ and R ⁸ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkoxy group, an optionally substituted alkenyl group, an optionally substituted A good aryl group, an optionally substituted amino group or an optionally substituted cyclic amino group.
However, the case where each substituent is the following (1) to (10) is excluded. (1) when R ³ and R ⁴ are simultaneously hydrogen atoms, (2) when at least one of R ⁵ and R ⁶ is an unsubstituted carbamoyl group, (3) R ¹ , R ² , R ³ and R
^When at least one of ⁴ is a nitro group, (4) R ² ,
R ⁴ and R ⁵ are hydrogen atoms, R ⁶ is an ethoxycarbonyl group, and at least ^one of R ¹ and R ³ is p-
When it is a methoxy group, (5) R ¹ , R ² , R ⁴ and R
⁵ is a hydrogen atom, R ³ is a p-tert-butyl group, and R ⁶ is an ethoxycarbonyl group;
(6) R ¹ , R ² and R ⁴ are hydrogen atoms, and R ³ is p
(7) when R ⁵ is an isopropyl group and R ⁶ is a hydrogen atom or an acetyl group,
When R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are a hydrogen atom and R ³ is a p-chlorine atom, (8) R ⁷ is an unsubstituted phenyl group and R ⁸ is substituted (9) When R ¹ , R ² and R ³ are methoxy groups, R ⁴ is a hydrogen atom, and R ⁵ and R ⁶ are methyl groups, (10) A) when R ⁵ is a hydrogen atom and R ⁶ is a phenylsulfonyl group which may be substituted; A) a hydrazone-based compound or a salt thereof, a production method thereof, and a general formula (II-5):

[0005]

Embedded image (Wherein, R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, a halogen atom or an alkyl group optionally substituted with a halogen atom. However, each substituent is represented by the following (1) (1) R ¹² , R
^When R ¹³ and R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or a halogen atom, (2) R ¹² or R ¹³ is p-
When the group is CF ₃ and R ¹⁴ or R ¹⁵ is a p-CF ₃ group, (3) R ¹² or R ¹³ is a halogen atom, and R ¹⁴ or R ¹⁵ is a methyl group, an ethyl group or a propyl group. In some cases, (4) when R ¹² or R ¹³ is a methyl group, an ethyl group or a propyl group, and R ¹⁴ or R ¹⁵ is a halogen atom. )). The present invention also provides a compound of the general formula (IX):

[0006]

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ^5, and R ⁶ are as described above, except that R ³ and R ⁴ are simultaneously hydrogen atoms.) The present invention relates to a pesticidal agent characterized by containing a system compound or a salt thereof and a pesticidal method characterized by applying an effective amount thereof. The general formulas (I) and (IX)
An optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group,
Examples of the substituent of the optionally substituted alkenyl group and the optionally substituted alkynyl group include a halogen atom; an alkoxy group optionally substituted with a halogen atom; an alkyl group optionally substituted with a halogen atom or a halogen atom. A phenyl group which may be substituted; an alkyl group which may be substituted with a halogen atom or a phenoxy group which may be substituted with a halogen atom; a cyano group; an alkylamino group; or an alkoxycarbonyl group. The carboxyl group may be a group in which a hydrogen atom in the carboxyl group is substituted with another substituent, and the substituent may be an alkyl group which may be substituted with a halogen atom; And an aryl group which may be substituted with a halogen atom. Examples of the substituent of the optionally substituted heteroaryl group, the optionally substituted aryl group, the optionally substituted aryloxy group and the optionally substituted cycloalkyl group include a halogen atom; An alkoxy group which may be substituted with a halogen atom; an alkyl group which may be substituted with a halogen atom or a phenyl group which may be substituted with a halogen atom; an alkyl group which may be substituted with a halogen atom Or a phenoxy group which may be substituted with a halogen atom; a cyano group; an alkylamino group; or an alkoxycarbonyl group, and the like, and which may be a carbamoyl group, an amino group which may be substituted, and As the substituent for the cyclic amino group, an alkoxy group which may be substituted with a halogen atom; An alkyl group which may be substituted; an alkyl group which may be substituted with a halogen atom or a phenyl group which may be substituted with a halogen atom; an alkyl group which may be substituted with a halogen atom or may be substituted with a halogen atom A phenoxy group; a cyano group; an alkylamino group; or an alkoxycarbonyl group. The number of these substituents is 1 or 2 or more, and the number of halogen atoms, alkyl group, halogen-substituted alkyl group and halogen atom of halogen-substituted alkyl in these substituents is 1 or 2 or more. In the above case, they may be the same or different.

Formulas (I), (II-5) and (IX)
Examples of the alkyl group or alkyl moiety contained therein include those having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. 2
To 6, such as a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, and the like. Examples thereof include a pentynyl group and a hexynyl group, and the above-mentioned groups or parts also include those having a linear or branched aliphatic chain with structural isomerism. The cycloalkyl group or cycloalkyl moiety contained in the general formulas (I) and (IX) has 3 to 6 carbon atoms.
For example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aryl group included in formulas (I) and (IX) include a phenyl group and a naphthyl group, and examples of the heteroaryl group include a furyl group, a thienyl group, and a pyridyl group. Examples of the cyclic amino group contained in the general formulas (I) and (IX) include -N = (CH ₂ ) _n (where n is an integer of 2 to 7). As the halogen atom contained in the general formulas (I) and (IX),
Examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Preferred embodiments of the compounds represented by formulas (I) and (IX) are described below. (1) R ¹ , R ² and R ⁴ are each independently a hydrogen atom,
It is preferably a halogen atom, an alkyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted or a carboxyl group which may be substituted, and a hydrogen atom, a halogen atom or a substituted More preferably, it is a good alkyl group or an optionally substituted alkoxy group, most preferably a hydrogen atom, a halogen atom, an alkyl group which may be substituted with a halogen atom or an alkoxy group which may be substituted with a halogen atom. desirable. (2) R ³ is a halogen atom, an alkyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, a carboxyl group which may be substituted or an X ⁵ SO ₃ — group (X ⁵ Is an alkyl group which may be substituted), more preferably a halogen atom, an alkyl group which may be substituted or an alkoxy group which may be substituted, and more preferably a halogen atom, which is substituted with a halogen atom. Most preferred is an alkyl group which may be substituted or an alkoxy group which may be substituted with a halogen atom. (3) ^{R 5} and ^{R 6} are each independently a hydrogen atom, an optionally substituted alkyl ^group, X 7 CO- group ^{(X 7} are as defined ^above), X 8 OCO- group ^{(X 8} is An optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group), a substituted carbamoyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, A heteroaryl group or an = CR ⁷ R ⁸ group formed by combining R ⁵ and R ⁶ (where R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group which may be substituted, A cycloalkyl group which may be substituted, an alkoxy group which may be substituted, an alkenyl group which may be substituted or an amino group which may be substituted), and a hydrogen atom or an alkyl group which may be substituted. Group, ⁷ CO- group ^{(X 7} is a hydrogen atom or an optionally substituted alkyl ^group), X 8 OCO- group ^{(X 8} is an alkyl group which may be substituted), a carbamoyl group, or ^{R 5} is substituted And R ⁶ are formed together = C
R ⁷ R ⁸ groups (R ⁷ and R ⁸ are each independently a hydrogen atom,
An alkyl group which may be substituted, a cycloalkyl group which may be substituted, an alkoxy group which may be substituted or an amino group which may be substituted), and R ⁵ is a hydrogen atom or an alkyl group. And R ⁶ is X ⁷
A CO— group (X ⁷ is a hydrogen atom or an alkyl group) or an X ⁸ OCO— group (X ⁸ is an alkyl group);
⁵ and R ⁶ together form a = CR ⁷ R ⁸ group (R
⁷ is a hydrogen atom or an alkyl group, and R ⁸ is an amino group or an alkoxy group which may be substituted with an alkyl group)
Is most desirable. (4) Among the compounds represented by formulas (I) and (IX), the following compounds are most desirable. [4'-chloro-2-
(4-trifluoromethylphenyl) acetophenone]
N '-[1- (dimethylamino) ethylidene] hydrazone, [4'-fluoro-2- (4-trifluoromethylphenyl) acetophenone] N'-[1- (dimethylamino) ethylidene] hydrazone, ethyl 3- [ 1- (4
-Chlorophenyl) -2- (4-trifluoromethylphenyl) ethylidene] carbazate, [4'-chloro-
2- (4-tert-butylphenyl) acetophenone] N '-[1- (dimethylamino) ethylidene] hydrazone or [4'-fluoro-2- (4-tert-butylphenylphenyl) acetophenone] N'-[1- (Dimethylamino) ethylidene] hydrazone

The compounds represented by the general formulas (I) and (IX) can take a salt with an acidic substance or a basic substance. Examples of the salt with the acidic substance include inorganic salts such as hydrochloride and sulfate, and examples of the salt with the basic substance include sodium salt, potassium salt, calcium salt, ammonium salt, and dimethylamine salt. And a salt with an inorganic base or an organic base. The compounds represented by the general formulas (I) and (IX) include E-form and Z-form geometric isomers due to a hydrazone double bond, and each of these isomers and a mixture of each isomer are present. Are included in the present invention.

The compound represented by the general formula (I) can be produced, for example, by the following reaction steps 1 to 7.

<Reaction step 1>

[0012]

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are as described above) When R ⁵ and R ⁶ together form a ＝ CR ⁷ R ⁸ group

<Reaction step 2>

[0014]

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁷ and R ⁸ are as described above, and J ¹ is an alkyl group.) R ⁵ and R ⁶ are taken together to form ＣＲCR ⁷ R ⁸ groups are formed,
And when R ⁷ and R ⁸ are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group

<Reaction step 3>

[0016]

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are as described above, and R ⁹ and R ¹⁰ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl A group, an optionally substituted alkenyl group or an optionally substituted aryl group) R ⁵ and R ⁶ together form a = CR ⁷ R ⁸ group,
And when R ⁸ is an optionally substituted amino group or an optionally substituted cyclic amino group

<Reaction step 4>

[0018]

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁷ are as described above, and J ² and J ³ are each independently a hydrogen atom; an alkyl group optionally substituted by a halogen atom; An alkoxy group optionally substituted with a halogen atom; an alkyl group optionally substituted with a halogen atom or a phenyl group optionally substituted with a halogen atom; an alkyl group optionally substituted with a halogen atom or substituted with a halogen atom A phenoxy group; a cyano group; an alkylamino group; an alkoxycarbonyl group or a cyclic amino group in which J ² and J ³ may be substituted together with an adjacent nitrogen atom.

<Reaction step 5>

[0020]

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁷ , J ² and J ³
Is the same as described above.) R ⁶ is an X ⁷ CO— group, an X ⁸ OCO— group or an X ⁹ SO ₂ —.
Group

<Reaction step 6>

[0022]

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are as described above, R ¹¹ is a hydrogen atom, an alkyl group which may be substituted,
X ⁷ CO— group, X ⁸ OCO— group, X ⁹ SO ₂ — group (X ⁷ , X ⁸ and X ⁹ are as described above), an optionally substituted carbamoyl group, an optionally substituted alkenyl group , An optionally substituted alkynyl group or an optionally substituted heteroaryl group, and J ⁴ is independently of R ¹¹ , an X ⁷ CO— group, an X ⁸ OCO— group, an X ⁹ SO ₂ — group (X ^{7, X 8} and ^{X 9} are the a) defined above] when R ^{6 J} 5 NHCO- group (part of a carbamoyl group which may be substituted)

<Reaction step 7>

[0024]

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ and R ¹¹ are as described above, and J ⁵ is an alkyl group optionally substituted with a halogen atom; an alkyl group optionally substituted with a halogen atom or hydrogen atom of J ⁵ NHCO- group in an alkylamino group or an alkoxycarbonyl group) said reaction step 7, the compound represented by the general formula (I-7) is a halogen atom phenyl group which may be substituted by the It can be alkylated by a usual alkylation reaction. The compound represented by the general formula (II) can be produced, for example, by the following reaction steps 8 to 16.

<Reaction step 8>

[0026]

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are as described above)

<Reaction step 9>

[0028]

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are as described above, and Hal is a halogen atom)

<Reaction step 10>

[0030]

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ and Hal are as described above)

<Reaction step 11>

[0032]

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ and Hal are as described above, and Ph is a phenyl group)

<Reaction step 12>

[0034]

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ , Hal and Ph are as described above)

<Reaction step 13>

[0036]

Embedded image (In the formula, R ¹ , R ² , R ³ and R ⁴ are as described above.) When R ³ is an X ² CO ₂ — group or an X ⁵ SO ₃ — group.

<Reaction step 14>

[0038]

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ and Hal are as described above, and J ⁶ is an X ² CO— group or an X ⁵ SO ₂ — group (X ² and X ⁵ are as described above. When R ³ is X ¹ SO ₂ NH— group

<Reaction step 15>

[0040]

Embedded image (In the formula, R ¹ , R ² , R ⁴ and X ¹ are as described above.) When R ³ is an X ³ SO— group or an X ⁴ SO ₂ — group

<Reaction step 16>

[0042]

Embedded image (Wherein R ¹ , R ² and R ⁴ are as described above, and X
¹⁰ is the same as X ³ or X ⁴ and n is 1 or 2.) The compound represented by the general formula (I-2) can be produced, for example, by the following reaction step 17.

<Reaction step 17> The compound represented by the general formula (VI) can be produced, for example, by the following reaction step 18.

<Reaction step 18>

[0045]

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ and X ⁷ are as described above) The compound represented by the general formula (VIII) can be produced, for example, by the following reaction step 19.

<Reaction step 19> (Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁷ and X ⁷ are as described above) The compound represented by the general formula (VI) is a compound represented by the general formula (I) Or can be produced by a method for producing a compound represented by the general formula (I-2),
The compound represented by the general formula (XII) and the compound represented by the general formula (XI
The compound represented by II) can be produced in the same manner as in the method for producing the compound represented by the general formula (II). Further, the compound represented by the general formula (IX), which is out of the range of the compound represented by the general formula (I), can also be produced according to the above method.

The reactions in the above reaction steps 1, 3 and 17 are usually carried out in the presence of a solvent, if necessary, in the presence of an acid catalyst. The reaction temperature is usually -20 to + 200 ° C, preferably -10 to + 150 ° C. The reaction time is usually 0.1 to 1
50 hours. Examples of the solvent include ethers such as diethyl ether, tetrahydrofuran, and dioxane; ethylene glycol, glycerin, methanol,
Alcohols such as ethanol; aprotic polar solvents such as N, N-dimethylformamide, N'N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide and sulfolane; benzene, toluene and chlorobenzene Aromatic hydrocarbons; halogenated hydrocarbons such as methylene chloride and chloroform;
Aliphatic hydrocarbons such as pentane, hexane and heptane; alicyclic hydrocarbons such as cyclohexane; pyridines such as pyridine and picoline; acetic acid; water; You may. Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid; formic acid,
Organic acids such as acetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; and acid addition salts of amines such as pyridine hydrochloride and triethylamine hydrochloride.

The reaction in the reaction step 2 is carried out in the presence of a solvent and / or an acid catalyst, if necessary. 1 to 100 hours. Examples of the solvent include ethers, alcohols, aprotic polar solvents, aromatic hydrocarbons, halogenated hydrocarbons and water as used in the reaction steps 1, 3 and 17, and acetonitrile. Nitriles and the like, and these solvents may be mixed and used. As the acid catalyst, for example, those similar to those used in the above reaction steps 1, 3 and 17 can be mentioned.

The reactions in the above reaction steps 4 and 5 are carried out in the presence of a solvent if necessary, and the reaction temperature is usually -20 to +2.
The reaction temperature is usually 00 ° C, preferably 0 ° C to 100 ° C, and the reaction time is usually 0.1 to 100 hours. Examples of the solvent include aromatic hydrocarbons, pyridines, halogenated hydrocarbons, aliphatic hydrocarbons, water and the like as used in the above reaction steps 1, 3 and 17, and these solvents are mixed. May be used. The reactions of the reaction steps 6, 7, 14 and 15 are usually carried out in the presence of a solvent, if necessary, in the presence of an acid binder, and the reaction temperature is usually −20 to + 200 ° C., preferably 0 to 150 ° C. Yes, the reaction time is usually 0.1 to
100 hours. Examples of the solvent include ethers, aprotic polar solvents, aromatic hydrocarbons, halogenated hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons as used in the above reaction steps 1, 3 and 17. , Pyridines, water, and inert organic solvents such as nitriles such as acetonitrile, and these solvents may be used as a mixture. Examples of the acid binder include tertiary alkylamines such as triethylamine, alkali metal carbonates such as sodium carbonate, and pyridine.

The reaction in the reaction step 8 is a usual Friedel-Crafts reaction, which is carried out in the presence of a solvent and a catalyst.
To + 100 ° C., and the reaction time is 0.1 to 100 hours. Examples of the solvent include carbon disulfide, halogenated hydrocarbons used in the above reaction steps 1, 3, and 17, and nitrobenzene. As a catalyst,
For example, Lewis acids such as aluminum chloride, lead chloride, ferrous chloride, ferric chloride, titanium tetrachloride, tin chloride, zinc chloride, polyphosphoric acid and the like can be mentioned.

The reaction in the above reaction steps 9 and 10 is a usual Grignard reaction, which is carried out in the presence of a solvent at a reaction temperature of -20 to + 200 ° C., preferably -10 to +1.
The reaction time is 0.1 to 100 hours.
Examples of the solvent include ethers used in the above-mentioned reaction steps 1, 3, and 17.

The first-stage reaction of the reaction steps 11 and 12 is a usual Wittig reaction, which is carried out in the presence of a base and a solvent, at a reaction temperature of -20 to + 200 ° C., preferably -10 to + 150 ° ° C and the reaction time is 0.1 to 1
00 hours. Examples of the base include hydroxides, carbonates, acetates, and organometallic compounds such as butyllithium of alkali (earth) metals. Examples of the solvent include hydrocarbons, ethers, alcohols, aprotic polar solvents, aromatic hydrocarbons, halogenated aromatic hydrocarbons, and the like, as used in Reaction Steps 1, 3, and 17.
Examples thereof include halogenated hydrocarbons and water, and these solvents may be used as a mixture.

The second-stage reaction of the above reaction steps 11 and 12 is a usual halogenation reaction, which is carried out in the presence of a peroxide or under irradiation with light. Is added). The reaction temperature is -20 to + 200 ° C, preferably -10 to + 100 ° C, and the reaction time is 0.1 to 100 hours. As the solvent, preferably used are hydrocarbons and halogenated hydrocarbons, but the solvents in the above reaction steps 1, 3 and 17 can also be used.

The third-stage reaction of the above reaction steps 11 and 12 is a usual dehalogenation reaction. As the dehalogenating agent carried out by a dehalogenating agent in the presence of a solvent, alkali metal and its alcoholate, Hydroxide and the like. The reaction temperature is -20 to + 200 ° C, preferably-
The reaction time is from 0.1 to 100 hours. The same solvent as that used in the first-stage reaction can be used as the solvent.

The fourth stage reaction in the above reaction steps 11 and 12 is a normal oxidation reaction, which is oxidized using a mercury (II) salt or the like in the presence of an acid catalyst. Reaction temperature is -20 to +
The temperature is 200C, preferably -10 to + 150C, and the reaction time is 0.1 to 100 hours. As the solvent, acetic acid and the same solvents as those used in the first-stage reaction can be used, and these solvents may be mixed and used. Examples of the acid catalyst include inorganic acids such as sulfuric acid and nitric acid, and organic acids such as acetic acid and trifluoroacetic acid. The reaction in the reaction step 13 is a normal oxidation reaction, and is performed in the presence of a solvent and an oxidizing agent. The reaction temperature is -20 to + 200 ° C, preferably -10 to + 150 ° C, and the reaction time is 0.1 to 1
00 hours. Examples of the oxidizing agent include chromium (VI) salt, lead tetraacetate, nitric acid, dimethyl sulfoxide and the like. As the solvent, water and acetic acid are mainly used, and hydrocarbons, halogenated aromatic hydrocarbons, and the above reaction steps 1, 3
And aprotic polar solvents, aromatic hydrocarbons, and halogenated hydrocarbons such as those used in (1) and (2), and these solvents may be used as a mixture.

The reaction in the reaction step 16 is a usual oxidation reaction using H ₂ O ₂ or the like, and is usually carried out in the presence of a solvent.
0 to + 100 ° C, and the reaction time is 0.1 to 100 hours. As the solvent, those similar to the ones which can be used in the reaction in the reaction step 13 can be used, and these solvents may be mixed and used.

The reactions in the above reaction steps 18 and 19 are carried out in the presence of a solvent if necessary.
The temperature is 50 ° C, preferably 10 to 180 ° C, and the reaction time is 0.1 to 100 hours. Examples of the solvent include aromatic hydrocarbons, halogenated hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and the like as used in the above reaction steps 1, 3 and 17. May be used in combination. Specific synthesis examples of the compound represented by the general formula (I) will be described.

Synthesis Example 1 [4'-chloro-2- (4-chlorophenyl) acetophenone] N '-[1- (dimethylamino) ethylidene]
Synthesis of Hydrazone (Compound No. 1) (1) 1.33 g (5 mmol) of 4′-chloro-2- (4-chlorophenyl) acetophenone was added to ethanol 25
hydrazine monohydrate (1.25 g)
(25 mmol) were added and these were heated to reflux for 2 hours. After completion of the reaction, ethanol was distilled off under reduced pressure, water was added to the residue, and the mixture was extracted with dichloromethane. After drying over anhydrous sodium sulfate and evaporating the solvent, 1.44 g of [4′-
Chloro-2- (4-chlorophenyl) acetophenone]
The hydrazone was obtained as a yellow oil. (2) [4′-chloro-2- obtained in the above step (1)
(4-Chlorophenyl) acetophenone] hydrazone (1.0 g, 3.6 mmol) and N, N-dimethylacetamide dimethyl acetal (0.51 g, 4.2 mmol)
1) and heated at 120 ° C. for 2 hours. After the reaction,
The reaction solution was purified by silica gel column chromatography (developing solvent = ethyl acetate: n-hexane = 1: 4).
The target compound having a melting point of 125 to 127 ° C (Compound No. 1)
56 g were obtained.

Synthesis Example 2 Synthesis of Methyl 3- [1,2-bis (4-chlorophenyl) ethylidene] carbazate (Compound No. 201) [4′-chloro-2-
(4-Chlorophenyl) acetophenone] hydrazone (0.43 g, 1.5 mmol) was dissolved in 5 ml of pyridine, and 0.2 ml (2.5 mmol) was added thereto while cooling with ice.
1) Methyl chlorocarbonate was added dropwise, and after completion of the addition, the mixture was stirred at room temperature for 3 hours. After completion of the reaction, the mixture was poured into water, extracted with dichloromethane, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (developing solvent = ethyl acetate: n-hexane = 3:
7) to obtain 0.37 g of the target compound (compound No. 201) having a melting point of 156 to 159 ° C.

Synthesis Example 3 Synthesis of [4'-chloro-2- (4-chlorophenyl) acetophenone] -4- (4-trifluoromethylphenyl) semicarbazone (Compound No. 200) 0.97 g of p-aminobenzotrifluoride (6mmo
l) was dissolved in 10 ml of ethyl acetate, and 1.1 m
After adding 1 (9 mmol) of trichloromethyl chloroformate and heating under reflux for 2 hours, excess trichloromethyl chloroformate and ethyl acetate were distilled off under reduced pressure. The residue was dissolved in 5 ml of ether.
[4′-chloro-2- (4
-Chlorophenyl) acetophenone] hydrazone 1.4
g (5 mmol) in 20 ml of diethyl ether was added dropwise under ice-cooling. After completion of the dropwise addition, the mixture was stirred at room temperature for 1.5 hours. After completion of the reaction, the solvent was distilled off, a small amount of water was added, the mixture was extracted with dichloromethane, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent = ethyl acetate: n-hexane = 1: 4) to give the desired product having a melting point of 194 to 198 ° C. (Compound No.
200) 1.53 g were obtained.

Synthesis Example 4 [4'-chloro-2- (4-tert-butylphenyl) acetophenone] N '-[1- (dimethylamino)
Synthesis of [ethylidene] hydrazone (compound No. 32) (1) After adding 0.7 g of magnesium (milled) and 100 mg of small pieces of iodine to 5 ml of anhydrous diethyl ether,
Under a nitrogen stream, a solution of 5.6 g of p-bromochlorobenzene in 10 ml of anhydrous diethyl ether was added dropwise at a rate sufficient to cause gentle reflux. This solution was stirred at room temperature for 20 minutes to react, and then p-tert-butylphenylacetonitrile was added to a solution of 5 ml of anhydrous diethyl ether.
The solution in which 8 g was dissolved was added dropwise at a rate sufficient to slowly reflux. The solution was stirred for an additional 30 minutes to react. After completion of the reaction, 10 g of ice and 130 m of 6N hydrochloric acid were used.
The mixture was added with l and extracted with ethyl acetate. The extract was washed with water and saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (developing solvent = ethyl acetate: n-
Hexane = 1: 9) to give 4'-chloro-2-
1.3 g of (4-tert-butylphenyl) acetophenone was obtained. (2) 1.3 g (4.5 mmol) of 4'-chloro-2- (4-tert-butylphenyl) acetophenone was dissolved in 15 ml of ethanol, and 0.2 g (4.5 mmol) of hydrazine monohydrate was added thereto. In addition, these were heated under reflux for 3 hours. After completion of the reaction, ethanol was distilled off under reduced pressure, water was added to the residue, and the mixture was extracted with dichloromethane. After drying over anhydrous sodium sulfate and evaporating the solvent, 1.3 g of [4'-chloro-2- (4-tert-butylphenyl) acetophenone] hydrazone was obtained as a yellow oil. (3) [4′-chloro-2- obtained in the above step (2)
(4-tert-butylphenyl) acetophenone]
1.3 g (4.3 mmol) of hydrazone was dissolved in 15 ml of acetonitrile, and 0.6 g (4.7 mmol) of N, N-dimethylacetamide dimethyl acetal was added thereto, followed by heating under reflux for 24 hours. After completion of the reaction, acetonitrile was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent = ethyl acetate: n-hexane = 1: 1).
Purification by 8) gave 0.4 g of the desired product (compound No. 32) having a melting point of 100 to 101 ° C.

Synthesis Example 5 Synthesis of [4′-fluoro-2- (4-trifluoromethylphenyl) acetophenone] N ′-[1- (dimethylamino) ethylidene] hydrazone (Compound No. 38) (1) 4- 8.9 g of fluorobenzaldehyde (72 m
mol), (4-trifluoromethylbenzyl) triphenylphosphonium chloride 32 g (72 mmol)
Is dissolved in 300 ml of methylene chloride, and while stirring vigorously, 280 ml of 3N sodium hydroxide (0.84
mol) was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. After the completion of the reaction, liquid separation was performed, and the organic layer was washed twice with water. After drying over anhydrous sodium sulfate, the solvent was distilled off. The residue was purified by silica gel column chromatography (developing solvent: n-hexane) to obtain 12.4 g of 4-fluoro-4′-trifluoromethylstilbene. (2) 12.4 g (47 mmol) of 4-fluoro-4'-trifluoromethylstilbene was added to 80 ml of chloroform.
l) was dissolved in a solution of 2.4 ml (47 mmol) of bromine in 20 m at 40 ° C while irradiating with a 160 w mercury lamp.
of chloroform solution was added dropwise, and stirring was continued for 30 minutes. After completion of the reaction, the solvent was distilled off to obtain a yellow oily substance. This was dissolved in 100 ml of ethanol without purification, and 12.3 g of potassium hydroxide was added to 45 ml of water while heating under reflux.
An aqueous solution in which was dissolved was added dropwise. After the completion of the dropwise addition, heating and reflux were continued for 3 hours. After completion of the reaction, ethanol was distilled off, water was added to the residue, and the mixture was extracted with ether. After drying over anhydrous sodium sulfate, the solvent was distilled off to obtain 12.2 g of 4-fluoro-4'-trifluoromethyltran as a yellow solid. This was used for the next reaction without purification. (3) Water (60 ml) and acetic acid (60 m) were added to 12.2 g (46 mmol) of 4-fluoro-4′-trifluoromethyltran.
1, 40 ml of sulfuric acid, 13.6 g of mercuric sulfate (46 mm
ol) and heated and stirred at 90 ° C. for 3.5 hours. After completion of the reaction, water was added, the mixture was extracted with ether, dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (developing solvent = ethyl acetate: n-hexane = 1: 10). 5.1 g of 4′-fluoro-2- (4-trifluoromethylphenyl) acetophenone having a melting point of 87 to 89 ° C. was obtained. (4) 5.1 g of 4'-fluoro-2- (4-trifluoromethylphenyl) acetophenone (18.1 mmol)
l) was dissolved in 100 ml of ethanol, 8.8 ml (181 mmol) of hydrazine monohydrate was added thereto, and these were heated under reflux for 2 hours. After completion of the reaction, ethanol was distilled off under reduced pressure, water was added to the residue, and the mixture was extracted with dichloromethane. After drying over anhydrous sodium sulfate and evaporating the solvent, [4'-fluoro-2- (4-trifluoromethylphenyl) acetophenone] hydrazone was obtained as a yellow oil. (5) [4′-fluoro-2 obtained in the above step (4)
-(4-Trifluoromethylphenyl) acetophenone] hydrazone, and 3.13 g (23.5 mmol) of N, N-dimethylacetamidodimethylacetal were added.
Heated at 20 ° C. for 2 hours. After completion of the reaction, the residue was subjected to silica gel column chromatography (developing solvent = ethyl acetate:
n-hexane = 1: 19) to give a melting point of 86-88.
3.10 g of the target product (compound No. 38) at ℃ was obtained.

Synthesis Example 6 [4'-chloro-2- (4-trifluoromethylphenyl) acetophenone] N '-[1- (dimethylamino)
[Ethylidene] hydrazone (Compound No. 9) Synthesis The synthesis was conducted in substantially the same manner as in Synthesis Example 5 except that 4-fluorobenzaldehyde in Synthesis Example 5 (1) was replaced with 4-chlorobenzaldehyde. The desired product (Compound No. 9) was obtained.

Synthesis Example 7 Synthesis of 4'-fluoro-2- (4-tert-butylphenyl) acetophenone N '-[1- (dimethylamino) ethylidene] hydrazone (Compound No. 60) (1) 4'-Fluoro -2- (4-tert-butylphenyl) acetophenone 3 g (11 mmol), acetylhydrazide 0.8 g (11 mmol), acetic acid 60 m
g (1 mmol) and ethanol 20 ml
The mixture was refluxed for 0 hours. After completion of the reaction, ethanol was distilled off under reduced pressure to concentrate the reaction product, and then silica gel column chromatography (developing solvent = n-hexane: ethyl acetate =
Purification by 4: 1) gave 1.09 g of 4'-fluoro-2- (4-tert-butylphenyl) acetophenone N'-acetylhydrazone having a melting point of 132 to 134 ° C. (2) 4'-fluoro-2- (4-tert-butylphenyl) acetophenone N'-acetylhydrazone 1
g (3.1 mmol), phosphorus pentachloride 0.64 g (3.1
(mmol) and 15 ml of dichloromethane were stirred at room temperature for 1 hour and then reacted under heating and reflux for 2 hours.
After completion of the reaction, the reaction solution was concentrated under reduced pressure, and 10 ml of dichloromethane was newly added.
38 g (15 mmol) was added at once at room temperature, and the mixture was stirred and reacted at the same temperature for 2 hours. After the completion of the reaction, the reaction mixture was diluted with 30 ml of dichloromethane, washed with water and dried over anhydrous sodium sulfate. After concentrating the solvent under reduced pressure, the residue was purified by silica gel column chromatography (developing solvent = n-hexane: ethyl acetate = 9: 1) to obtain 0.33 g of the desired product (compound No. 60) having a melting point of 65 to 67 ° C. Obtained. Next, typical examples of the compound represented by the general formula (I) are described in Tables 1 to 23.

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

[Table 3]

[0068]

[Table 4]

[0069]

[Table 5]

[0070]

[Table 6]

[0071]

[Table 7]

[0072]

[Table 8]

[0073]

[Table 9]

[0074]

[Table 10]

[0075]

[Table 11]

[0076]

[Table 12]

[0077]

[Table 13]

[0078]

[Table 14]

[0079]

[Table 15]

[0080]

[Table 16]

[0081]

[Table 17]

[0082]

[Table 18]

[0083]

[Table 19]

[0084]

[Table 20]

[0085]

[Table 21]

[0086]

[Table 22]

[0087]

[Table 23]

Further, Tables 24 to 26 show typical examples of the compounds represented by the general formula (IX), which are outside the range of the compounds represented by the general formula (I).

[0089]

[Table 24]

[0090]

[Table 25]

[0091]

[Table 26]

The compound represented by formula (II-5) is an intermediate of the compounds represented by formulas (I) and (IX), and is considered to be a novel compound. Representative examples of these compounds are shown in Tables 27 to 31.

[0093]

[Table 27]

[0094]

[Table 28]

[0095]

[Table 29]

[0096]

[Table 30]

[0097]

[Table 31]

In Tables 1 to 31, Ph represents a phenyl group and t represents
-Bu, n-Bu or s-Bu is a tertiary, normal or secondary butyl group, iso-Pr or n-Pr is an iso or normal propyl group, cyc
lo-Pr or cyclo-Hex represents a cyclopropyl group or a cyclohexyl group, respectively. The number of each substituent indicates the position of the substituent, for example, Compound No. 4-Cl of R 1 in ¹ represents that Cl is located at the 4-position of the benzene ring. Compound No. 221 is Compound No. 2
15 isomers.

The compounds represented by the general formulas (I) and (IX) exhibit excellent activity as an active ingredient of a pesticide. For example, plant parasitic mites such as spider mites, spider mites, mandarin spider mites, spider mites, mites, mothweeds, armyworms, tossinnia, codling moths, ball worms, tobacco bat worms, gypsy moths, kora nomeiga, cyano sylvestris, colorado beetles, turtle beetles, Agricultural pests such as ball-weevil, aphids, planthoppers, leafhoppers, scale insects, stink bugs, whiteflies, thrips, grasshoppers, flower flies, scarab beetles, tamanayaga, caprayaga, ants, etc., house dust mites, Sanitary pests such as cockroaches, house flies, and house mosquitoes, storage pests such as stag beetles, azuki beetles, kokusutomodoki, and beetles, clothing and house pests such as moths, bark beetles, termites, and others. livestock It is also effective against fleas, lice, flies, etc., which are parasitic on throats. It is also effective against various plant parasitic nematodes. It is also effective against soil pests. Examples of the soil pests mentioned here include gastropods such as slugs and snails, and isopods such as duck beetles and scabies.

Among the various pests described above, they exhibit excellent activity against lepidopteran and coleopteran pests. It is also effective against pests such as oak and housefly which are resistant to organophosphates and pyrethroids. In addition, because it has osmotic transfer, by treating the soil with the compound of the present invention, soil harmful insects, mites, nematodes, gastropods, and at the same time as controlling the foliage of the isopoda. Pests can also be controlled. In addition, it has high safety against mammals, fish and beneficial insects, and has good properties as a pesticide.

When the compound of the present invention is used as an active ingredient of a pesticidal agent, emulsions, powders, granules, wettable powders, granule hydration agents are used together with pesticidal auxiliaries as in the case of conventional pesticide preparations. It can be formulated in various forms such as agents, suspensions, solutions, aerosols, pastes and the like. The mixing ratio of these components is usually 0.1 to 90 parts by weight, preferably 0.5 to 90 parts by weight, more preferably 0.5 to 80 parts by weight.
10 to 99.9 parts by weight, preferably 10 to 99.5 parts by weight, more preferably 20 to 9 parts by weight of the pesticide adjuvant with respect to parts by weight.
99.5 parts by weight. In the actual use of these preparations, they can be used as they are or diluted to a predetermined concentration with a diluent such as water.

[0102] Examples of the pesticidal auxiliary herein include a carrier, an emulsifier, a suspending agent, a dispersing agent, a spreading agent, a penetrating agent, a wetting agent, a thickening agent, an antifoaming agent, a stabilizer, and an antifreezing agent. It may be added as needed. The carrier is divided into a solid carrier and a liquid carrier, and as the solid carrier, starch, activated carbon, soybean flour, wheat flour, wood flour, fish flour, animal and plant powders such as milk powder, talc, kaolin, bentonite, calcium carbonate, zeolite, Diatomaceous earth, white carbon, clay,
Mineral powders such as alumina, sulfur powder, anhydrous sodium sulfate, etc., and liquid carriers include water, alcohols such as methyl alcohol and ethylene glycol, ketones such as acetone, methyl ethyl ketone and N-methyl-2-pyrrolidone. , Dioxane, ethers such as tetrahydrofuran, kerosene, aliphatic hydrocarbons such as kerosene, xylene, trimethylbenzene, aromatic hydrocarbons such as tetramethylbenzene, cyclohexane, solvent naphtha, halogenated hydrocarbons such as chloroform and chlorobenzene , Acid amides such as dimethylformamide, esters such as ethyl acetate and glycerin ester of fatty acid, nitriles such as acetonitrile, sulfur-containing compounds such as dimethyl sulfoxide, soybean oil, corn oil What vegetable oils and the like.

Next, formulation examples of the pesticidal composition containing the compound of the present invention as an active ingredient will be described. The types, blending ratios, dosage forms, and the like of the active ingredient compound and the pesticide auxiliary are only described in the description examples. It is not limited.

Formulation Example 1 (A) Compound No. 9 20 parts by weight (b) Kaolin 52 parts by weight (c) Sodium ligninsulfonate 8 parts by weight (d) White carbon 20 parts by weight The above components are uniformly mixed to obtain a wettable powder.

Formulation Example 2 (a) Compound No. 325 parts by weight (b) 95 parts by weight of talc The above components are uniformly mixed to form a powder.

Formulation Example 3 (A) Compound No. 210 20 parts by weight (b) N-methyl-2-pyrrolidone 10 parts by weight (c) Polyoxyethylene alkylphenyl ether 10 parts by weight (d) xylene 60 parts by weight The above components are uniformly mixed and dissolved to form an emulsion. .

Formulation Example 4 (a) 83 parts by weight of kaolin (b) 2 parts by weight of sodium ligninsulfonate (c) 5 parts by weight of polyoxyethylene alkylaryl sulphate (d) 10 parts by weight of finely divided silica A mixture of the above components , Compound No. 38 and 4: 1
To obtain a wettable powder.

Formulation Example 5 (a) Compound No. 42 40 parts by weight (b) Oxylated polyalkylphenol phosphate-triethanolamine 2 parts by weight (c) Silicone 0.2 parts by weight (d) Xanthan gum 0.1 parts by weight (e) Ethylene glycol 5 parts by weight (f) 52.7 parts by weight of water The above components are uniformly mixed and pulverized to obtain an aqueous suspension.

Formulation Example 6 (a) Compound No. 60 75 parts by weight (b) Sodium polycarboxylate 13.5 parts by weight (c) Anhydrous sodium sulfate 10 parts by weight (d) Dextrin 0.5 parts by weight (e) Sodium alkyl sulfonate 1 part by weight Put in the mixing granulator, and then add 20
% Water is added and granulated and dried to obtain a wettable powder.

Formulation Example 7 (a) Compound No. 325 5 parts by weight (b) Bentonite 33 parts by weight (c) Kaolin 57 parts by weight (d) Sodium ligninsulfonate 5 parts by weight Add an appropriate amount of required granulating water to each of the above components, mix and granulate to obtain granules. can get.

Formulation Example 8 (a) Compound No. 9 2.5 parts by weight (b) N-methyl-2-pyrrolidone 2.5 parts by weight (c) Soybean oil 95.0 parts by weight
ra low volume formula
n).

Formulation Example 9 (A) Compound No. 605 5 parts by weight (b) N-methyl-2-pyrrolidone 5 parts by weight (c) polyoxyethylene alkylaryl (aryl) ether 10 parts by weight (d) xylene 80 parts by weight The above components are uniformly mixed to form an emulsion. .

Formulation Example 10 (a) Compound No. 38 10 parts by weight (b) Corn oil 77 parts by weight (c) Polyoxyethylene hydrogenated castor oil 12 parts by weight (d) Organic bentonite 1 part by weight The above components are uniformly mixed and pulverized to obtain a suspending agent.

The pesticidal composition containing the compound of the present invention as an active ingredient may contain other pesticides, if necessary.
For example, it can be mixed and used together with insecticides, acaricides, nematicides, fungicides, antiviral agents, attractants, herbicides, plant growth regulators, etc., and in this case, exhibiting even better effects There is also. For example, O- (4-bromo-2-chlorophenyl) is used as an insecticide, acaricide, or nematicide.
O-ethyl S-propyl phosphorothioate, O-
(2,2-dichlorovinyl) O, O-dimethyl phosphate, O-ethyl O- [3-methyl-4- (methylthio) phenyl] N-isopropyl phosphoramidate, O, O-dimethyl O- (4- Nitro-m-tolyl) phosphorothioate, O-ethyl O- (4-nitrophenyl) phenylphosphonothioate, O, O-diethyl O- (2-isopropyl-6-methylpyrimidin-4-yl) phosphorothioate, O, O -Dimethyl O- (3,5,6-trichloro-2-pyridyl) phosphorothioate, O, S-dimethyl N-acetyl phosphoramidothioate, O- (2,4-dichlorophenyl) O-ethyl S-propyl phosphoro Dithioate, (RS) -S-sec-butyl O-ethyl 2-
Organophosphate compounds such as oxo-1,3-thiazolidin-3-ylphosphonothioate;

1-naphthyl N-methyl carbamate,
2-isopropoxyphenyl N-methylcarbamate, 2-methyl-2- (methylthio) propionaldehyde O-methylcarbamoyloxime, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate, dimethyl N , N '-[thiobis (methylimino) carbonyloxy}] bisethanimidothioate, S-methyl N- (methylcarbamoyloxy) thioacetimidate, N, N-dimethyl-2
-Methylcarbamoyloxyimino-2- (methylthio) acetamide, 2- (ethylthiomethyl) phenyl N-methylcarbamate, 2-dimethylamino-5,
Carbamate compounds such as 6-dimethylpyrimidin-4-yl N, N-dimethylcarbamate, 2-sec-butylphenyl N-methylcarbamate;
Nereistoxin derivatives such as S'-2-dimethylaminotrimethylenebis (thiocarbamate), N, N-dimethyl-1,2,3-trithian-5-ylamine;
2,2,2-trichloro-1,1-bis (4-chlorophenyl) ethanol, 4-chlorophenyl-2,4,5
Organic chlorine compounds such as trichlorophenylsulfone; organometallic compounds such as bis [tris (2-methyl-2-phenyl-propyl) tin] oxide;

(RS) -α-cyano-3-phenoxybenzyl (RS) -2- (4-chlorophenyl) -3-methylbutyrate, 3-phenoxybenzyl (1RS)-
Cis, trans-3- (2,2-dichlorovinyl)-
2,2-dimethylcyclopropane carboxylate,
(RS) -α-cyano-3-phenoxybenzyl (1R
S) -cis, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate, (S) -α-cyano-3-phenoxybenzyl (1
R) -cis-3- (2,2-dibromovinyl) -2,2
-Dimethylcyclopropanecarboxylate, (RS)
-Α-cyano-3-phenoxybenzyl (1RS) -cis, trans-3- (2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylate, 4-methyl-2 , 3,5,6-tetrafluorobenzyl-3- (2-chloro-3,3,3-
Trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate, 2- (4-ethoxyphenyl) -2-methylpropyl 3-phenoxybenzyl ether (generic name: ethofenprox. Compound No. A- Pyrethroid compounds such as 1);

1- (4-chlorophenyl) -3- (2,
6-difluorobenzoyl) urea, 1- [3,5-dichloro-4- (3-chloro-5-trifluoromethyl-
2-pyridyloxy) phenyl] -3- (2,6-difluorobenzoyl) urea, 1- (3,5-dichloro-
Benzoylurea-based compounds such as 2,4-difluorophenyl) -3- (2,6-difluorobenzoyl) urea; isopropyl (2E, 4E) -11-methoxy-
Juvenile hormone-like compounds such as 3,7,11-trimethyl-2,4-dodecadienoate; 2-t-butyl-5
-(4-t-butylbenzylthio) -4-chloro-3
Pyridazinone compounds such as (2II) -pyridazinone; pyrazole compounds such as t-butyl 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl) methyleneaminooxymethyl] benzoate;

1- (6-chloro-3-pyridylmethyl)
-N-nitro-imidazolidine-2-ylideneamine (generic name: imidacloprid, hereinafter compound No. A-2)
1- [N- (6-chloro-3-pyridylmethyl) -N-ethylamino] -1-methylamino-2-nitroethylene (European publication No. 302389, hereinafter referred to as compound No. A-3) Abbreviated), 2-methylamino-2
-[N-methyl-N- (6-chloro-3-pyridylmethyl) amino] -1-nitroethylene (Europe published N
o. 302389, hereinafter referred to as Compound No. A-4),
1- (6-chloro-3-pyridylmethyl) amino-1-
Dimethylamino-2-nitroethylene (European publication No. 302389, hereinafter abbreviated as compound No. A-5), 1- (6-chloro-3-pyridylmethyl) -2-
(1-nitro-2-allylthioethylidene) imidazolidine (European publication No. 437784, hereinafter abbreviated as compound No. A-6), 1- (6-chloro-3-pyridylmethyl) -2- (1-nitro -2-ethylthioethylidene) imidazolidine (Europe Publication No. 4377)
84, hereinafter Compound No. A-7), 1- (6-chloro-3-pyridylmethyl) -2- (1-nitro-2-
β-methylallylthioethylidene) imidazolidine (European publication No. 4377784, hereinafter referred to as compound No. A)
-8), 1- (6-chloro-3-pyridylmethyl) -3-methyl-2-nitroguanidine (European publication No. 383091, hereinafter abbreviated as compound No. A-9), 1- (6- Chloro-3-pyridylmethyl) -3,
3-dimethyl-2-nitroguanidine (European publication No. 383091, hereinafter abbreviated as compound No. A-10), 3- (6-chloro-3-pyridylmethyl) -2-
Nitromethylene-thiazolidine (Europe Publication No.
192060, hereinafter referred to as Compound No. A-11), 1
-(6-chloro-3-pyridylmethyl) -2- (nitromethylene) -imidazolidine (European publication No. 1)
No. 63855, Compound No. A-12), 6-
(6-chloro-3-pyridylmethylamino) -1,3-
Dimethyl-5-nitro-1,2,3,4-tetrahydropyrimidine (European publication No. 366085, hereinafter abbreviated as compound No. A-13), 1- (6-chloro-3)
-Pyridylmethyl) -5-nitro-3-methyl-6-methylamino-1,2,3,4-tetrahydropyrimidine (European publication No. 366085, hereinafter referred to as Compound N)
o. Nitro compounds such as A-14);

Dinitro compounds, organic sulfur compounds, urea compounds, triazine compounds, hydrazine compounds,
In addition, as other compounds, 2-tert-butylimino-3-isopropyl-5-phenyl-3,4,5,
6-tetrahydro-2II-1,3,5-thiadiazin-4-one (generic name: profofezin, hereinafter compound N)
o. A-15), trans- (4-chlorophenyl) -N-cyclohexyl-4-methyl-2-oxothiazolidinone-3-carboxamide, N-methylbis (2,4-xylyliminomethyl) amine, N '-(4
-Chloro-o-tolyl) -N, N-dimethylformamidine, (4-ethoxyphenyl)-[3- (4-fluoro-3-phenoxyphenyl) propyl] (dimethyl)
Silane (general name: silafluofen, hereinafter referred to as Compound No.
A-16). Further, it can be mixed with or used in combination with a microbial pesticide such as a BT agent or an insect pathogenic virus agent, or an antibiotic such as avermectin or milbemycin. Among these insecticides, acaricides and nematicides, Compound No. A-
1, A-2, A-3, A-4, A-5, A-6, A-
7, A-8, A-9, A-10, A-11, A-12,
A-13, A-14, A-15 and A-16 are desirable, and Compound No. A-1, A-2, A-3, A-6, A
-15 and A-16 are more desirable.

In particular, the compound No. 9, 32,
38, 42, 60 and 210 and Compound No. A-1, A-2, A-3, A-6, A-15, and at least one of A-16 are mixed, and the former is 50 to 5
When the application is performed so as to be 000 g / ha and the latter at 10 to 5000 g / ha, an excellent effect is exhibited against harmful insects such as Japanese moth, Konomeiga mocha, Anopheles rotifer, leafhoppers, leafhoppers and aphids.

For example, as a bactericide, S-benzyl
Organic phosphorus compounds such as O, O-diisopropyl phosphorothioate, O-ethyl S, S-diphenyl phosphorodithioate, aluminum ethyl hydrogen phosphonate; 4,5,6,7-tetrachlorophthalide;
Organochlorine compounds such as tetrachloroisophthalonitrile; polymers of manganese ethylenebis (dithiocarbamate), polymers of zinc ethylenebis (dithiocarbamate), complex compounds of zinc and manganese ethylenebis (dithiocarbamate) A dithiocarbamate compound such as a polymer of dizincbis (dimethyldithiocarbamate), ethylenebis (dithiocarbamate), and zinc propylenebis (dithiocarbamate);

3a, 4,7,7a-Tetrahydro-N-
(Trichloromethylsulfenyl) phthalimide, 3
a, 4,7,7a-tetrahydro-N- (1,1,2,2
N-halogenothioalkyl compounds such as 2, -tetrachloroethylsulfenyl) phthalimide and N- (trichloromethylsulfenyl) phthalimide;
(3,5-dichlorophenyl) -N-isopropyl-
2,4-dioxoimidazolidin-1-carboxamide, (RS) -3- (3,5-dichlorophenyl) -5
-Methyl-5-vinyl-1,3-oxazolidine-2,
4-dione, N- (3,5-dichlorophenyl) -1,
Dicarboximide compounds such as 2-dimethylcyclopropane-1,2-dicarboximide;

Methyl 1- (butylcarbamoyl) benzimidazol-2-ylcarbamate, dimethyl 4,
Benzimidazole compounds such as 4 '-(o-phenylene) bis (3-thioallophanate; 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-
1,2,4-triazol-1-yl) butanone, 1-
(Biphenyl-4-yloxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl)
Butan-2-ol, 1- [N- (4-chloro-2-trifluoromethylphenyl) -2-propoxyacetimidoyl] imidazole, 1- [2- (2,4-dichlorophenyl) -4-ethyl- 1,3-dioxolan-2
-Ylmethyl] -1H-1,2,4-triazole, 1
-[2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl] -1H-
Azole compounds such as 1,2,4-triazole, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole; 2,4′-dichloro-α- (pyrimidine -5-yl) benzhydryl alcohol, (±) -2,4′-difluoro-α- (1H-
Carbinol compounds such as (1,2,4-triazol-1-ylmethyl) benzhydryl alcohol;

Benzanilide compounds such as 3'-isopropoxy-o-trianilide and α, α, α-trifluoro-3'-isopropoxy-o-toluanilide;
Methyl N- (2-methoxyacetyl) -N- (2,6-
Phenylamide compounds such as xylyl) -DL-alaninate; 3-chloro-N- (3-chloro-2,6-
Dinitro-4-α, α, α-trifluorotolyl) -5
Pyridinamine compounds such as trifluoromethyl-2-pyridinamine; piperazine compounds, morpholine compounds, anthraquinone compounds, quinoxaline compounds, crotonic acid compounds, sulfenic acid compounds, urea compounds, and other compounds As diisopropyl-1,3-dithiolan-2-ylidene-malonate;
5-methyl-1,2,4-triazolo [3,4-b] benzazole, 1,2,5,6-tetrahydropyrrolo [3,2,1-ij] quinolin-4-one, 6- (3 ,
5-dichloro-4-methylphenyl) -3 (2H) -pyridazinone, 3-allyloxy-1,2-benzisothiazole-1,1-dioxide, 1- (4-chlorobenzyl) -1-cyclopentyl-3- Compounds such as phenylurea; and the like. Further validamycin A
Can be mixed and used in combination with antibiotics such as.

The mixing ratio of the compound of the present invention to other pesticides is as follows:
1: 100 to 100: 1, desirably 1:50 to 50:
It is one. The application of the pesticidal composition containing the compound of the present invention as an active ingredient is generally from 1 to 100,000.
ppm, preferably 1 to 50,000 ppm, more preferably 10 to 20,000 ppm. The concentration of these active ingredients may deviate from these ranges depending on the form of the preparation, the method of application, the purpose, the time, the place and the occurrence of pests. For example, in the case of aquatic pests, even if a chemical solution having the above-mentioned concentration range is sprayed at the place of occurrence, control can be carried out. The application rate per unit area is about 1 to 50000 g, preferably 10 to 10 g, as an active ingredient compound per ha.
10,000 g and more preferably 50 to 5000 g are used. However, in special cases, it is possible to deviate from these ranges. In addition, the application is usually carried out in a generally practiced manner, that is, spraying (eg, spraying, spraying, misting, atomizing, granulation, water surface application, etc.), soil application (mixing, irrigation, etc.), surface application (application) , Dressing, coating, etc.), dipping poison bait and the like. Further, the livestock is fed with the active ingredient mixed with feed,
It is also possible to control the development and growth of harmful insects, especially harmful insects, in the excrement. The so-called micro-spraying method (ul
(tra low Volume). In this method, it is possible to contain 100% of the active ingredient.

Test Example 1 Spodoptera litura Insecticidal Test Each preparation of the active ingredient compound was dispersed in water to give 8
Cabbage leaf pieces were immersed in a chemical solution adjusted to a concentration of 00 ppm for about 10 seconds, and air-dried. A wet filter paper was spread on a petri dish having a diameter of 9 cm, and air-dried leaf pieces were placed thereon. Thereto were released 10 to 3 larvae of the cutworm cutworm, which were capped and left in a 26 ° C. illuminated incubator. On the 5th day after the release, the survival was determined, and the mortality was determined by the following formula. Mortality (%) = (number of dead insects / number of released insects) × 100 1, 2, 4 to 12, 15, 17, 30
~ 34, 36-39, 42, 43, 45, 47-49,
51, 53, 55-62, 74, 201, 202, 21
Nos. 0 to 215, 221, 224, 225 and 303 show a mortality of 100%. 20, 65, 200 and 304 showed a mortality of 90%.

Test Example 2 Insect Insecticidal Test A test was conducted in the same manner as in Test Example 1 except that the cutworm, Spodoptera litura, 2-3 years old was replaced with a 2-3 year old moth, and the mortality was determined. The compound No. 1, 2, 4,
5, 7-12, 30, 32, 34, 38, 39, 41-
45, 49, 60, 61, 201, 202, 210, 2
13 and 301 showed a mortality of 100%.

Test Example 3 Test for Insecticidal Test of Kobumemeiga Each of the active ingredient compounds was dispersed in water to give 8
Corn leaf pieces were immersed in a chemical solution adjusted to a concentration of 00 ppm for about 10 seconds and air-dried. A wet filter paper was spread over an ice cream cup having a diameter of 8 cm, and air-dried leaf pieces were placed thereon. There were released five 2-3-year-old larvae of the larvae of Kobumemeiga, which were capped and left in a 26 ° C. illuminated incubator.
On the 5th day after the release, the survival was determined, and the mortality was determined in the same manner as in Test Example 1. Compound No. 9, 32-34,
38, 210 and 211 showed a mortality of 100%.

Test Example 4 Insecticidal test of Anopheles japonicus
Each formulation of the test active ingredient compound was dispersed in water to give 8
An artificial feed [trade name:
In sector. A small piece of LFR (Nihon Nosan Kogyo Co., Ltd.) was immersed for 60 seconds, and then left indoor for about 1 hour. Filter paper was spread over an ice cream cup having a diameter of 8 cm, and the treated artificial feed was placed thereon. There, 10 larvae of the 2-3 year old larvae were released, covered, and 26
It was left in a thermostat with illumination at ℃. On the 8th to 9th days after the release, survival was determined, and the mortality was determined in the same manner as in Test Example 1. Compound No. 9, 32, 38, 42, 60 and 210 showed a mortality of 100%.

Test Example 5 Insecticidal test of beetle beetle Each preparation of the active ingredient compound was dispersed in water to give 8
Cucumber leaf pieces were immersed in a chemical solution adjusted to a concentration of 00 ppm for about 10 seconds and air-dried. A wet filter paper was spread over an ice cream cup having a diameter of 8 cm, and air-dried leaf pieces were placed thereon. Five adult beetles were released there, covered, and left in a 26 ° C. illuminated thermostat. On the 5th day after the release, survival was determined, and the mortality was determined in the same manner as in Test Example 1. Compound No. 9 showed a mortality of 100%.

[0131]

According to the present invention, there is provided a novel hydrazone compound having excellent pest control activity and a pesticide containing the hydrazone compound.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07C 257/22 C07C 257/22 281/04 281/04 (72) Inventor Hiroshi Sasaki 2-3-1 Nishi-Shibukawa, Kusatsu City, Shiga Prefecture No.Ishihara Sangyo Co., Ltd., Central Research Laboratory (72) Inventor Masayuki Morita 2-3-1 Nishi-Shibukawa, Kusatsu-shi, Shiga Prefecture In-Central Research Laboratory (72) Inventor Tetsuo Yoneda Nishi-Shibukawa, Kusatsu-shi, Shiga No.3-1, Ishihara Sangyo Co., Ltd. Examiner in Central Research Laboratory Takeshi Nimi (56) References JP-A-2-142777 (JP, A) JP-A-5-4958 (JP, A) 502414 (JP, A) European Patent Application Publication 462456 (EP, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 251/86 C07C 251/88 C07C 257/22 C07C 281/04 A01N 35/10 A01N 37/52 A01N 47/12 CA (STN ) REGISTRY (STN)

Claims (7)

(57) [Claims] 1. A compound of the general formula (I): ( Wherein R ¹ , R ² and R ⁴ are each independently a hydrogen atom
, A halogen atom, an atom which may be substituted with a halogen atom.
Alkoxy which may be substituted by alkyl group or halogen atom
R ³ is a halogen atom, substituted with a halogen atom
Substituted with an alkyl group or a halogen atom which may be
And R ⁵ is a hydrogen atom or an alkyl group.
And R ⁶ is an X ⁷ CO— group or an X ⁸ OCO— group.
Or R ⁵ and R ⁶ together form a = CR ⁷ R ⁸ group
And X ⁷ is a hydrogen atom or an alkyl group.
X ⁸ is an alkyl group; R ⁷ is a hydrogen atom or
R ⁸ is an alkyl group which may be substituted with an alkyl group.
It is a mino group or an alkoxy group. However, the case where each substituent is the following (1) to (3) is excluded. (1) R ² , R ⁴
And R ⁵ is a hydrogen atom, R ⁶ is an ethoxycarbonyl group, and at least ^one of R ¹ and R ³ is a p-methoxy group; (2) R ¹ , R ² , R ⁴ and R ^{When 5} is a hydrogen atom, R ³ is a p-tert-butyl group, and R ⁶ is an ethoxycarbonyl group,
(3) R ¹ , R ² and R ⁴ are hydrogen atoms, and R ³ is p
-A fluorine atom, R ⁵ is an isopropyl group and R ⁶ is a hydrogen atom or an acetyl group. Or a salt thereof. 2. The compound according to claim 1, wherein the compound represented by the general formula (I) is [4′-chloro-2- (4
-Trifluoromethylphenyl) acetophenone] N '
-[1- (dimethylamino) ethylidene] hydrazone,
[4'-Fluoro-2- (4-trifluoromethylphenyl) acetophenone] N '-[1- (dimethylamino) ethylidene] hydrazone, ethyl 3- [1- (4-
Chlorophenyl) -2- (4-trifluoromethylphenyl) ethylidene] carbazate, [4′-chloro-2]
-(4-tert-butylphenyl) acetophenone] N '-[1- (dimethylamino) ethylidene] hydrazone and [4'-fluoro-2- (4-tert-butylphenyl) acetophenone] N'-[1- ( A hydrazone compound which is at least one compound selected from the group consisting of [dimethylamino) ethylidene] hydrazone. 3. A compound of the general formula (I): ( Wherein R ¹ , R ² and R ⁴ are each independently a hydrogen atom
, A halogen atom, an atom which may be substituted with a halogen atom.
Alkoxy which may be substituted by alkyl group or halogen atom
R ³ is a halogen atom, substituted with a halogen atom
Substituted with an alkyl group or a halogen atom which may be
And R ⁵ is a hydrogen atom or an alkyl group.
And R ⁶ is an X ⁷ CO— group or an X ⁸ OCO— group.
Or R ⁵ and R ⁶ together form a = CR ⁷ R ⁸ group
And X ⁷ is a hydrogen atom or an alkyl group.
X ⁸ is an alkyl group; R ⁷ is a hydrogen atom or
R ⁸ is an alkyl group which may be substituted with an alkyl group.
It is a mino group or an alkoxy group. However, the case where each substituent is the following (1) to (3) is excluded. (1) R ² , R ⁴
And R ⁵ is a hydrogen atom, R ⁶ is an ethoxycarbonyl group, and at least ^one of R ¹ and R ³ is a p-methoxy group; (2) R ¹ , R ² , R ⁴ and R ^{When 5} is a hydrogen atom, R ³ is a p-tert-butyl group, and R ⁶ is an ethoxycarbonyl group,
(3) R ¹ , R ² and R ⁴ are hydrogen atoms, and R ³ is p
-A fluorine atom, R ⁵ is an isopropyl group and R ⁶ is a hydrogen atom or an acetyl group. A method for producing a hydrazone compound represented by the formula (I) or a salt thereof, which comprises the general formula (II): Wherein R ¹ , R ² , R ³ and R ⁴ are as described above, and a compound represented by the general formula (III): (Wherein R ⁵ and R ⁶ are as defined above). A process for producing a hydrazone-based compound or a salt thereof. 4. A compound of the general formula (I-1): ( Wherein R ¹ , R ² and R ⁴ are each independently a hydrogen atom
, A halogen atom, an atom which may be substituted with a halogen atom.
Alkoxy which may be substituted by alkyl group or halogen atom
R ³ is a halogen atom, substituted with a halogen atom
Substituted with an alkyl group or a halogen atom which may be
And R ⁷ is a hydrogen atom or an alkyl group.
R ⁸ is an amino group which may be substituted with an alkyl group.
Hydrazone compound represented by Bruno is a group or an alkoxy group), or a method for producing a salt thereof, the general formula (I-2): embedded image Wherein R ¹ , R ² , R ³ and R ⁴ are as described above, and a compound represented by the general formula (IV): (Wherein R ⁷ and R ⁸ are as described above, and J ¹ is an alkyl group). A process for producing a hydrazone compound or a salt thereof, which comprises reacting the compound with the compound represented by the formula: 5. A compound of the general formula (I-4): ( Wherein R ¹ , R ² and R ⁴ are each independently a hydrogen atom
, A halogen atom, an atom which may be substituted with a halogen atom.
Alkoxy which may be substituted by alkyl group or halogen atom
R ³ is a halogen atom, substituted with a halogen atom
Substituted with an alkyl group or a halogen atom which may be
And R ⁷ is a hydrogen atom or an alkyl group.
And J ² and J ³ are each independently a hydrogen atom or
Is an alkyl group ), or a hydrazone compound represented by the general formula (VI): Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁷ are as defined above, or a compound of the general formula (VIII): Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁷ are as described above, and a compound represented by the general formula (VII): (Wherein J ² and J ³ are as described above), and a method for producing a hydrazone-based compound or a salt thereof. 6. A pesticidal composition comprising the hydrazone compound according to claim 1 or a salt thereof. 7. A method for controlling pests, which comprises applying an effective amount of the hydrazone compound of claim 1 or a salt thereof.