JPH11152273A - Six-membered cyclic dione derivative containing nitrogen - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as an insecticide, acaricide and herbicide. SOLUTION: This compound is represented by formula I [R<1> and R<2> are each H, a 1-10C alkyl or a phenyl which may be substituted with a halogen or R<1> and R<2> are mutually coupled to provide a 3-6C bifunctional hydrocarbon forming a ring; R<3> and R<4> are each a 1-4C alkyl or R<3> and R<4> are mutually coupled to provide a 3-6C bifunctional hydrocarbon forming a ring or R<3> and R<4> together form divalent oxygen; R<5> is H, a 1-4C alkyl, a 1-8C acyl, benzoyl or the like; R<6> to R<8> are each H, a 1-4C alkyl or a halogen; Q is CH or N; (n) is 1-3], e.g. ethyl 1,2-dimethyl-2-[(2,4,6-trimethylphenyl) acetyl]hydrazino}glyoxylate. The compound of the formula I is produced by a method, etc., cyclizing, e.g. a phenylacetylhydrazinoacetic acid derivative of formula II (R is H or a 1-4C alkyl) in the presence of a base to provide a compound of formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a nitrogen-containing 6-membered ring dione derivative and to acaricides, insecticides and herbicides containing them as an active ingredient.

[0002]

2. Description of the Related Art Certain pyridazine derivatives have been known. For example, JP-A-48-54091 describes 1,2-diphenyl-3,6-dioxo-4-hydroxy-5-n-butyl-tetrahydropyridazine (abbreviation: DENPIDAZON). JP-A-48-54092 and Chemich. Berichte (Chem. Ber.) 90 , 537-542 (1957) also describe DENPIDA
A method for synthesizing ZON is described.

[0003]

In recent years, insecticides and acaricides have been used for many years, and in recent years, insect pests have acquired resistance and it has become difficult to control them. The development of acaricides is expected. In the field of herbicides, development of new drugs is also expected.

An object of the present invention is to provide a novel substance useful as an active ingredient of such an insecticide, acaricide, and herbicide, and an insecticide, acaricide, and a herbicide containing the novel substance as an active ingredient. Is to provide.

[0005]

Means for Solving the Problems In view of the above-mentioned situation, the present inventors have repeatedly studied on a nitrogen-containing 6-membered ring dione derivative, and as a result, have obtained 4-phenylpyridazine represented by the following general formula (1). It has been found that -3,5-dione derivatives and 3-phenylpiperidine-2,4-dione derivatives not only have extremely strong insecticidal and mite-killing activities, but also have strong herbicidal activities, and have completed the present invention. .

That is, the present invention provides the following general formula (1)
The present invention relates to a nitrogen-containing 6-membered ring dione derivative represented by the formula (1), and acaricide, insecticide and herbicide containing the same.

[0007]

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(Wherein R ¹ and R ² may be the same or different and each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group optionally substituted by a halogen atom, or Te represents a divalent saturated or unsaturated hydrocarbon group having 3 to 6 carbon atoms forming a ring .R ³ and R
⁴ may be the same or different and have 1 to 4 carbon atoms
An alkyl group having 3 to 3 carbon atoms which are linked to each other to form a ring
6 represents a divalent hydrocarbon group or, together, a divalent oxygen atom. R ⁵ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an acyl group having 1 to 8 carbon atoms, a benzoyl group, an alkoxycarbonyl group having 1 to 4 carbon atoms, a phenoxycarbonyl group, —C (＝ O) N ( R ⁹ ) R ¹⁰ (where R ⁹ and R
¹⁰ may be the same or different and represents an alkyl group having 1 to 4 carbon atoms. ) Represents a carbamoyl group or an alkylsulfonyl group having 1 to 4 carbon atoms. R ⁶ , R ⁷ ,
And R ⁸ may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom. Q represents CH or N. n represents an integer of 1 to 3. )

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The compound (1) of the present invention represented by the above general formula (1) includes the following compound (2) wherein Q in the general formula (1) is N.

[0010]

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(Wherein, R ¹ and R ² may be the same or different and are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group which may be substituted by a halogen atom, or Te represents a divalent saturated or unsaturated hydrocarbon group having 3 to 6 carbon atoms forming a ring .R ³ and R
⁴ may be the same or different and have 1 to 4 carbon atoms
An alkyl group having 3 to 3 carbon atoms which are linked to each other to form a ring
6 represents a divalent hydrocarbon group or, together, a divalent oxygen atom. R ⁵ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an acyl group having 1 to 8 carbon atoms, a benzoyl group, an alkoxycarbonyl group having 1 to 4 carbon atoms, a phenoxycarbonyl group, —C (＝ O) N ( R ⁹ ) R ¹⁰ (where R ⁹ and R
¹⁰ may be the same or different and represents an alkyl group having 1 to 4 carbon atoms. ) Represents a carbamoyl group or an alkylsulfonyl group having 1 to 4 carbon atoms. R ⁶ , R ⁷ ,
And R ⁸ may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom. n represents an integer of 1 to 3. In addition, the compound (1) of the present invention is a compound of the formula (1)
Wherein CH is CH.

[0012]

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(Wherein R ¹ and R ² may be the same or different and are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group which may be substituted with a halogen atom, or Te represents a divalent saturated or unsaturated hydrocarbon group having 3 to 6 carbon atoms forming a ring .R ³ and R
⁴ may be the same or different and have 1 to 4 carbon atoms
An alkyl group having 3 to 3 carbon atoms which are linked to each other to form a ring
6 represents a divalent hydrocarbon group or, together, a divalent oxygen atom. R ⁵ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an acyl group having 1 to 8 carbon atoms, a benzoyl group, an alkoxycarbonyl group having 1 to 4 carbon atoms, a phenoxycarbonyl group, —C (＝ O) N ( R ⁹ ) R ¹⁰ (where R ⁹ and R
¹⁰ may be the same or different and represents an alkyl group having 1 to 4 carbon atoms. ) Represents a carbamoyl group or an alkylsulfonyl group having 1 to 4 carbon atoms. R ⁶ , R ⁷ ,
And R ⁸ may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom. n represents an integer of 1 to 3. )

When R ⁵ is a hydrogen atom in the compound (1) of the present invention, there are tautomers represented by the following general formulas (1a) and (1b). The abundance ratio of these tautomers is represented by R ³ , R ⁴ , R ⁶ , R ⁷ and R ⁸
And the type of the solvent to be dissolved or the pH of the solvent. Therefore, it can be said that the compounds represented by the general formulas (1a) and (1b) are the same compound. In the above general formulas (2) and (3), when R ⁵ is a hydrogen atom, each tautomer similarly exists, and these tautomers can be said to be the same compound.

[0015]

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Specific examples of each substituent shown in the present specification are as follows. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Can be mentioned.

The alkyl group having 1 to 10 carbon atoms includes, in addition to the substituents exemplified as the alkyl group having 1 to 4 carbon atoms, for example, n-pentyl group, isopentyl group, neopentyl group, cyclopentyl group, n-hexyl group. Group, isohexyl group, cyclohexyl group, n-heptyl group, isoheptyl group, cycloheptyl group, benzyl group, n-octyl group, n-nonyl group, n-decanyl group and the like.

Examples of the acyl group having 1 to 8 carbon atoms include acetyl, propionyl, n-butyryl, isobutyryl, valeryl, pivaloyl, caproyl, n-heptanoyl, phenylacetyl and capryloyl. And the like.

The alkoxycarbonyl group having 1 to 4 carbon atoms includes, for example, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, sec-
Butoxycarbonyl group, tert-butoxycarbonyl group and the like.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms include methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl and the like. And a tert-butylsulfonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Among the compounds of the present invention represented by the above general formula (1), particularly, R ¹ is a methyl group or a tert-butyl group,
R ² is a methyl group; R ³ and R ⁴ are both methyl groups; or 1,5-, a divalent oxygen atom forming a carbonyl group or a 1,5-membering ring forming a 5-membered ring together.
A pentylene group, R ⁵ is a hydrogen atom or an acetyl group, R ⁶
And a compound wherein R ⁶ is both a methyl group, R ⁸ is a methyl group at the 6-position on the phenyl ring and n is 1.

The compound of the present invention is effective against various pests at a low dose. Examples of the pests include the following agricultural pests. As mites, for example,
Red spider mite, Red spider mite, Mandarin mite, Mandarin spider mite, Kanzawa spider mite and the like, and Hemiptera, for example, planthoppers such as brown planthopper, brown planthopper, leafhoppers such as leafhopper leafhopper, whitefly, etc.,
Whiteflies such as whiteflies such as tobacco whiteflies; Thrips, for example, Thrips palmi, Thrips palmi, Thrips palmi, and the like, and Diptera, for example, Thrips palmi, and the like. Further, the compound of the present invention is effective not only in controlling agricultural pests but also in controlling various sanitary pests such as house flies and Culex pipiens. Furthermore, the compound of the present invention,
It is effective for controlling low-dose weeds, which are agriculturally problematic, such as crabgrass, eel, squirrel, sedge, and sedge. These effects are specifically shown in the biological test examples described later.

The compound of the present invention can be produced by various methods. The typical production method is shown below.
The compound (1-1) of the present invention in which R ⁵ is a hydrogen atom in the general formula (2) can be obtained by reacting a compound represented by the following reaction formula-1:
The phenylacetylhydrazinoacetic acid derivative represented by the general formula (4) can be produced by ring-closing in the presence of a base.

[0024]

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(Wherein R ^{1 to} R ⁴ , R ^{6 to} R ⁸ and n are the same as described above, and R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). The ring closure reaction of the represented phenylacetylhydrazinoacetic acid derivative can be usually performed in a suitable solvent. As the solvent used, for example, methanol,
Alcohols such as ethanol, hydrocarbons such as hexane, cyclohexane and heptane; aromatic hydrocarbons such as benzene, chlorobenzene, toluene and xylene; halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride; Ethers such as diethyl ether, tetrahydrofuran and dioxane, acetone,
Examples thereof include ketones such as methyl ethyl ketone, amides such as N, N-dimethylformamide and hexamethylphosphoric triamide, dimethyl sulfoxide, acetonitrile, and a mixed solvent thereof. Examples of the base used include inorganic bases such as potassium carbonate, potassium hydroxide, cesium fluoride, cesium carbonate, sodium hydride, and potassium hydride; and organic metals such as lithium diisopropylamide, butyllithium, and potassium tert-butoxide. Bases and the like.

The ratio of the phenylacetylhydrazinoacetic acid derivative (4) and the base to be used is usually 0.5 to 3.0 equivalents, preferably 1 to 2.4 equivalents, for the former. The reaction can be usually carried out in a temperature range from room temperature to the boiling point of the solvent, and is completed usually in about 0.5 to 3 hours.

In the reaction formula-1, the phenylacetylhydrazinoacetic acid derivative represented by the general formula (4) used as a starting material can be produced, for example, by the method shown in the following reaction formula-2.

[0028]

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(Wherein R ³ , R ⁴ , R ⁶ -R ⁸ and n are the same as above. R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ¹ ′ and R ² ′ are They may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a saturated or unsaturated divalent hydrocarbon group having 3 to 6 carbon atoms which is linked to each other to form a ring. Z ¹ is a hydroxyl group, a halogen atom, a phenoxy group, a nitrophenoxy group, a phthalimidooxy group, a succinimidooxy group,
It represents a group that can be easily substituted with hydrazines such as an alkoxy group having 1 to 4 carbon atoms. Z ² represents each group of Z ¹ and, in addition, a tosyloxy group and a mesyloxy group. )

According to the reaction formula-2, a phenylacetic acid derivative represented by the general formula (6) is allowed to act on the hydrazine (5) to produce a hydrazide derivative represented by the general formula (7). By reacting the carboxylic acid derivative represented by (8), a phenylacetylhydrazinoacetic acid derivative represented by the general formula (12) can be obtained. Compound (12) can be produced in the same manner by changing the reaction order of hydrazine (5), compound (8), and then compound (6). When an alkylating agent is allowed to act on compound (12), general formula (4)
An N, N'-disubstituted-phenylacetylhydrazinoacetic acid derivative represented by -1) can be produced. Also,
The compound (4-1) can also be produced by reacting the compound (6) with the alkyl-substituted hydrazine (10) followed by the compound (8).

The reaction of reacting the compound (8) with the hydrazine (5) to obtain the compound (7) is carried out according to a method commonly used in the art and includes 1,1'-carbonyldiimidazole (CDI) and dicyclohexyl. A condensing agent such as carbodiimide (DCC) may be used. The reaction can be carried out without solvent or in a suitable solvent. As the solvent used, for example, alcohols such as methanol and ethanol, benzene, chlorobenzene, toluene, aromatic hydrocarbons such as xylene, dichloromethane, dichloroethane, chloroform, halogenated hydrocarbons such as carbon tetrachloride, Examples thereof include ethers such as diethyl ether, tetrahydrofuran and dioxane, esters such as ethyl acetate, pyridine, water, and a mixed solvent thereof. When a base is used for the reaction, examples of the base used include inorganic bases such as potassium carbonate, sodium hydrogen carbonate, potassium hydroxide, and sodium hydroxide, pyridine, triethylamine, diisopropylethylamine, and 4-dimethylaminopyridine. And the like. The amount of the base used is preferably 0.8 to 5 equivalents relative to compound (6).

In the reaction, the compound (6) and the hydrazine (5) are usually used in a ratio of 0.1 to the former.
-100 equivalents, preferably 0.5-50 equivalents. The reaction can be usually carried out in a temperature range from 0 ° C. to the boiling point of the solvent, and is completed usually in about 1 to 5 hours.

Reaction of compound (9) with compound (12), alkyl-substituted hydrazine (10) with compound (1)
The reaction to 1) can be carried out similarly. Further, the reaction from hydrazine (5) to compound (9), the reaction from compound (7) to compound (12), and the reaction from compound (11) to compound (4-1) can also be accomplished by converting compound (6) into compound (4-1). (8)
Can be carried out under the same conditions.

The reaction for producing compound (4-1) by reacting compound (12) with an alkylating agent can be usually carried out in a suitable solvent. Examples of the solvent used include alcohols such as methanol and ethanol; aromatic hydrocarbons such as benzene, chlorobenzene, toluene and xylene; ethers such as diethyl ether, tetrahydrofuran and dioxane; N, N-dimethylformamide; Examples thereof include amides such as hexamethylphosphoric triamide, dimethyl sulfoxide, acetonitrile, and a mixed solvent thereof. Reagents that can be used as the alkylating agent include methyl iodide, ethyl iodide, propyl iodide, methyl bromide, ethyl bromide, methyl chloride,
Examples thereof include alkyl halides such as 3-dibromopropane and 1,4-dibromobutane, and alkyl sulfates such as alkyl tosylate, dimethyl sulfate and diethyl sulfate. By adjusting the amount of the alkylating agent and the reaction time, R ¹ ′,
R ² 'can also introduce different substituents, at the same time by reacting 2 equivalents or more of an alkylating agent, R ^1', it is also possible to introduce the same alkyl group R ² '.

The ratio of the compound (12) to the alkylating agent is usually 0.5 to 5 equivalents, preferably 1 to 3 equivalents, of the former. It is preferable to use a base for the reaction. Examples of the base used include inorganic bases such as potassium carbonate, potassium hydroxide, cesium fluoride, cesium carbonate, sodium hydride, potassium hydride, lithium diisopropylamide, butyllithium, and the like. Potassium ter
Organic metal bases such as t-butoxide and the like can be mentioned. The use ratio of the compound (12) to the base is usually 0.5 to 10 equivalents, preferably 1 to 2.2 equivalents, for the former. It is effective to use an interlayer transfer catalyst for the reaction. As the interlayer transfer catalyst, conventionally known ones can be widely used. For example, tetramethylammonium bromide, tetra-n-butylammonium bromide, tetra-n-butylammonium iodide, tetra-n-butylammonium chloride, Tetra-n-pentyl ammonium bromide, tetra-n-hexyl ammonium bromide, tetra-n-octyl ammonium bromide, tetra-n-hexadecyl ammonium bromide, benzyl triethyl ammonium chloride, tri-n-octyl methyl ammonium chloride, etc. And quaternary phosphonium salts such as tetraphenylphosphonium bromide and tetra-n-butylphosphonium chloride. The reaction can be usually carried out within a temperature range from -20 ° C to the boiling point of the solvent, and is usually completed in about 1 to 6 hours.

The phenylacetylhydrazinoacetic acid derivative represented by the general formula (4) can also be produced, for example, by the following reaction formula-3.

[0037]

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(Wherein R ³ , R ⁴ , R ⁶ -R ⁸ , R and n are the same as above. R ¹ ″ is a phenyl group or a tert-butyl group optionally substituted with a halogen atom) R ² ″ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

According to the reaction formula-3, the substituted hydrazine (13) is reacted with the carboxylic acid derivative (8) to produce a hydrazide derivative represented by the general formula (14). 6) is reacted to form a compound of the general formula (4-
An N-substituted-phenylacetylhydrazinoacetic acid derivative represented by 2) can be produced. Further, an alkylating agent is allowed to act on compound (4-2) to obtain an N, N'-disubstituted-phenylacetylhydrazinoacetic acid derivative represented by the general formula (4-3). This reaction is effective for introducing a bulky substituent such as a phenyl group or a tert-butyl group as R ¹ of the compound (4) which is a precursor of the compound (1-1) of the present invention. Each condition of the reaction is the same as each reaction condition corresponding to the above-mentioned Reaction formula-2.

The phenylacetylhydrazinoacetic acid derivative represented by the general formula (4) can also be produced, for example, by the following reaction formula-4.

[0041]

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(Wherein, R ³ , R ⁴ , R ⁶ -R ⁸ , R and n are the same as above. R ¹ ″ ″ is a hydrogen atom, carbon atom number 1-10)
Represents an alkyl group. R ² ′ ″ represents a phenyl group or a tert-butyl group optionally substituted with a halogen atom. )

According to the reaction formula-4, the substituted hydrazine (15) is reacted with the phenylacetic acid derivative (6) to produce a hydrazide derivative represented by the general formula (16), and the carboxylic acid derivative ( 8) to react with the general formula (1)
An N-substituted-phenylacetylhydrazinoacetic acid derivative represented by the formula (8) is obtained and treated with an alkylating agent to give N, N'-disubstituted-phenylacetylhydrazino represented by the general formula (4-4). An acetic acid derivative is obtained. The reaction is carried out by adding a bulky substituent such as a phenyl group or a tert-butyl group to R ^{2 of} compound (4) which is a precursor of compound (1-1) of the present invention.
It is effective to introduce as. Each condition of the reaction is the same as each reaction condition corresponding to the above-mentioned Reaction formula-2.

The compound of the present invention wherein R ⁵ is a hydrogen atom in the general formula (3) can be produced, for example, by the following reaction formula -5.

[0045]

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(Wherein R ¹ , R ³ , R ⁴ , R ⁶ -R ⁸ ,
R and n are the same as above. According to the reaction formula-5, the aminopropionic acid derivative represented by the general formula (19) is reacted with the phenylacetic acid derivative (6) to produce the amide derivative represented by the general formula (20), To form a ring of the general formula (1-2)
This invention compound represented by these is obtained.

The respective conditions of the reaction are the same as the corresponding reaction conditions of the above-mentioned reaction formula-2. Compound (19), which is a starting material for the reaction, may be purchased commercially, or the corresponding cyanoacetic acid derivative may be converted to an amino compound by a reduction method commonly used by those skilled in the art, for example, a catalytic reduction method. It can also be obtained by subsequent alkylation.

In the compound of the present invention represented by the general formula (2), the hydrogen atom of R ⁵ can be replaced, for example, by the following reaction formula -6.

[0049]

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(Wherein, R ^{1 to} R ⁴ , R ^{6 to} R ⁸ and n are the same as above. R ⁵ ′ is an alkyl group having 1 to 4 carbon atoms, an acyl group having 1 to 8 carbon atoms, a benzoyl group) , An alkoxycarbonyl group having 1 to 4 carbon atoms, a phenoxycarbonyl group, -C
A carbamoyl group represented by (＝ O) N (R ⁹ ) R ¹⁰ (where R ⁹ and R ¹⁰ may be the same or different and represent an alkyl group having 1 to 4 carbon atoms), Represents an alkylsulfonyl group of 1 to 4; Z ³ is a halogen atom,
Represents a tosyloxy group or a mesyloxy group. )

According to the reaction formula-6, the compound of the present invention (1-
The compound of the present invention (1-3) can be produced by reacting 1) with the reaction reagent represented by the general formula (21). The reaction is
Usually, it can be carried out in a suitable solvent. As the solvent used, for example, dichloromethane, dichloroethane,
Halogenated hydrocarbons such as chloroform and carbon tetrachloride,
Aromatic hydrocarbons such as benzene, chlorobenzene, toluene and xylene; ethers such as diethyl ether, tetrahydrofuran and dioxane; amides such as N, N-dimethylformamide and hexamethylphosphoric triamide; esters such as ethyl acetate , Dimethyl sulfoxide, acetonitrile, pyridine, a mixed solvent thereof and the like. The reaction is usually performed in the presence of a base. Examples of the base used include sodium hydride, pyridine, triethylamine, diisopropylethylamine, 4-dimethylaminopyridine and the like. The ratio of the compound (1-1) to the base used is usually 0.5 to 3 equivalents, preferably 1 to 1.2 equivalents, for the former. Examples of the reagent represented by the general formula (21) include alkylating agents such as alkyl halides, alkyl tosylates, alkyl sulfates such as dimethyl sulfate and diethyl sulfate, acetyl chloride, acetyl bromide, benzoyl chloride, and propionyl chloride. Acylating agents, halogenated formic esters, halogenated formic acid amides and the like. Compound (1
The use ratio of -1) to compound (21) is usually 0.5 to 8 equivalents, preferably 1 to 2 equivalents, for the former. The reaction is allowed to proceed usually within a temperature range from -20 ° C to the boiling point of the solvent, and is usually completed in about 0.5 to 3 hours.

In the compound of the present invention represented by the general formula (3), the hydrogen atom of R ⁵ can be substituted, for example, by the following reaction formula -7.

[0053]

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(In the formula, R ^{1 to} R ⁴ , R ^{6 to} R ⁸ , R ⁵ ′ and n are the same as described above.) According to Reaction Scheme-7, the compound (1-2) of the present invention has the general formula (1-2) The compound of the present invention (1-4) can be produced by reacting the reaction reagent represented by 21). The conditions used for the reaction are:
The conditions are the same as those used in the above Reaction Formula-6.

The 4-phenylpyridazine of the present invention
3,5-dione derivatives (1-1) and (1-3) or 3-phenylpiperidine-2,4-dione derivative (1
-2) and (1-4) can be purified by a usual method such as a solvent extraction method, a recrystallization method, and various chromatography methods such as a column chromatography method and a preparative thin-layer chromatography method. .

When the compound of the present invention is used as an active ingredient of an insecticide, an acaricide or a herbicide, it may be used as it is without adding other components. Mix carriers and add surfactants and other formulation auxiliaries as needed to formulate into oils, emulsions, wettable powders, flowables, granules, powders, aerosols, aerosols, etc. I do. These preparations usually contain the compound of the present invention as an active ingredient in an amount of 0.01% to 9% by weight.
Contains 5%.

Examples of the solid carrier used in the preparation include, for example, clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.), talcs, ceramics, and other inorganic minerals (celite, Quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), chemical fertilizers (ammonium sulfate, phosphorous ammonium, ammonium nitrate, urea, salt ammonium, etc.)
Examples of the liquid carrier include water, alcohols (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), and aromatic hydrocarbons (benzene, toluene, xylene, etc.). Ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, gas oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl) Ether, dioxane, etc.),
Acid amides (N, N-dimethylformamide, N, N-
Dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, soybean oil, vegetable oils such as cottonseed oil, and the like. As the gaseous carrier, that is, the propellant, for example, butane gas, LPG ( Liquefied petroleum gas), dimethyl ether, carbon dioxide gas and the like.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyethylene glycol ethers, polyhydric alcohol esters, and sugar alcohols. Derivatives and the like.

Examples of auxiliary agents for preparations such as fixatives and dispersants include casein, gelatin, polysaccharides (starch, starch,
Gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, saccharides, synthetic water-soluble polymers (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids, etc.). Examples of stabilizers include PAP (acidic phosphoric acid). Isopropyl), BHT (2,
6-di-tert-butyl-4-methylphenol), BH
A (2-tert-butyl-4-methoxyphenol and 3-
tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids, or esters thereof.

The preparation thus obtained is used as it is or after dilution with water or the like. Also other insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators,
They can be used simultaneously with or without mixing with synergists, soil conditioners, animal feeds and the like.

When the compound of the present invention is used as an agricultural pesticide, acaricide or herbicide, its application rate is usually
0.1 g to 500 g per 100 m ^{2. When} an emulsion, a wettable powder, a flowable or the like is diluted with water and used, the application concentration is usually 10 ppm to 500 g.
ppm, and granules, powders, and the like can be applied as they are without dilution.

The application rate and application concentration vary depending on the type of preparation, application time, application place, application method, type of pest or weed, degree of damage, etc., and increase without being limited to the above range. Can be reduced or reduced.

[0063]

EXAMPLES The present invention will be described in more detail with reference to Production Examples, Formulation Examples and Test Examples below, but the present invention is not limited to these Examples. First, Production Examples of the compound of the present invention will be shown.

Production Example 1: Reaction route (5 → 7 → 12 → 4-
1) Synthesis of ethyl {1,2-dimethyl-2-[(2,4,6-trimethylphenyl) acetyl] hydrazino} glyoxylate Ethyl 2,4,6-trimethylphenylacetate (20 g)
And hydrazine monohydrate (70 ml) were heated and stirred for 1 hour. The mixture was cooled to 0 ° C., and the precipitated solid was taken out and washed with water and hexane. After drying under reduced pressure,
17.5 g of 4,6-trimethylphenylacetic acid hydrazide
(100%). The NMR data of the obtained compound are shown below.

¹ H NMR (CDCl ₃ , δ ppm):
2.24 (6H, s), 2.29 (3H, s), 3.6
1 (2H, s), 3.80 (2H, brs), 6.50
(1H, brs), 6.89 (2H, s)

2,4,6-Trimethylphenylacetic acid hydrazide (17.4 g) was added to anhydrous tetrahydrofuran (15
0 ml) and cooled to 0 ° C. Pyridine (7.
After adding 4 ml), ethyl oxalyl chloride (12.2) was added.
ml) in anhydrous tetrahydrofuran (50 ml).
It was added dropwise over 0 minutes. After stirring at room temperature for 2 hours, the mixture was poured into ice water (500 ml). Ethyl acetate (100ml)
And extracted three times. The obtained organic layer was dried by a conventional method, and then dried under reduced pressure. The solid obtained was purified by silica gel column chromatography (hexane: ethyl acetate = 5: 1) to give white crystals of ethyl {2-[(2,4,6-trimethylphenyl) acetyl] hydrazino} glyoxylate 14 0.2 g (53.7%) were obtained. The NMR data of the obtained compound are shown below.

¹ H NMR (CDCl ₃ , δ ppm):
1.43 (3H, m), 2.18 (6H, s), 2.2
5 (3H, s), 3.92 (2H, s), 4.46 (2
H, m), 6.90 (2H, s), 8.09 (1H, b
rs), 9.21 (1H, brs)

{2-[(2,4,6-trimethylphenyl) acetyl] hydrazino} ethyl glyoxylate (1
4.2 g), methyl iodide (11.7 g), potassium carbonate (14.2 g) and acetonitrile (100 ml) were mixed, and heated under reflux overnight. The reaction solution was filtered, and the filtrate was dried under reduced pressure. The obtained solid was washed with ethyl acetate (100
ml) and washed twice with 0.5N hydrochloric acid (30 ml) and then with water (30 ml). The obtained ethyl acetate solution was dried by a conventional method, and then dried under reduced pressure. The obtained solid was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1) to give the target compound as yellow crystals.
93 g (31.7%) were obtained. NMR of the obtained compound
The data is shown below.

¹ H NMR (CDCl ₃ , δ ppm):
1.35 (3H, m), 2.18 (6H, s), 2.2
5 (3H, s), 3.30-3.60 (2H, m),
4.30-4.43 (2H, m), 6.86 (2H,
s)

Production Example 2: Reaction route (9 → 12 → 4-1) Synthesis of ethyl 1- {1,2-dimethyl-2- (2,4,6-trimethylphenyl) acetylhydrazino} cyclohexanecarboxylate 1 Ethyl hydrazinocyclohexanecarboxylate dihydrochloride (7.4 g) was dissolved in dichloromethane (100 ml), and a solution of 2,4,6-trimethylphenylacetyl chloride (5 g) in dichloromethane (50 ml) was added at 5 ° C. Next, a dichloromethane (50 ml) solution of triethylamine (12.3 ml) was added dropwise at 10 ° C. or lower.
After stirring the reaction solution for 3 hours, the organic layer was washed with saturated aqueous sodium hydrogen carbonate,
The concentrate obtained by concentration under reduced pressure was purified by silica gel column chromatography (hexane: ethyl acetate = 4: 1) to give 1-{[2- (2,4,6-trimethylphenyl) acetyl] hydrazino} cyclohexane 5 g (51%) of ethyl carboxylate were obtained. NMR of the obtained compound
The data is shown below.

¹ H NMR (CDCl ₃ , δ ppm):
1.13 (3H, t, J = 7 Hz), 1.3-2.0
(10H, m), 2.24 (6H, s), 2.26 (3
H, s), 3.58 (2H, s), 4.01 (2H,
q, J = 7 Hz), 4.80 (1H, brs), 6.7
1 (1H, brs), 6.88 (2H, s)

Ethyl 1-{[2- (2,4,6-trimethylphenyl) acetyl] hydrazino} cyclohexanecarboxylate (1 g) and methyl iodide (1.23 g) were dissolved in tetrahydrofuran (30 ml), and the mixture was heated to 0 ° C. Under cooling, sodium hydride (60% oily, 0.35 g) was added. After stirring for 3 hours, the mixture was partitioned with ethyl acetate-water, the organic layer was collected, dried by a conventional method, and concentrated under reduced pressure. The resulting concentrate was purified by silica gel column chromatography (hexane: ethyl acetate = 8: 2). 0.66 of the oily target
g (61.0%). The NMR data of the obtained compound are shown below.

¹ H NMR (CDCl ₃ , δ ppm):
1.31 (3H, t, J = 7 Hz), 1.2-2.0
(10H, m), 2.20 (6H, s), 2.24 (3
H, s), 2.68 (3H, s), 2.93 (3H,
s), 3.80 (1H, d, J = 18 Hz), 3.92
(1H, d, J = 18 Hz), 4.30 (2H, q, J
= 7 Hz), 6.84 (2H, s)

Production Example 3: Reaction route (10 → 11 → 4-
1) Synthesis of ethyl {2- [2- (2,4,6-trichlorophenyl) acetyl] tetrahydropyridazin-1-yl} glyoxylate A solution of hexahydropyridazine (2.14 g) in anhydrous tetrahydrofuran (40 ml) at 0 ° C. And pyridine (2.31 ml) in anhydrous tetrahydrofuran (2.
0 ml) and 2,4,6-trichlorophenylacetic chloride (4.27 g) in anhydrous tetrahydrofuran (2 ml).
0 ml) was simultaneously added dropwise over 15 minutes. After stirring at room temperature for 1 hour, the mixture was poured into ice water (200 ml). 1N
After adjusting the pH to 11 to 12 with sodium hydroxide, the mixture was extracted three times with chloroform (50 ml), and the obtained organic layer was dried by a conventional method and then dried under reduced pressure. The obtained solid was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to give yellow crystals of 1- (2,4,6).
2.32 g (45.6%) of -trichlorophenyl) acetyltetrahydropyridazine were obtained. The NMR data of the obtained compound are shown below.

¹ H NMR (CDCl ₃ , δ ppm):
1.60-1.78 (4H, m), 3.00 (2H,
m), 3.46 (1H, m), 3.66 (2H, br)
s), 4.21 (2H, s), 7.34 (2H, s)

1- (2,4,6-trichlorophenyl)
After cooling an anhydrous dichloromethane solution (30 ml) of acetyltetrahydropyridazine (2.32 g) to 0 ° C.,
Triethylamine (1.3 ml) was added. A solution of ethyl oxalyl chloride (1.1 ml) in anhydrous dichloromethane (10 ml) was added dropwise over 10 minutes, and the mixture was stirred at room temperature for 2 hours. The reaction solution was washed three times with water (50 ml), and the obtained dichloromethane solution was dried by a conventional method and then dried under reduced pressure. The obtained solid was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1) to obtain 2.44 g (79.2%) of the target substance as yellow crystals. The NMR data of the obtained compound are shown below.

¹ H NMR (CDCl ₃ , δ ppm):
1.36 (3H, m), 1.75-1.88 (4H,
m), 2.94-3.15 (4H, m), 3.97-
4.02 (2H, m), 4.40-4.42 (2H,
m), 7.37 (2H, s)

Production Example 4: Reaction route (13 → 14 → 4-
2) Synthesis of ethyl {2-tert-butyl-2- (2,4,6-trimethylphenylacetyl) hydrazino} glyoxylate Tert-butylhydrazine hydrochloride (6.0 g) was dispersed in anhydrous dichloromethane (200 ml). Triethylamine (15 ml) was added. After cooling to −10 ° C., an anhydrous dichloromethane solution (30 ml) of ethyl oxalyl chloride (5.4 ml) was added dropwise with stirring over 20 minutes.
After stirring at room temperature for 90 minutes, the reaction solution was washed with water (80 ml).
And washed three times. The obtained dichloromethane solution was dried by a conventional method and then dried under reduced pressure. The obtained solid was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to obtain 4.2 g of ethyl (2-tert-butylhydrazino) glyoxylate as white crystals.
6.4%). The NMR data of the obtained compound are shown below.

¹ H NMR (CDCl ₃ , δ ppm):
1.14 (9H, s), 1.28 (3H, m), 4.3
9 (2H, m), 8.39 (1H, brs), 9.08
(1H, brs)

Ethyl (2-tert-butylhydrazino) glyoxylate (3.0 g) was added to anhydrous toluene (30 m
l) and stirred under stirring in a solution of 2,4,6-trichlorophenylacetic acid chloride (3.5 g) in anhydrous toluene (10 g).
ml) was added dropwise over 2 minutes. After heating and stirring for 3 hours,
Washed three times with water (40 ml). The obtained toluene solution was dried by a conventional method, and then dried under reduced pressure. The obtained solid was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1) to give the target compound as white crystals.
9 g (34.2%) were obtained. The NMR data of the obtained compound are shown below.

¹ H NMR (CDCl ₃ , δ ppm):
1.40 (3H, m), 1.44 (9H, s), 2.1
8 (6H, s), 2.23 (3H, s), 3.45-
3.65 (2H, m), 4.42 (2H, m), 6.8
3 (2H, s), 8.76 (1H, brs)

Production Example 5: Reaction route (4-2 → 4-3) {2-tert-butyl-1-methyl-2- (2,4,
Synthesis of 6-trimethylphenylacetyl) hydrazino ethyl glyoxylate {2-tert-butyl-2- produced in Production Example 4 above
A mixture of ethyl (2,4,6-trimethylphenylacetyl) hydrazino diglyoxylate (1.9 g), methyl iodide (1.2 g), potassium carbonate (1.2 g) and acetonitrile (40 ml) was heated to reflux overnight. did. After removing insolubles by filtration, the residue was dried under reduced pressure. The solid obtained was dissolved in ethyl acetate (25 ml),
Washed twice with N hydrochloric acid (15 ml) and water (15 ml). The obtained ethyl acetate solution is dried by a conventional method, and then dried under reduced pressure. The obtained solid is purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1) to give a white crystal of the target compound. 1.5 g (75.9%) were obtained. The NMR data of the obtained compound are shown below.

¹ H NMR (CDCl ₃ , δ ppm):
1.40 (3H, m), 1.44 (9H, s), 2.2
0 (6H, s), 2.26 (3H, s), 3.38 (3
H, s), 3.45 (1H, m), 4.13 (1H,
m), 4.40 (2H, m), 6.86 (2H, s)

Production Example 6: Reaction route (15 → 16 → 18 →
4-4) Synthesis of ethyl {2-methyl-2- (2,4,6-trimethylphenylacetyl) -1-phenylhydrazino} glyoxylate 1,1'-carbonyldiimidazole (9.6 g) was added to anhydrous tetrahydrofuran. (150 ml), and cooled to 0 ° C. Under stirring, a solution of 2,4,6-trimethylphenylacetic acid (10.0 g) in anhydrous tetrahydrofuran (40
ml) was added dropwise over 15 minutes. After stirring at room temperature for 1 hour, the mixture was cooled to 0 ° C., and phenylhydrazine (6.7 g) was added.
An anhydrous tetrahydrofuran solution (40 ml) was added dropwise over 5 minutes. After stirring at room temperature for 24 hours, ice water (300
ml) was added. The precipitated white crystals were taken and washed with water. The obtained crystals were dried under reduced pressure to give white crystals of 1-.
15.3 g (100%) of (2,4,6-trimethylphenylacetyl) -2-phenylhydrazine were obtained. The NMR data of the obtained compound are shown below.

¹ H NMR (CDCl ₃ , δ ppm):
2.25 (3H, s), 2.34 (6H, s), 3.7
1 (2H, s), 6.02 (1H, m), 6.71 (2
H, m), 6.88 (1H, m), 6.95 (2H,
s), 7.03 (1H, brs), 7.22 (2H,
m)

The obtained 1- (2,4,6-trimethylphenylacetyl) -2-phenylhydrazine (15.0
g) in the same manner as in Production Example 1 with ethyl oxalyl chloride (9.0).
g) to give 16.3 g (79.2%) of ethyl {2- (2,4,6-trimethylphenylacetyl) -1-phenylhydrazino} glyoxylate as white crystals. The compound was obtained as a mixture of conformational isomers, but had no effect on the next reaction. The NMR data of the obtained compound are shown below.

¹ H NMR (CDCl ₃ , δ ppm):
0.99, 1.34 (3H, m), 2.22 (3H,
s), 2.28 (3H, s), 2.31 (3H, s),
3.66, 3.72 (2H, s), 4.06, 4.30
(2H, m), 6.91 (2H, s), 7.35 (5
H, s), 7.53, 7.80 (1H, brs)

{2- (2,4,6-trimethylphenylacetyl) -1-phenylhydrazino} ethyl glyoxylate (6.0 g), methyl iodide (2.8 g), potassium carbonate (3.4 g) and Acetonitrile (50ml)
The mixture was heated to reflux overnight. After removing insolubles by filtration, the residue was dried under reduced pressure. The obtained solid was dissolved in ethyl acetate (50 ml), and 0.5N hydrochloric acid (20 ml) was added.
And twice with water (20 ml). The obtained ethyl acetate solution is dried by a conventional method, and then dried under reduced pressure. The obtained solid is purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to obtain a yellow liquid. 6.60 g (100%) were obtained. N of the obtained compound
The MR data is shown below.

¹ H NMR (CDCl ₃ , δ ppm):
1.41 (3H, m), 2.03 (6H, s), 2.2
3 (3H, s), 3.51 (3H, s), 3.70-
4.10 (2H, m), 4.33-4.52 (2H,
m), 6.83 (2H, s), 7.31-7.65 (5
H, m)

Production Example 7: Reaction route (4-1 → 1-1) 5-hydroxy-1,2-dimethyl-4- (2,4,6
-Trimethylphenyl) -1,2-diazaspiro [5.
5] -4-Undecen-3-one (Compound 52 of the present invention)
Synthesis of

Potassium tert-butoxide (0.43
5 g) in tetrahydrofuran (20 ml).
C. and heated to ethyl 1- {1,2-dimethyl-2- (2,4,6-trimethylphenyl) acetylhydrazino} cyclohexanecarboxylate (0.6
A solution of 6 g) in toluene (15 ml) was added dropwise.
After refluxing for 1 hour, the mixture was neutralized with dilute hydrochloric acid and extracted with dichloromethane. The organic layer was dried and concentrated under reduced pressure by a conventional method, and the obtained concentrate was purified by silica gel column chromatography (hexane: ethyl acetate = 8: 2), and the obtained solid was dissolved in ethyl acetate to remove hexane. In addition, a crystal was precipitated, and this was taken out and taken as a colorless powdery target product (560 m).
g (97%). The compounds produced in Production Examples 2 to 6 were similarly reacted to produce the corresponding 4-phenylpyridazine-3,5-dione derivatives.

Production Example 8: Reaction route (1-1 → 1-3) 5-acetoxy-1,2-dimethyl-4- (2,4,6
-Trimethylphenyl) -1,2-diazaspiro [5.
5] -4-Undecen-3-one (Compound 53 of the present invention)
Compound 52 (460 mg) of the present invention and triethylamine (0.5 ml) produced in Production Example 7 were dissolved in dichloromethane (20 ml), and acetyl chloride (0.4 ml) was added under cooling.
ml) was added. After stirring for 1 hour, the reaction solution was washed with dilute hydrochloric acid and saturated aqueous sodium hydrogen carbonate and concentrated under reduced pressure. The obtained concentrate is purified by silica gel column chromatography (hexane: ethyl acetate = 8: 2) to give 400 m of a colorless powdery target substance.
g (62%).

Production Example 9: Reaction route (1-1 → 1-3) 4-methoxy-1,2-dimethyl-5- (2,4,6-
Trimethylphenyl) -1,2-dihydropyridazine-
Synthesis of 3,6-dione (Compound 11 of the present invention) 4-hydroxy-1,2-dimethyl-5- (2,4,6
-Trimethylphenyl) -1,2-dihydropyridazine-3,6-dione (Compound 9: 0.2 g), methyl iodide (0.13 g), potassium carbonate (0.17 g)
And a mixture of acetonitrile (15 ml) was heated to reflux overnight. After removing insolubles by filtration, the residue was dried under reduced pressure. After dissolving the obtained solid in ethyl acetate (10 ml), 0.5N hydrochloric acid (10 ml) and water (10 m
Washed twice in l). The obtained ethyl acetate solution was dried by a conventional method, and then dried under reduced pressure. The obtained solid was purified by silica gel column chromatography (hexane: chloroform: ethyl acetate = 1: 1: 1) to obtain 0.15 g (71.0%) of the target substance as a pale yellow liquid.

Production Example 10: Reaction route (19 → 20) Synthesis of methyl 1-{[N-methyl-N- (2,4,6-trimethylphenylacetyl) amino] methyl} cyclohexanecarboxylate 1-cyanocyclohexanecarboxylate Acid (10.8 g) was dissolved in acetic acid (200 ml), and platinum dioxide (0.3
g) was added, and the mixture was stirred under a hydrogen atmosphere at normal pressure at room temperature until the required amount of hydrogen was consumed. The residue was dried under reduced pressure and washed twice with hexane (15 ml) to give white crystals of 1-.
5.5 g of (aminomethyl) cyclohexanecarboxylic acid
(49.8%), followed by anhydrous methanol (50 m
1) and cooled to -10 ° C. Thionyl chloride (90 ml) was added dropwise with stirring, and the mixture was heated under reflux for 4 hours. After cooling to room temperature and drying under reduced pressure to obtain a solid, the solid was dissolved in methanol, and diethyl ether was added to precipitate crystals. The crystals were taken and taken as white crystals of 1- (aminomethyl) cyclohexanecarboxylic acid. Acid methyl hydrochloride 6.7g
(86.8%).

Methyl 1- (aminomethyl) cyclohexanecarboxylate hydrochloride (1.0 g) was dispersed in anhydrous dichloromethane (20 ml), and pyridine (1.4 ml) was stirred under stirring.
l) was added. After cooling to 0 ° C., trifluoroacetic anhydride (0.8 ml) was added dropwise over 5 minutes. After stirring at room temperature for 1 hour, the reaction solution was washed twice with 0.5 N hydrochloric acid (8 ml) and further with water (10 ml). The obtained dichloromethane solution was dried by a conventional method and then dried under reduced pressure to obtain pale yellow crystals of methyl 1-{(2,2,2-trifluoroacetylamino) methyl} cyclohexanecarboxylate.
1 g (66.5%) was obtained.

Sodium hydride (0.11 g) was dispersed in anhydrous N, N-dimethylformamide (20 ml),
Cooled to 0 ° C. Under stirring, a solution of methyl 1-{(2,2,2-trifluoroacetylamino) methyl} cyclohexanecarboxylate (1.1 g) in anhydrous N, N-dimethylformamide (10 ml) was added dropwise over 10 minutes, and the mixture was stirred at room temperature. 1
Stirred for hours. Cool to 0 ° C. and add methyl iodide (0.31
ml) of anhydrous N, N-dimethylformamide solution (10 ml).
ml) was added dropwise over 10 minutes and stirred at room temperature for 3 hours. The reaction solution was dropped into ice water (250 ml), and ethyl acetate (3
0 ml). The obtained ethyl acetate solution was dried by a conventional method, and then dried under reduced pressure to give a yellow liquid, 1-{[N
Methyl-(2,2,2-trifluoroacetyl) -N-methylamino] methyl} cyclohexanecarboxylate
0 g (86.4%) were obtained. This was mixed with water (25 ml) and methanol (63 ml), and potassium carbonate (2.8 g) was added with stirring. After 6 hours, insolubles were removed by filtration, and the filtrate was dried under reduced pressure. A 5% aqueous sodium hydroxide solution (30 ml) was added to the obtained solid, and the mixture was extracted three times with chloroform (20 ml). The obtained chloroform solution was dried by a usual method, and then dried under reduced pressure to obtain 0.32 g (53.7%) of pale yellow liquid methyl 1-((methylamino) methyl) cyclohexanecarboxylate. The NMR data of the obtained compound are shown below.

¹ H NMR (CDCl ₃ , δ ppm):
1.23-1.57 (8H, m), 2.04-2.10
(2H, m), 2.39 (3H, s), 2.61 (2
H, s), 3.72 (3H, s)

Methyl 1-((methylamino) methyl) cyclohexanecarboxylate (1.32 g) was prepared according to Preparation Example 2 described above.
Was reacted with 2,4,6-trimethylphenylacetic acid chloride to obtain 2.33 g (94%) of the target substance as a yellow liquid. The NMR data of the obtained compound are shown below.

¹ H NMR (CDCl ₃ , δ ppm):
1.26 (8H, m), 1.84 (2H, m), 2.2
0 (6H, s), 2.25 (3H, s), 3.10 (3
H, s), 3.56 (2H, s), 3.59 (2H,
s), 3.64 (3H, s), 6.84 (2H, s)

Production Example 11: Reaction route (20 → 1-2) 5-hydroxy-2-methyl-4- (2,4,6-trimethylphenyl) -2-azaspiro [5.5] -4-undecene- Synthesis of 3-one (Compound 57 of the present invention) 1-{[N-methyl-N-
(2,4,6-trimethylphenylacetyl) amino]
Ethyl methyl cyclohexanecarboxylate (2.33
g) was obtained in the same manner as in Production Example 7, to obtain 0.3 g (14.1%) of the target product as white crystals.

Production Example 12: Reaction route (1-2 → 1-4) 5-acetoxy-2-methyl-4- (2,4,6-trimethylphenyl) -2-azaspiro [5.5] -4- Synthesis of Undecene-3-one (Compound 58 of the Present Invention) Compound 57 of the present invention (0.4
g) was reacted with acetyl hydrochloride in the same manner as in Production Example 8 to obtain 0.11 g (24.2%) of the target compound as white crystals.

The compounds prepared according to any of the methods described in the above Preparation Examples are shown in Tables 1 and 2, and the physical properties of these compounds are shown in Tables 3 to 9. In Tables 1 and 2, Me is methyl, Et is ethyl, i-Pr is isopropyl, t-Bu is tert-butyl, Oct is octyl, Ph is phenyl, Ac is acetyl, cHex is cyclohexyl, and p-Cl- Ph represents parachlorophenyl.

[0103]

[Table 1]

[0104]

[Table 2]

[0105]

[Table 3]

[0106]

[Table 4]

[0107]

[Table 5]

[0108]

[Table 6]

[0109]

[Table 7]

[0110]

[Table 8]

[0111]

[Table 9]

Next, preparation examples will be shown. Parts are parts by weight,%
Indicates% by weight. Formulation Example 1: Emulsion 10 parts of each of the compounds of the present invention were mixed with Solvesso 150 45
And 35 parts of N-methylpyrrolidone, 10 parts of Solpol 3005X (Emulsifier manufactured by Toho Chemical Co., Ltd.) was added and mixed with stirring to obtain 10% emulsions of each.

Formulation Example 2: Wettable powder 20 parts of each of the compounds of the present invention are added to a mixture obtained by mixing 2 parts of sodium lauryl sulfate, 4 parts of sodium ligninsulfonate, 20 parts of synthetic hydrous silicon oxide fine powder and 54 parts of clay. Then, the mixture was stirred and mixed with a juice mixer to obtain a 20% wettable powder.

Formulation Example 3: Granules To 5 parts of each of the compounds of the present invention, 2 parts of sodium dodecylbenzenesulfonate, 10 parts of bentonite and clay 83
And mix well with stirring. An appropriate amount of water was added, further stirred, granulated by a granulator, and dried by ventilation to obtain 5% granules.

Formulation Example 4: Powder One part of each of the compounds of the present invention was dissolved in an appropriate amount of acetone.
To this were added 5 parts of synthetic hydrous silicon oxide fine powder, 0.3 parts of acidic isopropyl phosphate (PAP) and 93.7 parts of clay, followed by stirring and mixing with a juice mixer, and acetone was removed by evaporation to obtain a 1% powder. .

Formulation Example 5: Flowable Each 20 parts of the compound of the present invention and 1.5 parts of sorbitan triolate are mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and finely pulverized with a sand grinder (particle size). Then, 40 parts of an aqueous solution containing 0.05 parts of xanthan gum and 0.1 parts of aluminum magnesium silicate are added thereto, and 10 parts of propylene glycol are further added, followed by stirring and mixing, and a 20% suspension in water. I got Next, Test Examples show that the compound of the present invention is useful as an active ingredient of acaricide, insecticide and herbicide.

Test Example 1: Insecticidal test against spider mite A non-woven fabric (4.5 × 5.5 cm) was dropped into a plastic cup through a notch on the lid, and tap water was put into the cup and the lid was closed. A kidney bean leaf (approximately 3.5 × 4.5 cm) is placed on a non-woven fabric that has sufficiently absorbed water, and a kidney bean leaf infested with a spider mite (about 30 individuals) is further placed on the leaf, and placed in a thermostatic chamber at 25 ± 2 ° C. and 40% humidity. It was left still. Next, Sorpol 3 was added to a methanol solution of the compound of the present invention.
A 55 (manufactured by Toho Chemical) aqueous solution (100 ppm) was added to prepare a drug solution (200 ppm) of the compound of the present invention. next,
After spraying this chemical solution, air dry it and keep it in a constant temperature room (25 ± 2 ° C,
(Humidity: 50%), and 2 days after the treatment, the mortality of the spider mite was examined. As a result, the following compounds showed a mortality of 50% or more. Compound of the present invention: 10, 24, 25, 55, 59

Test Example 2: Insecticidal test on brown planthopper
2.5 ml (concentration: 20) of the compound of the present invention prepared in Test Example 1 on the soil surface of rice planted in a test pot (3 × 4 × 4 cm)
0 ppm) was added dropwise. After the chemical has penetrated the soil, cover with an acrylic cup and release the third instar larvae of the brown planthopper (approximately 30 individuals / cup) from the upper hole, cover the hole with absorbent cotton, and keep in a constant temperature room (25 ± 2 ° C, 50% humidity). And the mortality of the brown planthopper was investigated 7 days after the treatment. As a result, the following compounds showed a mortality of 50% or more. Compound of the present invention: 9,10,21,22,23,2
4,25,31,52,54,55,59

Test Example 3: Killing against peach aphid
An insect test non-woven fabric (4.5 × 5.5 cm) was dropped into the cup through a cut made in the lid of the plastic cup, and the cup was filled with tap water and covered. Leaf pieces of cabbage 2nd leaf (diameter 2c) with peach aphids parasitic on nonwoven fabric
m) was placed, covered with an acrylic cup, and allowed to stand in a thermostatic chamber at 25 ± 2 ° C. and 40% humidity. The next day, the drug solution (200 ppm) prepared in Test Example 1 was sprayed, air-dried, and allowed to stand in a constant temperature room (25 ± 2 ° C., humidity 50%) for 3 days, and the mortality of peach aphid was investigated. As a result, the following compounds showed a mortality of 50% or more. Compound of the present invention: 53

Test Example 4: Herbicidal activity test (soil treatment test and
Foliage treatment test) A predetermined amount of the compound of the present invention is dissolved in a small amount of acetone, and Tw
It was diluted with an aqueous solution of een 80 to prepare a drug solution of 2000 ppm. Paddy soil was filled in a 5 cm square pot, seeds of chickweed, kusanem, nobie, and crabgrass were sown in an appropriate amount, and lightly covered with soil. The soil treatment was performed immediately after sowing, and the foliage treatment was performed by growing test plants for 8 days in a room lit at room temperature of 23 ° C. for 16 hours.
In the foliage treatment, a chemical solution was sprayed.

The test dose is 0.4 g / m ^{2 in} terms of active ingredient.
, And 0.5 ml of the drug solution was supplied for both soil and foliage treatments. After transferring the soil-treated pot into a constant-temperature room at 23 ° C. and the foliage-treated pot into a glass greenhouse and growing the plants for 14 days, the plants were grown for 0 (no effect), 10, 20, 30, 40, 50 (complete withering). The herbicidal activity was evaluated in six steps, and the results were shown in Table 1.
0 and Table 11.

[0122]

[Table 10]

[0123]

[Table 11]

Test Example 5: Herbicidal activity test (flooding treatment test) A pot having a diameter of 8 cm was filled with paddy field soil, and water was added to make a flooded state. The next day, while seeds of oak, cyperacea and nobies were sown, tubers of Spodoptera litura were buried and then treated with a drug. The test dose is 0 in terms of active ingredient.
4 g / m ² , 1 m of the drug solution prepared in Test Example 4 above
1 was dropped on the flooded surface. After growing the plants in a glass greenhouse for 14 days after the treatment, 0 (no effect), 10, 20, 3
The herbicidal activity was evaluated in six stages of 0, 40, 50 (complete death), and the results are shown in Table 12.

[0125]

[Table 12]

[0126]

The compound of the present invention exhibits excellent insecticidal and acaricidal activity against many agricultural pests. In addition, the compounds of the present invention exhibit excellent herbicidal activity against many weeds that are agriculturally problematic. Therefore, the compound of the present invention can provide an effective pesticide.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 221/20 C07D 221/20 237/26 237/26 487/04 147 487/04 147

Claims (4)

[Claims] 1. A nitrogen-containing 6-membered ring dione derivative represented by the following general formula (1). Embedded image (Wherein, R ¹ and R ² may be the same or different and each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group optionally substituted by a halogen atom, or Represents a saturated or unsaturated divalent hydrocarbon group having 3 to 6 carbon atoms formed, wherein R ³ and R ⁴ may be the same or different, and have an alkyl group having 1 to 4 carbon atoms, A ring-forming divalent hydrocarbon group having 3 to 6 carbon atoms or a divalent oxygen atom together, wherein R ⁵ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, 8, an acyl group, a benzoyl group, an alkoxycarbonyl group having 1 to 4 carbon atoms, a phenoxycarbonyl group,-
A carbamoyl group represented by C (＝ O) N (R ⁹ ) R ¹⁰ (where R ⁹ and R ¹⁰ may be the same or different and represent an alkyl group having 1 to 4 carbon atoms); Numbers 1-4
Represents an alkylsulfonyl group. R ⁶ , R ⁷ , and R ⁸
May be the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom. Q is C
Represents H or N. n represents an integer of 1 to 3. ) 2. The nitrogen-containing 6-membered ring dione derivative according to claim 1, wherein Q in the general formula (1) is N. 3. The nitrogen-containing 6-membered ring dione derivative according to claim 1, wherein Q in the general formula (1) is CH. 4. An acaricide, an insecticide or a herbicide, comprising one or more of the nitrogen-containing 6-membered ring dione derivatives according to claim 1, 2 or 3 as an active ingredient.