JP2001055387A - Oxime derivative, production method and agrochemical - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound providing no fear of phytotoxicity to a useful plant body, having efficient activities for controlling plant disease, and useful as an agrochemical, especially a plant disease-controlling agent. SOLUTION: This new compound is the one of formula I (HetA is a group of formula II or the like; Q is H, a halogen or a lower alkyl; HetB is a group of formula III or the like; Y is H or a lower alkyl; HetC is a group of formula IV or the like; X is a lower alkoxy, cyano or the like; n is 0-3; with the proviso that the case in which HetA is a group of formula II or the like, HetB is a group of formula III or the like, and HetC is a group of formula IV is omitted), e.g. (E)-3-(3-methyl-1,2,5-thiadiazol-4-yl)pyridylmethanone O-(2-pyridyl)methyloxime. The compound of formula I is obtained by reacting a compound of formula V [e.g. 3-(3-methyl-1,2,5-thiadiazol-4-yl)pyridinemethanone oxime] with an alkylating agent (e.g. 2-picolyl chloride) in the presence of a base such as potassium carbonate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel oxime derivative, a pesticide containing the same as an active ingredient, particularly a plant disease controlling agent, a method for producing the same, and a novel hydroxyme derivative useful as an intermediate in the production method. About.

[0002]

2. Description of the Related Art An oxime derivative having an effect as a pesticide is disclosed, for example, in Japanese Patent Application Laid-Open No. 7-252242 according to the invention of the present inventors.
It is disclosed that 2,3-thiadiazole derivatives are effective as plant disease controlling agents. These compounds are
There is a need for the development of drugs that exhibit significant efficacy but are more effective in smaller doses.

[0003]

The problem to be solved by the present invention is to provide a novel oxime derivative which has no concern about phytotoxicity to useful plants and has a sufficient activity for controlling plant diseases, and using the same as an active ingredient. An object of the present invention is to provide a pesticide to be contained, especially a plant disease controlling agent, a method for producing the same, and a novel hydroxyme derivative useful as an intermediate in the production method.

[0004]

Means for Solving the Problems The present inventors have synthesized various novel oxime derivatives in order to solve the above-mentioned problems and have investigated their physiological activities.
It has been found that the oxime derivative represented by the general formula (1) has no concern about phytotoxicity to useful plants and exhibits particularly excellent plant disease control activity as an agrochemical, and also a method for producing the derivative and an intermediate of the production method. The present inventors have found a hydroxyme derivative represented by the general formula (2), and have completed the present invention. That is, the present invention

(1) The following general formula (1)

[0006]

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[Where the HetA is the following three formulas:

[0008]

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Wherein Q is a hydrogen atom, a halogen atom or a lower alkyl group, and R ¹ is a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a cycloalkyl group, a lower alkenyl group, Lower alkynyl group,
An aralkyl group, an aryl group or an aryl group substituted with one or more substituents selected from the group consisting of a halogen atom, a lower alkyl group and a lower alkoxy group;
² is a hydrogen atom or a lower alkyl group. Represents a group represented by any one of the above,

HetB is the following 9 formulas

[0011]

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Wherein Y is a hydrogen atom or a lower alkyl group, and R ³ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. Represents a group represented by any one of the above,

HetC is the following 9 formulas

[0014]

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Wherein R ⁴ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group, and X is a hydrogen atom, a halogen atom, a lower alkyl group. A lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom or a cyano group, Z is a hydrogen atom, a halogen atom or a lower alkyl group, and n
Is 0-3. ) Is a group represented by any one of the above.

However, HetA is the following two formulas

[0017]

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Wherein Q is a hydrogen atom, a halogen atom or a lower alkyl group, and R ¹ is a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a cycloalkyl group, a lower alkenyl group, Lower alkynyl group,
An aralkyl group, an aryl group or an aryl group substituted with one or more substituents selected from the group consisting of a halogen atom, a lower alkyl group and a lower alkoxy group;
² is a hydrogen atom or a lower alkyl group. ) Is a group represented by any one of the

HetB is the following three formulas

[0020]

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(Wherein, Y represents a hydrogen atom or a lower alkyl group), and HetC is represented by the following formula:

[0022]

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Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom or a cyano group, and n is 0 to 3). An oxime derivative represented by

(2) General formula (1)

[0025]

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[Wherein HetA is the following three formulas:

[0027]

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Wherein Q is a hydrogen atom, a halogen atom, or a lower alkyl group, and R ¹ is a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a cycloalkyl group, a lower alkenyl group, Lower alkynyl group,
An aralkyl group, an aryl group or an aryl group substituted with one or more substituents selected from the group consisting of a halogen atom, a lower alkyl group and a lower alkoxy group;
² is a hydrogen atom or a lower alkyl group. )), And HetB represents the following three formulas

[0029]

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(Wherein, Y represents a hydrogen atom or a lower alkyl group), and represents a group represented by any one of the following ring structures:

HetC is the following eight formulas

[0032]

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Wherein Z is a hydrogen atom, a halogen atom or a lower alkyl group, and R ⁴ is a hydrogen atom, a lower alkyl group or a lower alkoxy group which may have a silyl group. X is a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, and n is 0 to 3.). An oxime derivative represented by the formula:

(3) The following general formula (1)

[0035]

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[Wherein HetA is the following formula:

[0037]

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(Wherein Q is a hydrogen atom, a halogen atom, or a lower alkyl group; R ¹ is a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a cycloalkyl group, a lower alkenyl group, Lower alkynyl group,
An aralkyl group, an aryl group or an aryl group substituted with one or more substituents selected from the group consisting of a halogen atom, a lower alkyl group and a lower alkoxy group;
² is a hydrogen atom or a lower alkyl group. ) Represents a group represented by

HetB is the following three formulas

[0040]

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(Wherein, Y represents a hydrogen atom or a lower alkyl group), and represents a group represented by any one of the following ring structures:

HetC is given by the following formula:

[0043]

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Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom, or a cyano group; Is from 0 to 3.). An oxime derivative represented by the formula:

(4) The following general formula (1)

[0046]

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[Wherein HetA is the following three formulas:

[0048]

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Wherein Q is a hydrogen atom, a halogen atom or a lower alkyl group, and R ¹ is a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a cycloalkyl group, a lower alkenyl group, An alkynyl group, an aralkyl group, an aryl group or 1 selected from the group consisting of a halogen atom, a lower alkyl group and a lower alkoxy group
Aryl groups substituted with species or more substituents; a and, R ²
Is a hydrogen atom or a lower alkyl group. Any one of)
Represents a group represented by

HetB is the following six formulas

[0051]

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Wherein Y is a hydrogen atom or a lower alkyl group, and R ³ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. Represents a group represented by any one of the above,

HetC is represented by the following six formulas

[0054]

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(Wherein R ⁴ is a hydrogen atom or a lower alkyl group, and X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group or a halogen atom. Z is a hydrogen atom, a halogen atom or a lower alkyl group, and n is 0 to 3.). An oxime derivative represented by the formula:

(5) In the general formula (1), HetC is represented by the following three formulas

[0057]

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Wherein Z is a hydrogen atom, a halogen atom or a lower alkyl group, X is a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, and n is 0 or 1. The oxime derivative according to (2), which is a group represented by any one ring structure,

(6) In the general formula (1), HetA is represented by the following formula:

[0060]

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(Wherein Q is a hydrogen atom, a halogen atom, or a lower alkyl group, R ¹ is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom). Show,

HetC is represented by the following formula:

[0063]

Embedded image (In the formula, Z is a hydrogen atom.)
The oxime derivative according to (2),

(7) In the general formula (1), HetA is represented by the following formula:

[0065]

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Wherein Q is a hydrogen atom, a halogen atom or a lower alkyl group, R ¹ is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom. Show,

HetC is represented by the following formula:

[0068]

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(Wherein, X is a hydrogen atom or a halogen atom, and n is 0 or 1).
The oxime derivative according to (2),

(8) In the general formula (1), HetA is represented by the following formula:

[0071]

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Wherein Q is a hydrogen atom or a lower alkyl group, R ¹ is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom.

HetC has the following three formulas:

[0074]

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An oxime derivative according to (2), wherein X is a hydrogen atom or a halogen atom, Z is a hydrogen atom, and n is 0 or 1.

(9) In the general formula (1), HetA is represented by the following formula:

[0077]

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Wherein Q is a hydrogen atom or a lower alkyl group, R ¹ is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom.

HetC is represented by the following formula:

[0080]

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(Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, or a cyano group, and n is 0 to 3). An oxime derivative according to (3),

(10) In the general formula (1), HetC
Is the following formula

[0083]

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Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group or a lower alkoxy group substituted with a halogen atom; The oxime derivative according to (4), which is a group represented by the formula (11):
In the general formula (1), HetA is represented by the following formula:

[0085]

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Wherein Q is a hydrogen atom, a halogen atom or a lower alkyl group, R ¹ is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom. ,

HetB has the following three formulas

[0088]

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Wherein Y is a hydrogen atom or a lower alkyl group, and R ³ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. Is a group represented by any one of

HetC is represented by the following formula:

[0091]

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(Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkyl group substituted with a halogen atom, and n is 0 or 1). The oxime derivative according to 4),

(12) General formula (2)

[0094]

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[Wherein HetB is the following nine formulas:

[0096]

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Wherein Y is a hydrogen atom or a lower alkyl group, and R ³ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. Represents a group represented by any one of the above,

HetC is represented by the following nine formulas:

[0099]

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Wherein R ⁴ is a hydrogen atom, a lower alkyl group or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group, and X is a hydrogen atom, a halogen atom, a lower alkyl group. A lower alkyl group, a lower alkoxy group substituted with a halogen atom, or a lower alkoxy group substituted with a halogen atom; Z is a hydrogen atom, a halogen atom or a lower alkyl group; ) Is a group represented by any one of the above. The hydroxyme derivative represented by)

[However, the following compounds

[0102]

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Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom, or a cyano group; A hydrogen atom or a lower alkyl group, and n is 0 or 1.)

And the following compounds

[0105]

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And the following compounds

[0107]

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Is excluded. ].

(13) In the general formula (2), HetB
Is the following three equations

[0110]

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(Wherein, Y represents a hydrogen atom or a lower alkyl group), and represents a group represented by any one of the following ring structures:

HetC has the following eight formulas

[0113]

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Wherein Z is a hydrogen atom, a halogen atom or a lower alkyl group, and R ⁴ is a hydrogen atom, a lower alkyl group or a lower alkoxy group which may have a silyl group. X is a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, and n is 0 to 3.) (12) (14) In the general formula (2), HetB is represented by the following six formulas:

[0115]

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(Wherein Y is a hydrogen atom or a lower alkyl group, and R ³ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group) Represents a group represented by any one of the above,

HetC has the following six formulas

[0118]

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Wherein R ⁴ is a hydrogen atom or a lower alkyl group, and X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group or a halogen atom. (12) wherein Z is a hydrogen atom, a halogen atom or a lower alkyl group, and n is 0 to 3.) Derivative

(15) In the general formula (2), HetC
Is the following three equations

[0121]

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Wherein Z is a hydrogen atom, a halogen atom or a lower alkyl group, X is a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, and n is 0 or 1. The hydroxyme derivative according to (13), which is a group represented by any one of ring structures, (1)
6) In the general formula (2), HetC is the following formula

[0123]

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A hydroxyme derivative according to (13), which is a group represented by the formula: wherein Z is a hydrogen atom.

(17) In the general formula (2), HetC
Is the following formula

[0126]

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(Wherein X is a hydrogen atom or a halogen atom, and n is 0 or 1).
The hydroxyme derivative according to (13),

(18) In the general formula (2), HetC
Is the following formula

[0129]

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Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group or a lower alkoxy group substituted with a halogen atom; The hydroxyme derivative according to (14), which is a group represented by the formula:

(19) In the general formula (2), HetB
Is the following three equations

[0132]

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Wherein Y is a hydrogen atom or a lower alkyl group, and R ³ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. Is a group represented by any one of

HetC is represented by the following formula:

[0135]

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(Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkyl group substituted with a halogen atom, and n is 0 or 1). The hydroxyme derivative according to 14),

(20) The following general formula (3)

[0138]

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[Wherein HetB is the following nine formulas:

[0140]

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(Wherein Y is a hydrogen atom or a lower alkyl group, and R ³ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group) Represents a group represented by any one of the above,

HetC is the following nine formulas

[0143]

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(Wherein, R ⁴ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group, and X is a hydrogen atom, a halogen atom, a lower alkyl A lower alkyl group, a lower alkoxy group substituted with a halogen atom, or a lower alkoxy group substituted with a halogen atom; Z is a hydrogen atom, a halogen atom or a lower alkyl group; ) Is a group represented by any one of the above. A ketone compound represented by

[However, the following compounds

[0146]

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Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom or a cyano group, and Y is A hydrogen atom or a lower alkyl group, and n is 0 to 3.)

And the following compounds

[0149]

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And the following compounds

[0151]

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Is excluded. ] With an oximation agent, characterized by the following general formula (2):

[0153]

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(Wherein HetB and HetC are as defined in the general formula (3)).

(21) In the general formula (3), HetB
Is the following three equations

[0156]

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(Wherein Y represents a hydrogen atom or a lower alkyl group), and represents a group represented by any one of the following ring structures:

HetC is represented by the following eight formulas

[0159]

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Wherein Z is a hydrogen atom, a halogen atom, or a lower alkyl group, and R ⁴ is a hydrogen atom, a lower alkyl group, or a lower alkoxy group optionally having a silyl group. X is a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, and n is 0 to 3.) (20) A method for producing a hydroxyme derivative according to the above,

(22) In the general formula (3), HetB
Is the following six equations

[0162]

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Wherein Y is a hydrogen atom or a lower alkyl group, and R ³ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. Represents a group represented by any one of the above,

HetC has the following six formulas

[0165]

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Wherein R ⁴ is a hydrogen atom or a lower alkyl group, and X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group or a halogen atom. A lower alkoxy group, Z is a hydrogen atom, a halogen atom or a lower alkyl group, and n is 0 to 3.) Production method of

(23) In the general formula (3), HetC
Is the following three equations

[0168]

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Wherein Z is a hydrogen atom, a halogen atom or a lower alkyl group, X is a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, and n is 0 or 1. The method for producing a hydroxyme derivative according to (21), which is a group represented by any one ring structure,

(24) In the general formula (3), HetC
Is the following formula

Embedded image (In the formula, Z is a hydrogen atom.)
A method for producing the hydroxyme derivative according to (21),

(25) In the general formula (3), HetC
Is the following formula

[0172]

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(Wherein, X is a hydrogen atom or a halogen atom, and n is 0 or 1).
A method for producing the hydroxyme derivative according to (21),

(26) In the general formula (3), HetC
Is the following formula

[0175]

Embedded image

Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group or a lower alkoxy group substituted with a halogen atom, and n is 0 to 3 The method for producing a hydroxyme derivative according to (22), which is a group represented by the formula:

(27) In general formula (3), HetB
Is the following three equations

[0178]

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Wherein Y is a hydrogen atom or a lower alkyl group, and R ³ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. Is a group represented by any one of

HetC is represented by the following formula:

[0181]

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(Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkyl group substituted with a halogen atom, and n is 0 or 1). 22) The method for producing a hydroxyme derivative according to the above,

(28) The following general formula (2)

[0184]

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[Wherein HetB is the following nine formulas:

[0186]

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(Wherein Y is a hydrogen atom or a lower alkyl group, and R ³ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group) Represents a group represented by any one of the above,

HetC is represented by the following nine formulas:

[0189]

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(Wherein R ⁴ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group, and X is a hydrogen atom, a halogen atom, a lower alkyl A lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom or a cyano group, Z is a hydrogen atom, a halogen atom or a lower alkyl group, and n
Is 0-3. ) Is a group represented by any one of the above.

Here, HetA is represented by the following two formulas.

[0192]

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Wherein Q is a hydrogen atom, a halogen atom, or a lower alkyl group, and R ¹ is a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a cycloalkyl group, a lower alkenyl group, Lower alkynyl group,
An aralkyl group, an aryl group or an aryl group substituted with one or more substituents selected from the group consisting of a halogen atom, a lower alkyl group and a lower alkoxy group;
² is a hydrogen atom or a lower alkyl group. ) Is a group represented by any one of the

HetB has the following three formulas

[0195]

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(Wherein Y represents a hydrogen atom or a lower alkyl group), and HetC is a group represented by the following formula:

[0197]

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Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom or a cyano group; 0 to 3). ] To the hydroxyme derivative represented by the following general formula (4):

[0199]

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[Wherein HetA is represented by the following three formulas:

[0201]

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Wherein Q is a hydrogen atom, a halogen atom, or a lower alkyl group, and R ¹ is a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a cycloalkyl group, a lower alkenyl group, Lower alkynyl group,
An aralkyl group, an aryl group or an aryl group substituted with one or more substituents selected from the group consisting of a halogen atom, a lower alkyl group and a lower alkoxy group;
² is a hydrogen atom or a lower alkyl group. ) Represents a group represented by any one of the above, and L represents a leaving group. Wherein the alkylating agent represented by the general formula (1) is reacted in the presence of a base.

[0203]

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(Wherein HetA is as defined in the general formula (4), and HetB and HetC are as defined in the general formula (2)).

(29) In the general formula (2), HetB
Is the following three equations

[0206]

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(Wherein, Y represents a hydrogen atom or a lower alkyl group), and represents a group represented by any one of the following ring structures:

HetC is the following eight formulas

[0209]

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Wherein Z is a hydrogen atom, a halogen atom, or a lower alkyl group, and R ⁴ is a hydrogen atom, a lower alkyl group, or a lower alkoxy group optionally having a silyl group. X is a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, and n is 0 to 3.) (28) A method for producing the oxime derivative according to

(30) In the general formula (2), HetB
Is the following three equations

[0212]

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(Wherein, Y represents a hydrogen atom or a lower alkyl group), and represents a group represented by any one of the following ring structures:

HetC is represented by the following formula:

[0215]

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Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom, or a cyano group; Is from 0 to 3.), and in the general formula (4), He is
tA is the following formula

[0219]

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(Wherein Q is a hydrogen atom, a halogen atom, or a lower alkyl group; R ¹ is a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a cycloalkyl group, a lower alkenyl group, Lower alkynyl group,
An aralkyl group, an aryl group or an aryl group substituted with one or more substituents selected from the group consisting of a halogen atom, a lower alkyl group and a lower alkoxy group;
² is a hydrogen atom or a lower alkyl group. (28) The method for producing an oxime derivative according to (28), wherein in the general formula (2), HetB is a group represented by the following six formulas:

[0219]

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In the formula, Y represents a hydrogen atom or a lower alkyl group, and R ³ represents a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. Represents a group represented by any one of the above,

HetC has the following six formulas

[0222]

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Wherein R ⁴ is a hydrogen atom or a lower alkyl group, and X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group or a halogen atom. Oxime according to (28), wherein Z is a hydrogen atom, a halogen atom or a lower alkyl group, and n is 0 to 3. A method for producing a derivative,

(32) In the general formula (2), HetC
Is the following three equations

[0225]

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Wherein Z is a hydrogen atom, a halogen atom or a lower alkyl group, X is a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, and n is 0 or 1. The method for producing an oxime derivative according to (29), which is a group represented by any one ring structure,

(33) In the general formula (2), HetC
Is the following formula

[0228]

Embedded image

(Wherein Z is a hydrogen atom).

In the general formula (4), HetA is represented by the following formula:

[0231]

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(Wherein Q is a hydrogen atom, a halogen atom or a lower alkyl group, R ¹ is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom). A method for producing the oxime derivative according to (29),

(34) In the general formula (2), HetC
Is the following formula

[0234]

Embedded image

Wherein X is a hydrogen atom or a halogen atom, and n is 0 or 1. In the general formula (4), HetA is represented by the following formula:

[0236]

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(Wherein Q is a hydrogen atom, a halogen atom or a lower alkyl group, R ¹ is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom). A method for producing the oxime derivative according to (29),

(35) In the general formula (2), HetC
Is the following three equations

[0239]

Embedded image

(Wherein X is a hydrogen atom or a halogen atom, Z is a hydrogen atom, and n is 0 or 1).

In the general formula (4), HetA is represented by the following formula:

[0242]

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(Wherein Q is a hydrogen atom or a lower alkyl group, R ¹ is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom).
A method for producing the oxime derivative according to (29),

(36) In the general formula (2), HetC
Is the following formula

[0245]

Embedded image

(Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, or a cyano group, and n is 0 to 3). Yes,

In the general formula (4), HetA is represented by the following formula:

[0248]

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(Wherein Q is a hydrogen atom or a lower alkyl group, R ¹ is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom).
(30) The method for producing an oxime derivative according to (30),

(37) In the general formula (2), HetC
Is the following formula

[0251]

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(Wherein, X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group or a lower alkoxy group substituted with a halogen atom, and n is 0 to 3 The method for producing an oxime derivative according to (31), which is a group represented by:

(38) In the general formula (2), HetB
Is the following three equations

[0254]

Embedded image

Wherein Y is a hydrogen atom or a lower alkyl group, and R ³ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. Is a group represented by any one of

HetC is represented by the following formula:

[0257]

Embedded image

(Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkyl group substituted with a halogen atom, and n is 0 or 1).

In the general formula (4), HetA is represented by the following formula:

[0260]

Embedded image

(Wherein Q is a hydrogen atom, a halogen atom or a lower alkyl group, R ¹ is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom). , A method for producing an oxime derivative according to (31),

(39) A pesticide containing the oxime derivative according to (1) to (11) as an active ingredient, (40)
(1) A plant disease controlling agent comprising the oxime derivative according to (11) as an active ingredient, (41) a plant disease controlling agent according to (40), which is effective against a plant disease caused by a filamentous fungus. Is what you do.

DETAILED DESCRIPTION OF THE INVENTION The general formula (1) of the present invention

[0263]

Embedded image

HetA of the oxime derivative represented by the following three formulas

[0265]

Embedded image

(Wherein Q is a hydrogen atom, a halogen atom or a lower alkyl group, R ¹ is a hydrogen atom, a lower alkyl group,
One or more substituents selected from the group consisting of a lower alkyl group, a cycloalkyl group, a lower alkenyl group, a lower alkynyl group, an aralkyl group, an aryl group, and a halogen atom, a lower alkyl group and a lower alkoxy group substituted with a halogen atom; R ² is a hydrogen atom or a lower alkyl group. A) represents a group represented by any one of the above.

The halogen atom represented by Q in HetA includes a fluorine atom, a chlorine atom and a bromine atom, and a chlorine atom is preferred. The lower alkyl group represented by Q of HetA includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s
Examples thereof include a linear or branched lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as an ec-butyl group, and specifically, a methyl group is particularly preferable. The substitution position of Q may be any position on the carbon atom. Preferred as Q is
When HetA is a thiazole ring, a hydrogen atom, a chlorine atom and a methyl group are particularly preferred, and when HetA is a pyridine ring, a hydrogen atom is particularly preferred.

The lower alkyl group represented by R ^{1 of} HetA includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, an n-butyl group, an isobutyl group, a sec-butyl group and an n-butyl group. Examples thereof include a linear or branched lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as a pentyl group, a neopentyl group, a 1,1-dimethylpropyl group, and a 1-ethylpropyl group. Is methyl, ethyl, n-propyl, isopropyl, te
rt-butyl group, n-butyl group, isobutyl group, sec
-Butyl groups are particularly preferred.

Examples of the lower alkyl group substituted by a halogen atom represented by R ^{1 of} HetA include a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a trifluoromethyl group,
Pentafluoroethyl group, heptafluoropropyl group,
Examples thereof include a halogen-substituted lower alkyl group having 1 to 3 carbon atoms such as a chlorodifluoromethyl group and a 1-bromo-1-methylethyl group.

Examples of the cycloalkyl group represented by R ^{1 of} HetA include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like.
To 6, and more specifically, cyclopropyl, cyclopentyl, and cyclohexyl.

Examples of the lower alkenyl group represented by R ^{1 of} HetA include a linear or branched lower alkenyl group having 2 to 4 carbon atoms such as a vinyl group, an allyl group, a 1-propenyl group and a 1-methyl-2-propenyl group. Is mentioned.

The lower alkynyl group represented by R ^{1 of} HetA includes a lower alkynyl group having 1 to 4 carbon atoms such as an ethynyl group, a propargyl group and a 2-butynyl group.

Examples of the aralkyl group represented by R ^{1 of} HetA include a benzyl group and a phenethyl group. The aryl group represented by R ^{1 of} HetA includes a phenyl group.

R ^{1 of} HetA represents: an aryl group substituted with at least one substituent selected from the group consisting of a halogen atom, a lower alkyl group and a lower alkoxy group; 2-chlorophenyl group, 3-chlorophenyl group , 4-chlorophenyl group, 2,4-dichlorophenyl group, 3,4
-Dichlorophenyl group, 3,5-dichlorophenyl group,
2,6-dichlorophenyl group, 2,3-dichlorophenyl group, 2,4,6-trichlorophenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 3,4-
Difluorophenyl group, 3,5-difluorophenyl group, 2,6-difluorophenyl group,

2,3-difluorophenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethyl Phenyl group, 2,6-
Dimethylphenyl group, 2,4-dimethylphenyl group,
2,4,6-trimethylphenyl group, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl Group, 2-trifluoromethoxyphenyl group, 3-
Trifluoromethoxyphenyl group, 4-trifluoromethoxyphenyl group, 2-chlorodifluoromethoxyphenyl group, 3-chlorodifluoromethoxyphenyl group, 4
-Chlorodifluoromethoxyphenyl group and the like,
More specifically, 4-methylphenyl and 4-chlorophenyl are particularly preferred.

[0276] hydrogen atoms as R ¹ in HetA,. 1 to carbon atoms
A straight-chain or branched lower alkyl group having 6 or a cycloalkyl group having 3 to 6 carbon atoms is preferable.

The lower alkyl group represented by R ^{2 of} HetA includes a methyl group, an ethyl group and the like having 1 to 6, preferably 1 to 4 carbon atoms, and more specifically, a methyl group is preferred. Particularly preferred as R ² is a hydrogen atom.

In the general formulas (1), (2) and (3), HetB is the following nine formulas:

[0279]

Embedded image

(Wherein, Y is a hydrogen atom or a lower alkyl group, and R ³ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with an alkoxy group which may have a silyl group.) Represented by any one of the ring structures,
1,2,3-thiadiazol-4-yl group, 1,2,5
A thiadiazol-3-yl group, or 1,2,5-
It represents an oxadiazol-3-yl group or a lower alkyl group-substituted derivative thereof, or an optionally substituted 5- to 6-membered nitrogen-containing aromatic heterocycle.

The lower alkyl group represented by Y in HetB includes a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group and an isopropyl group. More specifically, a methyl group is preferable.

The lower alkyl group represented by R ^{3 of} HetB includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group having 1 to 6 carbon atoms, preferably 1 to 6 carbon atoms.
4 lower alkyl groups, more preferably a methyl group.

The lower alkyl group substituted by a lower alkoxy group which may have a silyl group represented by R ^{3 of} HetB refers to a lower alkyl group substituted by a lower alkoxy group having 1 to 4 carbon atoms and having 1 to 6 carbon atoms. Preferably represents a lower alkyl group having 1 to 4 carbon atoms, or 1 to 6 carbon atoms substituted with a lower alkoxy group having 1 to 4 carbon atoms having a silyl group, preferably 1 to 4 carbon atoms.
Means a lower alkyl group. However, the silyl group means a silyl group having 1 to 3 hydrogen atoms or lower alkyl groups having 1 to 4 carbon atoms as substituents. Specifically, a methoxymethyl group, a 2-methoxyethyl group, a 1-ethoxyethyl group, a 2-trimethylsilylethoxymethyl group,
t-butoxymethyl group, 3-methoxypropyl group, 1-
(Isopropoxy) ethyl group, 2-ethoxyethyl group,
It is a 1-methyl-1-methoxyethyl group, a 3-ethoxypropyl group or a benzoyloxymethyl group, more preferably a 2-trimethylsilylethoxymethyl group.

As R ³ , a methyl group and a 2-trimethylsilylethoxymethyl group are particularly preferred.

In the general formulas (1), (2) and (3), HetC is the following nine formulas:

[0286]

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Wherein R ⁴ is a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a lower alkoxy group which may have an acyl group or a benzoyloxymethyl group, and X is a hydrogen atom, a halogen atom An atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom or a cyano group; Z is a hydrogen atom, a halogen atom or a lower alkyl group; Is an integer of 0 to 3.)
A group represented by any one of the ring structures.

Here, the lower alkyl group represented by R ⁴ of HetC includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group having 1 to 6 carbon atoms, preferably 1 to 6 carbon atoms.
4 lower alkyl groups, and more preferably a methyl group. The lower alkyl group substituted by a lower alkoxy group which may have a silyl group represented by R ^{4 of} HetC is a C 1 to C 6, preferably substituted by a lower alkoxy group having 1 to 4 carbon atoms, preferably It means a lower alkyl group having 1 to 4 carbon atoms, or a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, which is substituted by a lower alkoxy group having 1 to 4 carbon atoms having a silyl group. However, the term "silyl group" includes a silyl group having 1 to 3 hydrogen atoms or lower alkyl groups having 1 to 4 carbon atoms as substituents. Specifically, a methoxymethyl group, a 2-methoxyethyl group, a 1-ethoxyethyl group, a 2-trimethylsilylethoxymethyl group, a tert-butoxymethyl group,
Examples include a methoxypropyl group, a 1- (isopropoxy) ethyl group, a 2-ethoxyethyl group, a 1-methyl-1-methoxyethyl group, and a 3-ethoxypropyl group, and more preferably a 2-trimethylsilylethoxymethyl group. .

As R ⁴ of HetC, a methyl group and a 2-trimethylsilylethoxymethyl group are preferable, and a 2-trimethylsilylethoxymethyl group is particularly preferable.

Examples of the halogen atom represented by X in HetC include a chlorine atom, a bromine atom and a fluorine atom, preferably a chlorine atom or a fluorine atom.

The lower alkyl group represented by X in HetC includes a methyl group, an ethyl group and the like having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
And a methyl group is particularly preferred.

Examples of the lower alkyl group substituted by the halogen atom represented by X in HetC include a trifluoromethyl group, a difluoromethyl group and a difluorochloromethyl group, and further preferably a trifluoromethyl group.

The lower alkoxy group represented by X of HetC includes a lower alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group and an n-propoxy group, and a methoxy group is more preferable.

Examples of the lower alkoxy group substituted by the halogen atom represented by X in HetC include a difluoromethoxy group and a trifluoromethoxy group.

N is an integer not greater than 3;
Indicates an integer of 3. When n is 2 or 3, X may be the same or different.

Preferred as X in HetC are a hydrogen atom, a lower alkyl group having 1 to 2 carbon atoms, a fluoroalkyl group having 1 carbon atom or a halogen atom, and particularly preferably n is 0 or 1. Examples of the halogen atom represented by Z in HetC include a chlorine atom, a bromine atom and a fluorine atom, and a chlorine atom is preferred. The lower alkyl group represented by Z in HetC includes a methyl group, an ethyl group, etc.
To 6, preferably 1 to 4 lower alkyl groups,
More specifically, a methyl group is preferred.

As Z of HetC, a hydrogen atom or a chlorine atom is preferable, and a hydrogen atom is particularly preferable. The substitution position of the substituents X and Z may be on any carbon atom.

The general formula (4) of the present invention

[0299]

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HetA of the alkylating agent represented by the formula is the same as defined in the general formula (1). Examples of the leaving group L include a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, and a sulfonyloxy group such as a methanesulfonyloxy group, a p-toluenesulfonyloxy group, and a trifluoromethanesulfonyloxy group. It is a halogen atom such as a chlorine atom and a bromine atom.

In the present invention, in the general formula (1), He
tA is the following two formulas

[0302]

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(Wherein Q is a hydrogen atom, a halogen atom, or a lower alkyl group, and R ¹ is a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a cycloalkyl group, a lower alkenyl group, Lower alkynyl group,
An aralkyl group, an aryl group or an aryl group substituted with one or more substituents selected from the group consisting of a halogen atom, a lower alkyl group and a lower alkoxy group;
² is a hydrogen atom or a lower alkyl group. HetB is a group represented by any one of the following three formulas

[0304]

Embedded image

(Wherein Y represents a hydrogen atom or a lower alkyl group), and HetC is a group represented by the following formula:

[0306]

Embedded image

Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom or a cyano group, and n is 0 to 3) is excluded.

Further, in the general formula (2), the following compound

[0309]

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(Where X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom or a cyano group, and Y is A hydrogen atom or a lower alkyl group, and n is 0 or 1.)

[0311]

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And the following compounds

[0313]

Embedded image

Is excluded.

In the general formula (2), HetB is represented by the following 3
Two expressions

[0316]

Embedded image

(Wherein, Y represents a hydrogen atom or a lower alkyl group), and represents a group represented by any one of the following ring structures;

Embedded image

(In the formula, X is a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom, or a cyano group; 3) is represented by the general formula (5).

The lower alkyl group of Y in HetB in the general formula (5) includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like, having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
Lower alkyl group of the following, more specifically,
A methyl group is preferably exemplified.

The halogen atom of X in the general formula (5) includes a chlorine atom, a bromine atom and a fluorine atom.
Examples of the lower alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group and a sec-butyl group.
To 6, preferably 1 to 4, linear or branched lower alkyl groups. Examples of the lower alkyl group substituted with a halogen atom include a trifluoromethyl group, a difluoromethyl group, and a difluorochloromethyl group. Can be

The lower alkoxy group represented by X in the formula (5) includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy. Examples thereof include lower alkoxy groups having 1 to 4 carbon atoms, and examples of the lower alkoxy group substituted with a halogen atom include a difluoromethoxy group and a trifluoromethoxy group.

The substitution position of X in the general formula (5) is not particularly limited, and n represents an integer of 1 to 3. When n is 2 or 3, X may be the same or different. X in general formula (5)
Are preferably a lower alkyl group having 1 to 2 carbon atoms, a fluoroalkyl group having 1 carbon atom, a halogen atom or a cyano group, and particularly preferably a trifluoromethyl group, a fluorine atom or a chlorine atom.

The stereostructure of the oxime moiety present in the oxime derivative represented by the general formula (1) and the oxime derivative represented by the general formula (2) includes (E) -form and (Z) -form. Are included in the present invention. Usually, the synthetic product is obtained as a mixture of the (E) form and the (Z) form, and these can be isolated from each other by separation and purification.

In the oxime derivatives represented by the general formulas (1) and (2), the (Z) -form is more excellent in controlling plant diseases than the (E) -form, but the (Z) -form is also subject to natural environment. In this case, the compound changes to the (E) form by light or the like, and exists as a mixture at a certain ratio of the (E) form and the (Z) form. The stabilized ratio between the (E) -form and the (Z) -form differs for each compound.

The method for producing the oxime derivative represented by the general formula (1) in the present invention will be described. General formula (1)
Can be produced, for example, by the following method, but the production method of the compound is not limited to these production methods. The following general formula (3)

[0326]

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(Wherein HetB and HetC are the same as those defined in the general formula (1)) and an oximation agent is reacted with a ketone compound represented by the following general formula (2)

[0328]

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A hydroxyme derivative represented by the following general formula (4)

[0330]

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The oxime derivative represented by the general formula (1) can be produced by reacting the alkylating agent represented by the formula (1) in the presence of a base.

The ketone compound represented by the general formula (3) is
Raw materials used in the production method of the present invention, for example, ethyl 5-methyl (1,2,3-thiadiazoyl-4-yl) carboxylate (Acta Pharm. Suecica, Vol. 10, p. 297 (197
3)), 5-methyl (1,2,3-thiadiazoyl-4-)
Il) Carboxylic acid (Acta Pharm. Suecica, 10, 297
(1973)), 3-formyl-4-methyl-1,2,5-oxadiazole (J. Org. Chem., 32, 3865 (196
7)), 3-formyl-4-methyl-1,2,5-thiadiazole (Heterocyclic Chem., 22, 325 (1985))
And other methods described in the literature (eg, New Experimental Chemistry Course 1
Synthesis and reaction of four organic compounds II, 1997, Maruzen Co., Ltd.
CA Buehler, DE Pearson, Survey of Organic Sy
ntheses, John Wiley and Sons, New York, 532, 197
6) can be synthesized.

Examples of the oximation agent used in this reaction include hydroxylamine and hydroxylamine salts such as hydroxylamine hydrochloride, hydroxylamine sulfate and hydroxylamine acetate.
The amount of the oximation agent used is usually in the range of 1 to 10 moles, preferably 1 to 2 moles, relative to the ketone.

When a hydroxylamine salt is used, the reaction is carried out in the presence of a base. As the base, for example, an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, pyridine, triethylamine, tripropylamine, tributylamine, diisopropylethylamine,
Trioctylamine, N, N-dimethylaniline, N-
Organic bases such as methylpyrrolidine, N-methylmorpholine, N-ethylmorpholine, and 1,8-diazabicyclo [5.4.0] undec-7-ene are exemplified. The amount of the base used is at least equimolar to the hydroxylamine salt.

This reaction can be carried out in the presence or absence of a solvent. The solvent that can be used is not particularly limited as long as it is inert to the reaction.For example, pentane, hexane, heptane, petroleum ether, benzene, toluene,
Hydrocarbon solvents such as xylene, dichloromethane, 1,2
-Halogenated solvents such as dichloroethane, chloroform, carbon tetrachloride, methanol, ethanol, propanol,
2-propanol, alcohol solvents such as trifluoroethanol, acetonitrile, nitrile solvents such as propionnitrile, diethyl ether, diisopropyl ether, dimethoxyethane, dioxane, tetrahydrofuran, ether solvents such as diglyme,

N, N-dimethylformamide, N, N-
Non-protic polar solvents such as dimethylacetamide and dimethylsulfoxide, water, and a mixed solvent system of two or more thereof, preferably, methanol, ethanol, dioxane, tetrahydrofuran and the like, and a mixed solvent of these solvents and water is there. The proportion of water is between 1% and 99%, preferably between 10% and 90%.

The temperature of this reaction is in the range of -78 to 250 ° C, preferably in the range of -10 to 120 ° C. The reaction time varies depending on the amount of the reaction reagent and the reaction temperature, but ranges from 30 minutes to 24 hours. After the completion of the reaction, the product can be easily purified by distillation, recrystallization or column chromatography if necessary.

In the reaction between the hydroxyme derivative (2) and the alkylating agent (4) in the presence of a base, the amount of the alkylating agent to be used is generally 1 to 5 mol, preferably 1 to 2 mol. Is a mole.

As the base, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Inorganic bases such as cesium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate, pyridine, triethylamine, tripropylamine, tributylamine, diisopropylethylamine, trioctylamine, N, N-dimethylaniline, N-methylpyrrolidine, N-methylmorpholine; N
-Ethyl morpholine,

Organic bases such as 1,8-diazabicyclo [5.4.0] undec-7-ene; alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide and sodium isopentanate; sodium hydride And alkali metal hydrides such as potassium hydride, and organic lithiums such as methyllithium, butyllithium, and phenyllithium. The amount of the base to be used is generally 1 to 10 mol, preferably 1 to 3 mol, per mol of the hydroxyme derivative.

This reaction can be carried out in the presence or absence of a solvent. The solvent that can be used is not particularly limited as long as it is inert to the reaction.For example, pentane, hexane, heptane, petroleum ether, benzene, toluene,
Hydrocarbon solvents such as xylene, dichloromethane, 1,2
-Halogenated solvents such as dichloroethane, chloroform, carbon tetrachloride, methanol, ethanol, propanol,
2-propanol, alcohol solvents such as trifluoroethanol, acetonitrile, nitrile solvents such as propionnitrile, diethyl ether, diisopropyl ether, dimethoxyethane, dioxane, tetrahydrofuran, ether solvents such as diglyme,

N, N-dimethylformamide, N, N-
Examples include aprotic polar solvents such as dimethylacetamide and dimethylsulfoxide, or a mixed solvent system of two or more thereof. Preferably, dioxane, tetrahydrofuran, acetonitrile, N, N-dimethylformamide,
N, N-dimethylacetamide, dimethylsulfoxide and the like.

The reaction temperature is in the range of -78 to 250 ° C, preferably in the range of -10 to 100 ° C. The reaction time varies depending on the amount of the reaction reagent and the reaction temperature, but ranges from 30 minutes to 24 hours. After the completion of the reaction, the product can be easily purified by distillation, recrystallization or column chromatography if necessary.

The general formula (1) produced by the above method
Illustrating the specific structure of the oxime derivative represented by
The results are shown in Tables 1 to 60. However, in the table, HetA, Het
B, HetC, R ¹ , R ² , R ³ , R ⁴ , Q, X, Y, Z and n correspond to the definition in the general formula (1), Me is a methyl group, Et is an ethyl group, and Pr is Propyl group, Bu is butyl group, Ph
Represents a phenyl group, respectively.

[0345]

[Table 1]

[0346]

[Table 2]

[0347]

[Table 3]

[0348]

[Table 4]

[0349]

[Table 5]

[0350]

[Table 6]

[0351]

[Table 7]

[0352]

[Table 8]

[0353]

[Table 9]

[0354]

[Table 10]

[0355]

[Table 11]

[0356]

[Table 12]

[0357]

[Table 13]

[0358]

[Table 14]

[0359]

[Table 15]

[0360]

[Table 16]

[0361]

[Table 17]

[0362]

[Table 18]

[0363]

[Table 19]

[0364]

[Table 20]

[0365]

[Table 21]

[0366]

[Table 22]

[0367]

[Table 23]

[0368]

[Table 24]

[0369]

[Table 25]

[0370]

[Table 26]

[0371]

[Table 27]

[0372]

[Table 28]

[0373]

[Table 29]

[0374]

[Table 30]

[0375]

[Table 31]

[0376]

[Table 32]

[0377]

[Table 33]

[0378]

[Table 34]

[0379]

[Table 35]

[0380]

[Table 36]

[0381]

[Table 37]

[0382]

[Table 38]

[0383]

[Table 39]

[0384]

[Table 40]

[0385]

[Table 41]

[0386]

[Table 42]

[0387]

[Table 43]

[0388]

[Table 44]

[0389]

[Table 45]

[0390]

[Table 46]

[0391]

[Table 47]

[0392]

[Table 48]

[0393]

[Table 49]

[0394]

[Table 50]

[0395]

[Table 51]

[0396]

[Table 52]

[0397]

[Table 53]

[0398]

[Table 54]

[0399]

[Table 55]

[0400]

[Table 56]

[0401]

[Table 57]

[0402]

[Table 58]

[0403]

[Table 59]

[0404]

[Table 60]

Further, Table 61 to Table 71 show specific structures of the hydroxyme derivative represented by the general formula (2) produced by the above method. However, He in the table
tB, HetC, R ³ , R ⁴ , X, Y, Z and n correspond to the definitions in the general formula (2), Me is a methyl group, Et is an ethyl group, Pr is a propyl group, Bu is a butyl group, Ph Represents a phenyl group, respectively.

[0406]

[Table 61]

[0407]

[Table 62]

[0408]

[Table 63]

[0409]

[Table 64]

[0410]

[Table 65]

[0411]

[Table 66]

[0412]

[Table 67]

[0413]

[Table 68]

[0414]

[Table 69]

[0415]

[Table 70]

[0416]

[Table 71]

The pesticides containing the oxime derivative of the present invention as an active ingredient, particularly plant disease controlling agents, are effective against various plant diseases caused by phytopathogenic viruses, bacteria and fungi, and particularly against various plant diseases caused by filamentous fungi. It is effective for. Plant diseases caused by filamentous fungi include a wide range of plant diseases caused by oomycetes (Oomycetes) and blast fungi (Pyricul
aria oryzae) and the like.

[0418] These are downy mildew (dow) on various plants.
ny mildew) and plague (late blight or Phytophthora rot et
c.), for example, downy mildew of grape ( Plasmopara viti
cola ), downy mildew of cucumber ( Pseudoperonospora cubensi)
s ), dead blight ( Phytophthora melonis ), tomato gray blight ( Phytophthora capsici ), plague ( Phytophtho
ra infestans ), downy mildew of cruciferous vegetables ( Peronospor)
a brassicae ), downy mildew on green onion ( Peronospora destructo)
r ), spinach downy mildew ( Peronospora spinacia)
e ), soybean downy mildew ( Peronospora manshurica ),

Downy mildew of broad bean ( Peronospora vicia)
e ), the plague of tobacco ( Phytophthora nicotianae var. nic)
otianae ), Potato Blight ( Phytophthora infestan)
s ), downy mildew of hops ( Pseudoperonospora humuli ),
Pineapple plague ( Phytophthora cinnamomi ), Bell pepper plague ( Phytophthora capsici ), Strawberry root rot ( Phytophthora fragariae ), Damping on various crops ( Pythophthora fragariae )
bacillus ), benthgrass red blight ( Pythium a
phanidermatum ) and a wide range of plant diseases caused by oomycetes and rice blast ( Pyricularia oryzae )
It has an excellent control effect on

[0420] Furthermore, cucumber powdery mildew ( Sphaerotheca)
Fuliginea ), Cucumber seedling blight ( Rhizoctonia solan)
i ), apple spot leaf blight ( Alternaria mali ), cucumber vine rot ( Fusarium oxysporum ) are also effective.

Although the present drug can use the active ingredient alone, it is generally known and used as solid and liquid carriers used in the preparation of agricultural chemicals, as well as dispersants, diluents, emulsifiers, spreading agents, and the like. It can be mixed with an auxiliary agent such as a thickener and formulated into a dosage form such as a wettable powder, a liquid preparation, an oil preparation, a powder preparation, a granule preparation, a sol preparation (flowable) and the like.

Examples of the solid and liquid carriers include talc, clay, bentonite, kaolin, diatomaceous earth, montmorillonite, mica, vermiculite, gypsum, calcium carbonate, white carbon, wood powder, starch, alumina, silicate, and saccharide polymer. , Waxes, water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, ethylene glycol, benzyl alcohol, etc.), petroleum fractions (petroleum ether, kerosene, solvent naphtha, etc.), Aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.),

Aromatic hydrocarbons (benzene, toluene,
Xylene, ethylbenzene, chlorobenzene, cumene,
Methyl naphthalene, etc.), halogenated hydrocarbons (chloroform, dichloromethane, etc.), ethers (isopropyl ether, ethylene oxide, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, etc.), esters (ethyl acetate, Butyl acetate, ethylene glycol acetate, amyl acetate, etc.), acid amides (dimethylformamide, dimethylacetanilide, etc.), nitriles (acetonitrile, propionitrile, acrylonitrile, etc.), sulfoxides (dimethylsulfoxide, etc.), alcohol ethers ( Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.).

Examples of the auxiliary include nonionic surfactants (polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, etc.),
Anionic surfactants (alkylbenzenesulfonate, alkylsulfosuccinate, polyoxyethylene alkylsulfate, arylsulfonate, etc.), and cationic surfactants (alkylamines, polyoxyethylenealkylamines, quaternary) Ammonium salts), amphoteric surfactants (alkylaminoethylglycine, alkyldimethylbetaine, etc.), polyvinyl alcohol, hydroxypropylcellulose, carboxymethylcellulose, gum arabic, tragacanth gum, xanthan gum, polyvinyl acetate, gelatin, casein, sodium alginate, etc. Is mentioned.

Further, the present medicament can be used by mixing with various known and commonly used agricultural and horticultural fungicides, herbicides, plant growth regulators, pesticides such as insecticides, acaricides, and fertilizers. The active ingredient content of this drug varies depending on the form of preparation, application method and other conditions, but is usually 0.5 to 95%.
(Weight), preferably 2 to 70% (weight). The method of application of this chemical can be applied to plants (foliage application), application to plant growing soil (soil application), application to paddy water (water application), application to seeds (seed treatment), etc. It is.

The application rate of this drug varies depending on the plant to be applied, the disease to be applied and the like. In the case of foliar application, the concentration of the active ingredient is 1 to 10000 ppm, preferably 10 to 10 ppm.
~ 1000 ppm solution per 10 ares
It is preferable to apply 0 L, and in the case of soil application and surface application, 0.1 to 100 per 10 ares in the amount of the active ingredient.
It is preferable to apply 0 g, particularly preferably 10 to 100 g. In the case of seed treatment, 0.001 to 50 g of the active ingredient is preferably applied to 1 kg of seed.

[0427]

EXAMPLES Next, the present invention will be described with reference to Production Examples, Preparation Examples and Test Examples, but the present invention is not limited to these. The compound number is (number in the table) −
(Symbol of HetB)-(compound number in the table).

(Production Example 1) 3- (3-methyl-1,2,2,3
5-Thiadiazol-4-yl) pyridinemethanone oxime (150 mg, 0.68 mmol, E: Z =
To a solution of 1: 4) in acetonitrile (20 ml) was added potassium carbonate (160 mg, 1.15 mmol) and 2-picolyl chloride (149 mg, 0.87 mmol), and the mixture was heated under reflux for 7 hours. Water was added to the reaction solution, extracted with ethyl acetate, washed with water, and dried over magnesium sulfate. The solvent was distilled off, the residue was purified by column chromatography, and (Z) -3- (3-methyl-1,2,5-thiadiazol-4-yl) pyridylmethanone O- (2-pyridyl) methyl Oxime (157 mg) and (E) -3-
(3-Methyl-1,2,5-thiadiazol-4-yl) pyridylmethanone O- (2-pyridyl) methyl oxime (47 mg) (Compound No. 31- (b) -2
4) was obtained. (Z) -3- (3-Methyl-1,2,5-thiadiazol-4-yl) pyridylmethanone O- (2-pyridyl) methyl oxime 1H-NMR (CDCl ₃ ): δ 2.50 (s, 3)
H), 5.39 (s, 2H), 7.10 to 7.48
(M, 3H), 7.69 (t, j = 7.7 Hz,
1H), 7.81 (d, j = 7.9 Hz, 1
H), 8.48 to 8.70 (m, 3H). MS (m / z): 312 (M ⁺⁺ 1). (E) -3- (3-Methyl-1,2,5-thiadiazol-4-yl) pyridylmethanone O- (2-pyridyl) methyl oxime 1H-NMR (CDCl ₃ ): δ 2.66 (s, 3)
H), 5.42 (s, 2H), 7.13-7.51.
(M, 3H), 7.70 (t, j = 7.6 Hz,
1H), 7.85 (d, j = 7.9 Hz, 1
H), 8.60 (d, j = 4.8 Hz, 1H),
8.67 (d, j = 4.95 Hz, 1H), 8.7
5 (d, j = 2.2 Hz, 1H). MS (m / z): 312 (M ⁺⁺ 1).

(Production Example 2) DMF (6 ml) was added to 60%
Add sodium hydride (80 mg, 2 mmol)
After cooling on ice, 2- (3-methyl-1,2,5-oxadiazol-4-yl) pyridinemethanone oxime (160 m
g, 0.78 mmol, E: Z = 1: 4) DMF
(6 ml) and stirred for 30 minutes. 4
-Chloromethyl-2-isopropionylaminothiazole (222 mg, 1.02 mmol) in DMF (6 m
l) The solution was added and stirred at room temperature for 21 hours. After the reaction solution was concentrated under reduced pressure, the residue was extracted with ethyl acetate / aqueous ammonium chloride solution. The extract was washed with water and dried over magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography to give (Z) -2- (3-methyl-1,
2,5-oxadiazol-4-yl) pyridylmethanone O- (2-isopropionylaminothiazole-4
-Yl) methyl oxime (135 mg) (Compound No.
32- (c) -5) was obtained.

1H-NMR (CDCl ₃ ): δ 1.28
(D, j = 6.9 Hz, 6H), 2.28 (s,
3H), 2.43 to 2.80 (m, 1H), 5.
29 (s, 2H), 6.92 (s, 1H),
7.75 (t, j = 7.7 Hz, 1H), 7.9
4 (d, j = 8.0 Hz, 1H), 8.53
(D, j = 4.8 Hz, 1H), 8.83-9.
09 (brd, 1H). MS (m / z): 386 (M ^<+> ).

(Production Example 3) DMF (2 ml) was added with 60%
Sodium hydride (19 mg, 0.47 mmol) was added, and the mixture was cooled on ice, and 3- (3-methyl-1,2,5-thiadiazol-4-yl) pyridinemethanone oxime (44
mg, 0.2 mmol, E: Z = 1: 2.3) and stirred for 30 minutes. To this reaction solution was added 2-bromomethyl-6-isopropionylaminopyridine (57 mg,
(0.22 mmol) in DMF (1 ml) was added and stirred at room temperature for 3 days. After the reaction solution was concentrated under reduced pressure, ethyl acetate / aqueous sodium hydrogen carbonate solution was added to the residue, followed by extraction. The extract was washed with water and dried over magnesium sulfate. The solvent was distilled off, the residue was purified by column chromatography, and (Z) -3- (3-methyl-1,2,5-thiadiazol-4-yl) pyridylmethanone O- (6-isopropionylamino (Pyridin-2-yl) methyl oxime (74 mg) (Compound No. 29- (b) -25) was obtained.

1H-NMR (CDCl ₃ ): δ 1.27
(D, j = 6.9 Hz, 6H), 2.49 (s, 3
H), 2.56 (m, 1H), 5.25 (s,
2H), 7.02 (d, j = 7.6 Hz, 1
H), 7.30 (dd, j = 4.8, 8.0H
z, 1H), 7.71 (t, j = 8.0 Hz,
1H), 7.80 (dt, j = 1.9, 8.1H
z, 1H), 7.94 (brs, 1H), 8.
17 (d, j = 8.1 Hz, 1H), 8.63
(Dd, j = 1.4, 7.6 Hz, 1H),
8.63 (d, j = 4.8 Hz, 1H). MS (m / z): 396 (M ^<+> ).

(Production Example 4) (Z) -2- (5-methyl-
1,2,3-thiadiazol-4-yl) thienylmethanone oxime (130 mg, 0.58 mmol,
E: Z = 1: 4) in acetonitrile (7.5 ml) solution was mixed with potassium carbonate (140 mg, 0.99 mmol) and 2-picolyl chloride (91 mg, 0.72 mmol).
l) was added and the mixture was heated under reflux for 16 hours. Water was added to the reaction solution, extracted with ethyl acetate, washed with water, and dried over magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography to obtain (Z) -2- (5-methyl-1,2,2,3).
3-thiadiazol-4-yl) thienylmethanone O
-(2-Pyridyl) methyl oxime (163 mg) (Compound No. 22- (a) -25) was obtained.

1H-NMR (CDCl ₃ ): δ2.56
(S, 3H), 5.36 (s, 2H), 6.85
(Dd, j = 1.1, 3.7 Hz, 1H),
6.99 (dd, j = 3.7, 5.1 Hz, 1
H), 7.20 (m, 1H), 7.33 (d, j
= 8.5 Hz, 1H), 7.36 (dd, j =
1.1, 5.1 Hz, 1H), 7.67 (dd
d, j = 1.6, 7.7, 7.7 Hz, 1H),
8.56 (m, 1H). MS (m / z): 316 (M ^<+> ).

(Production Example 5) 3- (5-Methyl-1,2,2,3)
3-thiadiazol-4-yl) thienylmethanone (1
80 mg, 0.86 mmol) and hydroxylamine hydrochloride (147 mg, 2.11 mmol) were dissolved in pyridine (4 ml) and stirred at 60 ° C. for 17 hours. The reaction solution was concentrated under reduced pressure, and the residue was extracted with ethyl acetate / dilute hydrochloric acid. The extract was washed with diluted hydrochloric acid, water and saturated saline in this order, and then dried over magnesium sulfate. The solvent was distilled off and the residue was purified by column chromatography,
(Z) -3- (5-Methyl-1,2,3-thiadiazol-4-yl) thienylmethanone oxime (136 m
g) and (E) -3- (5-Methyl-1,2,3-thiadiazol-4-yl) thienylmethanone oxime (57 mg) (Compound No. 36- (a) -6).

(Z) -3- (5-Methyl-1,2,3-
Thiadiazol-4-yl) thienylmethanone oxime 1H-NMR (CDCl ₃ ): δ 2.60 (s, 3)
H), 7.18 (dd, j = 1.3, 3.0 Hz,
1H), 7.36 (dd, j = 3.0, 5.1H)
z, 1H), 7.49 (dd, j = 1.3,
5.1 Hz, 1H), 7.90 (brd, 1
H). MS (m / z): 225 (M ^<+> ).

(E) -3- (5-Methyl-1,2,3-
Thiadiazol-4-yl) thienylmethanone oxime 1H-NMR (CDCl ₃ ): δ 2.64 (s, 3)
H), 7.33 (dd, j = 3.0, 5.1 Hz,
1H), 7.42 (dd, j = 1.3, 5.1H)
z, 1H), 8.03 (dd, j = 1.3,
3.0 Hz, 1H), 9.2 (brd, 1H). MS (m / z): 225 (M ⁺ )

(Production Example 6) 4-Chlorophenyl (5-methyl-1,2,3-thiadiazol-4-yl) methanone (3.24 g, 13.6 mmol) and hydroxylamine hydrochloride (2.32 g, 33.3 g). 4 mmol) was dissolved in pyridine (60 ml) and stirred at 70 ° C. for 6.5 hours. The reaction solution was concentrated under reduced pressure, and the residue was extracted with ethyl acetate / dilute hydrochloric acid. The extract was washed with diluted hydrochloric acid, water and saturated saline in this order, and then dried over magnesium sulfate. The solvent was distilled off and the residue was purified by column chromatography to give (Z) -4-chlorophenyl (5-methyl-
1,2,3-thiadiazol-4-yl) methanone oxime (2.35 g) and (E) -4-chlorophenyl (5-methyl-1,2,3-thiadiazol-4-yl) methanone oxime ( 1.14 g) (Compound No. 3)
4- (a) -3) was obtained.

(Z) -4-Chlorophenyl (5-methyl-1,2,3-thiadiazol-4-yl) methanone oxime 1H-NMR (CDCl ₃ ): δ2.57 (s, 3
H), 7.34 (d, j = 8.9 Hz, 2H),
7.43 (d, j = 8.9 Hz, 2H), 8.0
4 (s, 1H). MS (m / z): 253 (M ⁺ ).

(E) -4-Chlorophenyl (5-methyl-1,2,3-thiadiazol-4-yl) methanone oxime 1H-NMR (CDCl ₃ ): δ 2.70 (s, 3)
H), 7.43 (d, j = 8.9 Hz, 2H),
7.50 (d, j = 8.9 Hz, 2H), 8.1
3 (s, 1H). MS (m / z): 253 (M ⁺ ).

(Production Example 7) 4-Fluorophenyl (3-
Methyl-1,2,5-thiadiazol-4-yl) methanone (1.0 g, 4.5 mmol) and hydroxylamine hydrochloride (0.44 g, 6.3 mmol) are dissolved in ethanol (10 ml) and water (5 ml). Then, potassium carbonate (0.37 g, 2.7 mmol) was added, and the mixture was stirred at 90 ° C. for 16 hours. The reaction solution was concentrated under reduced pressure, and the residue was extracted with ethyl acetate / water. The extract was washed sequentially with water and saturated saline, and then dried over magnesium sulfate. The solvent was distilled off, the residue was purified by column chromatography, and (Z) -4-fluorophenyl (3-methyl-1,2,5-thiadiazol-4-yl) methanone oxime and (E) -4 Mixture of -fluorophenyl (3-methyl-1,2,5-thiadiazol-4-yl) methanone oxime (E: Z = 1: 3.7, 1.13 g)
(Compound No. 34- (b) -13) was obtained.

1H-NMR (CDCl ₃ ): δ2.53
(Z), 2.70 (E) (s, 3H), 6.90
~ 7.21 (m, 2H), 7.22 ~ 7.60
(M, 2H), 8.52 to 8.82 (brd, 1
H). MS (m / z): 237 (M ^<+> ).

(Production Example 8) 4-Fluorophenyl (3-
Methyl-1,2,5-oxadiazol-4-yl) methanone (752 mg, 3.65 mmol) and 50% aqueous hydroxylamine solution (730 mg, 11.0 mm)
ol) was dissolved in methanol (10 ml) and water (2 ml) and stirred at 80 ° C for 16 hours. After the reaction solution was concentrated under reduced pressure, the residue was extracted with ethyl acetate. The extract was washed with saturated saline and dried over magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography to give (Z) -4-fluorophenyl (3-methyl-1,
2,5-oxadiazol-4-yl) methanone oxime (557 mg) (Compound No. 34- (c) -13)
I got

1H-NMR (CDCl ₃ ): δ 2.38
(Z) (s, 3H), 7.00 to 7.18 (m,
2H), 7.46 to 7.64 (m, 2H), 7.
90 (s, 1H). MS (m / z): 221 (M ^<+> ).

(Production Example 9) DMF (1 ml) was added with 60%
Sodium hydride (20 mg, 0.51 mmol) was added, and the mixture was ice-cooled, and (Z) -4-fluorophenyl (3-methyl-1,2,5-thiadiazol-4-yl) methanone oxime (48 mg, 0.1 mg) was added. 2 mmol) and 1
Stirred for 0 minutes. To this reaction solution was added 2-bromomethyl-6-
Isopropionylaminopyridine (52 mg, 0.2
0 mmol) in DMF (1 ml).
Stir for 8 hours. After the reaction solution was concentrated under reduced pressure, ethyl acetate / water was added to the residue and extracted. The extract was washed with water and dried over magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography to give (Z) -4-fluorophenyl (3-methyl-1,2,5-thiadiazole-
4-yl) methanone O- (6-isopropionylaminopyridin-2-yl) methyl oxime (36 mg) (Compound No. 12- (b) -13) was obtained.

1H-NMR (CDCl ₃ ): δ 1.21
(D, j = 7.0 Hz, 6H), 2.47 (s,
3H), 2.54 (m, 1H), 5.21 (s,
2H), 7.03 (dd, j = 8.2, 9.0
Hz, 2H), 7.05 (d, j = 7.2 Hz,
1H), 7.41 (dd, j = 5.4, 9.0
Hz, 2H), 7.69 (dd, j = 7.2,
8.2 Hz, 1H), 7.86 (brs, 1H),
8.15 (d, j = 8.2 Hz, 1H). MS (m / z): 414 (M ⁺⁺ l).

(Production Example 10) DMF (1 ml) was mixed with 60
% Sodium hydride (18 mg, 0.46 mmol)
, And cooled on ice to give (Z) -4-fluorophenyl (3-
Methyl-1,2,5-oxadiazol-4-yl) methanone oxime (41 mg, 0.18 mmol) was added and stirred for 10 minutes. To this reaction solution was added 2-bromomethyl-6-tert-butyroylaminopyridine (50 m
g, 0.18 mmol) in DMF (1 ml) and stirred at room temperature for 18.5 hours. After the reaction solution was concentrated under reduced pressure, ethyl acetate / water was added to the residue and extracted. The extract was washed with water and dried over magnesium sulfate. The solvent was distilled off and the residue was purified by column chromatography,
(Z) -4-fluorophenyl (3-methyl-1,2,2,
5-oxadiazol-4-yl) methanone O- (6
-Tert-butyroylaminopyridin-2-yl) methyl oxime (22 mg) (Compound No. 14- (c)
-13) was obtained.

1H-NMR (CDCl ₃ ): δ 1.33
(S, 9H), 2.33 (s, 3H), 5.25
(S, 2H), 7.01 (d, j = 7.6 Hz,
1H), 7.06 (dd, j = 7.6, 8.2)
Hz, 1H), 7.52 (dd, j = 5.3,
8.9 Hz, 2H), 7.70 (dd, j = 7.
6, 8.2 Hz, 1H), 7.98 (brs,
1H), 8.18 (d, j = 8.2 Hz, 1
H). MS (m / z): 412 (M ⁺⁺ 1).

(Production Example 11) (1- (2-trimethylsilylethoxymethyl) -4-methylpyrazol-3-yl) phenylmethanone (0.30 g, 0.95 mmol)
To a solution of 1) in pyridine (8 ml) was added hydroxylamine hydrochloride (0.17 g, 2.4 mmol), and the mixture was heated with stirring at 70 ° C. for 6.5 hours. After concentrating the reaction solution, the residue was dissolved in ethyl acetate, washed sequentially with diluted hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over magnesium sulfate. The solvent was distilled off and the residue was purified by column chromatography,
(Z)-(1- (2-trimethylsilylethoxymethyl) -4-methylpyrazol-3-yl) phenylmethanone oxime and (E)-(1- (2-trimethylsilylethoxymethyl) -4-methylpyrazole-3 -Yl) phenylmethanone oxime mixture (Z / E = 60
/ 40, 0.31 g) (Compound No. 70- (a)-
21) was obtained. ¹ H-NMR (CDCl ₃ ): δ-0.03, 0.00
(S, 9H), 0.88, 0.92 (m, 2
H), 1.90, 2.03 (s, 3H), 3.5
3, 3.59 (m, 2H), 5.33, 5.4
4 (s, 2H), 7.30-7.55 (m, 6
H), 7.72, 8.98 (brd, 1H).

(Production Example 12) (Z)-(1- (2-Trimethylsilylethoxymethyl) -4-methylpyrazol-3-yl) phenylmethanone oxime and (E)-
(1- (2-trimethylsilylethoxymethyl) -4-
Methylpyrazol-3-yl) phenylmethanone oxime mixture (0.10 g, 0.30 mmol) in DM
The F (4 ml) solution was cooled with ice, and sodium hydride (30 m
g, 0.75 mmol) and 4-chloromethyl-2-isopropionylaminothiazole (82 mg, 0.3
8 mmol) were added with stirring. The reaction solution was returned to room temperature and stirred for 3 hours. A saturated aqueous ammonium chloride solution was added to the reaction solution, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline and dried over magnesium sulfate. Evaporate the solvent,
The residue was purified by column chromatography to give (Z)-
(1- (2-trimethylsilylethoxymethyl) -4-
Methylpyrazol-3-yl) phenylmethanone O-
(2-Isopropylaminothiazol-4-yl) methyloxime and (E)-(1- (2-trimethylsilylethoxymethyl) -4-methylpyrazol-3-yl) phenylmethanone O- (2-isopropylaminothiazole- Mixture of 4-yl) methyl oximes (Z / E = 65
/ 35, 110 mg) (Compound No. 59- (a)-
5) was obtained. ¹ H-NMR (CDCl ₃ ): δ-0.03, 0.00
(S, 9H), 0.87, 0.90 (m, 2
H), 1.24 (d, j = 7.0 Hz, 6H),
1.94, 2.03 (s, 3H), 2.59
(Seq, j = 7.0 Hz, 1H), 3.51,
3.55 (m, 2H), 5.20, 5.24
(S, 2H), 5.31, 5.40 (s, 2
H), 6.85, 6.88 (s, 1H), 7.2
5-7.40 (m, 3H), 7.40-7.56
(M, 3H), 9.30 (brd, 1H). MS (m / z): 513 (M ^<+> ).

(Production Example 13) 4-Fluorophenyl (3
-Methylpyrazin-2-yl) methanone (0.58 g,
To a solution of (2.7 mmol) in pyridine (10 ml) was added hydroxylamine hydrochloride (0.47 g, 6.7 mmol), and the mixture was heated and stirred at 60 ° C for 5 hours. After concentrating the reaction solution, the residue was dissolved in ethyl acetate, washed sequentially with diluted hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over magnesium sulfate. The solvent was distilled off, the residue was purified by column chromatography, and (Z) -4-fluorophenyl (3-
Methylpyrazin-2-yl) methanone oxime (0.4
3g), and (E) -4-fluorophenyl (3-methylpyrazin-2-yl) methanone oxime (0.13
g, Compound No. 64- (d) -13) was obtained. (Z) -4-fluorophenyl (3-methylpyrazine-
2-yl) methanone oxime ¹ H-NMR (CDCl ₃ ): δ 2.52 (s, 3
H), 7.04 (m, 2H), 7.42 (m,
2H), 8.18 (brd, 1H), 8.56
(S, 2H). (E) -4-fluorophenyl (3-methylpyrazine-
2-yl) methanone oxime ¹ H-NMR (CDCl ₃ ): δ2.58 (s, 3
H), 7.09 (m, 2H), 7.56 (m,
2H), 8.48 (d, j = 2.6 Hz, 1
H), 8.50 (d, j = 2.6 Hz, 1H),
9.86 (brd, 1H).

(Production Example 14) DMF of (Z) -4-fluorophenyl (3-methylpyrazin-2-yl) methanone oxime (90 mg, 0.39 mmol) (4 m
l) The solution was cooled on ice and sodium hydride (47 mg,
1.2 mmol) and 4-chloromethyl-2-tert-
Butyroylaminothiazole (100 mg, 0.43
mmol) was added with stirring. The reaction solution was returned to room temperature and stirred for 3.5 hours. A saturated aqueous ammonium chloride solution was added to the reaction solution, and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline and dried over magnesium sulfate. The solvent was distilled off and the residue was purified by column chromatography,
(Z) -4-fluorophenyl (3-methylpyrazine-
2-yl) methanone O- (2-tert-butyroylaminothiazol-4-yl) methyl oxime (123
mg, Compound No. 50- (d) -4) was obtained. ¹ H-NMR (CDCl ₃ ): δ 1.32 (s, 9
H), 2.44 (s, 3H), 5.19 (s,
2H), 6.84 (s, 1H), 7.03 (m,
2H), 7.42 (m, 2H), 8.52
(S, 2H), 8.94 (brd, 1H).

Tables 72 to 91 collectively show physicochemical data such as ¹ H-NMR spectrum and mass spectrum of the oxime derivative and hydroxyme derivative produced in the same manner as in these Production Examples. The indication of the compounds in the table is, for example, that the compound of 1- (a) -1 is the compound of Table 1 with Het.
No. B in which B is (a). 1 is shown.

[0454]

[Table 72]

[0455]

[Table 73]

[0456]

[Table 74]

[0457]

[Table 75]

[0458]

[Table 76]

[0459]

[Table 77]

[0460]

[Table 78]

[0461]

[Table 79]

[0462]

[Table 80]

[0463]

[Table 81]

[0464]

[Table 82]

[0465]

[Table 83]

[0466]

[Table 84]

[0467]

[Table 85]

[0468]

[Table 86]

[0469]

[Table 87]

[0470]

[Table 88]

[0471]

[Table 89]

[0472]

[Table 90]

[0473]

[Table 91]

Next, Formulation Examples using the compound of the present invention will be shown. Formulation Examples and the compound of the present invention used in the control test,
Unless otherwise specified, it is a mixture of the (Z) form and the (E) form.

(Preparation Example 1) Powder 2 parts by weight of the oxime derivative of the present invention was added to clay 9
8 parts by weight were mixed and pulverized to obtain a powder.

(Formulation Example 2) Wettable powder 20 parts by weight of the oxime derivative of the present invention were mixed and ground with 68 parts by weight of clay, 8 parts by weight of white carbon and 4 parts by weight of polyoxyethylene nonylphenyl ether, respectively. And

(Formulation Example 3) Granules 5 parts by weight of the oxime derivative of the present invention were mixed and ground with 90 parts by weight of an equal mixture of bentonite and talc and 5 parts by weight of sodium alkylbenzenesulfonate to form granules.

Next, Test Examples show that the present invention is useful as a plant disease controlling agent. In the pot test, in the pot test, the disease state of the test plant at the time of the investigation, ie, the flora of leaves, stems, etc., the degree of lesions are visually observed, and in the antibacterial activity test, the flora diameter is measured, the flora, "5" if no lesions are found, "4" if about 10%, "3" if about 30%, "2", 70% if about 50%
If the degree is recognized, it is evaluated as “1”, and if it is higher, it is evaluated as “0”, and it is evaluated on a 6-point scale, and is indicated as 5, 4, 3, 2, 1, 0, respectively.

(Test Example 1) Rice Blast Control Effect Test (Pot Test) A 3 to 4 leaf stage rice (cultivar: Aichi Asahi) grown in a plastic pot having a diameter of 9 cm was prepared according to the method of (Formulation Example 2). The prepared wettable powder was diluted with water containing a surfactant (0.02%) so that the active ingredient concentration became 250 mg / L, and sprayed with foliage.
After air drying, a spore suspension of rice blast fungus ( Pyricularia oryzae ) was spray-inoculated, left in a moist chamber at 25 ° C. for 48 hours, then allowed to develop disease in a greenhouse, and 7 days after inoculation, the extent of the disease was investigated. The results are shown in Table 92.

[0480]

[Table 92] Table 92

(Test Example 2) Tomato late blight control effect test (pot test) Tomatoes of 3 to 4 leaf stage (cultivar: Toyofuku) grown in plastic pots having a diameter of 9 cm were prepared according to the method of (Formulation Example 2). The wettable powder was diluted with water containing a surfactant (0.02%) so that the active ingredient concentration became 250 mg / L, and sprayed with foliage.
After air-drying, spray inoculation of a spore suspension of the tomato blight fungus ( Phytophthora infestans ), and after placing in a 20 ° C moist chamber for 24 hours,
The disease was caused in a greenhouse, and the severity of the disease was investigated 5 days after inoculation.
The results are shown in Table 93.

[0482]

[Table 93]

(Test Example 3) Test for controlling effect of apple spot leaf rot and cucumber wilt (antibacterial activity test) A wettable powder prepared according to the method of (Formulation Example 2) was prepared by adjusting the active ingredient concentration to 250 mg / L. It was diluted with water containing a surfactant (0.02%) to obtain a solution. Mix this with a potato dextrose agar in a 5 cm diameter plastic petri dish and add 50
A sample-containing medium of mg / L was prepared. In this medium, apple spot rot fungus ( Alternaria) punched with a cork borer
mali ) and cucumber vine wilt ( Fusarium oxysporu)
m ) was inoculated and cultured at 24 ° C. for 48 hours. After the growth of the bacteria, the flora diameter was measured, and the growth inhibition rate was calculated. The results are shown in Table 94 (Apple spot leaf disease) and Table 95 (Cucumber vine disease).

[0484]

[Table 94]

[0485]

[Table 95]

(Test Example 4) Test for controlling efficacy of grape downy mildew A wettable powder prepared according to the method of (Formulation Example 2) was placed in a test tube, and diluted with water so that the active ingredient concentration became 5 mg / L. did. Three leaf disks of grapes (variety: Neo Muscat) punched with a cork borer having a diameter of 10 mm were put in this test solution. Thirty minutes later, the leaf disk was taken out and placed on a filter paper laid on a plastic petri dish with the back of the leaf facing upward. Absorb the filter paper and remove the grape downy mildew ( Plasmopara)
viticola ) was spray inoculated onto leaf disks. After sealing the plastic Petri dish, growth cabinet (25 ℃, 5000Lx, 14 hours, 18 ℃ dark condition, 10 ℃)
Time, humidity 70%). Seven days later, the severity of the disease was investigated. The results are shown in Table 96.

[0487]

[Table 96]

[0488]

Industrial Applicability The present invention provides a novel oxime derivative having a low phytotoxicity to useful plants and having a sufficient pharmacological effect.
It is possible to provide a production method and a pesticide containing the same as an active ingredient, particularly a plant disease controlling agent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01N 43/78 A01N 43/78 D A 43/828 55/00 D 43/832 C07D 231/12 A 55 / 00 233/64 105 C07D 231/12 241/12 233/64 105 271/08 241/12 277/10 271/08 285/06 277/10 285/10 285/06 401/12 285/10 401/14 401 / 12 409/14 401/14 413/06 409/14 413/12 413/06 413/14 413/12 417/06 413/14 417/14 417/06 A01N 43/82 102 417/14 103 (72) Inventor, Hiroyuki Tsuboi 72) Inventor Takashi Goto 3-5-1 Osakidai, Sakura City, Chiba Prefecture (72) Inventor Kenichi Sato 35-11 Kamimizo, Sagamihara City, Kanagawa Prefecture (72) Inventor Matsu Sanae 3-4-1 Matsushiro, Tsukuba City, Ibaraki Prefecture (72) Inventor Tomoko Goto 3-5-1 Osakidai, Sakura City, Chiba Prefecture (72) Inventor Emiko Hagiwara 1-333 Kyowa, Sagamihara City, Kanagawa Prefecture F-term (reference) ) 4C036 AD04 AD06 AD17 4C056 AA01 AB02 AC06 AD01 AE03 AF01 FA03 FA13 4C063 AA01 AA03 BB04 BB07 CC22 CC25 CC34 CC58 CC62 CC67 CC75 CC92 DD04 DD12 DD22 DD25 DD34 DD62 EE03 4H011 AA01 AA03 BA01 BC15 DD03 DD03 DD01 DF05 DG05

Claims (41)

[Claims] 1. The following general formula (1): [Wherein HetA is the following three formulas: (In the formula, Q is a hydrogen atom, a halogen atom, or a lower alkyl group, and R ¹ is a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a cycloalkyl group, a lower alkenyl group, or a lower alkynyl group. R ² is a hydrogen atom or a lower alkyl group; an aralkyl group, an aryl group or an aryl group substituted with one or more substituents selected from the group consisting of a halogen atom, a lower alkyl group and a lower alkoxy group; HetB is a group represented by any one of the following nine formulas: (Wherein, Y represents a hydrogen atom or a lower alkyl group, R ³
Represents a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. ) Represents a group represented by any one of the above, HetC
Is the following 9 formulas (Wherein, R ⁴ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group, and X is a hydrogen atom, a halogen atom, a lower alkyl group, a halogen atom, It is a lower alkyl group, a lower alkoxy group, a lower alkoxy group or a cyano group substituted with an atom, Z is a hydrogen atom, a halogen atom or a lower alkyl group, and n is 0-3. ) Is a group represented by any one of the above. However, Het
A is the following two formulas: (In the formula, Q is a hydrogen atom, a halogen atom, or a lower alkyl group, and R ¹ is a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a cycloalkyl group, a lower alkenyl group, or a lower alkynyl group. R ² is a hydrogen atom or a lower alkyl group; an aralkyl group, an aryl group or an aryl group substituted with one or more substituents selected from the group consisting of a halogen atom, a lower alkyl group and a lower alkoxy group; HetB is a group represented by any one of the following three formulas: (Wherein, Y represents a hydrogen atom or a lower alkyl group), and HetC is a group represented by the following formula: Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom or a cyano group, and n is 0 to 3 ) Is excluded. An oxime derivative represented by the formula: 2. A compound of the general formula (1) [Wherein HetA is the following three formulas: (In the formula, Q is a hydrogen atom, a halogen atom, or a lower alkyl group, and R ¹ is a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a cycloalkyl group, a lower alkenyl group, or a lower alkynyl group. R ² is a hydrogen atom or a lower alkyl group; an aralkyl group, an aryl group or an aryl group substituted with one or more substituents selected from the group consisting of a halogen atom, a lower alkyl group and a lower alkoxy group; Is a group represented by any one of the following, and HetB represents the following three formulas: (Wherein, Y represents a hydrogen atom or a lower alkyl group), and a group represented by any one of the ring structures, and HetC represents the following eight formulas: (Wherein, Z is a hydrogen atom, a halogen atom, or a lower alkyl group, and R ⁴ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. X is a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, and n is 0 to 3.). ] The oxime derivative represented by these. 3. The following general formula (1): Wherein HetA is represented by the following formula: (In the formula, Q is a hydrogen atom, a halogen atom, or a lower alkyl group, and R ¹ is a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a cycloalkyl group, a lower alkenyl group, or a lower alkynyl group. R ² is a hydrogen atom or a lower alkyl group; an aralkyl group, an aryl group or an aryl group substituted with one or more substituents selected from the group consisting of a halogen atom, a lower alkyl group and a lower alkoxy group; Represents a group represented by
HetB has the following three formulas: Wherein Y represents a hydrogen atom or a lower alkyl group, and HetC represents a group represented by the following formula: (Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom, or a cyano group, and n is from 0 to 3).) ] The oxime derivative represented by these. 4. The following general formula (1): [Wherein HetA is represented by the following three formulas: (In the formula, Q is a hydrogen atom, a halogen atom or a lower alkyl group, and R ¹ is a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a cycloalkyl group,
Lower alkenyl group, lower alkynyl group, aralkyl group,
An aryl group or an aryl group substituted with one or more substituents selected from the group consisting of a halogen atom, a lower alkyl group and a lower alkoxy group; and R ² is a hydrogen atom or a lower alkyl group. ) Represents a group represented by any one of the following, and HetB represents the following six formulas: (Wherein, Y represents a hydrogen atom or a lower alkyl group, R ³
Represents a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. ) Represents a group represented by any one of the above, HetC
Is the following six formulas: (Wherein R ⁴ is a hydrogen atom or a lower alkyl group;
Is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group or a lower alkoxy group substituted with a halogen atom,
Z is a hydrogen atom, a halogen atom or a lower alkyl group, and n is 0-3. ) Is a group represented by any one of the above. ] The oxime derivative represented by these. 5. In the general formula (1), HetC is represented by the following three formulas: (Wherein, Z is a hydrogen atom, a halogen atom, or a lower alkyl group, X is a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group, and n is 0 or 1). The oxime derivative according to claim 2, which is a group represented by two ring structures. 6. In the general formula (1), HetA is represented by the following formula: (Wherein Q is a hydrogen atom, a halogen atom or a lower alkyl group, R ¹ is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom). Is the following formula: (In the formula, Z is a hydrogen atom.)
The oxime derivative according to claim 2. 7. In the general formula (1), HetA is represented by the following formula: (Wherein Q is a hydrogen atom, a halogen atom or a lower alkyl group, R ¹ is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom). Is the following formula: (Where X is a hydrogen atom or a halogen atom, and n is 0
Or 1. The oxime derivative according to claim 2, which is a group represented by: 8. In the general formula (1), HetA is represented by the following formula: (Wherein, Q is hydrogen atom or a lower alkyl group, R ¹
Is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom. HetC is represented by the following three formulas: The oxime derivative according to claim 2, wherein X is a hydrogen atom or a halogen atom, Z is a hydrogen atom, and n is 0 or 1. 9. In the general formula (1), HetA is represented by the following formula: (Wherein Q is a hydrogen atom or a lower alkyl group;
¹ is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom. ) Wherein HetC is represented by the following formula: (Wherein, X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, or a cyano group, and n is 0 to 3). Item 4. The oxime derivative according to item 3. 10. In the general formula (1), HetC is represented by the following formula: (In the formula, X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group or a lower alkoxy group substituted with a halogen atom, and n is 0 to 3. The oxime derivative according to claim 4, which is a group represented by: 11. In the general formula (1), HetA is represented by the following formula: Wherein Q is a hydrogen atom, a halogen atom or a lower alkyl group, R ¹ is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom. The following three formulas (Wherein, Y represents a hydrogen atom or a lower alkyl group, R ³
Represents a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. ) Is a group represented by any one of HetC
Is the following formula: (Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkyl group substituted with a halogen atom, and n is 0 or 1). The oxime derivative according to the above. 12. A compound of the general formula (2) [Wherein HetB is the following 9 formulas: (Wherein, Y represents a hydrogen atom or a lower alkyl group, R ³
Represents a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. ) Represents a group represented by any one of the above, HetC
Is the following nine formulas: (Wherein, R ⁴ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group, and X is a hydrogen atom, a halogen atom, a lower alkyl group, a halogen atom, A lower alkyl group substituted with an atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom, Z is a hydrogen atom, a halogen atom or a lower alkyl group, and n is 0 to 3). Or a group represented by one. A hydroxyme derivative [provided that the following compound: (Wherein, X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom or a cyano group, and Y is a hydrogen atom or A lower alkyl group, and n is 0 or 1.) and the following compounds: And the following compounds: Except when. ]. 13. In the general formula (2), HetB is represented by the following three formulas: (Wherein, Y represents a hydrogen atom or a lower alkyl group), and represents a group represented by any one of the ring structures, wherein HetC is represented by the following eight formulas: (Wherein, Z is a hydrogen atom, a halogen atom, or a lower alkyl group, and R ⁴ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. X is a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, and n is 0 to 3.), and is a group represented by any one of the ring structures. Hydroxime derivatives. 14. In the general formula (2), HetB is represented by the following six formulas: (Wherein, Y represents a hydrogen atom or a lower alkyl group, R ³
Represents a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. ) Represents a group represented by any one of the above, HetC
Is the following six formulas (Wherein R ⁴ is a hydrogen atom or a lower alkyl group;
Is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group or a lower alkoxy group substituted with a halogen atom,
Z is a hydrogen atom, a halogen atom or a lower alkyl group, and n is 0-3. The hydroxyme derivative according to claim 12, which is a group represented by any one of the above. 15. In the general formula (2), HetC is represented by the following three formulas: (Wherein, Z is a hydrogen atom, a halogen atom, or a lower alkyl group, X is a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group, and n is 0 or 1). The hydroxyme derivative according to claim 13, which is a group represented by two ring structures. 16. In the general formula (2), HetC is represented by the following formula: (In the formula, Z is a hydrogen atom.)
The hydroxyme derivative according to claim 13. 17. In the general formula (2), HetC is represented by the following formula: (Where X is a hydrogen atom or a halogen atom, and n is 0
Or 1. The hydroxyme derivative according to claim 13, which is a group represented by the formula: 18. In the general formula (2), HetC is represented by the following formula: (In the formula, X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group or a lower alkoxy group substituted with a halogen atom, and n is 0 to 3. The hydroxyme derivative according to claim 14, which is a group represented by: 19. In the general formula (2), HetB is represented by the following three formulas: (Wherein, Y represents a hydrogen atom or a lower alkyl group, R ³
Represents a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. ) Is a group represented by any one of HetC
Is the following formula: (Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkyl group substituted with a halogen atom, and n is 0 or 1). The hydroxyme derivative according to the above. 20. The following general formula (3): [Wherein HetB is the following 9 formulas: (Wherein, Y represents a hydrogen atom or a lower alkyl group, R ³
Represents a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. ) Represents a group represented by any one of the above, HetC
Is the following nine formulas: (Wherein, R ⁴ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group, and X is a hydrogen atom, a halogen atom, a lower alkyl group, a halogen atom, A lower alkyl group substituted with an atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom, Z is a hydrogen atom, a halogen atom or a lower alkyl group, and n is 0 to 3). Or a group represented by one. And a ketone compound represented by the following formula: (Wherein, X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom or a cyano group, and Y is a hydrogen atom or A lower alkyl group, and n is 0 to 3.) and the following compounds: And the following compounds: Except when. Wherein an oximation agent is reacted with the compound represented by the following general formula (2): (Wherein HetB and HetC are as defined in the general formula (3)). 21. In the general formula (3), HetB is represented by the following three formulas: (Wherein, Y represents a hydrogen atom or a lower alkyl group), wherein HetC is a group represented by the following eight formulas: (Wherein, Z is a hydrogen atom, a halogen atom, or a lower alkyl group, and R ⁴ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. And X is a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, and n is 0 to 3.), wherein X is a group represented by any one of the ring structures. A method for producing a hydroxyme derivative. 22. In the general formula (3), HetB is represented by the following six formulas: (Wherein, Y represents a hydrogen atom or a lower alkyl group, R ³
Represents a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. ) Represents a group represented by any one of the above, HetC
Is the following six formulas (Wherein R ⁴ is a hydrogen atom or a lower alkyl group;
Is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group or a lower alkoxy group substituted with a halogen atom,
Z is a hydrogen atom, a halogen atom or a lower alkyl group, and n is 0-3. 21. The method for producing a hydroxyme derivative according to claim 20, which is a group represented by any one of the above. 23. In the general formula (3), HetC is represented by the following three formulas. (Wherein, Z is a hydrogen atom, a halogen atom, or a lower alkyl group, X is a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group, and n is 0 or 1). The method for producing a hydroxyme derivative according to claim 21, which is a group represented by two ring structures. 24. In the general formula (3), HetC is represented by the following formula: (In the formula, Z is a hydrogen atom.)
A method for producing the hydroxyme derivative according to claim 21. 25. In the general formula (3), HetC is represented by the following formula: (Where X is a hydrogen atom or a halogen atom, and n is 0
Or 1. The method for producing a hydroxyme derivative according to claim 21, which is a group represented by: 26. In the general formula (3), HetC is represented by the following formula: Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group or a lower alkoxy group substituted with a halogen atom, and n is 0 to 3. The method for producing a hydroxyme derivative according to claim 22, which is a group represented by: 27. In the general formula (3), HetB is represented by the following three formulas: (Wherein, Y represents a hydrogen atom or a lower alkyl group, R ³
Represents a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. ) Is a group represented by any one of HetC
Is the following formula: (Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkyl group substituted with a halogen atom, and n is 0 or 1). A method for producing the hydroxyme derivative described above. 28. The following general formula (2): [Wherein HetB is the following 9 formulas: (Wherein, Y represents a hydrogen atom or a lower alkyl group, R ³
Represents a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. ) Represents a group represented by any one of the above, HetC
Is the following 9 formulas (Wherein, R ⁴ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group, and X is a hydrogen atom, a halogen atom, a lower alkyl group, a halogen atom, It is a lower alkyl group, a lower alkoxy group, a lower alkoxy group or a cyano group substituted with an atom, Z is a hydrogen atom, a halogen atom or a lower alkyl group, and n is 0-3. ) Is a group represented by any one of the above. However, Het
A is the following two formulas: (In the formula, Q is a hydrogen atom, a halogen atom, or a lower alkyl group, and R ¹ is a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a cycloalkyl group, a lower alkenyl group, or a lower alkynyl group. R ² is a hydrogen atom or a lower alkyl group; an aralkyl group, an aryl group or an aryl group substituted with one or more substituents selected from the group consisting of a halogen atom, a lower alkyl group and a lower alkoxy group; HetB is a group represented by any one of the following three formulas: Wherein Y represents a hydrogen atom or a lower alkyl group, and HetC is a group represented by the following formula: Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom or a cyano group, and n is 0 to 3 ) Is excluded. ] To the hydroxyme derivative represented by the following general formula (4): [Wherein HetA is represented by the following three formulas: (In the formula, Q is a hydrogen atom, a halogen atom, or a lower alkyl group, and R ¹ is a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a cycloalkyl group, a lower alkenyl group, or a lower alkynyl group. R ² is a hydrogen atom or a lower alkyl group; an aralkyl group, an aryl group or an aryl group substituted with one or more substituents selected from the group consisting of a halogen atom, a lower alkyl group and a lower alkoxy group; And L represents a leaving group. Wherein an alkylating agent represented by the following general formula (1) is reacted in the presence of a base: (Wherein HetA is as defined in general formula (4), and HetB and HetC are as defined in general formula (2)). 29. In the general formula (2), HetB is represented by the following three formulas: (Wherein, Y represents a hydrogen atom or a lower alkyl group), wherein HetC is a group represented by the following eight formulas: (Wherein, Z is a hydrogen atom, a halogen atom, or a lower alkyl group, and R ⁴ is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. And X is a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, and n is 0 to 3.), wherein X is a group represented by any one of the ring structures. A method for producing an oxime derivative. 30. In the general formula (2), HetB is represented by the following three formulas: (Wherein, Y represents a hydrogen atom or a lower alkyl group), wherein HetC is a group represented by the following formula: (Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom, or a cyano group, and n is from 0 to 3). In the general formula (4), HetA is represented by the following formula: (In the formula, Q is a hydrogen atom, a halogen atom, or a lower alkyl group, and R ¹ is a hydrogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a cycloalkyl group, a lower alkenyl group, or a lower alkynyl group. R ² is a hydrogen atom or a lower alkyl group; an aralkyl group, an aryl group or an aryl group substituted with one or more substituents selected from the group consisting of a halogen atom, a lower alkyl group and a lower alkoxy group; Is a group represented by
A method for producing the oxime derivative according to claim 28. 31. In the general formula (2), HetB is represented by the following six formulas: (Wherein, Y represents a hydrogen atom or a lower alkyl group, R ³
Represents a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. ) Represents a group represented by any one of the above, HetC
Is the following six formulas (Wherein R ⁴ is a hydrogen atom or a lower alkyl group;
Is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group or a lower alkoxy group substituted with a halogen atom,
Z is a hydrogen atom, a halogen atom or a lower alkyl group, and n is 0-3. 29. The method for producing an oxime derivative according to claim 28, which is a group represented by any one of the above. 32. In the general formula (2), HetC is represented by the following three formulas: (Wherein, Z is a hydrogen atom, a halogen atom, or a lower alkyl group, X is a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group, and n is 0 or 1). 30. The method for producing an oxime derivative according to claim 29, which is a group represented by two ring structures. 33. In the general formula (2), HetC is represented by the following formula: (Wherein, Z is a hydrogen atom).
In the general formula (4), HetA is represented by the following formula: Wherein Q is a hydrogen atom, a halogen atom or a lower alkyl group, R ¹ is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom. Item 30. The method for producing an oxime derivative according to Item 29. 34. In the general formula (2), HetC is represented by the following formula: (Where X is a hydrogen atom or a halogen atom, and n is 0
Or 1. In the general formula (4), HetA is a group represented by the following formula: Wherein Q is a hydrogen atom, a halogen atom or a lower alkyl group, R ¹ is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom. Item 30. The method for producing an oxime derivative according to Item 29. 35. In the general formula (2), HetC is represented by the following three formulas: Wherein X is a hydrogen atom or a halogen atom, Z is a hydrogen atom, and n is 0 or 1. In the general formula (4), HetA is represented by the following formula: 88 (Wherein, Q is hydrogen atom or a lower alkyl group, R ¹
Is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom. 30. The method for producing an oxime derivative according to claim 29, which is a group represented by the formula: 36. In the general formula (2), HetC is represented by the following formula: (Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, or a cyano group, and n is 0 to 3), and is a group represented by the general formula: In the formula (4), HetA is represented by the following formula: (Wherein Q is a hydrogen atom or a lower alkyl group;
¹ is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom. 31. The method for producing an oxime derivative according to claim 30, which is a group represented by: 37. In the general formula (2), HetC is represented by the following formula: (In the formula, X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group or a lower alkoxy group substituted with a halogen atom, and n is 0 to 3. The method for producing an oxime derivative according to claim 31, which is a group represented by: 38. In the general formula (2), HetB is represented by the following three formulas: (Wherein, Y represents a hydrogen atom or a lower alkyl group, R ³
Represents a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a lower alkoxy group which may have a silyl group. ) Is a group represented by any one of HetC
Is the following formula: (Wherein X is a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkyl group substituted with a halogen atom, and n is 0 or 1), and is a group represented by the general formula (4) In the above formula, HetA is represented by the following formula: (Wherein Q is a hydrogen atom, a halogen atom or a lower alkyl group, R ¹ is a lower alkyl group or a cycloalkyl group, and R ² is a hydrogen atom). 32. The method for producing an oxime derivative according to item 31. 39. An agrochemical containing the oxime derivative according to claim 1 as an active ingredient. 40. A plant disease controlling agent comprising the oxime derivative according to claim 1 as an active ingredient. 41. The plant disease controlling agent according to claim 40, which is effective against a plant disease caused by a filamentous fungus.