JPH11269176A - Oxime derivative and agrochemical containing the derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound having sufficient drug action, exhibiting excellent plant disease controlling activity as an agrochemical and free from the problem of phytotoxicity to useful plants. SOLUTION: The objective compound is expressed by formula I [R<1> is H or a lower alkyl; X is a halogen, nitro, hydroxy or the like; (n) is 0-3; HetA is a (substituted) 6-membered nitrogen-containing aromatic ring or a benzo- condensed ring type nitrogen-containing aromatic ring; HetB is a ring structure of formula II, formula III or formula IV (Y is H, a halogen, a lower alkyl or the like)]m e.g. (Z)-(5-methyl-1,2,3-thiadiazol-4-yl)phenylmethanone oxime. The compound of formula I can be produced by reacting an azolemethanone compound with hydroxylamine and reacting the resultant hydroxymino compound with a halide, or the like, in the presence of a base (e.g. sodium hydride, potassium hydroxide or cesium carbonete). The agrochemical containing the compound as an active component is effective against plant diseases caused by mold fungi.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel oxime derivative and a pesticide containing the same as an active ingredient, particularly a plant disease controlling agent.

[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 smaller and more potent drugs that exhibit significant efficacy.

[0003]

The problem to be solved by the present invention is that there is no fear of phytotoxicity to plants, and
It is an object of the present invention to provide a novel oxime derivative having a sufficient medicinal effect, and an agricultural chemical containing the same as an active ingredient, particularly a plant disease controlling agent.

[0004]

Means for Solving the Problems The present inventors have synthesized various novel oxime derivatives and investigated their physiological activities in order to solve such problems.
The present inventors have found that the oxime derivatives represented by the general formulas (1) and (2) have no concern about phytotoxicity to useful plants and exhibit particularly excellent plant disease control activity as an agricultural chemical, thereby completing the present invention.

That is, the present invention provides (1) the following general formula (1)

[0006]

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[Wherein, R1 represents a hydrogen atom or a lower alkyl group, and X represents a halogen atom, a nitro group, a hydroxy group, a cyano group, a carboxyl group, an alkoxycarbonyl group, a lower alkyl group, or a lower group substituted with a halogen atom. Alkyl group, lower alkoxy group, lower alkoxy group substituted with a halogen atom, lower alkylthio group, lower alkylthio group substituted with a halogen atom, lower alkylsulfonyl group, lower alkylsulfonyl group substituted with a halogen atom, aryl group, An aryl group substituted with a halogen atom or a lower alkyl group, an aryloxy group, an aryloxy group substituted with a halogen atom or a lower alkyl group, an amino group or an amino group substituted with a lower alkyl group; Represents an integer of 3,

HetA is a halogen atom, a lower alkyl group, a lower alkylthio group, a lower alkylsulfonyl group,
6-membered nitrogen-containing aromatic ring containing one or two nitrogen atoms, which may be substituted with one or two substituents selected from the group consisting of lower alkoxy, trifluoromethyl and cyano groups Or a benzo-fused ring type nitrogen-containing aromatic ring thereof, and HetB is

[0009]

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[0010]

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[0011]

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(Wherein, Y represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkyl group substituted with a halogen atom). An oxime derivative represented by the following general formula (2):

[0013]

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Wherein R1, X, n, HetB and Y are the same as defined in the general formula (1), and HetC is 1
A 5-membered nitrogen-containing aromatic ring or a benzo-fused ring-type nitrogen-containing aromatic thereof, which contains at least one nitrogen atom and may further contain a sulfur or oxygen atom, and which may be substituted with one or two substituents. A substituent on the nitrogen atom of the 5-membered nitrogen-containing aromatic ring is a lower alkyl group, a lower alkylsulfonyl group, a triphenylmethyl group, a lower alkoxymethyl group or a lower alkyl group, -A group selected from the group consisting of di-substituted sulfamoyl groups,

The substituent on the carbon atom of the 5-membered nitrogen-containing aromatic ring is a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, C3-C6 cycloalkyl group, C2-C6
An alkenyl group, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms substituted with a halogen atom, a lower alkylthio group, a lower alkylthio group substituted with a halogen atom A lower alkylsulfonyl group, a lower alkylsulfonyl group substituted with a halogen atom, a lower alkylsulfinyl group, a lower alkylsulfinyl group substituted with a halogen atom, an amino group, a lower alkyl group or a cycloalkyl group having 3 to 6 carbon atoms or An amino group substituted with a triphenylmethyl group,

Lower alkoxycarbonyl group, carbamoyl group, carbamoyl group substituted by lower alkyl group, aminomethyl group, aminomethyl group substituted by lower alkyl group, acylaminomethyl group, N-alkoxycarbonylaminomethyl group, alkylthio group A methyl group, an aryl group, an aryl group substituted with a halogen atom, a heteroaryl group, or

A —N (R2) C (＝ O) R3 group (where
R2 represents a hydrogen atom or a methyl group, R3 represents a hydrogen atom,
C1-C10 alkyl group, C1-C10 alkyl group substituted by halogen atom, C3-C8 cycloalkyl group, C2-C6 alkenyl group, C2-C2
4, alkynyl group, aralkyl group, lower alkyl group substituted with amino group, aralkyl group substituted with amino group, lower alkyl group substituted with acylamino group, aralkyl group substituted with acylamino group, alkoxycarbonylamino group A lower alkyl group substituted with an aralkyl group substituted with an alkoxycarbonylamino group, an aryl group,

An aryl group substituted with a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkylthio group, an amino group, a nitro group and a cyano group; A heteroaryl group, a lower alkoxy group,
Represents a cycloalkyloxy group, a benzyloxy group or an aryloxy group having 3 to 6 carbon atoms. ). An oxime derivative represented by the formula:

(3) The oxime derivative according to (1), wherein in formula (1), HetA is a pyridyl group or a pyridyl group substituted with one halogen atom or lower alkyl group; In equation (2), HetC
But,

[0020]

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[Wherein R4 represents a hydrogen atom, an amino group, an alkoxy group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms substituted with a halogen atom, a lower alkylthio group, or a lower alkyl group substituted with a halogen atom. An alkylthio group, a lower alkylsulfonyl group, a lower alkylsulfonyl group substituted with a halogen atom, a lower alkylsulfinyl group, a lower alkylsulfinyl group substituted with a halogen atom, or

-NHC (= O) R3 group (wherein R3 is a hydrogen atom, an alkyl group having 1-10 carbon atoms, an alkyl group having 1-10 carbon atoms substituted by a halogen atom, 3-8 carbon atoms)
Cycloalkyl group, alkenyl group having 2 to 6 carbon atoms, alkynyl group having 2 to 4 carbon atoms, lower alkyl group substituted with amino group, aralkyl group, aralkyl group substituted with amino group, substituted with acylamino group Lower alkyl group, an aralkyl group substituted with an acylamino group, a lower alkyl group substituted with an alkoxycarbonylamino group,
An aralkyl group substituted with an alkoxycarbonylamino group, an aryl group,

An aryl group substituted with a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, a lower alkylthio group, an amino group, a nitro group, and a cyano group; A heteroaryl group, a lower alkoxy group,
Represents a cycloalkyloxy group, a benzyloxy group or an aryloxy group having 3 to 6 carbon atoms. ), And R5 represents
Represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkyl group substituted with a halogen atom. An oxime derivative according to (2), which is a thiazolyl group represented by the formula:

(5) R4 is a —NHC (＝ O) R3 group (where R3 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
An alkyl group having 1 to 6 carbon atoms substituted with a halogen atom,
A cycloalkyl group having 3 to 6 carbon atoms, an aralkyl group, an aryl group, a group selected from the group consisting of a halogen atom, a lower alkyl group, a lower alkyl group and a lower alkoxy group substituted with a halogen atom, an amino group, and a cyano group , A heteroaryl group, or a lower alkoxy group. The oxime derivative according to (4), wherein R5 is a hydrogen atom;

(6) Any one of the above (1) to (5)
A pesticide containing the oxime derivative according to any one of the above as an active ingredient; (7) a plant disease controlling agent containing the oxime derivative according to any one of the above (1) to (5) as an active ingredient; The plant disease control agent according to (7), which is effective against a plant disease caused by a filamentous fungus.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The general formulas (1) and (2) of the present invention
R1 of the oxime derivative represented by represents a hydrogen atom or a lower alkyl group, and the lower alkyl group may be linear, branched, or cyclic. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Examples thereof include those having 1 to 4 carbon atoms such as n-butyl group, isobutyl group, sec-butyl group, cyclopropyl group and the like. Particularly preferred as R1 is a hydrogen atom or a methyl group.

In the general formulas (1) and (2), X represents a halogen atom, a nitro group, a hydroxy group, a cyano group, a carboxyl group, an alkoxycarbonyl group, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkyl group. Alkoxy group, lower alkoxy group substituted by halogen atom, lower alkylthio group, lower alkylthio group substituted by halogen atom, lower alkylsulfonyl group, lower alkylsulfonyl group substituted by halogen atom, aryl group, halogen atom or lower It represents an aryl group substituted with an alkyl group, an aryloxy group, an aryloxy group substituted with a halogen atom or a lower alkyl group, an amino group or an amino group substituted with a lower alkyl group.

Here, the halogen atom includes a chlorine atom, a bromine atom, an iodine atom and a fluorine atom, and the alkoxycarbonyl group includes a methoxycarbonyl group, an ethoxycarbonyl group and an n-propoxycarbonyl group. Lower alkyl groups, lower alkyl groups substituted with halogen atoms include methyl group, ethyl group, n-
A linear or branched lower alkyl group having 1 to 4 carbon atoms such as propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group; chloromethyl group; difluoromethyl group; Halogen-substituted lower alkyl groups such as fluoromethyl group, difluorochloromethyl group, pentafluoroethyl group, and 3,3,3-trifluoro-n-propyl group.

The lower alkoxy group and the lower alkoxy group substituted by a halogen atom include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert- -Butoxy group, cyclopropyloxy group, difluoromethoxy group, trifluoromethoxy group, etc., and the lower alkylthio group, and the lower alkylthio group substituted with a halogen atom include methylthio group, ethylthio group, n-propylthio group, isopropyl Thio group, n-butylthio group, isobutylthio group, sec-butylthio group, difluoromethylthio group, trifluoromethylthio group, cyclopropylthio group and the like,

Examples of the lower alkylsulfonyl group and the lower alkylsulfonyl group substituted by a halogen atom include a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an isopropanesulfonyl group, an n-butanesulfonyl group and a difluoromethanesulfonyl group. , A trifluoromethanesulfonyl group, and the like. Examples of the aryl group, an aryl group substituted with a halogen atom or a lower alkyl group include a phenyl group, a 4-chlorophenyl group, a 4-tolyl group, and a 3-fluorophenyl group. ,

Examples of the aryloxy group, the aryloxy group substituted with a halogen atom or a lower alkyl group include a phenoxy group and a 4-fluorophenoxy group.
Amino groups, amino groups substituted with lower alkyl groups include amino group, methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, isobutylamino group, sec-butylamino Group, tert
-Butylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, di-n-butylamino group, ethylmethylamino group, methyl-n-propylamino group, ethyl-n-propylamino group, cyclo And a propylamino group.

The substitution position of X is not particularly limited.
Represents an integer of 0 to 3. When n is 2 or 3, X may be the same or different. X is preferably a hydrogen atom, a lower alkyl group having 1 to 2 carbon atoms, a fluoroalkyl group having 1 to 2 carbon atoms, or a halogen atom, and particularly preferably a hydrogen atom, a trifluoromethyl group, or a fluorine atom. Or a chlorine atom.

In the general formula (1), HetA is a 6-membered nitrogen-containing aromatic ring containing one or two nitrogen atoms and optionally substituted with one or two substituents, or a benzo-fused ring thereof. 1 shows a type nitrogen-containing aromatic ring. Examples of the 6-membered nitrogen-containing aromatic ring include a pyridine ring, a pyrimidine ring, a pyrazine ring and a pyridazine ring, and examples of the benzo-fused ring-type nitrogen-containing aromatic ring include a quinoline ring,
A quinazoline ring and a quinoxaline ring;

The group which can be substituted on HetA is a halogen atom, a lower alkyl group, a lower alkylthio group, a lower alkylsulfonyl group, a lower alkoxy group, a trifluoromethyl group or a cyano group. Represents a chlorine atom, a bromine atom, a fluorine atom, and the lower alkyl group includes a methyl group, an ethyl group, and n-
A propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a linear or branched lower alkyl group such as a sec-butyl group, and the like, and examples of the lower alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, and isopropyl. Examples thereof include a linear or branched lower alkylthio group such as a thio group, an n-butylthio group, an isobutylthio group, and a sec-butylthio group.

The lower alkylsulfonyl group includes
A methanesulfonyl group, an ethanesulfonyl group, a propanesulfonyl group, an isopropanesulfonyl group, a butanesulfonyl group, an isobutanesulfonyl group, a straight-chain or branched lower alkylsulfonyl group such as a sec-butanesulfonyl group, and a lower alkoxy group. Is a straight-chain or branched lower alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a sec-butoxy group.

The preferred HetA is pyridine-2
Pyridine-2-yl substituted with an yl group or a lower alkyl group
Yl group, and among these, particularly preferred are
Examples include a pyridin-2-yl group and a 5-methylpyridin-2-yl group.

In the general formulas (1) and (2), HetB
Below

[0038]

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[0039]

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[0040]

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Wherein Y represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkyl group substituted with a halogen atom.
2,3-thiadiazol-4-yl group, 1,2,5-thiadiazol-3-yl group or 1,2,5-oxadiazol-3-yl group or a halogen derivative thereof,
Represents a halogen-substituted or unsubstituted lower alkyl derivative.

Examples of the halogen atom represented by Y include a fluorine atom, a chlorine atom and a bromine atom, and include a lower alkyl group,
Examples of the lower alkyl group substituted with a halogen atom include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a difluoromethyl group and a trifluoromethyl group.
Although lower alkyl groups of 4 to 4 are mentioned, a particularly preferable one is a methyl group.

In the general formula (2), HetC contains one or more nitrogen atoms, may further contain a sulfur or oxygen atom, and contains a 5-membered ring which may be substituted with one or two substituents. A nitrogen aromatic ring or a benzo-fused ring type nitrogen-containing aromatic ring thereof is shown. Examples of the 5-membered nitrogen-containing aromatic ring include a pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, 1,2,3
-Triazole ring, 1,2,4-triazole ring, 1,
2,3-oxadiazole ring,

1,2,4-oxadiazole ring,
2,5-oxadiazole ring, 1,3,4-oxadiazole ring, 1,2,3-thiadiazole ring, 1,2,4
-A thiadiazole ring, a 1,3,4-thiadiazole ring,
A 1,2,5-thiadiazole ring and a tetrazole ring; examples of the benzo-fused ring type nitrogen-containing aromatic ring include a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, an imidazo [1,2-a] pyridine ring, [1,
2,4] triazo [1,5-a] pyridine ring.

The group which can be substituted on the nitrogen atom of HetC is a lower alkyl group, a lower alkylsulfonyl group, a triphenylmethyl group, a lower alkoxymethyl group, or an N, N-disubstituted sulfamoyl group substituted by a lower alkyl group. However, as the lower alkyl group, a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and as the lower alkylsulfonyl group, methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl group, isopropanesulfonyl group, n -Butanesulfonyl group and isobutanesulfonyl group; methoxymethyl group and ethoxymethyl group as lower alkoxymethyl group; and N, N-disubstituted sulfamoyl group substituted with lower alkyl group as dimethylsulfonyl group. A famoyl group and a diethylsulfamoyl group.

The group which can be substituted on the carbon atom of HetC includes a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted by a halogen atom, and a 3 to 6 carbon atoms. Cycloalkyl group, alkenyl group having 2 to 6 carbon atoms, alkynyl group having 2 to 6 carbon atoms, alkoxy group having 1 to 5 carbon atoms, 1 to 5 carbon atoms substituted with a halogen atom
An alkoxy group, a lower alkylthio group, a lower alkylthio group substituted with a halogen atom, a lower alkylsulfonyl group, a lower alkylsulfonyl group substituted with a halogen atom, a lower alkylsulfinyl group, a lower alkylsulfinyl group substituted with a halogen atom, An amino group, an amino group substituted with a lower alkyl group, a cycloalkyl group having 3 to 6 carbon atoms or a triphenylmethyl group,

Lower alkoxycarbonyl group, carbamoyl group, carbamoyl group substituted by lower alkyl group, aminomethyl group, aminomethyl group substituted by lower alkyl group, acylaminomethyl group, N-alkoxycarbonylaminomethyl group, alkylthio group A methyl group, an aryl group, an aryl group substituted with a halogen atom, a heteroaryl group, or

A —N (R2) C (＝ O) R3 group (wherein R
2 represents a hydrogen atom or a methyl group, R3 represents a hydrogen atom, an alkyl group having 1 to 10, preferably 1 to 8 carbon atoms,
A halogen atom-substituted alkyl group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, An alkynyl group having 2 to 4 carbon atoms, an aralkyl group, a lower alkyl group substituted with an amino group, an aralkyl group substituted with an amino group, a lower alkyl group substituted with an acylamino group, an aralkyl group substituted with an acylamino group, A lower alkyl group substituted with an alkoxycarbonylamino group, an aralkyl group substituted with an alkoxycarbonylamino group,

An aryl group, which is substituted by a group selected from the group consisting of a halogen atom, a lower alkyl group, a lower alkyl group, a lower alkoxy group, a lower alkylthio group, an amino group, a nitro group, and a cyano group substituted with a halogen atom. An aryl group; a heteroaryl group, a lower alkoxy group, a cycloalkyloxy group having 3 to 6 carbon atoms,
It represents a benzyloxy group or an aryloxy group. ).

More specifically, as the halogen atom,
A chlorine atom, a fluorine atom, and a bromine atom;
To 6 alkyl groups, 1 carbon atom substituted with a halogen atom
Examples of the alkyl group of (6) to (6) include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a n-hexyl group, a difluoromethyl group, and a trifluoromethyl group. Examples of the 3 to 6 cycloalkyl group include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, and examples of the C2 to C6 alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group.

Examples of the alkynyl group having 2 to 6 carbon atoms include an ethynyl group, a propargyl group and a butynyl group.
Examples of the lower alkoxy group having 1 to 5 carbon atoms and the lower alkoxy group having 1 to 5 carbon atoms substituted with a halogen atom include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group and an isobutoxy group. , Sec-butoxy group,
n-pentyloxy group, difluoromethoxy group, trifluoromethoxy group and the like, and a lower alkylthio group, as a lower alkylthio group substituted with a halogen atom,
Methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-
Examples thereof include a butylthio group, a difluoromethylthio group, and a trifluoromethylthio group.

The lower alkylsulfonyl group and the lower alkylsulfonyl group substituted with a halogen atom include methanesulfonyl, ethanesulfonyl, propanesulfonyl, isopropanesulfonyl, butanesulfonyl, difluoromethanesulfonyl, trifluoromethanesulfonyl and the like. And a lower alkylsulfinyl group, and examples of the lower alkylsulfinyl group substituted with a halogen atom include a difluoromethanesulfinyl group and a trifluoromethanesulfinyl group.

An amino group, a lower alkyl group or a group having 3 to 3 carbon atoms
Examples of the amino group substituted with the cycloalkyl group 6 include:
Amino group, methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, sec-butylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, ethyl Examples include a methylamino group, a methylpropylamino group, an ethylpropylamino group, a cyclopropylamino group, a cyclopentylamino group, and a cyclohexylamino group.

The lower alkoxycarbonyl group includes a methoxycarbonyl group, an ethoxycarbonyl group and a propoxycarbonyl group. The carbamoyl group and the carbamoyl group substituted by a lower alkyl group include N-methylcarbamoyl group and N-ethyl group. Carbamoyl group, N-
Isopropylcarbamoyl group, N, N-diethylcarbamoyl group, and the like. Examples of the aminomethyl group substituted with an aminomethyl group or a lower alkyl group include an aminomethyl group, an N-methylaminomethyl group, and an N-ethylaminomethyl group. , N-propylaminomethyl group, N-isopropylaminomethyl group, N-butylaminomethyl group, N, N-
Examples include a dimethylaminomethyl group and an N, N-diethylaminomethyl group.

Examples of the acylaminomethyl group include formylaminomethyl, acetylaminomethyl, propionylaminomethyl, butyrylaminomethyl, isobutyrylaminomethyl, benzoylaminomethyl, N-
Examples of the acetyl-N-isopropylaminomethyl group include N-alkoxycarbonylaminomethyl groups such as methoxycarbonylaminomethyl group, ethoxycarbonylaminomethyl group, t-butoxycarbonylaminomethyl group, N- (t-butoxycarbonyl group). ) -N-isopropylaminomethyl group and the like; and the alkylthiomethyl group include an isopropylthiomethyl group and the like.

The aryl group and the aryl group substituted with a halogen atom include phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl,
-Chlorophenyl group, 2,4-dichlorophenyl group,
A 3,4-dichlorophenyl group, a 2,6-dichlorophenyl group, a naphthyl group, a biphenyl group and the like, and the heteroaryl group includes a pyridin-2-yl group, a pyridin-4-yl group, a pyrimidin-3-yl group A 2-furyl group, a 3-furyl group, a 2-thienyl group, a 3-thienyl group,
Examples include a quinoyl group, an indolyl group, a benzofuranyl group, a benzothienyl group, a benzothiazolyl group, a benzoisoxazolyl group, and a benzoisothiazoyl group.

Specific examples of R3 of —N (R2) C (＝ O) R3 group include an alkyl group having 1 to 10, preferably 1 to 8 carbon atoms, and a carbon atom substituted by a halogen atom. Examples of the alkyl group having 1 to 10, preferably 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, t-butyl, n-butyl, isobutyl, and sec-
Butyl, n-pentyl, 1-ethylpropyl, n-decyl, chloromethyl, trifluoromethyl, trichloromethyl, 1-bromoisopropyl, chlorodifluoromethyl, 1-chloromethyl-1- A methylethyl group and the like, having 3 to 8 carbon atoms, preferably 3 carbon atoms.
As the cycloalkyl group of ~ 6, a cyclopropyl group,
Examples include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

Examples of the alkenyl group having 2 to 6 carbon atoms include vinyl group, allyl group, butenyl group and hexenyl group. Examples of the alkynyl group having 2 to 4 carbon atoms include ethynyl group, propargyl group and butynyl group. Examples of the aralkyl group include a benzyl group and a 2-phenylethyl group. Examples of the lower alkyl group substituted with an amino group include an aminomethyl group and a 1-aminoisobutyl group. As the aralkyl group substituted with
Examples include a 1-amino-2-phenylethyl group and the like, and examples of the lower alkyl group substituted with an acylamino group include an acetylaminomethyl group and a 1-acetylaminoisobutyl group.

Examples of the aralkyl group substituted with an acylamino group include a 1-acetylamino-2-phenylethyl group and the like, and examples of the lower alkyl group substituted with an alkoxycarbonylamino group include t-butoxycarbonylaminomethyl. Group, a 1- (t-butoxycarbonylamino) isobutyl group and the like, and an aralkyl group substituted with an alkoxycarbonylamino group include a 1- (benzyloxycarbonylamino) -2-phenylethyl group and the like.

An aryl group; and a group selected from the group consisting of a halogen atom, a lower alkyl group, a lower alkyl group and a lower alkoxy group, and a lower alkylthio group, and an amino group, a nitro group, and a cyano group. Aryl group; phenyl group,
2-fluorophenyl group, 3-fluorophenyl group, 4
-Fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,4-dichlorophenyl group, 3,4-dichlorophenyl group, 2,6
-Dichlorophenyl group, 4-methylphenyl group, 2-methylphenyl group, 2,4-dimethylphenyl group, 4-trifluoromethylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-methylthiophenyl group, 4-aminophenyl group, 4-acetylaminophenyl group, 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group,
Examples thereof include a 4-nitrophenyl group and a naphthyl group.

The heteroaryl groups include 2-furyl, 2-thienyl, pyridin-4-yl, pyridin-2-yl, thiazol-4-yl, oxazol-4-yl, pyrazol-3 and the like. -Yl group, imidazol-4-yl group, isothiazol-5-yl group, isoxazol-5-yl group, pyrazinyl group, pyrimidine-2-
Yl, pyridazin-3-yl, (1,2,3-thiadiazole) -4-yl, (1,2,5-thiadiazole) -3-yl, furazanyl, benzothiazol-2-yl Benzoimidazol-2-yl group, quinolin-2-yl group, isoquinolin-1-yl group, quinoxalin-2-yl group and the like.

As the lower alkoxy group, a methoxy group,
An ethoxy group, an n-propoxy group, an isopropoxy group, a butoxy group, a t-butoxy group, a 1-ethylpropoxy group and the like are mentioned. As the cycloalkyloxy group having 3 to 6 carbon atoms, a cyclopropyloxy group, a cyclopentyloxy group Group, cyclohexyloxy group and the like, and the aryloxy group include a phenoxy group and the like. HetC
Two or more of these substituents which may be substituted on the nitrogen atom and the carbon atom may be present simultaneously.

Preferred as HetC are an optionally substituted thiazol-2-yl group, an optionally substituted thiazol-4-yl group and an optionally substituted thiazol-5-yl group. Of these, particularly preferred are a thiazol-2-yl group, a thiazol-4-yl group, a 2-aminothiazol-4-yl group,
-Acylaminothiazol-4-yl group, 2-alkoxycarbonylaminothiazol-4-yl group, 2-alkoxythiazol-4-yl group, 2-alkylthiothiazol-4-yl group, 2-alkylsulfinylthiazole-4- An yl group, a 2-alkylsulfonylthiazol-4-yl group, a 2-arylthiazol-4-yl group,
A 2-bromothiazol-4-yl group is exemplified.

The steric structure of the oxime moiety present in the oxime derivatives represented by the general formulas (1) and (2) includes:
(E) form or (Z) form, and these stereoisomers are
Both are included in the present invention. Usually, synthetic products are:
It is obtained as a mixture of the (E) -form and the (Z) -form, and these can be isolated by separation and purification.

The (Z) form is more excellent in plant disease control activity than the (E) form, but the (Z) form changes to the (E) form by light or the like under a natural environment, and a certain (E) form. Stabilizes as a mixture at the ratio of the isomer to the (Z) isomer. The stabilized ratio between the (E) -form and the (Z) -form differs for each compound.

The oxime derivatives represented by the general formulas (1) and (2) in the present invention can be produced, for example, by the following method, but the production method of the compound is not limited to these production methods. is not.

Production Example (A):

[0068]

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(Where HetA, HetB, HetC, X, n and R1 are as defined above, Z is a chlorine atom,
Shows a bromine atom or an iodine atom. ) Azolemethanone compound (a) is reacted with hydroxylamine to give a hydroxyimino compound (b), and then a base (for example, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Cesium carbonate, triethylamine, pyridine, N, N-
When the halide (c) or (d) is reacted in the presence of dimethylaminopyridine or the like, the oxime compound (1) or (2) can be produced. As a method for synthesizing an azole methanone compound, for example, a method described in literature (Synthesis P976 (19
82)).

The general formula (1) produced by the method described above
Tables 1 to 66 show examples of specific structures of the compounds represented by (2) and (2). However, in the table, HetA, H
etB, HetC, X, Y, n and R1 correspond to the definitions in general formulas (1) and (2), and 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.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

[Table 3]

[0074]

[Table 4]

[0075]

[Table 5]

[0076]

[Table 6]

[0077]

[Table 7]

[0078]

[Table 8]

[0079]

[Table 9]

[0080]

[Table 10]

[0081]

[Table 11]

[0082]

[Table 12]

[0083]

[Table 13]

[0084]

[Table 14]

[0085]

[Table 15]

[0086]

[Table 16]

[0087]

[Table 17]

[0088]

[Table 18]

[0089]

[Table 19]

[0090]

[Table 20]

[0091]

[Table 21]

[0092]

[Table 22]

[0093]

[Table 23]

[0094]

[Table 24]

[0095]

[Table 25]

[0096]

[Table 26]

[0097]

[Table 27]

[0098]

[Table 28]

[0099]

[Table 29]

[0100]

[Table 30]

[0101]

[Table 31]

[0102]

[Table 32]

[0103]

[Table 33]

[0104]

[Table 34]

[0105]

[Table 35]

[0106]

[Table 36]

[0107]

[Table 37]

[0108]

[Table 38]

[0109]

[Table 39]

[0110]

[Table 40]

[0111]

[Table 41]

[0112]

[Table 42]

[0113]

[Table 43]

[0114]

[Table 44]

[0115]

[Table 45]

[0116]

[Table 46]

[0117]

[Table 47]

[0118]

[Table 48]

[0119]

[Table 49]

[0120]

[Table 50]

[0121]

[Table 51]

[0122]

[Table 52]

[0123]

[Table 53]

[0124]

[Table 54]

[0125]

[Table 55]

[0126]

[Table 56]

[0127]

[Table 57]

[0128]

[Table 58]

[0129]

[Table 59]

[0130]

[Table 60]

[0131]

[Table 61]

[0132]

[Table 62]

[0133]

[Table 63]

[0134]

[Table 64]

[0135]

[Table 65]

[0136]

[Table 66]

The pesticides containing the oxime derivative of the present invention as an active ingredient, in particular, plant disease controlling agents are effective against various plant diseases caused by phytopathogenic viruses, bacteria and fungi, and particularly effective 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 and blast fungi (Pyric fungi).
ularia oryzae) and the like.

These include downy mildew on various plants (do
wny mildew and plague (late blightor Phytophthora rot)
etc.), for example, grape downy mildew (Plasmopara v
iticola), downy mildew of cucumber (Pseudoperonospora cubensi)
s), dead blight (Phytophthora melonis), tomato gray blight (Phytophthora capsici), plague (Phytophthora infe
stans), downy mildew of cruciferous vegetables (Peronospora brassic
ae), downy mildew of leek (Peronospora destructor), downy mildew of spinach (Peronospora spinaciae), downy mildew of soybean (Peronospora manshurica),

Downy mildew of broad bean (Peronospora viciae),
Tobacco plague (Phytophthora nicotianae var.nicotian
ae), potato blight (Phytophthora infestans), hop downy mildew (Pseudoperonospora humuli), pineapple blight (Phytophthora cinnamomi), bell pepper blight (P
hytophthora capsici), root rot of strawberries (Phytophthoraf
ragariae), damping-off of various crops (due to Pythium spp., etc.),
It has an excellent control effect on a wide range of plant diseases caused by oomycetes (Oomycetes) such as red blight (Pythium aphanidermatum) of bentgrass and rice blast (Pyricularia oryzae).

Although the present drug can use the active ingredient alone, it is generally known and used solid and liquid carriers used in the preparation of agricultural chemicals, and 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 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 sugar 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 agent 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 the present 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 10,000 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.

[0146]

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.

(Production Example 1) (5-Methyl-1,2,3-
Thiadiazol-4-yl) phenylmethanone (0.2
Hydroxylamine hydrochloride (0.20 g, 2.82 m) was added to a solution of 9 g, 1.41 mmol) in ethanol (20 ml).
mol) and triethylamine (0.4 ml, 2.8 m
mol), and the mixture was heated under reflux for 48 hours. After concentrating the reaction solution, the residue was dissolved in ethyl acetate, washed with water, and dried over magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography to give (Z)-(5-methyl-
1,2,3-Thiadiazol-4-yl) phenylmethanone oxime (0.16 g) and (E)-(5-methyl-1,2,3-thiadiazol-4-yl) phenylmethanone oxime (0. 04g).

(Z)-(5-methyl-1,2,3-thiadiazol-4-yl) phenylmethanone oxime; 1
H-NMR (CDCl 3): δ 2.54 (s, 3
H), 7.30 to 7.50 (m, 5H), 8.30 to
8.45 (brd, 1H). MS (m / e): 219 (M +). (E)-(5-methyl-1,2,3-thiadiazole-
4-Hyl) phenylmethanone oxime; 1H-NMR
(CDCl3): δ 2.67 (s, 3H), 7.35
~ 7.60 (m, 5H), 8.00 to 8.20 (br
d, 1H). MS (m / e): 219 (M +).

(Production Example 2) (Z)-(5-methyl-1,
2,3-Thiadiazol-4-yl) phenylmethanone oxime (9.31 g, 0.04 mol) was dissolved in acetonitrile (677 ml), and potassium carbonate (9.98) was dissolved.
g, 0.07 mol) and the hydrochloride of 2-picolyl chloride (10.40 g, 0.06 mol) were added, and the mixture was stirred with heating under reflux for 5 hours. After concentrating the reaction solution, the residue was 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)-(5-methyl-1,2,3-thiadiazol-4-yl) phenylmethanone O- (2-pyridyl) methyloxime ( 9.67 g) (Compound No. 1-
(a) -1 (Z)).

1H-NMR (CDCl3): δ 2.5
3 (s, 3H), 5.40 (s, 2H), 7.19 (d
d, J = 4.9 Hz, J = 7.6 Hz, 1H), 7.3
0 to 7.42 (m, 3H), 7.35 (d, J = 7.8
Hz, 1H), 7.44 to 7.50 (m, 2H), 7.
7. 67 (J = 7.8 Hz, J = 7.6 Hz, 1H);
56 (d, J = 4.9 Hz, 1H). MS (m / e): 310 (M +).

(Production Example 3) (E)-(5-methyl-1,
2,3-Thiadiazol-4-yl) phenylmethanone oxime (0.30 g, 1.40 mmol) was dissolved in acetone (20 ml), and potassium carbonate (0.32 g,
2.0 mmol) and hydrochloride of 2-picolyl chloride (0.34 g, 2.0 mmol) were added, and the mixture was stirred at room temperature for 3 days. After concentrating the reaction solution, the residue was 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,
(E)-(5-methyl-1,2,3-thiadiazole-
4-yl) phenylmethanone O- (2-pyridyl) methyl oxime (0.07 g) (Compound No. 1- (a) -1 (E))
I got

1H-NMR (CDCl3): δ 2.5
9 (s, 3H), 5.40 (s, 2H), 7.21 (d
d, J = 4.83, 8.70 Hz, 1H), 7.31-
7.72 (m, 7H), 8.58 (d, J = 4.88H)
z, 1H). MS (m / e): 310 (M +).

(Production Example 4) (3-Methyl-1,2,5-
Thiadiazol-4-yl) phenylmethanone (3.2
Hydroxylamine hydrochloride (4.48 g, 63.1 m) was added to a solution of 2 g, 15.7 mmol) in ethanol (85 ml).
mol) and triethylamine (8.8 ml, 63.1).
mmol) and heated under reflux for 8 hours. After concentrating the reaction solution, ethyl acetate / water was added to the residue and extracted. After drying over magnesium sulfate, the solvent was distilled off. The residue was purified by column chromatography, and (Z)-(3-
Methyl-1,2,5-thiadiazol-4-yl) phenylmethanone oxime (2.18 g) was obtained.

1H-NMR (CDCl3): δ 2.5
3 (s, 3H), 7.27 to 7.56 (m, 5H),
8.52 to 8.78 (brd, 1H). MS (m / e): 219 (M +).

(Production Example 5) DMF (150 ml) was mixed with 6
0% sodium hydride (2.41 g, 60.0 mmol
l), ice-cooled, and (Z)-(3-methyl-1,2,2,
5-Thiadiazol-4-yl) phenylmethanone oxime (6.0 g, 27.0 mmol) was added, and the mixture was stirred for 40 minutes. 4-Chloromethyl-2-iso was added to the reaction mixture.
-Propionylaminothiazole (7.76 g, 35.
6 mmol) in DMF (110 ml) was added dropwise.
The reaction solution was gradually returned to room temperature and then stirred for 20 hours.
The solvent was distilled off from the reaction solution under reduced pressure, and the residue was extracted with ethyl acetate / water. 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)-(3-methyl-1,
2,5-thiadiazol-4-yl) phenylmethanone O- (2-iso-propionylaminothiazole-
4-yl) methyl oxime (9.08 g) (Compound No. 8
-(b) -7 (Z)).

1H-NMR (CDCl3): δ 1.2
2 (d, J = 6.91 Hz, 6H), 2.41 (s, 3
H), 2.47 to 2.76 (m, 1H), 5.21.
(S, 2H), 6.89 (s, 1H), 7.28-7.
60 (m, 5H), 9.50 to 9.90 (brd, 1
H). MS (m / e): 401 (M +).

(Production Example 6) (3-Methyl-1,2,5-
Oxadiazol-4-yl) phenylmethanone (3.
Hydroxylamine hydrochloride (5.19 g, 73.0 m) was added to a solution of 43 g (18.0 mmol) in pyridine (55 ml).
mol), and the mixture was heated and stirred at 70 ° C for 21 hours. After concentrating the reaction solution, the residue was dissolved in ethyl acetate, washed with dilute hydrochloric acid, then with water, and dried over magnesium sulfate. The solvent was distilled off, the residue was purified by column chromatography, and (Z)-(3-methyl-1,2,5-oxadiazol-4-yl) phenylmethanone oxime (2.13 g), and (E)-(3-methyl-1,2,2
5-oxadiazol-4-yl) phenylmethanone oxime (0.79 g) was obtained.

(Z)-(3-methyl-1,2,5-oxadiazol-4-yl) phenylmethanone oxime;
1H-NMR (CDCl3): δ 2.38 (s, 3
H), 7.30-7.48 (m, 3H), 7.48-
7.62 (m, 2H), 7.89 to 8.00 (brd,
1H). MS (m / e): 219 (M +). (E)-(3-methyl-1,2,5-oxadiazol-4-yl) phenylmethanone oxime; 1H-NMR
(CDCl3): δ 2.55 (s, 3H), 7.30
To 7.48 (m, 3H), 7.48 to 7.62 (m, 2
H), 7.89-8.00 (brd, 1H). MS (m / e): 219 (M +).

(Production Example 7) DMF (16 ml) was added with 60
% Sodium hydride (0.43 g, 10.6 mmol)
And cooled on ice to give (Z)-(3-methyl-1,2,5-
Oxadiazol-4-yl) phenylmethanone oxime (0.94 g, 4.63 mmol) in DMF (20 m
l) The solution was added and stirred for 40 minutes. 4-
Chloromethyl-2-triphenylmethylaminothiazole (2.71 g, 6.94 mmol) in DMF (15 m
l) The solution was added dropwise. The reaction solution was gradually returned to room temperature and then stirred for 4 days. The solvent was distilled off from the reaction solution under reduced pressure, and the residue was extracted with ethyl acetate / water. 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)-(3-methyl-1,2,5-oxadiazol-4-yl) phenylmethanone O- (2-triphenylmethylaminothiazol-4-yl) methyl oxime (0.59 g) (compound No. 9- (c) -6 (Z)).

1H-NMR (CDCl3): δ 2.2
3 (s, 3H), 5.11 (s, 2H), 6.27
(S, 1H), 6.80-6.97 (brd, 1H),
7.13 to 7.60 (m, 20H). MS (m / e): 557 (M +).

(Production Example 8) (Z)-(3-methyl-1,
2,5-oxadiazol-4-yl) phenylmethanone O- (2-triphenylmethylaminothiazole-
4-yl) methyl oxime (0.43 g, 0.77 mm
ol) in acetone (15 ml).
ml) and heated under reflux for 8 hours. The solvent was distilled off from the reaction solution under reduced pressure, and the residue was added with ethyl acetate / saturated sodium hydrogen carbonate solution to adjust the pH to 7, followed by extraction. 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)-(3-Methyl-1,2,5-oxadiazol-4-yl) phenylmethanone O- (2-aminothiazol-4-yl) methyloxime (0.05 g) (Compound No. 8 -(c) -1 (Z)).

1H-NMR (CDCl3): δ 2.3
1 (s, 3H), 4.85 to 5.10 (brd, 1
H), 5.14 (s, 2H), 6.46 (s, 1H),
7.32 to 7.66 (m, 5H). MS (m / e): 315 (M +).

(Production Example 9) (Z)-(3-methyl-1,
2,5-oxadiazol-4-yl) phenylmethanone To O- (2-aminothiazol-4-yl) methyl oxime (0.053 g, 0.168 mmol) was added trifluoroacetic anhydride (7 ml), and The mixture was heated and stirred for an hour. The reaction solution was concentrated, the residue was purified by column chromatography, and (Z)-(3-methyl-1,2,5-oxadiazol-4-yl) phenylmethanone O- (2
-Trifluoroacetylaminothiazol-4-yl)
Methyl oxime (0.063 g) (Compound No. 8- (c) -14
(Z)).

1H-NMR (CDCl3): δ 2.2
6 (s, 3H), 5.26 (s, 2H), 7.07
(S, 1H), 7.28 to 7.56 (m, 5H), 7.
68-8.10 (brd, 1H). MS (m / e): 411 (M +).

Tables 67 to 81 summarize physicochemical data such as 1H-NMR spectrum and mass spectrum of the oxime derivative produced in the same manner as in these Production Examples. The indication of the compound in the table indicates, for example, that the compound of 1- (a) -1 is the compound of Table 1 and the compound of No. 1 in which HetB is (a).

[0166]

[Table 67]

[0167]

[Table 68]

[0168]

[Table 69]

[0169]

[Table 70]

[0170]

[Table 71]

[0171]

[Table 72]

[0172]

[Table 73]

[0173]

[Table 74]

[0174]

[Table 75]

[0175]

[Table 76]

[0176]

[Table 77]

[0177]

[Table 78]

[0178]

[Table 79]

[0179]

[Table 80]

[0180]

[Table 81]

Next, preparation 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. (Formulation Example 1) Dust Compound No. 2 parts by weight of the oxime derivatives represented by 1- (a) -1 to 66- (b) -10 were each mixed and pulverized with 98 parts by weight of clay to obtain a powder.

(Formulation Example 2) Wettable powder Compound No. 20 parts by weight of the oxime derivatives represented by 1- (a) -1 to 66- (b) -10 were each mixed and pulverized with 68 parts by weight of clay, 8 parts by weight of white carbon and 4 parts by weight of polyoxyethylene nonylphenyl ether. , A wettable powder.

(Formulation Example 3) Granules Compound No. 5 parts by weight of the oxime derivatives represented by 1- (a) -1 to 66- (b) -10 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, respectively. It was molded into an agent.

Next, Test Examples show that the compound of the present invention is useful as an active ingredient of various plant disease controlling agents. When the control effect was investigated, the diseased state of the test plant, that is, the degree of lesions appearing on foliage, etc., and the number of diseased individuals in the case of wilt disease, were visually observed, and no lesions or diseased individuals were observed. If not, "A" is evaluated, "B" is recognized when about 10% is recognized, "C" is recognized when about 25% is recognized, and "D" is recognized when it is 50% or more compared to the non-treated section.

(Test Example 1) Control Test of Tomato Blight Disease The wettable powder prepared by the method of (Formulation Example 2) was effectively applied to 3 to 4 leaf stage tomatoes (variety: Toyofuku) grown in plastic pots having a diameter of 9 cm. It was diluted with water containing a surfactant (0.02%) so that the component concentration became 250 ppm, and sprayed with foliage. After air-drying, Phytophthora infestan
The spore suspension of s) was spray-inoculated, left in a moist chamber at 20 ° C. for 24 hours, then allowed to develop disease in a greenhouse, and 5 days after inoculation, the extent of the disease was investigated. Table 82 shows the test results of the tomato blight. In addition, 1250 ppm and 250 ppm of manzeb wettable powder were used as control drugs.

[0186]

[Table 82]

(Test Example 2) Cucumber downy mildew controlling effect test A wettable powder prepared by the method of (Formulation Example 2) was added to a cucumber (cultivar: Tokiwa Shinjiro) at the 3 leaf stage grown in a plastic pot having a diameter of 9 cm. Was diluted with water containing a surfactant (0.02%) so that the active ingredient concentration became 50 ppm, and sprayed with foliage. After air drying, the cucumber downy mildew (Pseudoperonos
pora cubensis) was sprayed and inoculated, left in a moist room at 25 ° C. for 24 hours, then allowed to develop disease in a greenhouse, and 7 days after inoculation, the extent of the disease was investigated. Table 83 shows the test results of cucumber downy mildew. Manzeb wettable powder 1 was used as a control drug.
250 ppm and 50 ppm were used.

[0188]

[Table 83]

(Test Example 3) Cucumber downy mildew control test (leaf disk test) The first leaf of cucumber (variety: Tokiwa Shinjiro) at the 2nd to 3rd leaf stage was punched into a 10 mm diameter disk, and this was used as a preparation example. It was immersed for 30 minutes in a chemical solution having an active ingredient concentration of 10 ppm prepared using a wettable powder prepared according to the method of 2). After air-drying, a spore suspension of cucumber downy mildew (Pseudoperonospora cubensis, metalaxyl-resistant strain) was inoculated dropwise, placed in a moist chamber, and placed in an artificial weather device (14 hours daylength, day temperature 25 ° C, night temperature 18).
C) for 7 days, and the degree of disease development was investigated. Table 84 shows the results of the cucumber downy leaf leaf disk test. In addition, as a control drug, 10% of manzeb wettable powder and metalaxyl wettable powder were used.
ppm was used.

[0190]

[Table 84]

(Test Example 4) Test for controlling grape downy mildew (leaf disk test) Leaves of a grape (cultivar: Neo Muscat) planted in the open field with a diameter of 1
A 0 mm disk was punched out, and the active ingredient concentration was adjusted using a wettable powder prepared according to the method of (Formulation Example 2).
It was immersed in a 10 ppm solution for 30 minutes. After air-drying, a spore suspension of a metalaxyl-sensitive strain A and a metalaxyl-resistant strain B of grape downy mildew (Plasmopara viticola) was inoculated dropwise, placed in a moist chamber, and placed in an artificial weather device (14 hours daylength, day temperature 25 days).
C., night temperature 18 ° C.) for 7 days, and the degree of onset was investigated.
Table 85 shows the results of the grape downy mildew leaf disk test.
In addition, 10 ppm of manzeb wettable powder and metalaxyl wettable powder were used as control drugs.

[0192]

[Table 85]

(Test Example 5) Control test of cucumber seedling blight On a deep-bottom petri dish of 15 cm in diameter, sterilized soil and soil bran were cultivated.
m) was mixed and packed. After sowing 10 cucumber seeds (variety: Dark Green Shin Tokiwa) per pot, the wettable powder prepared by the method of (Preparation Example 2) was used, and the active ingredient concentration was 1000 ppm.
And diluted with water to irrigate with soil. After the treatment, the cells were placed in an artificial weather device at 25 ° C. for 14 hours in a wet room as a wet chamber, and the disease severity was examined 4 days later. Table 86 shows the test results of the cucumber seedling blight. In addition, 1000 ppm of captan wettable powder was used as a control drug.

[0194]

[Table 86]

(Test Example 6) Rice blast control effect test A wettable powder prepared by the method of (Formulation Example 2) was applied to rice (cultivar: Aichi Asahi) at the 3-4 leaf stage grown in a plastic pot having a diameter of 9 cm. Was diluted with water containing a surfactant (0.02%) so that the active ingredient concentration became 250 ppm, and sprayed with foliage. After air drying, rice blast fungus (Pyricularia oryzae)
The spore suspension was spray-inoculated, left in a moist room at 25 ° C. for 24 hours, then allowed to develop disease in a greenhouse, and 7 days after inoculation, the extent of the disease was investigated. Table 87 shows the results of the rice blast test. In addition,
500 ppm of Fusaride wettable powder and 2
50 ppm was used.

[0196]

[Table 87]

The specific structures of the compounds according to the present invention are further illustrated in Tables 88 to 90. However, in the table,
HetB, HetC, X, Y and n correspond to the definitions in general formulas (1) and (2), and Me represents a methyl group.

[0198]

[Table 88]

[0199]

[Table 89]

[0200]

[Table 90]

Physical chemistry data such as 1H-NMR spectrum and mass spectrum of the oxime derivative produced in the same manner as in Production Examples 1 to 9 are shown in Tables 91 to 97.

[0202]

[Table 91]

[0203]

[Table 92]

[0204]

[Table 93]

[0205]

[Table 94]

[0206]

[Table 95]

[0207]

[Table 96]

[0208]

[Table 97]

Test examples of the compound of the present invention will be further shown. A
The meanings of the evaluations of -D are the same as those of Test Examples 1-6.

(Test Example 7) Cucumber downy mildew controlling effect test A cucumber downy mildew controlling effect test was performed in the same manner as described in Test Example 2. The test results are shown in Table 98.

[0211]

[Table 98]

(Test Example 8) Cucumber downy mildew controlling effect test (leaf disk test) A cucumber downy mildew controlling effect test (leaf disk test) was carried out in the same manner as described in Test Example 3. The test results are shown in Table 99.

[0213]

[Table 99]

(Test Example 9) Grape downy mildew controlling effect test (leaf disk test) A grape downy mildew controlling effect test (leaf disk test) was carried out in the same manner as described in Test Example 4. As the grape downy mildew (Plasmopara viticola), a resistant strain b was used. The test results are shown in Table 100.

[0215]

[Table 100]

[0216]

According to the present invention, there is provided a novel oxime derivative which is free from concern about phytotoxicity to a plant and has a sufficient medicinal effect, and an agricultural chemical containing the oxime derivative as an active ingredient, particularly a plant disease control agent. it can.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07D 417/12 235 C07D 417/12 235 237 237 239 239 241 241 249 249 257 257 257 261 261 261 263 263 269 269 269 275 275 277 277 A01N 43 / 828 271/08 43/832 285/06 C07D 271/08 285/10 285/06 413/12 207 285/10 213 413/12 207 215 213 231 215 233 231 235 233 237 235 239 237 241 239 249 241 241 257 249 261 257 263 261 471 471/04 101 263 108A 471/04 101 A01N 43/82 102 108 103 (72) Inventor Jin Jin Chito Taito, Wakaba-ku, Chiba-shi, Chiba 1-25-16- 205 (72) Inventor Hiroyuki Tsuboi 10-12-4, Yachiyo-Taishi, Yachiyo-shi, Chiba Prefecture (72) Inventor Mika Iiyama 143-205, Musaki, Sakura-shi, Chiba Prefecture (72) Inventor Takashi Asada Chiba Prefecture 4-18-6 Chuodai, Shisui-machi, Inba-gun (72) Inventor Takashi Goto 3-5-1-101, Osakidai, Sakura-shi, Chiba

Claims (8)

[Claims] 1. The following general formula (1): Wherein R 1 represents a hydrogen atom or a lower alkyl group;
Represents a halogen atom, a nitro group, a hydroxy group, a cyano group,
Carboxyl group, alkoxycarbonyl group, lower alkyl group, lower alkyl group substituted with halogen atom, lower alkoxy group, lower alkoxy group substituted with halogen atom, lower alkylthio group, lower alkylthio group substituted with halogen atom, lower Alkylsulfonyl group, lower alkylsulfonyl group substituted with halogen atom, aryl group, aryl group substituted with halogen atom or lower alkyl group, aryloxy group, aryloxy group substituted with halogen atom or lower alkyl group, amino Represents an amino group substituted with a group or a lower alkyl group, n represents an integer of 0 to 3, and HetA represents a halogen atom, a lower alkyl group, a lower alkylthio group, a lower alkylsulfonyl group, a lower alkoxy group, and trifluoromethyl. Group or a cyano group A 6-membered nitrogen-containing aromatic ring or a benzo-fused ring-type nitrogen-containing aromatic ring containing one or two nitrogen atoms, which may be substituted with one or two substituents selected from the group, HetB is: Embedded image Embedded image (Wherein, Y represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkyl group substituted with a halogen atom). ] The oxime derivative represented by these. 2. The following general formula (2): [Wherein, R1, X, n, HetB and Y are the same as defined in the general formula (1), and HetC contains one or more nitrogen atoms and further contains a sulfur or oxygen atom. Or a 5-membered nitrogen-containing aromatic ring or a benzo-fused ring-type nitrogen-containing aromatic ring thereof which may be substituted with one or two substituents; The substituent is
A group selected from the group consisting of a lower alkyl group, a lower alkylsulfonyl group, a triphenylmethyl group, a lower alkoxymethyl group, and an N, N-disubstituted sulfamoyl group substituted with a lower alkyl group, including the 5-membered ring. The substituent on the carbon atom of the nitrogen aromatic ring includes a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, and a cycloalkyl having 3 to 6 carbon atoms. Group, alkenyl group having 2 to 6 carbon atoms, alkynyl group having 2 to 6 carbon atoms, alkoxy group having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms substituted with a halogen atom, lower alkylthio group, halogen atom A lower alkylthio group, a lower alkylsulfonyl group, a lower alkylsulfonyl group, a lower alkylsulfinyl group, a halogen atom substituted with a halogen atom A lower alkylsulfinyl group substituted with an atom, an amino group, a lower alkyl group or an amino group substituted with a cycloalkyl group having 3 to 6 carbon atoms or a triphenylmethyl group, a lower alkoxycarbonyl group, a carbamoyl group, or a lower alkyl group; A substituted carbamoyl group, an aminomethyl group, an aminomethyl group substituted with a lower alkyl group, an acylaminomethyl group, an N-alkoxycarbonylaminomethyl group, an alkylthiomethyl group, an aryl group, an aryl group substituted with a halogen atom, Heteroaryl group or -N (R2) C (= O) R3
A group (where R2 represents a hydrogen atom or a methyl group;
Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom,
A cycloalkyl group having 8 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, an aralkyl group, a lower alkyl group substituted with an amino group, an aralkyl group substituted with an amino group, and an acylamino group. A substituted lower alkyl group, an aralkyl group substituted with an acylamino group, a lower alkyl group substituted with an alkoxycarbonylamino group, an aralkyl group substituted with an alkoxycarbonylamino group, an aryl group; a halogen atom and a lower alkyl group; A lower alkyl group and a lower alkoxy group, a lower alkylthio group, and an aryl group substituted with a group selected from the group consisting of an amino group, a nitro group, and a cyano group; a heteroaryl group, a lower alkoxy group, and a carbon atom. A cycloalkyloxy group, a benzyloxy group or a It represents an aryloxy group. ). ] The oxime derivative represented by these. 3. The oxime derivative according to claim 1, wherein in Formula (1), HetA is a pyridyl group or a pyridyl group substituted with one halogen atom or lower alkyl group. 4. In the general formula (2), HetC is [Wherein R4 represents a hydrogen atom, an amino group, an alkoxy group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms substituted with a halogen atom, a lower alkylthio group, a lower alkylthio group substituted with a halogen atom, A lower alkylsulfonyl group, a lower alkylsulfonyl group substituted with a halogen atom, a lower alkylsulfinyl group, a lower alkylsulfinyl group substituted with a halogen atom, or -NHC (=
O) an R3 group (wherein, R3 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms substituted with a halogen atom)
An alkyl group, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, an aralkyl group, a lower alkyl group substituted with an amino group, and an amino group. Aralkyl groups, lower alkyl groups substituted with acylamino groups, aralkyl groups substituted with acylamino groups, lower alkyl groups substituted with alkoxycarbonylamino groups, aralkyl groups substituted with alkoxycarbonylamino groups, aryl groups; An aryl group substituted with a halogen atom and a lower alkyl group and a lower alkyl group and a lower alkoxy group substituted with a halogen atom, a lower alkylthio group, and an amino group, a nitro group and a cyano group; Group, lower alkoxy group, cycloalkyloxy group having 3 to 6 carbon atoms, Njiruokishi represents a group or an aryloxy group. R5 represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkyl group substituted with a halogen atom. The oxime derivative according to claim 2, which is a thiazolyl group represented by the formula: 5. R4 is a —NHC (＝ O) R3 group (wherein,
R3 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom,
Substituted with a group selected from the group consisting of a cycloalkyl group, an aralkyl group, an aryl group, a lower alkyl group and a lower alkoxy group, an amino group and a cyano group substituted with a halogen atom and a lower alkyl group and a halogen atom. Represents an aryl group; a heteroaryl group or a lower alkoxy group. The oxime derivative according to claim 4, wherein R5 is a hydrogen atom. 6. An agricultural chemical containing the oxime derivative according to claim 1 as an active ingredient. 7. A plant disease controlling agent comprising the oxime derivative according to any one of claims 1 to 5 as an active ingredient. 8. The plant disease control agent according to claim 7, which is effective against a plant disease caused by a filamentous fungus.