JPH10324687A - Pyrrole compound, production and agricultural and horticultural microbicide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound capable of being industrially and advantageously synthesized and useful as agricultural or horticultural microbicide providing precise effects and safe use. SOLUTION: This compound is a compound of formula I [X and Z are each independently H, a halogen, cyano, formyl, nitro, carbamoyl, etc.; Y is a halogen, cyano, formyl, nitro, and carbamoyl, etc.; Ar is a pyridyl (substituted with a halogen, cyano, hydroxy, benzyloxy, etc.); R is H, a metal atom, hydroxyl, a 1-6C alkoxy, etc.], or the salt thereof, for example, 4-bromo-2-(chloropyridin-2- yl)pyrrole. The compound of formula I can be obtained, for example, by reacting a compound of formula II (Y<1> is a 1-6C alkyl, etc.), with an amino acid esters of formula III (R<3> is a 1-6C alkyl; X<1> is H, a 1-6C alkyl, etc.), in nonsolvent or a suitable solvent at 0-200 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel pyrrole compound, a process for producing the same, and a fungicide for agricultural and horticultural use containing the same.

[0002]

2. Description of the Related Art In the cultivation of agricultural and horticultural crops, a large number of control agents are used against crop diseases, but their use is insufficient due to insufficient control effect or the emergence of drug-resistant pathogens. Due to their limitations, their potential to cause phytotoxicity and contamination of plants, and their high toxicity to humans, fish and livestock, there are not many satisfactory control agents that are not always satisfactory. Therefore, there is a strong demand for a drug that can be safely used with few such disadvantages. As a technique related to the present invention, JP-A-61-37705 describes that the following compounds are useful as agricultural and horticultural fungicides. However, there is no specific description other than the compound in which the substituent of the pyrrole ring N is a methyl group.

[0003]

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[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel pyrrole compound which can be advantageously synthesized industrially, has a certain effect, and can be used as a fungicide for agricultural and horticultural use.

[0005]

According to the present invention, there is provided a compound represented by the general formula (1):

[0006]

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In the formula, X and Z each independently represent a hydrogen atom, a halogen atom, a cyano group, a formyl group, a nitro group, a carbamoyl group, a thiocarbamoyl group, a C _1-6 alkyl group, a C _1-6 An alkoxy group, a C _1-6 haloalkyl group,
C _1-6 haloalkylcarbonyl group, C _1-6 alkoxycarbonyl group, hydroxyimino C _1-6 alkyl group, C _1-
6 alkoxyimino C _1-6 alkyl group, C _1-6 alkylthio group, C _1-6 dialkoxy C _1-6 alkyl group, C _1-6
An amino group optionally substituted with an alkyl group, a phenyl group (optionally substituted with a halogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group) or a (halogen atom, a C _1-6 alkyl group) Or a benzoyl group which may be substituted with a C _1-6 alkoxy group).

Y is a halogen atom, a cyano group, formyl
Group, nitro group, carbamoyl group, thiocarbamoyl group,
C_1-6 Alkyl group, C_1-6 Alkoxy group, C_1-6 Haloa
Lucyl group, C_1-6 Haloalkylcarbonyl group, C_1-6 A
Lucoxycarbonyl group, hydroxyimino C_1-6 Archi
Le group, C_1-6 Alkoxy imino C_1-6 Alkyl group, C
_1-6 Alkylthio group, C_1-6 Dialkoxy C_1-6 Archi
Le group, C_1-6 Amino optionally substituted with an alkyl group
Group, (halogen atom, C_1-6 Alkyl group or C _1-6 A
Phenyl group, which may be substituted by
(Halogen atom, C_1-6 Alkyl group or C_1-6 Arco
A benzoyl group which may be substituted by a xy group).

Ar represents [halogen atom, cyano group, hydrid
Roxy group, benzyloxy group, nitro group, cyanate
Group, thiocyanate group, C_1-6 Alkyl group, C_1-6 Halo
Alkyl group, C_1-6 Alkoxy C_1-6 Alkyl group, hydr
Roxy C_1-6 Alkyl group, C_{1- 6} Alkylsulfonyl C
_1-6 Alkyl group, cyano C_1-6 Alkyl group, hydroxy
Imino C_1-6 Alkyl group, C_1-6 Alkoxy imino C
_1-6 Alkyl group, C_1-6 Alkylcarbonylhydrazino
C_1-6 Alkyl group, C_1-6 Alkoxy C_1-6 Alkoxy
C_1-6 Alkyl group, C_2-6 Alkenyl group, C_2-6 Haloa
Lucenyl group, cyano C_2-6 Alkenyl group, C_1-6 Arco
Xycarbonyl C_2-6 Alkenyl group, C_1-6Alkoxy
C_2-6 Alkenyl group, C_2-6 Alkynyl group, C_2-6 Halo
Alkynyl group, hydroxy C_2-6 Alkynyl group, trime
Cylsilyl-substituted C_2-6 Alkynyl group, C_1-6 Alkoxy
C_2-6 Alkynyl group, C_1-6 Alkylthio group, C_1-6 C
Loalkylthio group, C_1-6 Alkylsulfinyl group, C
_1-6 Alkylsulfonyl group, C _1-6 Alkoxycarboni
Le group, C_3-8 Cycloalkyl group, C_3-8 Cycloalkyl
C_1-6 Alkyl group, C_1-6 Alkylcarbonyl group, C
_1-6 Alkoxy group, C_1-6Haloalkoxy group, C_1-6 A
Alkylcarbonyloxy group, C_1-6 Haloalkyl sulfo
Nyloxy group, C_1-6 Alkylcarbamoyloxy group,
1,2-epoxy C _2-6 Alkyl group, C_1-6 Alkyl group
An amino group optionally substituted with a (halogen atom,
Toro group, C_1-6 Alkyl group, C_1-6 Alkoxy group, C
_1-6 Haloalkyl group or C_1-6 Replace with haloalkoxy group
Phenyl or (halogen)
Child, nitro group, C_1-6 Alkyl group, C_1-6 Alkoxy
Group, C_1-6 Haloalkyl group or C_1-6 Haloalkoxy
Substituted with a benzyl group]
Represents an optionally substituted pyridyl group.

R represents a hydrogen atom, a metal atom, a hydroxyl group, a C _1-6 alkoxy group, a C _1-6 alkoxy C _1-6 alkyl group, a C _1-6 alkylcarbonyloxymethyl group,
_1-6 alkylthiomethyl group, C _1-6 alkylsulfinylmethyl group, C _1-6 alkylsulfonylmethyl group, C
_1-6 alkylcarbonyl group, C _1-6 alkoxycarbonyl group, C _1-6 alkylsulfonyl group, C _1-6 alkoxycarbonyloxy methyl group, N-C _1-6 alkyl -N-
C _1-6 alkylcarbonylaminomethyl group, N, N-diC _1-6 alkylthiocarbamoylthiomethyl group, tri-C
_1-6 alkylsilyl group, a triphenylsilyl group is substituted with (halogen atom, a nitro group, C _1-6 alkyl, C _1-6 alkoxy, C _1-6 haloalkyl group or a C _1-6 haloalkoxy group Benzoyl group, (halogen atom, nitro group, C _1-6 alkyl group, C _1-6 alkoxy group, C _1-6 haloalkyl group or C _1-6 haloalkoxy group) ) Benzoyloxymethyl group or phenyl (optionally substituted by halogen atom, nitro group, C _1-6 alkyl group, C _1-6 alkoxy group, C _1-6 haloalkyl group or C _1-6 haloalkoxy group) Represents a sulfonyl group. (However, Z is a C _1-6 alkoxycarbonyl group, and Y is a C _1-6 alkyl group or C
Excludes compounds that are _1-6 alkoxycarbonyl groups and compounds where Z is a cyano group and X and Y are both halogen atoms. ) A compound represented by｝ or a salt thereof.

Further, the present invention provides a compound represented by the following general formula (2):

[0012]

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Wherein the γ-ketoaldehyde compound represented by the formula (3) is reacted with ammonia or an ammonium salt.

[0014]

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(In the formula, Ar represents the same meaning as described above.)
This is a method for producing a pyridylpyrrole compound represented by the formula: In addition, the present invention relates to the above general formula (1 ′)

[0016]

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In the formula, X, Y 'and Z each independently represent a hydrogen atom, a halogen atom, a cyano group, a formyl group,
Nitro group, carbamoyl group, thiocarbamoyl group, C
_1-6 alkyl group, C _1-6 alkoxy group, C _1-6 haloalkyl group, C _1-6 haloalkylcarbonyl group, C _1-6 alkoxycarbonyl group, hydroxyimino C _1-6 alkyl group, C _1-6 alkoxy Imino C _1-6 alkyl group, C _{1-6
Alkylthio} group, C _1-6 dialkoxy C _1-6 alkyl group, amino group optionally substituted with C _1-6 alkyl group, (halogen atom, C _1-6 alkyl group or C _1-6 alkoxy group Represents a phenyl group (optionally substituted) or a benzoyl group (optionally substituted with a halogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group).

Ar is [halogen atom, cyano group, hydrid
Roxy group, benzyloxy group, nitro group, cyanate
Group, thiocyanate group, C_1-6 Alkyl group, C_1-6 Halo
Alkyl group, C_1-6 Alkoxy C_1-6 Alkyl group, hydr
Roxy C_1-6 Alkyl group, C_{1- 6} Alkylsulfonyl C
_1-6 Alkyl group, cyano C_1-6 Alkyl group, hydroxy
Imino C_1-6 Alkyl group, C_1-6 Alkoxy imino C
_1-6 Alkyl group, C_1-6 Alkylcarbonylhydrazino
C_1-6 Alkyl group, C_1-6 Alkoxy C_1-6 Alkoxy
C_1-6 Alkyl group, C_2-6 Alkenyl group, C_2-6 Haloa
Lucenyl group, cyano C_2-6 Alkenyl group, C_1-6 Arco
Xycarbonyl C_2-6 Alkenyl group, C_1-6Alkoxy
C_2-6 Alkenyl group, C_2-6 Alkynyl group, C_2-6 Halo
Alkynyl group, hydroxy C_2-6 Alkynyl group, trime
Cylsilyl-substituted C_2-6 Alkynyl group, C_1-6 Alkoxy
C_2-6 Alkynyl group, C_1-6 Alkylthio group, C_1-6 C
Loalkylthio group, C_1-6 Alkylsulfinyl group, C
_1-6 Alkylsulfonyl group, C _1-6 Alkoxycarboni
Le group, C_3-8 Cycloalkyl group, C_3-8 Cycloalkyl
C_1-6 Alkyl group, C_1-6 Alkylcarbonyl group, C
_1-6 Alkoxy group, C_1-6Haloalkoxy group, C_1-6 A
Alkylcarbonyloxy group, C_1-6 Haloalkyl sulfo
Nyloxy group, C_1-6 Alkylcarbamoyloxy group,
1,2-epoxy C _2-6 Alkyl group, C_1-6 Alkyl group
An amino group optionally substituted with a (halogen atom,
Toro group, C_1-6 Alkyl group, C_1-6 Alkoxy group, C
_1-6 Haloalkyl group or C_1-6 Replace with haloalkoxy group
Phenyl or (halogen)
Child, nitro group, C_1-6 Alkyl group, C_1-6 Alkoxy
Group, C_1-6 Haloalkyl group or C_1-6 Haloalkoxy
Substituted with a benzyl group]
Represents an optionally substituted pyridyl group.

R represents a hydrogen atom, a metal atom, a hydroxyl group, a C _1-6 alkoxy group, a C _1-6 alkoxy C _1-6 alkyl group, a C _1-6 alkylcarbonyloxymethyl group,
_1-6 alkylthiomethyl group, C _1-6 alkylsulfinylmethyl group, C _1-6 alkylsulfonylmethyl group, C
_1-6 alkylcarbonyl group, C _1-6 alkoxycarbonyl group, C _1-6 alkylsulfonyl group, C _1-6 alkoxycarbonyloxy methyl group, N-C _1-6 alkyl -N-
C _1-6 alkylcarbonylaminomethyl group, N, N-diC _1-6 alkylthiocarbamoylthiomethyl group, tri-C
_1-6 alkylsilyl group, a triphenylsilyl group is substituted with (halogen atom, a nitro group, C _1-6 alkyl, C _1-6 alkoxy, C _1-6 haloalkyl group or a C _1-6 haloalkoxy group Benzoyl group, (halogen atom, nitro group, C _1-6 alkyl group, C _1-6 alkoxy group, C _1-6 haloalkyl group or C _1-6 haloalkoxy group) ) Benzoyloxymethyl group or phenyl (optionally substituted by halogen atom, nitro group, C _1-6 alkyl group, C _1-6 alkoxy group, C _1-6 haloalkyl group or C _1-6 haloalkoxy group) Represents a sulfonyl group. A fungicide for agricultural and horticultural use, characterized by containing one or more of the compound represented by the formula or a salt thereof as an active ingredient.

Further, the present invention provides a compound represented by the following general formula (4):

Embedded image A cyanopyridine represented by ArCN (4) wherein Ar represents the same meaning as described above, and a compound represented by the formula (5):

[0021]

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(Wherein V represents a halogen atom, R ¹ ,
R ² each independently represents a C _1-6 alkyl group.
R ¹ and R ² may together form a C _2-4 alkylene group. Wherein the compound is treated with a Grignard reagent represented by the formula (1), and then treated under acidic conditions.

[0023]

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(In the formula, Ar represents the same meaning as described above.)
A process for producing a γ-ketoaldehyde compound represented by the formula:

The γ-ketoaldehyde represented by the general formula (2) is an intermediate for producing the pyridylpyrrole compound of the present invention, and many of them are novel substances. Hereinafter, the present invention will be described in detail.

The present invention is a pyridylpyrrole compound represented by the aforementioned general formula (I), and a fungicide for agricultural and horticultural use containing the compound. In the general formula (I), examples of the halogen atom in X, Y, and Z include chlorine, bromine, and fluorine. _{Examples of the} C _1-6 alkyl group include methyl, ethyl, propyl, isopropyl, butyl, t-butyl and the like, and examples of the C _1-6 alkoxy group include:
Methoxy, ethoxy, propoxy, butoxy, etc.
_{Examples of the 1-6} haloalkyl group include fluoromethyl, 1-fluoroethyl. 2-fluoroethyl, difluoromethyl, trifluoromethyl, difluorochloromethyl, fluorochloromethyl, trichloromethyl, tribromomethyl, 2,2,2-trifluoroethyl, pentafluoroethyl and the like.

The C _1-6 haloalkylcarbonyl group includes fluoromethylcarbonyl, 1-fluoroethylcarbonyl, 2-fluoroethylcarbonyl, difluoromethylcarbonyl, trifluoromethylcarbonyl, difluorochloromethylcarbonyl, fluorochloromethylcarbonyl, trichloromethyl Carbonyl, tribromomethylcarbonyl, 2,2,2-trifluoroethylcarbonyl, pentafluoroethylcarbonyl, etc.
Examples of the _1-6 alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, and butoxycarbonyl, and examples of the hydroxyimino C _1-6 alkyl group include hydroxyiminomethyl, hydroxyiminoethyl, and hydroxyiminopropyl. Is mentioned.

The C _1-6 alkoxyimino C _1-6 alkyl group includes methoxyiminomethyl, 1-methoxyiminoethyl, 2-ethoxyiminoethyl and the like, and the C _1-6 alkylthio group includes methylthio, ethylthio, propylthio. , Isopropylthio, etc. is a C _1-6 dialkoxy C
_{Examples of the 1-6} alkyl group include dimethoxymethyl, diethoxymethyl and the like.

Examples of the amino group which may be substituted with a C _1-6 alkyl group include mono- or di-C _1-6 alkylamino such as amino, methylamino, ethylamino, dimethylamino and diethylamino, and phenyl. Examples of the halogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group as a substituent of the group or the benzoyl group include those described above.

Ar represents a 2-pyridyl group which may have a substituent, a 3-pyridyl group which may have a substituent or a 4-pyridyl group which may have a substituent. Of these, compounds having a 2-pyridyl group are more preferred. In this case, the preferred substituent position is the 3- or 5-position of the pyridine ring, and more preferred Ar is a 3-substituted-2-pyridyl group, a 5-substituted-2-pyridyl group, or a 3,5 -Disubstituted-2-pyridyl group.

Examples of the halogen atom for the substituent in Ar include chlorine, bromine, and fluorine. _{Examples of the} C _1-6 alkyl group include methyl, ethyl, propyl, isopropyl, butyl, t-butyl and the like, and examples of the C _1-6 haloalkyl group include fluoromethyl, 1-fluoroethyl, 2-fluoroethyl, difluoromethyl, Trifluoromethyl, difluorochloromethyl, fluorochloromethyl,
Trichloromethyl, tribromomethyl, 2,2,2-trifluoroethyl, pentafluoroethyl and the like are C _1-6
The alkoxy C _1-6 alkyl group, methoxymethyl, ethoxymethyl, propoxymethyl, 1-ethoxyethyl, 2-propoxyethyl, 1-propoxypropyl, isopropoxymethyl, 2-isopropoxyethyl and the like, hydroxy C _1- Examples of the ₆ alkyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl and the like.

C_1-6 Alkylsulfonyl C_1-6 Alkyl
The group includes methylsulfonylmethyl, ethylsulfonyl
Methyl, propylsulfonylmethyl, 1-methylsul
Phonylethyl, 2-ethylsulfonylethyl, 1-pro
Pyrsulfonylethyl and the like, cyano C_1-6 Alkyl group and
For example, cyanomethyl, 1-cyanoethyl, 2-cyano
Ethyl, 1-cyanopropyl, 2-cyanopropyl, 3
-Cyanopropyl, 1-cyanobutyl, 2-cyanobuty
, 3-cyanobutyl, etc._1-6 A
As the alkyl group, hydroxyiminomethyl, 1-hydrido
Roxyiminoethyl, 1-hydroxyiminopropyl, etc.
But C_1-6 Alkoxy imino C_1-6 As an alkyl group
Is methoxyiminomethyl, 1-methoxyiminoethyl
, 2-ethoxyiminoethyl, etc._1-6 Alkylka
Rubonyl hydrazino C_1-6 As the alkyl group, acetyl
Ruhydrazinomethyl, acetylhydrazinoethyl, pro
Pionyl hydrazinomethyl, propionyl hydrazinoe
Chill etc. are C_1-6 Alkoxy C _1-6 Alkoxy C_1-6 A
As the alkyl group, methoxymethoxymethyl, ethoxy
Methoxymethyl, 2-methoxyethoxymethyl, 2-E
Toxiethoxymethyl, 2- (methoxymethoxy) ethyl
2- (ethoxymethoxy) ethyl, 2- (ethoxy)
-2-ethoxy) ethyl group and the like.

As the C _2-6 alkenyl group for the substituent in Ar, vinyl, 1-propenyl, allyl, crotyl, butadienyl and the like are mentioned, and as the C _2-6 haloalkenyl group, 1-chlorovinyl, 2- Chlorovinyl, 3-chloroallyl, 2-chlorocrotyl and the like, as a cyano C _2-6 alkenyl group, 1-cyanovinyl, 2-cyanovinyl and the like, and as a C _1-6 alkoxycarbonyl C _2-6 alkenyl group, 1- Methoxycarbonylvinyl, 2-methoxycarbonylvinyl, 1-methoxycarbonylallyl, 2-methoxycarbonylallyl, 3-methoxycarbonylallyl, etc., and as the C _2-6 alkynyl group, ethynyl, 1-propynyl, 2-propynyl, etc. No.

The C _2-6 haloalkynyl group includes 2-chloroethynyl, 2-bromoethynyl, 3-chloro-2-
Propynyl, 3,3,3-trifluoro-1-propynyl and the like include hydroxy C _2-6 alkynyl groups,
Hydroxy-1-propynyl, 3-hydroxypropargyl and the like are trimethylsilyl-substituted C _2-6 alkynyl groups; 2-trimethylsilylethynyl, 3-trimethylsilylpropargyl and the like are C _1-6 alkoxy C _2-6 alkynyl groups; 2-methoxyethynyl, 2-ethoxyethynyl, 2-propoxyethynyl, 3-methoxypropargyl, 3-ethoxypropargyl, 3-methoxy-1-propynyl and the like, and as the C _1-6 alkylthio group, methylthio, ethylthio, propylthio, Isopropylthio and the like; C _1-6 haloalkylthio groups such as chloromethylthio, fluoromethylthio and trifluoromethylthio; C _1-6 alkylsulfinyl groups such as methylsulfinyl and ethylsulfinyl;
_{Examples of the 1-6} alkylsulfonyl group include methylsulfonyl, ethylsulfonyl and the like.

Further, as the C _1-6 alkoxycarbonyl group for the substituent in Ar, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl and the like are mentioned, and as the C _3-8 cycloalkyl group, cyclopropyl, cyclopentyl, Cyclohexyl and the like, as C _3-8 cycloalkyl C _1-6 alkyl group, cyclopropylmethyl, 2-cyclopropylethyl, 1-cyclopropylpropyl, 1-cyclopropylbutyl, cyclopentylmethyl, 2-cyclopentylethyl, cyclohexyl Methyl, 2-cyclohexylethyl and the like; C _1-6 alkylcarbonyl as acetyl and propionyl; C _1-6 alkoxy as methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy and the like. Is raised It is.

Examples of the C _1-6 haloalkoxy group include trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, trichloromethoxy, difluoromethoxy and the like.
The C _1-6 alkylcarbonyloxy group, methyl carbonyloxy, ethyl carbonyloxy, propyl carbonyloxy, isopropyl carbonyloxy and the like,
Examples of the C _1-6 haloalkylsulfonyloxy group include trifluoromethylsulfonyloxy, trichloromethylsulfonyloxy, and pentafluoroethylsulfonyloxy. Examples of the C _1-6 alkylcarbamoyloxy group include methylcarbamoyloxy, ethylcarbamoyloxy, and propyl. Carbamoyloxy and the like.

As the 1,2-epoxy C _2-6 alkyl group, 1,2-epoxyethyl, 1,2-epoxypropyl and the like may be an amino group which may be substituted with a C _1-6 alkyl group. Examples thereof include mono- or di-C _1-6 alkylamino such as amino, methylamino, ethylamino, dimethylamino and diethylamino; halogen atom as a substituent of phenyl group and benzyl group; C _1-6 alkyl group; Examples of the _1-6 alkoxy group, C _1-6 haloalkyl group or C _1-6 haloalkoxy group include those described above as examples of Ar.

As the metal atom for R, copper, zinc,
Tin, manganese, nickel, cobalt, iron, etc.
You. C_1-6 Examples of the alkoxy group include methoxy and ethoxy.
Si, propoxy, isopropoxy, butoxy, t-but
Kissi etc. are C_1-6 Alkoxy C _1-6 As an alkyl group
Means methoxymethyl, ethoxymethyl, propoxymethyl
, Isopropoxymethyl, butoxymethyl, t-but
Xymethyl, methoxymethyl, 1-ethoxyethyl, 1
-Propoxyethyl, 1-isopropoxyethyl, 1-
Butoxyethyl, 1-t-butoxyethyl, 1-methoxy
Cypropyl, 1-ethoxypropyl, 1-propoxy
Ropyl, 1-isopropoxypropyl, 1-butoxy
Ropyl, 2-trimethylsilylethoxymethyl group and the like.
I can do it.

[0039] As C _1-6 alkylcarbonyloxy methyl group, acetoxymethyl, propionyloxymethyl, propyl carbonyloxy methyl, isopropyl carbonyloxy methyl, butyl carbonyl oxymethyl, and the like t- butylcarbonyloxy methyl, C _1-6 Examples of the alkylthiomethyl group include methylthiomethyl, ethylthiomethyl, propylthiomethyl, isopropylthiomethyl, butylthiomethyl, and t-butylthiomethyl, and examples of the C _1-6 alkylsulfinylmethyl group include methylsulfinylmethyl and ethylsulfinyl. Methyl,
Propylsulfinylmethyl, isopropynylsulfinylmethyl, butylsulfinylmethyl, t-butylsulfinylmethyl, etc., and the C _1-6 alkylsulfonylmethyl group is methylsulfonylmethyl, ethylsulfonylmethyl, propylsulfonylmethyl, isopropylsulfonylmethyl, butylsulfonyl Methyl, t-butylsulfonylmethyl and the like.

As the C _1-6 alkylcarbonyl group for R, acetyl, propionyl, propylcarbonyl, isopropylcarbonyl, butylcarbonyl,
t-butylcarbonyl and the like; C _1-6 alkoxycarbonyl groups as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and isopropoxycarbonyl; and C _1-6 alkylsulfonyl groups as methylsulfonyl, ethylsulfonyl and propylsulfonyl. , Isopropylsulfonyl, butylsulfonyl, t-butylsulfonyl and the like; and _C1-6 alkoxycarbonyloxymethyl groups include methoxycarbonyloxymethyl, ethoxycarbonyloxymethyl, propoxycarbonyloxymethyl, isopropoxycarbonyloxymethyl, butoxycarbonyloxy. Methyl, t-butoxycarbonyloxymethyl and the like.

The N-C _1-6 alkyl-N-C _1-6 alkylcarbonylaminomethyl group includes N-methyl-N-
Acetylaminomethyl, N-ethyl @ N-acetylaminomethyl, N-propyl-N-acetylaminomethyl,
N-isopropyl-N-acetylaminomethyl, N-butyl-N-acetylaminomethyl, Nt-butyl-N
-Acetylaminomethyl, N-methyl-N-propionylaminomethyl and the like include N, N-diC _1-6 alkylthiocarbamoylthiomethyl as N, N-dimethylthiocarbamoylthiomethyl, N, N-diethylthio. Carbamoylmethyl, N-methyl-N-ethylthiocarbamoylthiomethyl and the like; C _1-6 trialkylsilyl groups such as trimethylsilyl and triisopropylsilyl; benzoyl, benzoyloxymethyl and phenylsulfonyl groups A halogen atom as C
Examples of the _1-6 alkyl group, C _1-6 alkoxy group, C _1-6 haloalkyl group or C _1-6 haloalkoxy group include those described above as examples of the substituent of Ar.

In the present invention, the phenyl, benzoyl, pyridyl group and the like may have two or more substituents, and these substituents may be the same or different.

The salt of the pyrrole compound of the present invention is not particularly limited as long as it is an agriculturally and horticulturally acceptable salt. For example, salts of alkaline earth metals such as magnesium and calcium, metal salts such as iron, copper, zinc, nickel, cobalt, tin and manganese, salts of mineral acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, and methanesulfonic acid And salts of organic acids such as benzenesulfonic acid and oxalic acid which may be substituted, such as ethanesulfonic acid and p-toluenesulfonic acid.

[0044]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention can be produced by the following method. Production method (i)

[0045]

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(Wherein X ¹ represents a hydrogen atom, a C _1-6 alkyl group or a phenyl group which may be substituted,
¹ represents a C _1-6 alkyl group, a C _1-6 haloalkyl group or a C _1-6 dialkoxymethyl group, R ³ represents a C _1-6 alkyl group, and Ar has the same meaning as described above. )

In this method, the compound represented by the general formula (6) is reacted with an amino acid ester in a solvent-free or suitable organic solvent at 0 to 200 ° C. to give the compound (1-1). It is manufactured. Solvents that can be used for the reaction include aromatic hydrocarbons such as benzene and toluene, diethyl ether, tetrahydrofuran (T
Ethers such as HF), acetonitrile, N, N-dimethylformamide (DMF), and dimethylsulfoxide (DMSO). The amount of the amino acid ester to be used is preferably 1 to 100 equivalents relative to 1 equivalent of compound (6).

Formula (1-1) obtained by the above production method
Of the compounds of the formula (I), compounds in which Y ¹ is a trihalomethyl group such as trifluoromethyl can be prepared by a general synthetic chemical method such as the following formula, wherein Y ¹ is a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, or a cyano group Can be converted to

[0049]

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(Wherein, X ¹ , Y ¹ , and Ar have the same meanings as described above, and R ⁴ represents a C _1-6 alkyl group.)

In addition, the formula (1-
Among the compounds of 1), from the compound in which Y ¹ is a C _1-6 dialkoxymethyl group, Y ¹ is a hydroxyiminomethyl group, C _1-6
It can be derived into compounds such as an alkoxyiminomethyl group, a cyano group and a thiocarbamoyl group.

[0052]

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(In the formula, X ¹ and Ar have the same meanings as described above, and R ⁵ and R ⁶ each represent a C _1-6 alkyl group.)

Production method (ii)

[0055]

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(In the formula, X ¹ , R, and Ar represent the same meaning as described above.)

This method is described, for example, in Tetrahedr.
on. , 52 , 8707 (1996), etc., the γ-ketoaldehyde or γ-ketoaldehyde represented by the general formula (7) is used.
The compound represented by the formula (1-2) is produced by reacting a diketone compound with various amines, ammonium salts and the like at 0 to 200 ° C. in a solvent-free or suitable organic solvent.

Examples of the amine that can be used in this reaction include methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, t-butylamine, pentylamine, hexylamine, and cycloalkyl represented by the general formula RNH _2. Propylamine, cyclopentylamine, cyclohexylamine, benzylamine, benzylamine in which any position of the benzene ring may be substituted with a halogen atom, lower alkyl group, lower alkoxy group, nitro group, cyano group, alkoxycarbonyl group, etc. And the like.

Examples of the ammonium salt include ammonium acetate, ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium chloride, ammonia gas, and ammonia water.

Examples of the solvent that can be used in the reaction include aromatic hydrocarbons such as benzene and toluene, and alcohols such as methanol and ethanol.
The reaction proceeds smoothly at normal temperature to 150 ° C.

The raw material γ-ketoaldehyde is
It can be manufactured as follows. That is, equation (4)

[0062]

Embedded image ArCN (4) (Ar represents the same meaning as described above.)

A cyanopyridine represented by the formula (5)

[0064]

Embedded image

(Wherein V represents a halogen atom such as chlorine, bromine or iodine, and R ¹ and R ² each independently represent
Represents a C _1-6 alkyl group such as a methyl, ethyl and propyl group. Further, R ¹ and R ² may be combined to form a C _2-4 alkylene group such as ethylene, propylene, and butylene. )

After reacting with a Grignard reagent represented by

[0067]

Embedded image

(Ar has the same meaning as described above) can be produced.

Solvents that can be used in this reaction include diethyl ether, tetrahydrofuran (TH
F), ether solvents such as dimethoxyethane, and aromatic hydrocarbons such as benzene, toluene, and xylene. The reaction proceeds smoothly in a temperature range from -20 ° C to the boiling point of the solvent used.

Examples of the acid which can be used in the acid treatment include mineral acids such as hydrochloric acid, and organic acids such as oxalic acid and organic sulfonic acid. The reaction temperature is
−20 to 150 ° C., the molar ratio of the acid to be added is 3
The reaction is carried out using water or a water-containing organic solvent within an equivalent range.
Table 1 shows examples of the γ-ketoaldehyde produced as described above.

[0071]

[Table 101]

[0072]

[Table 102]

Production method (iii)

[0074]

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Wherein L represents a leaving group such as a 1-benzotriazolyl group or a tosyl group, Y ² represents a hydrogen atom, a cyano group or a C _1-6 haloalkyl group;
¹ represents a hydrogen atom or a C _1-6 alkoxycarbonyl group. Ar represents the same meaning as described above. )

This method comprises reacting a thioimidate represented by the general formula (8) with an olefin in a suitable organic solvent at -78 to 100 ° C. in the presence of a base to obtain a compound of the formula (1-3) To produce a compound represented by the formula: Examples of the base used in the reaction include inorganic bases such as NaH and KOH, and organic bases such as n-BuLi and LDA (lithium diisopropylamide). Organic solvents used for the reaction include DMF, DMSO, T
HF, benzene, toluene. Diethyl ether and the like. When Z ¹ is an alkoxycarbonyl group,
By hydrolysis and decarboxylation, Z ¹
Can be derived to a compound of a hydrogen atom.

Production method (iv)

[0078]

Embedded image

(Wherein X ² represents a C _1-6 haloalkyl group, V ′ and V ″ represent a halogen atom, U represents a cyano group or a C _1-6 alkoxycarbonyl group. Ar represents Represents the same meaning.)

This method comprises reacting an imidoyl halide represented by the general formula (9) with a haloolefin in an appropriate organic solvent at -78 to 150 ° C. in the presence of a base. This is for producing a compound represented by the formula (1-4). In addition, a compound represented by the formula (1-5) can be obtained at the same time by adding a trivalent phosphorus compound such as tributylphosphine or triphenylphosphine to the reaction system during the reaction. As a base used in this reaction, an inorganic base such as NaH, triethylamine,
Organic bases such as pyridine and n-BuLi can be mentioned. Examples of the solvent used for the reaction include acetonitrile, DMF, DMSO, THF, toluene and the like.

Production method (v)

[0082]

Embedded image

(Where X ³ , Y ³ , and Z ² each represent
Represents a hydrogen atom, a halogen atom, a formyl group, a cyano group, a nitro group, or an acyl group such as acetyl or benzoyl.
However, this excludes the case where X ³ , Y ³ and Z ² are all hydrogen atoms. R and Ar represent the same meaning as described above. )

In this method, a halogenating agent such as bromine, sulfuryl chloride, N-chlorosuccinimide (NCS) or N-bromosuccinimide (NBS) is added to pyridylpyrrole represented by the general formula (1-6). -7 in a suitable solvent
The reaction is carried out at a temperature of 8 to 150 ° C. in the presence of a radical reaction initiator such as benzoyl peroxide (BPO), if necessary, to introduce a halogen atom.
The obtained halogen compound is reacted with n-BuLi or the like to form a lithium compound, and further reacted with DMF. Formyl compounds can be derived.

The compound of the formula (1-6) and an acylating agent such as a Vilsmeier reagent or acetyl chloride are optionally added to a BF ₃ .OEt in an appropriate organic solvent at −78 to 150 ° C. ₂ , Formyl groups and acyl groups can be introduced by reacting in the presence of a Lewis acid such as AlCl ₃ . Examples of the organic solvent used for the reaction include halogenated hydrocarbons such as DMF, DMSO, THF, benzene, toluene, diethyl ether, dichloromethane, and chloroform.

Further, the pyridylpyrrole represented by the general formula (1-6) is reacted with a nitrating agent such as a mixed acid (concentrated nitric acid-concentrated sulfuric acid), nitric acid-acetic acid, or a nitrate such as copper nitrate to form X ³ , Y ³ and Z ² are nitro groups. The obtained formyl compound, acyl compound or nitro compound can be derived into a hydroxyiminoalkyl compound, an alkoxyiminoalkyl compound, a cyano compound or an amino compound by a usual synthetic chemical technique.

The compound of the present invention can be obtained by carrying out a usual post-treatment after completion of the reaction. The structure of the compound of the present invention was determined from IR, NMR, MS and the like.

[0088]

Next, the present invention will be described more specifically with reference to examples.

Example 1 Production of 2- (5-ethyl-2-pyridyl) -4-trifluoromethylpyrrole (Compound No. 1-151)

[0090]

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4,4,4-trifluoro-1- (5-ethyl-2-pyridyl) -butane-1,3-dione
To 85 g (375 mmol) of DMF solution (1 l) was added 523.28 g of glycine ethyl ester hydrochloride (3.75 g).
mol), and the mixture was heated under reflux for 20 hours. After cooling, the mixture was poured into water, brine was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography (benzene) to obtain 4.70 g of the desired compound. Yield 5.2% n _D ^24.5 1.5461

Example 2 (a) 1- (2-trimethylsilylethoxymethyl)-
Production of 2-bromo-3-trifluoromethyl-5- (5-ethyl-2-pyridyl) pyrrole (Compound No. 4-20)

[0093]

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0.70 g (1.84 mmol) of 1- (2-trimethylsilylethoxymethyl) -2- (5-ethyl-2-pyridyl) -4-trifluoromethylpyrrole
1.4 ml (2.2 mmol) of a 1.6N n-BuLi hexane solution was added dropwise at −10 ° C. to a dimethoxyethane solution (10 ml) of
After stirring for 5 minutes, 0.52 g of 1,2-dibromoethane
(2.8 mmol), and the mixture was stirred at -10 ° C for 2 hours and at room temperature for 3 hours. Water was added to the reaction solution, and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography (n-hexane-ethyl acetate = 25: 1),
0.21 g of the desired product was obtained. 25% yield

¹ H-NMR (CDCl ₃ , TMS, δ pp
m): -0.13 (9H, s), 0.78 (2H, d
d), 1.27 (3H, t), 2.67 (2H, q),
5.40 (2H, dd), 5.96 (2H, s), 6.
73 (1H, s), 7.47 (1H, d), 7.55
(1H, dd), 8.45 (1H, d)

(B) Preparation of 2-bromo-3-trifluoromethyl-5- (5-ethyl-2-pyridyl) pyrrole (Compound No. 1-156)

[0097]

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1- (2-trimethylsilylethoxymethyl) -2-bromo-3-trifluoromethyl-5- (5
-Ethyl-2-pyridyl) pyrrole 0.21 g (0.46
mmol) in 10 ml of acetonitrile solution under ice-cooling.
0.26 g (1.83 mmol) of BF ₃ .OEt ₂ was added, and the mixture was stirred at 0 ° C. for 2 hours and at room temperature for 3.5 hours. An aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with chloroform.
The organic layer was washed with water and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was subjected to silica gel chromatography (n-
The product was purified by hexane-ethyl acetate = 15: 1) to obtain 0.13 g of the desired product. Yield 87% mp. 88-89 ° C

Example 3 5- (5-ethyl-2-pyridyl) -2-methyl-3-
Trifluoromethylpyrrole (Compound No. 1-154)
Manufacturing of

[0100]

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1- (1-ethoxyethyl) -2- (5-
To a THF solution of 0.40 g (1.28 mmol) of ethyl-2-pyridyl) -4-trifluoromethylpyrrole was added:
Under a nitrogen atmosphere, at −78 ° C., 0.9 ml (1.4 mmol) of a 1.6N n-BuLi hexane solution was added dropwise.
After stirring at 78 ° C. for 1 hour, 0.27 g (1.9 mmol) of methyl iodide was added at −78 ° C., and the temperature was gradually raised from −78 ° C. to room temperature, followed by stirring for 24 hours. Water was added to the reaction mixture, and extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 0.39 g of a crude product. The reaction mixture is mixed with 4 ml of methanol.
, And 1.5 ml of 1N hydrochloric acid was added, and the mixture was heated under reflux at room temperature for 4 hours and 21 hours. Further, 0.5 ml of concentrated hydrochloric acid was added, and the mixture was heated under reflux for 51 hours. After cooling, an aqueous solution of sodium hydrogen carbonate was added, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (n-hexane-ethyl acetate = 15: 1) to obtain 0.11 g of the desired product.
Yield 34% mp. 89-90 ° C

Example 4 (a) Production of N- (1-benzotriazolylmethyl) -3 {chlorothiopicolinamide

[0103]

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3-Chlorothiopicolinamide 37.23
g (216 mmol) and a solution of 32.13 g (216 mmol) of 1-hydroxymethylbenzotriazole in 300 ml of toluene were heated and refluxed overnight using Dean-Stark. The reaction mixture was concentrated under reduced pressure, and the residue was subjected to silica gel chromatography (n-hexane-ethyl acetate = 3:
Purification was performed in 2) to obtain 7.83 g of the desired product. Yield 11.9
%

(B) Production of N- (1-benzotriazolylmethyl) -S-methyl-3-chloropicolinethioimidate

[0106]

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N- (1-benzotriazolylmethyl)-
7.80 g of 3-chlorothiopicolinamide (25.7 m
mol) of THF solution was cooled to -78 ° C,
1.6N n-BuLi hexane solution 1 under a nitrogen atmosphere
6.9 ml (27.0 mmol) was added dropwise, and the mixture was added at −78 ° C. for 3 hours.
After stirring for 0 minutes, 4.01 g of methyl iodide was added at -78 ° C.
(28.2 mmol) was added dropwise, and the mixture was stirred at -78 ° C for 1 hour. The reaction mixture was added to water and extracted with ethyl acetate.
After washing with a saturated saline solution, the organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain 7.70 g of a crude product. 94.3% yield

(C) Production of 2- (3-chloropyridin-2-yl) -3-t-butoxycarbonyl-4-trifluoromethylpyrrole (Compound No. 1-25)

[0109]

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N- (1-benzotriazolylmethyl)-
8.30 g (26.1 mmol) of a crude product of S-methyl-3-chloropicoline thioimidate and 6.15 g of 4,4,4-trifluorocrotonic acid t-butyl ester (3
1.4 mmol) in THF 200 ml, DMSO 40 m
1) and 3.24 g (81 mm) of 60% NaH under ice-cooling.
ol) and stirred at room temperature overnight. The reaction mixture was added to ice water and extracted with ethyl acetate. After washing with saturated saline,
The organic layer was dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel chromatography (n-hexane-ethyl acetate = 3: 2) to give 2.51 of the desired product.
g was obtained. Yield 27.7%

¹ H-NMR (CDCl ₃ , TMS, δ pp
m): 1.42 (9H, s), 7.18 (1H, d),
7.25 (1H, dd), 7.80 (1H, d), 8.
42 (1H, d), 9.75 (1H, br)

(D) Production of 2- (3-chloropyridin-2-yl) -4-trifluoromethylpyrrole-3-carboxylic acid (Compound No. 1-33)

[0113]

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2- (3-chloropyridin-2-yl)-
2.51 g (7.24 mmol) of 3-t-butoxycarbonyl-4-trifluoromethylpyrrole and 2.17 g (14.5 mmol) of sodium iodide were added under reduced pressure to 30-4.
After heating to 0 ° C., the atmosphere was replaced with nitrogen to return to normal pressure, acetonitrile 30 ml, trimethylsilyl chloride 1.57
g (14.6 mmol) was added, and the mixture was stirred at 80 to 85 ° C for 3 hours. After cooling, the mixture was added to ice water and extracted with diethyl ether. The organic layer was washed with an aqueous solution of Na ₂ S ₂ O ₃ and saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was crystallized from diethyl ether to obtain 0.80 g of the desired carboxylic acid. Yield 38% mp. 2
04-206 ° C

(E) 2- (3-chloropyridin-2-yl) -4-trifluoromethylpyrrole (Compound No. 1)
Production of -1)

[0116]

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2- (3-chloropyridin-2-yl)-
4-trifluoromethylpyrrole-3-carboxylic acid
80 g (2.75 mmol) was dissolved in 7 ml of quinoline, and barium-promoted copper chromite was dissolved in 0.1 ml of quinoline.
28 g was added, and the mixture was stirred at 210 to 220 ° C. for 5 minutes. After cooling, ice water was added, and insolubles were filtered using celite,
The filtrate was extracted with diethyl ether. After washing with an aqueous sodium hydrogen carbonate solution, activated carbon was added to the organic layer, and the mixture was stirred for 30 minutes, and then dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel chromatography (n-hexane-ethyl acetate = 5: 1) to obtain 90 mg of the desired product. Yield 13.2% mp. 75-76 ° C

Example 5 Preparation of 2- (3-chloropyridin-2-yl) -4-cyanopyrrole (Compound No. 1-5)

[0119]

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2- (3-chloropyridin-2-yl)-
50 mg of 4-trifluoromethylpyrrole (0.20 m
mol) was dissolved in 1 ml of acetonitrile, 1 ml of concentrated aqueous ammonia, 0.03 g of sodium hydroxide (0.75 m
mol), and the mixture was stirred at room temperature for 2 hours. Water was added and extracted with ethyl acetate. After washing with saturated saline, the organic layer was dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure.
The crude product was purified by silica gel chromatography (n-hexane-ethyl acetate = 3: 1) to obtain 20 mg of the desired product. Yield 49% mp. 124-126 ° C In addition, the present compound was prepared in the same manner as in Example 4- (c).
It could be obtained by using acrylonitrile instead of 4,4,4-trifluorocrotonic acid t-butyl ester (yield 16%).

Example 6 (a) Production of 3-chloro-2- {3- (1,3-dioxolan-2-yl) propionyl} -pyridine

[0122]

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12.63 g of magnesium (0.52 mol)
l) was added to 300 ml of THF, and 2-nitrogen was added under a nitrogen atmosphere.
(2-bromoethyl) -1,3-dioxolane 94.1
4 g (0.52 mol) of a THF solution was added dropwise at 40 ° C. or lower, and after the addition was completed, the mixture was further stirred at room temperature for 1 hour. The resulting Grignard solution was added dropwise to 30% or less of a THF solution (400 ml) of 30.00 g ((0.22 mol) of 3-chloro-2-cyanopyridine) at 30 ° C., and after the addition was completed, the mixture was further stirred at room temperature overnight. To the solution was added 10 ml of 3N hydrochloric acid to adjust the pH to 3, and after stirring for a while, 3N-hydrochloric acid was added.
The mixture was neutralized with an aqueous NaOH solution and extracted with diethyl ether and further with ethyl acetate. The organic layers were combined, washed with saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain 65 g of a crude desired ketoacetal product.

(B) Production of 3-chloro-2- (4-oxobutyryl) pyridine

[0125]

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The crude 3-chloro-2- {3-
(1,3-dioxolan-2-yl) propionyl}-
60 g of pyridine is converted to 27.74 g of oxalic acid dihydrate
(0.22 mol) water 300 ml and ethanol 10
The mixture was added to 0 ml of the solution, and heated under reflux for 6 hours. The reaction solution was concentrated under reduced pressure, neutralized with a saturated aqueous solution of sodium hydrogen carbonate, and extracted with 300 ml of diethyl ether. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (n-hexane-ethyl acetate = 3: 1) to obtain 18.27 g of the desired keto-aldehyde. Yield 42.7%

¹ H-NMR (CDCl ₃ , TMS, δp
pm): 2.92 (2H, t), 3.46 (2H, t), 7.38 (1H, dd
), 7.80 (1H, d), 8.54 (1H, d), 9.88 (1H, s)

(C) Preparation of 2- (3-chloropyridin-2-yl) pyrrole (Compound No. 1-34)

[0129]

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3-chloro-2- (4-oxobutyryl)
3.90 g (19.7 mmol) of pyridine was dissolved in 40 ml of ethanol, and 3.04 g (3.
(9.5 mmol) and heated under reflux for 30 minutes. After the reaction solution was concentrated under reduced pressure, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (n-hexane-ethyl acetate =
Purification by 3: 1) gave 3.16 g of the desired product. Yield 8
9.7% mp. 44-46 ° C

(D) Production of 2- (3-chloropyridin-2-yl) -1-triisopropylsilylpyrrole

[0132]

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0.40 g (2.24 mmol) of 2- (3-chloropyridin-2-yl) pyrrole was added to 5 m of DMF.
and 60% sodium hydride 0.11 under ice-cooling.
g (2.75 mmol) and further stirred at 0 ° C. for 5 minutes, and then 0.54 g of triisopropylsilyl chloride.
(2.80 mmol) was added, the temperature was gradually raised from 0 ° C. to room temperature, and the mixture was stirred overnight. Ice water and then brine were added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane-ethyl acetate = 50: 1),
0.55 g of the desired product was obtained. 73.3% yield

(E) Production of 4-bromo-2- (3-chloropyridin-2-yl) -1-triisopropylsilylpyrrole (Compound No. 4-39)

[0135]

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2- (3-chloropyridin-2-yl)-
0.55 g of 1-triisopropylsilylpyrrole (1.
64 mmol) was dissolved in 15 ml of THF and cooled to -78 ° C. A solution of 0.30 g (1.69 mmol) of NBS (N-bromosuccinimide) in 7 ml of THF was added dropwise thereto, and the temperature was gradually returned from -78 ° C to room temperature, followed by stirring overnight. Water was added to the reaction solution, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography (benzene-n-hexane = 1: 1) to obtain 0.60 g of the desired product. 88.2% yield

(F) Production of 4-bromo-2- (3-chloropyridin-2-yl) pyrrole (Compound No. 1-14)

[0138]

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4-bromo-2- (3-chloropyridine-
2-yl) -1-triisopropylsilylpyrrole
To a solution of 0.40 g (0.97 mmol) in 5 ml of THF was added 0.1 ml of tetrabutylammonium fluoride trihydrate.
31 g (0.98 mmol) was added, and the mixture was stirred at room temperature for 20 minutes. Water and then brine were added to the reaction solution, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate.
After the solvent was distilled off under reduced pressure, the residue was subjected to silica gel column chromatography (n-hexane-ethyl acetate = 5: 1).
Then, 0.21 g of the desired product was obtained. 84.3% yield
mp. 83-84 ° C

Representative examples of the compounds of the present invention, including the compounds obtained in the above Examples, are shown in Tables 2 to 5.

[0141]

[Table 201]

[0142]

[Table 202]

[0143]

[Table 203]

[0144]

[Table 204]

[0145]

[Table 205]

[0146]

[Table 206]

[0147]

[Table 207]

[0148]

[Table 208]

[0149]

[Table 209]

[0150]

[Table 210]

[0151]

[Table 211]

[0152]

[Table 212]

[0153]

[Table 213]

[0154]

[Table 214]

[0155]

[Table 215]

[0156]

[Table 216]

[0157]

[Table 217]

[0158]

[Table 301]

[0159]

[Table 302]

[0160]

[Table 303]

[0161]

[Table 304]

[0162]

[Table 305]

[0163]

[Table 306]

[0164]

[Table 401]

[0165]

[Table 402]

[0166]

[Table 403]

[0167]

[Table 404]

[0168]

[Table 405]

[0169]

[Table 501]

[0170]

[Table 502]

[0171]

[Table 503]

Further, the compounds in the table The H-NMR data are summarized in Table 6.

[0173]

[Table 6]

[0174]

BEST MODE FOR CARRYING OUT THE INVENTION Since the compound of the present invention has excellent bactericidal activity against a wide variety of filamentous fungi, it is useful for controlling various diseases that occur during the cultivation of agricultural and horticultural crops including flowers, turf and pasture. Can be used. For example, rice blast disease (Pyricularia oryzae) Sheath Blight (Rhizoctonia solani) bakanae (Gibberella fujikuroi) Gomaha blight (Cochliobolus miyabeanus) barley brownish ear disease (Ustilago nuda) Wheat Fusarium head blight (Gibberella zeae) brown rust ( Puccinia recondita) Memonbyo (Pseudocercosporella herpotrichoides) glume blotch (Leptosphaeria nodorum) powdery mildew (Erysiphe graminis f. sp. tritici ) pink snow mold disease (Monographella nivalis) potato late blight (Phytophthora infestans) peanut brown spot disease (Mycosphaerella arachidis ) sugar beet brown spot disease (Cercospora beticola) cucumber powdery mildew (Sphaerotheca fuliginea) rot (Sclerotinia sclerotiorum) gray mold (Botrytis cinerea) downy mildew (Pseudoperonospora cubensis) tomato leaf blight (Cladosporium fulvum) late blight (Phytophthora infestans ) Eggplant Black blight ( Corynespora melongenae ) Onion Gray rot ( Botrytis all ii) strawberry powdery mildew (Sohaerotheca humuli) apple powdery mildew (Podosphaera leucotricha) scab (Venturia inaequalis) blossom disease (Monilinia mali) persimmon anthracnose (Gloeosporium kaki) Peach Haihoshibyo (Monilinia fructicola) grape powdery mildew (Uncinula necator) and downy mildew (Plasmopara viticola) without gymnosporangium (gymnosporangium asiaticum) black spot disease (Alternaria kikuchiana) tea Wamadarabyo (Pestalotia theae) and anthracnose (Colletotrichum theae-sinensis) citrus scab (Elisinoe fawcetti) It can be used to control blue mold ( Pennisillium italicum ), western grass, snow rot, and Sclerotinia borealis .

In recent years, various pathogens have developed resistance to benzimidazole agents, dicarboximide agents, and the like, resulting in a lack of efficacy of these agents, and drugs effective against resistant pathogens are desired. The compound of the present invention is not only sensitive but also has an excellent bactericidal effect against pathogenic bacteria resistant to benzimidazole agents and dicarboximide agents. Diseases that are more preferably applied include apple scab and cucumber gray mold.

The compound of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to underwater objects such as ship bottoms and fish nets. Also, by mixing the compound of the present invention into paints, fibers, and the like, it can be used as an antibacterial and fungicide for walls and bathtubs, shoes and clothes. Some of the compounds of the present invention exhibit insecticidal, acaricidal and herbicidal activities.

[Bactericide] When the compound of the present invention thus obtained is actually applied, it can be used in a pure form without adding other components, and it can be used as a pesticide for general pesticides. It can also be used in the form to be obtained, that is, wettable powder, granule, powder, emulsion, aqueous solvent, suspension, flowable and the like. When the solid additive is intended as an additive and carrier, soybean grains, vegetable powder such as flour, diatomaceous earth,
Mineral fine powders such as apatite, gypsum, talc, bentonite, pyrophyllite, and clay, and organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate are used. When a liquid dosage form is intended, petroleum fractions such as kerosene, xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, water Is used as a solvent. In order to obtain a uniform and stable form in these preparations, a surfactant may be added, if necessary. The wettable powder, emulsion, and flowable obtained in this manner are diluted to a predetermined concentration with water to prepare a suspension or an emulsion, and the powder and granules are used as they are by spraying them on plants.

Although the compound of the present invention exerts a sufficient effect even when used alone, it can be used in combination with one or more kinds of various fungicides, insecticides, acaricides or synergists.
Fungicides that can be used in combination with the compound of the present invention, insecticides,
Examples of the acaricide, nematicide, and plant growth regulator include the following.

Disinfectant: Copper agent: basic copper chloride, basic copper sulfate, etc. Sulfur agent: thiuram, maneb, mancozeb, polycarbamate, propineb, ziram, zineb, etc. Polyhaloalkylthio agent: captan, dichlorfluanide, phor Pets, etc. Organic chlorine agents: chlorothalonil, fthalide, etc. Organic phosphorus agents: IBP, EDDP, tolclofosmethyl,
Pyrazophos, fosetyl, etc. Benzimidazole agents: thiophanate methyl, benomyl, carbendazim, thiabendazole, etc. Dicarboximide agents: iprodione, vinclozolin, procymidone, fluoroimide, etc. Carboxamide agents: oxycarboxin, mepronil, flutranil, teclophthalam, triclamide, pencyclone, etc.

Phenylamide agent: metalaxyl, oxadixyl, furalaxyl, etc. SBI agent: triadimefon, triadimenol, bitertanol, microbutanyl, hexaconazole, propiconazole, trifumizol, prochloraz, pefurazoate, fenarimol, pyrifenox, triforine, flusilazole, Etaconazole, diclobutrazole, fluotrimazole, flutriafen, penconazole, diniconazole, cyproconazole, imazalil, tridemorph, fenpropimorph, butiobate, epoxyconazole, metconazole, etc.

Antibiotics: polyoxin, blasticidin S, kasugamycin, validamycin, dihydrostreptomycin sulfate, etc. Others: propamocarb hydrochloride, quintozene, hydroxyisoxazole, metasulfocarb, anilazine,
Isoprothiolane, probenazole, quinomethionate, dithianone, dinocab, diclomedine, mepanipyrim, ferimzone, fluazinam, pyroquilon, tricyclazole, oxolinic acid, dithianone, iminoctadine acetate, simoxanil, pyrrolnitrin, metasulfocarb, dietofencaribine, citapfencarburinabine , Dozine, dimethomorph, phenazine oxide, etc.

Insecticides and miticides: Organophosphorus and carbamate insecticides: phenthion, fenitrothion, diazinon, chlorpyrifos, ES
P, bamidothion, fentoate, dimethoate, formotion, marathon, trichlorfon, thiomethon,
Hosmet, dichlorvos, acephate, EPBP,
Methyl parathion, oxydimetone methyl, ethion,
Salithione, cyanophos, isoxathion, pyridafenthion, hosalon, methidathion, sulprophos, chlorfenvinphos, tetrachlorvinphos, dimethylvinphos, propaphos, isofenphos, ethylthiometon, profenophos, pyraclophos, monocrotophos, azinphosmethyl, aldicarb, mesomil, thiodicarb, Carbofuran, carbosulfan, benfracarb, flatiocarb, propoxur, BPMC,
MTMC, MIPC, carbaryl, pirimicarb, ethiophencarb, phenoxycarb and the like. Pyrethroid insecticides: permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatrin, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propasulin, phenothrin, protrin, fulvalinate, cyfluthrin, cyhalothrin, flucitrinate, etofenprox, Cycloprothrin, trolametrin, silafluofen,
Blofenprox, Acrinasuri etc.

Benzoylurea and other insecticides: diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, methoprene, cartap, thiocyclam, bensultap , Benzoepin, diafenthiuron, acetamiprid, nitenpyram, imidacloprid, fipronil, nicotine sulfate, rotenone, methaldehyde, machine oil, microbial pesticides such as BT and insect pathogenic virus. Nematicides: fenamiphos, phosthiazate and the like. Acaricides: chlorbenzilate, phenisobromolate, dicophor, amitraz, BPPS, benzomate,
Hexitiazox, fenbutatin oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentezin, cyhexatin, pyridaben, fenpyroximate, tebufenpyrad, pyrimidifen, phenothiocarb, dienochlor and the like. Plant growth regulator: gibberellins (eg gibberellin A
_3, gibberellin A _4, gibberellin A ₇₎ IAA, NA
A.

[0184]

【Example】

[Bactericide] Next, some examples of the composition of the present invention will be described. However, the additives and the addition ratio are not limited to these examples, and can be varied in a wide range. Parts in Formulation Examples are parts by weight.

Example 7 Water-dispersible powder 40 parts of the compound of the present invention 53 parts of diatomaceous earth 4 parts of higher alcohol sulfate 4 parts of alkylnaphthalene sulfonate If the above are uniformly mixed and finely pulverized, the active ingredient 40
% Wettable powder.

Example 8 Emulsion 30 parts of the compound of the present invention 30 parts of xylene 30 parts of dimethylformamide 7 parts of polyoxyethylene alkyl allyl ether By mixing and dissolving the above, an emulsion having an active ingredient of 30% is obtained.

Example 9 Suspending agent 10 parts of the compound of the present invention 4 parts of sodium ligninsulfonate 4 parts of sodium dodecylbenzenesulfonate 1 part of xanthan gum 0.2 parts of water 84.8 parts The above mixture was mixed until the particle size became 1 micron or less. If wet milled, a 10% active ingredient suspension is obtained.

[0188]

Next, Test Examples show that the compounds of the present invention are useful as effective components of various plant disease controlling agents. The control effect was determined by visually observing the growth of lesions and flora that appeared on leaves, stems and the like at the time of the survey, and calculating the control effect.

Test Example 1 Apple Scab Control Test Apple seedlings (cultivar “Kunimitsu”, 3
4 to the fourth leaf stage), the emulsion of Example 8 was treated with 200 ppm of the active ingredient.
At a concentration of After spraying, air-dry at room temperature, and scab of apple ( Venturia inaequalis )
Were maintained in a high humidity constant temperature room (20 ° C.) for 2 weeks, in which light and dark were repeated every 12 hours. As a result of comparing and investigating the appearance of lesions on the leaves with no treatment, the control effect was obtained,
The following compounds showed an excellent controlling effect of 75% or more. I-9, I-11, I-128, I-156, I-15
7

Test Example 2 Cucumber Gray Mold Control Test Cucumber cultivated in an unglazed pot (variety “Sagami Hanjiro”)
The seedling was sprayed with the emulsion of Example 8 at a concentration of 200 ppm of the active ingredient. After spraying, air-dry at room temperature, inoculate a spore suspension (containing glucose and yeast extract) of cucumber gray mold fungus ( Botrytis cinerea ) into cucumber cotyledons, and in a dark, high humidity, constant temperature room (20 ° C.). 4
Held for days. The diameter of lesions on cotyledons was compared with that of no treatment, and the control effect was determined. As a result, the following compounds showed excellent effects of 75% or more. I-1, I-5, I-9, I-11, I-14, I-3
4, I-124, I-128, I-151, I-15
4, I-156, I-157, I-163, I-174

Test Example 3 Grape Downy Mildew Control Test Leaves of an openly planted grape (variety “Kaiji”, 3rd grade) were punched into a 30 mm-diameter disk and immersed in a 200 ppm active ingredient chemical solution of the emulsion of Example 8. After immersion, air dry at room temperature, and the grape downy mildew fungus ( Plasmopara v
icola ) was spray inoculated with a zoosporang suspension and kept in a constant temperature room (20 ° C.) under illumination for 10 minutes . As a result of comparing and investigating the appearance of lesions on the leaves with no treatment, the control effect was obtained,
The following compounds showed an excellent controlling effect of 75% or more. I-128, I-151

Continuing from the front page (72) Inventor Shinsuke Sano 345 Takada, Odawara-shi, Kanagawa Japan Soda Co., Ltd. Odawara Research Laboratories (72) Inventor Susumu Shimoda Sugawara, Odawara-shi, Kanagawa Pref. Yoji Horikoshi 345 Takada, Odawara-shi, Kanagawa Nippon Soda Co., Ltd.

Claims (4)

[Claims] 1. A compound of the general formula (1)Wherein X and Z are each independently a hydrogen atom, a halo
Gen atom, cyano group, formyl group, nitro group, carbamo
Yl group, thiocarbamoyl group, C_1-6 Alkyl group, C
_1-6 Alkoxy group, C_1-6 Haloalkyl group, C_1-6Halo
Alkylcarbonyl group, C_1-6 Alkoxycarbonyl
Group, hydroxyimino C_1-6 Alkyl group, C_{1- 6} Arco
Kisimino C_1-6 Alkyl group, C_1-6 Alkylthio group,
C_1-6 Dialkoxy C_1-6 Alkyl group, C_1-6 Alkyl
An amino group which may be substituted with a group, (a halogen atom,
C_1-6 Alkyl group or C_1-6 Substituted with an alkoxy group
Phenyl group or (halogen atom, C
_1-6 Alkyl group or C_1-6 Substituted with an alkoxy group
Represents a benzoyl group. Y is halogen source
, Cyano group, formyl group, nitro group, carbamoyl
Group, thiocarbamoyl group, C_1-6 Alkyl group, C_1-6 A
Lucoxy group, C_1-6 Haloalkyl group, C_1-6Haloalk
Carbonyl group, C_1-6 Alkoxycarbonyl group, hydr
Roxiimino C_1-6 Alkyl group, C_1-6 Alkoxyimi
No C_1-6 Alkyl group, C _1-6 Alkylthio group, C_1-6 The
Alkoxy C_1-6 Alkyl group, C_1-6 Substitute with alkyl group
Optionally substituted amino group, (halogen atom, C_1-6 A
Alkyl group or C _1-6 Even if substituted with an alkoxy group
Good) phenyl group or (halogen atom, C_1-6 Archi
Group or C_1-6 May be substituted with an alkoxy group
I) represents a benzoyl group. Ar is [halogen atom, silicon
Ano group, hydroxy group, benzyloxy group, nitro group,
Cyanate group, thiocyanate group, C_1-6 Alkyl group,
C_1-6 Haloalkyl group, C_1-6 Alkoxy C_1-6 Archi
Group, hydroxy C_1-6 Alkyl group, C_{1- 6} Alkyls
Ruphonyl C_1-6 Alkyl group, cyano C_1-6 Alkyl group,
Hydroxyimino C_1-6 Alkyl group, C_1-6 Alkoxy
Imino C_1-6 Alkyl group, C_1-6 Alkyl carbonyl arsenic
Drazino C_1-6 Alkyl group, C_1-6 Alkoxy C_1-6 A
Lucoxy C_1-6 Alkyl group, C_2-6 Alkenyl group, C
_2-6 Haloalkenyl group, cyano C_2-6 Alkenyl group, C
_1-6 Alkoxycarbonyl C_2-6 Alkenyl group, C_1-6
Alkoxy C_2-6 Alkenyl group, C_2-6 Alkynyl group,
C_2-6 Haloalkynyl group, hydroxy C_2-6 Alkynyl
Group, trimethylsilyl substituted C_2-6 Alkynyl group, C_1-6 
Alkoxy C_2-6 Alkynyl group, C_1-6 Alkylthio
Group, C_1-6 Haloalkylthio group, C_1-6 Alkylsulf
Inyl group, C_1-6 Alkylsulfonyl group, C _1-6 Arco
Xycarbonyl group, C_3-8 Cycloalkyl group, C_3-8 Shi
Black alkyl C_1-6 Alkyl group, C_1-6 Alkyl carb
Nyl group, C_1-6 Alkoxy group, C_1-6Haloalkoxy
Group, C_1-6 Alkylcarbonyloxy group, C_1-6 Haloa
Alkylsulfonyloxy group, C_1-6 Alkyl carbamoy
Roxy group, 1,2-epoxy C _2-6 Alkyl group, C
_1-6 An amino group optionally substituted with an alkyl group, (C
Logen atom, nitro group, C_1-6 Alkyl group, C_1-6 Al
Coxy group, C_1-6 Haloalkyl group or C_1-6 Haloal
A phenyl group, which may be substituted
(Halogen atom, nitro group, C_1-6 Alkyl group, C_1-6 
Alkoxy group, C_1-6 Haloalkyl group or C_1-6 Halo
Optionally substituted with an alkoxy group) with a benzyl group]
Represents an optionally substituted pyridyl group. R is hydrogen source
Child, metal atom, hydroxyl group, C_1-6 Alkoxy group,
C_1-6 Alkoxy C_1-6 Alkyl group, C_1-6 Alkylka
Rubonyloxymethyl group, C_1-6Alkylthiomethyl
Group, C_1-6 Alkylsulfinylmethyl group, C_1-6 Al
Killsulfonylmethyl group, C_1-6 Alkylcarbonyl
Group, C_1-6 Alkoxycarbonyl group, C_1-6 Alkyls
Rufonyl group, C_1-6 Alkoxycarbonyloxymethyl
Group, NC_1-6 Alkyl-NC_1-6 Alkyl carboni
Ruaminomethyl group, N, N-di C_1-6 Alkylthiocal
Bamoylthiomethyl group, tri-C_1-6 Alkylsilyl group,
Triphenylsilyl group, (halogen atom, nitro group, C
_1-6 Alkyl group, C_1-6 Alkoxy group, C_1-6 Haloal
Kill group or C_1-6 Substituted with a haloalkoxy group
Benzoyl group, (halogen atom, nitro group, C
_1-6 Alkyl group, C_1-6 Alkoxy group, C_1-6 Haloal
Kill group or C_1-6 Substituted with a haloalkoxy group
Benzoyloxymethyl group or (halogen atom)
Child, nitro group, C_1-6 Alkyl group, C_1-6 Alkoxy
Group, C_1-6 Haloalkyl group or C_1-6 Haloalkoxy
Phenylsulfonyl group which may be substituted with
You. (However, Z is C_1-6 An alkoxycarbonyl group,
Y is C_1-6 Alkyl group or C_1-6 Alkoxycarbo
A compound wherein Z is a cyano group and X and Y are
Excludes compounds that are both halogen atoms. )｝
Compound or salt thereof. 2. A compound of the general formula (2) (Wherein, Ar represents the same meaning as described above)
-Reacting a ketoaldehyde compound with ammonia or an ammonium salt, characterized by the following formula (3): (In the formula, Ar represents the same meaning as described above.) 3. A compound of the general formula (1) '中 wherein X, Y 'and Z are each independently a hydrogen atom
Atom, halogen atom, cyano group, formyl group, nitro group,
Carbamoyl group, thiocarbamoyl group, C_1-6 Alkyl
Group, C_1-6 Alkoxy group, C_1-6 Haloalkyl group, C
_1-6 Haloalkylcarbonyl group, C_1-6 Alkoxycal
Bonyl group, hydroxyimino C_1-6 Alkyl group, C_1-6 
Alkoxy imino C_1-6 Alkyl group, C_1-6 Alkyl
Ohki, C_1-6 Dialkoxy C_1-6 Alkyl group, C_1-6 A
Amino group which may be substituted with alkyl group, (halogen
Atom, C_1-6 Alkyl group or C_1-6 Replace with alkoxy group
Phenyl or (halogen)
Child, C_1-6 Alkyl group or C_1-6Substitute with alkoxy group
A benzoyl group. Ar is [c
Logen atom, cyano group, hydroxy group, benzyloxy
Group, nitro group, cyanate group, thiocyanate group, C
_1-6 Alkyl group, C_1-6 Haloalkyl group, C_1-6 Arco
Kishi C_1-6 Alkyl group, hydroxy C_1-6 Alkyl group,
C_{1- 6} Alkylsulfonyl C_1-6 Alkyl group, cyano C
_1-6 Alkyl group, hydroxyimino C_1-6 Alkyl group,
C_1-6 Alkoxy imino C_1-6 Alkyl group, C_1-6 Al
Kill carbonyl hydrazino C_1-6 Alkyl group, C_1-6 A
Lucoxy C_1-6 Alkoxy C_1-6 Alkyl group, C_2-6 A
Lucenyl group, C_2-6 Haloalkenyl group, cyano C_2-6 A
Lucenyl group, C_1-6 Alkoxycarbonyl C_2-6 Arche
Nyl group, C_1-6Alkoxy C_2-6 Alkenyl group, C_2-6 
Alkynyl group, C_2-6 Haloalkynyl group, hydroxy C
_2-6 Alkynyl group, trimethylsilyl substituted C_2-6 Archi
Nyl group, C_1-6 Alkoxy C_2-6 Alkynyl group, C_1-6 
Alkylthio group, C_1-6 Haloalkylthio group, C_1-6 A
Rukylsulfinyl group, C_1-6 Alkylsulfonyl group,
C _1-6 Alkoxycarbonyl group, C_3-8 Cycloalkyl
Group, C_3-8 Cycloalkyl C_1-6 Alkyl group, C_1-6 A
Alkylcarbonyl group, C_1-6 Alkoxy group, C_1-6Halo
Alkoxy group, C_1-6 Alkylcarbonyloxy group, C
_1-6 Haloalkylsulfonyloxy group, C_1-6 Alkyl
Carbamoyloxy group, 1,2-epoxy C _2-6 Archi
Le group, C_1-6 Amino optionally substituted with an alkyl group
Group, (halogen atom, nitro group, C_1-6 Alkyl group, C
_1-6 Alkoxy group, C_1-6 Haloalkyl group or C_1-6 
A phenyl group which may be substituted by a haloalkoxy group)
Or (halogen atom, nitro group, C_1-6 Alkyl group,
C_1-6 Alkoxy group, C_1-6 Haloalkyl group or C
_1-6 Benzyl which may be substituted with a haloalkoxy group)
A pyridyl group which may be substituted. R
Represents a hydrogen atom, a metal atom, a hydroxyl group, C_1-6 Al
Coxy group, C_1-6 Alkoxy C_1-6 Alkyl group, C_1-6 
Alkylcarbonyloxymethyl group, C_1-6Alkyl
Omethyl group, C_1-6 Alkylsulfinylmethyl group, C
_1-6 Alkylsulfonylmethyl group, C_1-6 Alkyl cal
Bonyl group, C_1-6 Alkoxycarbonyl group, C_1-6 Al
Killsulfonyl group, C_1-6 Alkoxycarbonyloxy
Methyl group, NC_1-6 Alkyl-NC_1-6 Alkylka
Rubonylaminomethyl group, N, N-diC_1-6 Alkyl
Ocarbamoylthiomethyl group, tri-C_1-6 Alkyl sil
Group, triphenylsilyl group, (halogen atom, nitro
Group, C_1-6 Alkyl group, C_1-6 Alkoxy group, C_1-6 C
Loalkyl group or C_1-6 Substituted with a haloalkoxy group
Benzoyl group, (halogen atom, nitro
Group, C_1-6 Alkyl group, C_1-6 Alkoxy group, C_1-6 C
Loalkyl group or C_1-6 Substituted with a haloalkoxy group
Benzoyloxymethyl group or (halo)
Gen atom, nitro group, C_1-6 Alkyl group, C_1-6 Arco
Xy group, C_1-6 Haloalkyl group or C_1-6 Halo alco
A phenylsulfonyl group which may be substituted by an xy group)
Represents化合物 or one of its salts or
Is characterized by containing at least two active ingredients
Agricultural and horticultural fungicides. 4. A cyanopyridine represented by the general formula (4): ArCN (4) (wherein Ar has the same meaning as described above) and a compound represented by the formula (5): 6] (Wherein V represents a halogen atom, R ¹ and R ² each independently represent a C _1-6 alkyl group. In addition, R ¹ and R ² together form a C _2-4 alkylene And reacting it under acidic conditions after reaction with a Grignard reagent represented by the following general formula (2): (Wherein, Ar represents the same meaning as described above)
-Preparation of ketoaldehyde compounds.