JP3164762B2 - Substituted thiophene derivatives and fungicides for agricultural and horticultural use containing the same as active ingredients - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel substituted thiophene derivative, a fungicide for agricultural and horticultural use containing the same as an active ingredient, and a method for controlling plant diseases using the same.

[0002]

2. Description of the Related Art A disinfectant having a selective action developed in recent years shows a stable effect at a low dose unlike a non-selective disinfectant which has been used up to that time. Appears, and there is a problem that the efficacy is reduced. For example, benzimidazole bactericides have a broad germicidal spectrum and are also effective against gray mold, but resistant bacteria emerged in the 1970s, causing a significant decrease in efficacy. As a substitute, dicarboximide-based germicides have attracted attention.
In the 0's, resistant bacteria have emerged against dicarboximide-based drugs, and control measures for gray mold resistant bacteria have become a major problem not only in Japan but also worldwide. on the other hand,
Azole-based fungicides have a wide spectrum of fungicides, and are particularly effective at reducing the amount of powdery mildew, rust, apple, and pear scabs of various crops. As a result, a significant decrease in potency due to the emergence of resistant bacteria has become a problem. Such drug-resistant bacteria have become an inevitable problem for selective bactericides, and there is therefore an urgent need to develop new drugs.

[0003] By the way, many aromatic aniline derivatives exhibiting bactericidal activity have been known so far, and recently, for example, JP-A-5-221994 and JP-A-6-221994.
JP-199803-A describes that various aniline derivatives have an effect on gray mold. The present inventors tested the compounds specifically disclosed therein for bactericidal activity against various phytopathogenic fungi, and their control effect was low even in the case of gray mold, powdery mildew, and no effect in red rust etc. I was not able to admit.

[0004]

Accordingly, an object of the present invention is to provide a new agricultural / horticultural fungicide which has a broad disease spectrum against the pathogenic bacteria of various crops and which solves the problem of resistant bacteria which is now serious. As an issue.

[0005]

Means for Solving the Problems The inventors of the present invention have been interested in the biological activity of various heterocyclic amine derivatives, and have found that a derivative having a certain aminothiophene can prevent various plant diseases. It shows a strong control effect, and also has an excellent control effect on susceptible bacteria as well as susceptible bacteria of benzimidazole and dicarboximide drugs, as well as susceptible and resistant bacteria of azole drugs, and The present inventors have found that the safety is high and therefore the above-mentioned problem is satisfied, and completed this study. That is, the present invention provides a compound represented by the general formula (1):

[0006]

Embedded image [Wherein Q is a hydrogen atom, a methyl group, a trifluoromethyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, a methylthio group, a methylsulfoxy group, a methylsulfonyl group, a cyano group, an acetyl group, R represents a nitro group, an alkoxycarbonyl group or an amino group; R represents a linear or branched alkyl group having 1 to 12 carbon atoms;
2 straight-chain or branched halogenoalkyl groups, having 2 to 2 carbon atoms
10 linear or branched alkenyl groups, having 2 to 10 carbon atoms
A straight-chain or branched halogenoalkenyl group having 2 to 2 carbon atoms
Substituted by 10 alkylthioalkyl groups, alkyloxyalkyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, halogeno-substituted cycloalkyl groups having 3 to 10 carbon atoms, or 1 to 3 substituents A substituent of the phenyl group may be a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, 6 cycloalkyl group, C1-4 alkoxy group, C1-4 halogenoalkoxy group, C1-4 alkylthio group, C1-4 alkylsulfoxy group, C1-4 carbon atom Substituted with an alkylsulfonyl group, a halogen atom, a cyano group, an acyl group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, an amino group, or an alkyl group having 1 to 3 carbon atoms. An amino radical, R and -NHC
The OArs are adjacent to each other, and Ar is the following (A1)
To (A8)

[0007]

Embedded image (Wherein, R ¹ represents a trifluoromethyl group, a difluoromethyl group, a methyl group, an ethyl group, a chlorine atom, a bromine atom or an iodine atom, R ² represents a hydrogen atom, a methyl group, a trifluoromethyl group or an amino group, R ³ represents an alkyl group having 1 to 4 carbon atoms, and n represents a group represented by 0 to 2)], a substituted thiophene derivative represented by the following formula: Fungicide for plant, method for controlling plant diseases using the same, and general formula (2) which is an intermediate of general formula (1)

[0008]

Embedded image (Wherein Q represents a hydrogen atom, a methyl group, a trifluoromethyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, a methylthio group, a methylsulfoxy group, a methylsulfonyl group, a cyano group, an acetyl group, A nitro group, an alkoxycarbonyl group or an amino group, and Ym represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, and having 3 to 6 carbon atoms.
A cycloalkyl group, an alkoxy group having 1 to 4 carbon atoms, a halogenoalkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an alkylsulfoxy group having 1 to 4 carbon atoms,
An alkylsulfonyl group having 1 to 4 carbon atoms, a halogen atom,
Cyano group, acyl group having 2 to 4 carbon atoms, alkoxycarbonyl group having 2 to 4 carbon atoms, amino group, or 1 to 3 carbon atoms
An amino group substituted with an alkyl group of the formula:
Wherein the phenyl group and the amino group are adjacent to each other), and an aminothiophene derivative represented by the general formula (3):

[0009]

Embedded image (Wherein Q represents a hydrogen atom, a methyl group, a trifluoromethyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, a methylthio group, a methylsulfoxy group, a methylsulfonyl group, a cyano group, an acetyl group, A nitro group, an alkoxycarbonyl group or an amino group, and Ym represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, and having 3 to 6 carbon atoms.
A cycloalkyl group, an alkoxy group having 1 to 4 carbon atoms, a halogenoalkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an alkylsulfoxy group having 1 to 4 carbon atoms,
An alkylsulfonyl group having 1 to 4 carbon atoms, a halogen atom,
Cyano group, acyl group having 2 to 4 carbon atoms, alkoxycarbonyl group having 2 to 4 carbon atoms, amino group, or 1 to 3 carbon atoms
An amino group substituted with an alkyl group of the formula:
Wherein the phenyl and nitro groups are adjacent to each other).

The substituent R of the thiophene derivative represented by the general formula (1) of the present invention is specifically isopropyl, s
ec-butyl, tert-butyl, 1-methylbutyl,
1-methylhexyl, 1-ethylpropyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1-ethyl-
3-methylbutyl, 1,2-dimethylhexyl, 1,3
-Dimethyloctyl, 3-methylbutyl, 3-methylpentyl, 4-methyloctyl, 1,2,2,3-tetramethylbutyl, 1,3,3-trimethylbutyl, 1,
2,3-trimethylbutyl, 1,3-dimethylpentyl, 1,3-dimethylhexyl, 5-methyl-3-hexyl, 2-methyl-4-heptyl, 2,6-dimethyl-
A linear or branched alkyl group having 1 to 12 carbon atoms such as 4-heptyl, 1-methyl-2-cyclopropylethyl, n-butyl and n-hexyl group; 3-chloro-1
-Methylbutyl, 2-chloro-1-methylbutyl, 1-
Chlorobutyl, 3,3-dichloro-1-methylbutyl,
A linear or branched halogenoalkyl group having 1 to 12 carbon atoms such as 3-chloro-1-methylbutyl, 1-methyl-3-trifluoromethylbutyl, and 3-methyl-1-trifluoromethylbutyl; A linear or branched alkenyl group having 2 to 10 carbon atoms such as -methyl-1-propenyl, 1-ethyl-1-butenyl, 2,4-dimethyl-1-pentenyl, and 2,4-dimethyl-2-pentenyl group; A straight-chain or branched halogenoalkenyl group having 2 to 10 carbon atoms such as 2-chloro-1-methyl-1-butenyl and the like; a carbon atom having 3 carbon atoms such as cyclopropyl, cyclohexyl, 2-ethylcyclohexyl and 2-isopropylcyclohexyl group;
1 to 10 cycloalkyl groups; 1-methylthiomethyl, 1
C2-10 alkylthioalkyl groups such as -methylthioethyl, 1-ethylthioethyl, 1-methylthiopropyl and 1-isopropylthioethyl groups; C2-10 alkyloxyalkyl groups such as 1-isopropyloxyethyl groups A halogeno-substituted cycloalkyl group having 3 to 10 carbon atoms such as a 2-chlorocyclohexyl or 3-chlorocyclohexyl group; or a phenyl group optionally substituted by 1 to 3 substituents, Specific examples of the group include a hydrogen atom; a methyl group, an ethyl group, a propyl group, an isopropyl group, a sec-butyl group,
an alkyl group having 1 to 4 carbon atoms such as a t-butyl group; an alkenyl group having 2 to 4 carbon atoms such as a vinyl group, an isopropenyl group and a 1-methylpropenyl group; a carbon atom having 2 carbon atoms such as an ethynyl group and a 1-propynyl group; And alkynyl groups having 4 to 3 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.
Cycloalkyl group having 1 to 6 carbon atoms; alkoxy group having 1 to 4 carbon atoms such as methoxy group, ethoxy group and butoxy group; 1 carbon atom such as trifluoromethoxy group, 1,1,2,2,2-pentafluoroethoxy group and the like. C1 to C4 alkylthio groups such as methylthio and ethylthio groups; C1 to C4 alkylsulfoxy groups such as methylsulfoxy and butylsulfoxy; methylsulfonyl and isopropyl C1-C4 alkylsulfonyl group such as sulfonyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano group; C2-C4 acyl group such as acetyl group and propionyl group; 2 carbon atoms such as carbonyl group and ethoxycarbonyl group
And a substituted amino group substituted with an alkyl group having 1 to 3 carbon atoms such as a dimethylamino group, a diethylamino group, and a propylamino group. Particularly, R is preferably a branched alkyl group having 3 to 12 carbon atoms.

Specifically, Ar is substituted with a trifluoromethyl group, a difluoromethyl group, a methyl group, an ethyl group, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom in the 4-position, and the 2-position is a methyl group, 5-thiazolyl group optionally substituted by a fluoromethyl group or an amino group, for example, 2-methyl-4-trifluoromethyl-5-thiazolyl, 2-methyl-4-difluoromethyl-5-thiazolyl, 2-methyl- 4-chloro-5-thiazolyl, 2-
Methyl-4-iodo-5-thiazolyl, 4-trifluoromethyl-5-thiazolyl, 2,4-dimethyl-5-thiazolyl, etc .; trifluoromethyl, difluoromethyl, methyl, ethyl, fluorine at the 3-position A 4-pyrazolyl group substituted by a chlorine atom, a bromine atom or an iodine atom and substituted by a methyl group at the 1-position;
3-trifluoromethyl-4-pyrazolyl, 1-methyl-3-difluoromethyl-4-pyrazolyl, 1,3-dimethyl-4-pyrazolyl group, 1-methyl-3-chloro-
4-pyrazolyl, 1-methyl-3-bromo-4-pyrazolyl, 1-methyl-3-iodo-4-pyrazolyl group and the like;
3-furyl optionally substituted at the 2-position with a trifluoromethyl, difluoromethyl, methyl, ethyl, chlorine, bromine or iodine atom and substituted at the 5-position with a methyl or trifluoromethyl group Groups such as 2-methyl-3-furyl, 2,5-dimethyl-3-furyl;
A 2-thienyl group which may be substituted with a trifluoromethyl group, a difluoromethyl group, a methyl group, an ethyl group, a chlorine atom, a bromine atom or an iodine atom at the 3-position, and a methyl group at the 4-position or the 5-position, For example, 3-methyl-2-thienyl group, 3-chloro-2-thienyl group, 3-iodo-2-
Thienyl group, 3,4-dimethyl-2-thienyl group and the like; 2
A trifluoromethyl group, a difluoromethyl group, a methyl group, an ethyl group, a phenyl group substituted by a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a 2-chloronicotinyl group; a 3-chloro-2-pyrazinyl group; A 3-thienyl group substituted with a trifluoromethyl group, a difluoromethyl group, a methyl group, an ethyl group, a chlorine atom, a bromine atom or an iodine atom at the 4-position, for example, a 4-methyl-3-thienyl group;
4-chloro-3-thienyl group and the like. In particular, A
r is preferably an A2 group.

The substituted thiophene derivative represented by the general formula (1) of the present invention is a novel compound, and is obtained by a method similar to the known method shown in the following reaction formula (Formula 13). A substituted aminothiophene represented by the general formula (5)
Can be produced by reacting with a carboxylic acid halide represented by the following formula in a molten state or in a solvent.

[0013]

Embedded image (In the formula, Q, R and Ar represent the above-mentioned meanings, and X represents a chlorine atom, a bromine atom or an iodine atom.) The solvent used in this reaction may be any solvent that is inert to the reaction. Aliphatic hydrocarbons such as hexane and petroleum ether; aromatics such as benzene, toluene, chlorobenzene and anisole; ethers such as dioxane, tetrahydrofuran and diethyl ether; nitriles such as acetonitrile and propionitrile; acetic acid Esters such as ethyl; dichloromethane, chloroform, 1,
Halogenated hydrocarbons such as 2-dichloroethane; aprotic solvents such as dimethylformamide and dimethylsulfoxide; and mixed solvents thereof are also used.

This reaction may be carried out in the presence of a base. Examples of the base include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide and calcium hydroxide; Oxides of alkali metals and alkaline earth metals such as magnesium; hydrides of alkali metals and alkaline earth metals such as sodium hydride and calcium hydride; amides of alkali metals such as lithium amide and sodium amide; sodium carbonate and carbonic acid Carbonates of metals and alkaline earth metals such as potassium, calcium carbonate and magnesium carbonate; hydrogen carbonates of alkali metals and alkaline earth metals such as sodium hydrogen carbonate and potassium hydrogen carbonate; methyllithium, butyllithium, phenyllithium, methyl Alkaline such as magnesium chloride Metal alkyls; alkoxides of alkali metals and alkaline earth metals such as sodium methoxide, sodium ethoxide, potassium-t-butoxide, and dimethoxymagnesium; triethylamine, pyridine, N, N-dimethylaniline, N-methylpiperidine, lutidine, -Various organic bases such as dimethylaminopyridine, and particularly preferred are triethylamine and pyridine. The use amount of these bases is not particularly limited, but is preferably from 5 mol% to 20 mol% based on the carboxylic acid halide represented by the general formula (5).
Used in molar% excess.

In the above reaction, the substituted aminothiophenes represented by the general formula (4) and the carboxylic acid halides represented by the general formula (5) are generally used in equimolar amounts. Therefore, one is preferably 1 mol% to 2
It may be used in an excess of 0 mol%. The reaction temperature is usually
The temperature is 20 to 150 ° C, preferably 0 to 40 ° C.
The reaction time is not particularly limited, but is usually 30 minutes to 5 hours.

Next, a method for synthesizing a compound represented by the general formula (4), which is an intermediate of the present invention, will be described. 1) Synthesis of 2-substituted-3-aminothiophenes (when the substituent is other than phenyl) These compounds can be synthesized, for example, by the method shown in the following reaction formula (Formula 14), but are not limited to these methods. It is not something to be done. (Method A): 2-substituted-3-oxotetrahydrothiophene represented by the general formula (11) (wherein R ³ is a linear alkyl or branched alkyl group, a halogenoalkyl group, an alkylthioalkyl group, an alkyloxyalkyl group) , Cycloalkyl group, halogeno-substituted cycloalkyl group) in ethanol in the presence of barium hydroxide in the presence of hydroxylamine hydrochloride, followed by treatment with hydrogen chloride in ethyl ether to obtain a compound of formula (12) (US Pat. No. 4,317,915;
J. Org. Chem. , 52 , 2611 (198
7))

(Methods B-1 and B-2): Mercaptoacetones represented by the formula (13) (wherein R ⁴ is a linear alkyl or branched alkyl group, an alkylthioalkyl group,
Condensation with α-chloroacrylonitrile (method B-1; Synth. Commu)
n. , 9 , 731 (1979)), or acylation of 3-acetylaminothiophene with acyl chloride in the presence of anhydrous aluminum chloride, followed by hydrolysis (Method B-2,
Bull. soc. chim. Fr. , 1976 , 15
1) The 2-acyl-3-aminothiophene of the formula (14) obtained by the above method is protected with a t-butyloxycarbonyl group using di-t-butyl dicarbonate in the presence of triethylamine, and alkylated with a Grignard reagent or the like. Alkylating with an agent (wherein R ⁵ represents an alkyl group) to give a compound of formula (15), and then reducing with triethylsilane in trifluoroacetic acid to obtain an amine of formula (16)

(Method C): 3-Aminothiophene-2-carboxylic acid ester was prepared by adding di-t-tert-amine in the presence of triethylamine.
The compound is protected with a t-butyloxycarbonyl group using butyl dicarbonate and alkylated with an alkylating agent such as a Grignard reagent (wherein R ⁵ has the same meaning as described above) to give (17). Method for obtaining amine of formula (18) by reduction with triethylsilane in fluoroacetic acid

(Method D): After dehydrating the compound represented by the formula (20) with acetic anhydride and potassium hydrogen sulfate in DMF to obtain the formula (21), the Boc group is eliminated with trifluoroacetic acid. To obtain the amine of the formula (19).

[0020]

Embedded image

From the thus obtained 2-substituted-3-aminothiophene, the compound of the present invention represented by the general formula (1) can be synthesized by the method described in (Chemical Formula 13). Further, a 3-acylamino-2-alkenyl-substituted thiophene represented by the formula (22) (where Ar is the above-described general formula (1)
Which has the same meaning as in formula (3)),
Acylamino-2-alkylthiophenes can also be synthesized.

2) Synthesis of 4-alkyl-3-aminothiophene (Method E): These compounds are prepared by reacting 3-oxotetrahydrothiophene-4-carboxylic acid of the formula (24) as shown in the following (Formula 15). Acid esters (U.S. Pat.
No. 5 and J. J. Org. Chem. , 52 , 261
1 (1987)) is alkylated with an alkyl halide in the presence of potassium carbonate, and then hydrolyzed and decarboxylated to obtain 3-oxotetrahydrothiophene of the formula (25) (wherein R ⁶ represents an alkyl group) Is oximed with hydroxylamine hydrochloride in ethanol in the presence of barium hydroxide, and then treated with hydrogen chloride in ethyl ether to give a 4-alkyl-3-aminothiophene of formula (26). .

The thus obtained 4-alkyl-3
-The compound of the present invention represented by the general formula (1) can be synthesized from -aminothiophene by the method described in (Chemical formula 13).

[0024]

Embedded image The following Table 1-Table 7 (Tables 1 7) in the general formula (8)
Examples of 2-alkyl-3-aminothiophene derivative represented by Formula 16], Table 8 (Table 8) in the general formula (9) shown by the 4-alkyl-3-aminothiophene derivative (Formula 17) An example is illustrated.

[0025]

Embedded image

[0026]

[Table 1] ((1S) means that the 1-position is the (S) configuration, and unless otherwise specified, means the racemic body.)

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

[0030]

[Table 5]

[0031]

[Table 6]

[0032]

[Table 7] ((1S) means that the 1-position is the (S) configuration, and unless otherwise specified, means the racemic body.)

[0033]

Embedded image

[0034]

[Table 8]

3) When R is a phenyl group which may be substituted The compounds represented by the general formulas (2) and (3) are both novel compounds.
Can be produced.

[0036]

Embedded image (Wherein Q is a hydrogen atom, a methyl group, a trifluoromethyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, a methylthio group, a methylsulfonyl group, a cyano group, an acetyl group, a nitro group, an alkoxycarbonyl represents a group or an amino group, Z is a chlorine atom, a bromine atom or an iodine atom, Y _m is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, 2 to 4 carbon atoms Alkynyl group, cycloalkyl group having 3 to 6 carbon atoms, alkoxy group having 1 to 4 carbon atoms, halogenoalkoxy group having 1 to 4 carbon atoms, alkylthio group having 1 to 4 carbon atoms, 1 to 1 carbon atoms
4 alkylsulfoxy groups, alkylsulfonyl groups having 1 to 4 carbon atoms, halogen atoms, cyano groups, acyl groups having 2 to 4 carbon atoms, alkoxycarbonyl groups having 2 to 4 carbon atoms, amino groups or 1 to 3 carbon atoms And m is an integer of 1 to 3, and the phenyl group and the amino group in the formula (3) or the phenyl group and the nitro group in the formula (2) are adjacent to each other. Indicates that That is, the nitrothiophene derivative represented by the general formula (3) can be obtained, for example, by the method of Suzuki et al. (Synth. Commu).
n. , 11 , 513 (1981); Bull. Che
m. Soc. Jpn. , 61 , 3008 (1988);
Chem. Lett. , 1989 , 1405; Pe
ters et al. Heterocycl. Chem. ,
28 , 1613 (1991)).
It can be produced by reacting the halogenonitrothiophene represented by (6) with the phenylboric acid derivative represented by (7) in the presence of a Pd catalyst and a base, but is not limited to this method.

The solvent used in this reaction may be any solvent which is inert to the reaction, for example, aliphatic hydrocarbons such as hexane and petroleum ether; aromatics such as benzene, toluene, xylene and anisole; dioxane , Tetrahydrofuran, ethers such as diethyl ether; nitriles such as acetonitrile and propionitrile; esters such as ethyl acetate; dichloromethane, chloroform;
Halogenated hydrocarbons such as 1,2-dichloroethane; aprotic solvents such as dimethylformamide and dimethylsulfoxide; alcohols such as methanol and ethanol;
Water and the like are used, and a mixed solvent thereof is also used.

As the base to be used, for example, hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide and calcium hydroxide; alkali metals and alkaline earth metals such as calcium oxide and magnesium oxide Oxides; hydrides of alkali metals and alkaline earth metals such as sodium hydride and calcium hydride;
Amides of alkali metals such as lithium amide and sodium amide; carbonates of metals such as sodium carbonate, potassium carbonate, calcium carbonate and magnesium carbonate and alkaline earth metals; alkali metals and alkaline earths such as sodium hydrogen carbonate and potassium hydrogen carbonate Metal bicarbonates; alkali metal alkyls such as methyllithium, butyllithium, phenyllithium, and methylmagnesium chloride; alkali and alkaline earth metals such as sodium methoxide, sodium ethoxide, potassium-t-butoxide, and dimethoxymagnesium Alkoxide;
Examples include various organic bases such as triethylamine, pyridine, N, N-dimethylaniline, N-methylpiperidine, lutidine, and 4-dimethylaminopyridine, and particularly preferred are sodium carbonate and potassium carbonate. The use amount of these bases is not particularly limited, but is preferably 1.05 to 10 times, preferably 1.5 times, the mole of the halogenonitrothiophene represented by the general formula (6).
Used in 3-fold molar excess.

As a Pd catalyst, for example, Pd (PP
_{h 3) 4, PdCl 2,} Pd (OAc) 2 or the like is used.

The halogenonitrothiophenes represented by the general formula (6) and the phenylboric acid derivative represented by the general formula (7) are generally used in equimolar amounts. On the other hand, it may be used in an excess of 1 mol% to 100 mol% with respect to the other. The reaction temperature is usually from room temperature to 1
It is 50 degreeC, Preferably it is 80-110 degreeC. The reaction time is not particularly limited, but is usually 30 minutes to 7 hours.

On the other hand, the aminothiophene derivative represented by the general formula (2) is obtained by catalytically reducing (3) in an alcohol such as methanol or ethanol, in the presence of Pd / carbon, or in a solvent such as acetic acid. It can be synthesized by reduction with Fe powder.
15. Oxidation and reduction II (edited by The Chemical Society of Japan, Maruzen, 197)
6)] and can be synthesized by reduction using a general method as shown in [6].

The following Tables 9 to 11 (Tables 9 to 11)
Examples of the novel nitrothiophene derivatives of the general formula (3) (Chemical Formula 19) are shown in Tables 12 to 19 (Tables 12 to 19). An example was shown. In the latter case, the compound in which the amino group was substituted at the 2-position was generally unstable, and thus the reaction solution after reduction was directly amidated. Tables 9 to 19
In the table, the general formula (3) (Formula 19) and the general formula ( 2 )
Q in (Formula 20) represents a hydrogen atom.

[0043]

Embedded image

[0044]

[Table 9]

[0045]

[Table 10]

[0046]

[Table 11]

[0047]

Embedded image

[0048]

[Table 12] * Due to the instability, amidation was performed without isolation after catalytic reduction.

[0049]

[Table 13]

[0050]

[Table 14]

[0051]

[Table 15]

[0052]

[Table 16]

[0053]

[Table 17]

[0054]

[Table 18]

[0055]

[Table 19]

The compound of the present invention represented by the general formula (1) is
Agricultural and horticultural fungicides contained as active ingredients are
Chicken disease (Pyricularia oryzae), Sesame leaf blight (Cochliobolus 
miyabeanus), Sheath blight (Rhizoctonia solani), Idiot disease
(Gibberella fujikuroi), Wheat powdery mildew (Erysiph
e graminis f.sp.hordei; f.sp.tritici), Leaf spot disease (Pyre
nophora graminea), Reticulum disease(Pyrenophora teres), Red or
Blight (Gibberella zeae), Rust (Puccinia striiformi
s;P.graminis;P.recondita;P.hordei, Snow rot (Typh
ula sp .;Micronectriella nivalis), Naked smut (Ustila
go tritici;U.nuda), Eye spot disease (Pseudocercosporella he
rpotrichoides), Cloud disease (Rhynchosporium secalis),leaf
Blight (Septoria tritici), Fusarium wilt (Leptosphaeria nodor
um), Grape powdery mildew (Uncinula necator), Black pepper
disease(Elsinoe ampelina), Late rot (Glomerella cingulat
a), Rust (Phakopsora ampelopsidis), Apple udon
Sickness (Podosphaera leucotricha), Scab (Venturia i
naequalis), Spotted leaf disease (Alternaria mali), Scab (Gy
mnosporangium yamadae), Monilia disease (Sclerotinia mal
i), Rot (Valsa mali), Black spot of pear (Alternaria 
kikuchiana), Scab (Venturia nashicola), Scab (Gy
mnosporangium haraeanum), Peach ash disease (Sclerotinia
 cinerea), Scab (Cladosporium carpophilum),
Mopsis rot (Phomopsis sp.), oyster anthracnose (Gloeos
porium kaki), Deciduous disease (Cercospora kaki;Mycosphaerel
la nawae), Powdery mildew of cucumber (Sphaerotheca fuligin
ea), Anthracnose (Colletotrichum lagenarium), Vine blight (M
ycosphaerella melonis), Tomato ring rot (Alternaria 
solani), Leaf mold (Cladosporium fulvam), Eggplant udon
Sickness (Erysiphe cichoracoarum), Brassicaceae vegetable black
Leaf spot (Alternaria japonica), Vitiligo (Cerocosporella b
arassicae), Green onion rust (Puccinia allii), Soybean
Purpura (Cercospora kikuchii), Black rot (Elsinoe glyc
ines), Sunspot (Diaporthe phaseololum), Kidney charcoal
The disease (Colletotrichum lindemuthianum), Peanut
Black scab (Mycosphaerella personatum), Brown spot (Cercospo
ra arachidicola), Pea powdery mildew (Erysiphe pi
si), Potato summer blight (Alternaria solani), Cha's
Net blast (Exobasidium reticulatum), Scab (Elsinoe 
leucospila), Tobacco scab (Alternaria longipes),
Powdery mildew (Erysiphe cichoracearum), Anthracnose (Colleto
trichum tabacum), Sugar beet brown spot (Cercospora beti
cola), Rose scab (Diplocarpon rosae), Powdery mildew
(Sphaerotheca pannosa), Chrysanthemum spot of chrysanthemum (Septoria chry
santhemi-indici), White rust (Puccinia horiana), Ichi
Powdery mildew (Sphaerotheca humuli), Cucumber, toma
Gray mold on tomatoes, strawberries, grapes, etc.Botrytis cinere
a), Sclerotium disease (Sclerotinia sclerotiorum)
Shows control effect.

When the compound represented by the general formula (1) of the present invention is used as an agricultural and horticultural fungicide, the active ingredient may be used as it is for the plant to be treated, but it is generally inactive. It is mixed with a liquid carrier or a solid carrier, and used as powders, wettable powders, flowables, emulsions, granules and other commonly used preparations which are commonly used. If necessary for the preparation, an auxiliary agent can be added.

As used herein, the term "carrier" refers to a synthetic or natural inorganic or organic substance incorporated to help the active ingredient reach the site to be treated and to facilitate storage, transport, and handling of the active ingredient compound. Means As the carrier, any solid or liquid carrier can be used as long as it is generally used for agricultural and horticultural medicines, and it is not limited to a specific one.

For example, solid carriers include clays such as montmorillonite and kaolinite; diatomaceous earth, terra alba, talc, vermiculite, gypsum, calcium carbonate, silica gel, and ammonium sulfate; inorganic substances such as soybean powder, sawdust, and flour Vegetable organic substances and urea.

As the liquid carrier, toluene, xylene,
Aromatic hydrocarbons such as cumene; paraffinic hydrocarbons such as kerosene and mineral oil; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and diethylene glycol dimethyl ether; alcohols such as methanol, ethanol, propanol and ethylene glycol; Aprotic solvents such as dimethylformamide and dimethylsulfoxide; and water.

In order to further enhance the efficacy of the compound of the present invention, the following adjuvants may be used alone or in combination according to the purpose, taking into account the dosage form of the preparation, the application scene, and the like. . Examples of the adjuvant include surfactants, binders (eg, ligninsulfonic acid, alginic acid, polyvinyl alcohol, gum arabic, sodium CMC, etc.) and stabilizers (eg, phenol for antioxidation, which are usually used in agricultural and horticultural drugs). Compounds, thiol compounds or higher fatty acid esters, phosphates as pH adjusters, and sometimes light stabilizers) can be used alone or in combination as necessary. Further, depending on the case, an industrial bactericide, a bactericidal / antifungal agent or the like may be added for bactericidal / fungicidal purposes.

The auxiliary agent will be described in more detail. Emulsification,
Anionic interfaces such as lignin sulfonate, alkylbenzene sulfonate, alkyl sulfate, polyoxyalkylene alkyl sulfate, and polyoxyalkylene alkyl phosphate for dispersion, spreading, wetting, bonding, stabilization, etc. Activator; polyoxyalkylene alkyl ether, polyoxyalkylene alkylaryl ether, polyoxyalkylene alkylamine, polyoxyalkylene alkylamide, polyoxyalkylene alkylamide, polyoxyalkylene alkylthioether, polyoxyalkylene fatty acid ester, glycerin fatty acid ester, Nonionic surfactants such as sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxypropylene polyoxyethylene block polymer Agents; calcium stearate, lubricants such as wax; stabilizers isopropyl hydroperoxide diene phosphate, etc., other cellulose, carboxymethyl cellulose, casein, gum arabic, and the like. However, these components are not limited to those described above.

The content of the compound represented by the general formula (1) in the fungicide for agricultural and horticultural use according to the present invention varies depending on the form of the preparation.
0.1-80% by weight for wettable powders, 0.1-20% for granules
% By weight, 1 to 50% by weight in the emulsion, 1 to 50% by weight in the flowable preparation, 1 to 80% by weight in the dry flowable preparation, preferably 0.5 to 5% by weight in the powder,
5 to 80% by weight for wettable powders, 0.5 to 8% by weight for granules, 5 to 20% by weight for emulsions, 5 to 20% for flowable preparations
50% by weight and 5 to 50% by weight for dry flowable formulations. The content of the auxiliary agent is 0 to 80% by weight,
The content of the carrier is an amount obtained by subtracting the contents of the active ingredient compound and the auxiliary from 100% by weight.

The method of applying the composition of the present invention includes seed disinfection, foliage application, and the like. However, any method commonly used by those skilled in the art exerts a sufficient effect. The application rate and application concentration vary depending on the target crop, the target disease, the degree of occurrence of the disease, the dosage form of the compound, the application method and various environmental conditions, etc., but when sprayed, the active ingredient amount is 50 to 1,000 g per hectare. Is suitable, desirably from 100 to 500 g per hectare. When a wettable powder, a flowable or an emulsion is diluted with water and sprayed, the dilution ratio is suitably from 200 to 20,000 times, and preferably from 1,000 to 5,000 times.

The fungicides for agricultural and horticultural use of the present invention can be used not only in combination with other fungicides, pesticides, herbicides, plant growth regulators and other pesticides, soil improvers or fertilizers, but also with these fungicides. Mixed formulations are also possible. Examples of the disinfectant include azole disinfectants such as triadimefon, hexaconazole, prochloraz, and triflumizole; acylalanine disinfectants such as metalaxyl and oxadixyl; benzimidazole disinfectants such as thiophanate methyl and benomyl; manzeb and the like Dithiocarbamate fungicides and tetrachloroisophthalonitrile, sulfur and the like. Examples of insecticides include, for example, fenitrothion, diazinon, pyridafenthion, chlorpyrifos, marathon,
Fentoate, dimethoate, methylthiometon, prothiophos, DDVP, acephate, salicion, E
Phosphorus insecticides such as PN; NAC, MTMC, BPMC,
Examples include, but are not limited to, carbamate insecticides such as pirimicarb, carbosurphan, mesomil and the like, and pyrethroid insecticides such as etofenprox, permethrin, fenvalerate and the like.

[0066]

EXAMPLES The compounds of the present invention will be further described in the following examples.
Explain physically. Example 1 N- [2- {3- (4-tolyl)} thieni
3] -3-trifluoromethyl-1-methylpyrazole
Synthesis of -4-carboxylic acid amide (Compound No. 3.9) 1) 2-Nitro-3- (4-tolyl) thiophene 3-bromo-2-nitrothiophene (0.8 g), 4-
Tolyl boric acid (0.52g), 2M potassium carbonate aqueous solution
Solution (5 ml) and ethanol (2.5 ml) in toluene
(30 ml) and stirred at room temperature for 30 minutes under a nitrogen stream.
Later, Pd (PPh _Three)_Four(0.15 g) and add for 7 hours
Heated to reflux. After separating the two layers, wash with water and separate the organic layer with anhydrous sodium sulfate.
After drying with lithium, the solvent was distilled off under reduced pressure.
Purification by column chromatography, the desired product (0.5
6 g) were obtained as yellow crystals (yield: 70%).¹ H-NMR (CDCl_Three, δ value): 2.42 (s, 3H), 7.01 (d, J = 5.1, 1H), 7.2
5 (d, J = 8.1,2H), 7.37 (d, J = 8.1,2H), 7.47 (d, J = 5.1,1H) 2) 2-amino-3- (4-tolyl) thiophene 2-nitro- 3- (4-tolyl) thiophene (0.5
g) was dissolved in dioxane (20 ml) and 5% Pd / C
(0.25 g) and subjected to catalytic reduction at room temperature for 5 hours.
Was. This solution was used for the next reaction as it was after filtration.

3) N- [2- {3- (4-Tolyl)} thienyl] -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide The reaction solution obtained in the above 2) was filtered, , Pyridine (0.7
3g) and 3-trifluoromethyl-1-methylpyrazolecarboxylic acid chloride (0.45 g) were added, and the mixture was stirred at room temperature for 1 hour. The mixture was extracted with ethyl acetate, washed with a saturated sodium hydrogen carbonate solution, and dried over anhydrous sodium sulfate.
The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain the desired product (0.4 g) (yield:
47%: from nitro form).

Example 2 N- [2- {3- (4-chlorophenyl)} thienyl] -3-trifluoromethyl-1
Synthesis of -methylpyrazole-4-carboxylic acid amide (Compound No. 3.2) 1) 2-Nitro-3- (4-chlorophenyl) thiophene In Example 1, 4-chlorophenylboric acid was used instead of 4-tolylboric acid. It was synthesized in exactly the same manner except that it was used (yield: 91%). mp: 108-110 ° C ¹ H-NMR (CDCl ₃ , δ value): 7.00 (d, J = 5.1, 1H), 7.37-7.44 (m, 4
H), 7.50 (d, J = 5.1, 1H) 2) 2-amino-3- (4-chlorophenyl) thiophene In Example 1, 2-nitro-3- (4-tolyl) thiophene was used instead of 2-nitro-3- (4-tolyl) thiophene. The synthesis was carried out in exactly the same manner except that 3- (4-chlorophenyl) thiophene was used, and this was used for the next reaction as it was. 3) N- [2- {3- (4-chlorophenyl)} thienyl] -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide In Example 1, 2-amino-3- (4-tolyl) It was synthesized in exactly the same manner except that 2-amino-3- (4-chlorophenyl) thiophene was used in place of thiophene (yield: 41%: from nitro form).

Example 3 N- [3- {2- (4-chlorophenyl)} thienyl] -3-trifluoromethyl-1
Synthesis of -methylpyrazole-4-carboxylic acid amide (Compound No. 1.61) 1) 3-Nitro-2- (4-chlorophenyl) thiophene 1 g of 2-bromo-3-nitrothiophene and 50 g of 4-chlorophenyl in 50 ml of toluene 0.75 g of boric acid, 2M-
5 ml of aqueous potassium carbonate solution and 2 ml of ethanol were added,
After stirring at room temperature for 30 minutes under a nitrogen stream, Pd (PPh ₃ )
₄ 0.28 g was added, and the mixture was heated under reflux for 2 hours. After separating the two layers, the organic layer was washed with water, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 1.1 g of the desired product as yellow crystals (yield). : 98%). ¹ H-NMR (CDCl ₃ , δ value): 7.29 (d, J = 5.9, 1H), 7.43 (s, 4H), 7.6
6 (d, J = 5.9,1H) 2) 3-Amino-2- (4-chlorophenyl) thiophene 3-Nitro-2- (4-chlorophenyl) thiophene 1
g and iron powder (0.93 g) in acetic acid (20 ml).
Heated for hours. After the reaction solution was filtered through celite, ethyl acetate was added, and the mixture was extracted five times with a 5% aqueous hydrochloric acid solution. The aqueous layer was neutralized with sodium hydrogen carbonate, extracted with ethyl acetate, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 0.54 g of the desired product as yellow-brown crystals (yield:
62%). ¹ H-NMR (CDCl ₃ , δ value): 3.82 (brs, 2H), 6.64 (d, J = 5.1, 1H),
7.12 (d, J = 5.1, 1H), 7.34 to 7.39 (m, 2H), 7.43 to 7.48 (m, 2H) 3) N- [3- {2- (4-chlorophenyl)} thienyl] -3-tri Fluoromethyl-1-methylpyrazole-4-carboxylic acid amide 3-Amino-2- (4-chlorophenyl) thiophene 0.25 g, pyridine 0.38 g were treated with methylene chloride 20 m
3-trifluoromethyl-
1-methylpyrazole-4-carboxylic acid chloride
A solution of 3 g dissolved in 5 ml of methylene chloride was added dropwise.
After stirring at room temperature for 1 hour, the mixture was sequentially washed with 5% hydrochloric acid, saturated sodium hydrogen carbonate and saturated saline, and then dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography to obtain 0.37 g of the desired product as colorless crystals (yield: 81%).

Example 4 Synthesis of N- [3- {2- (4-tolyl)} thienyl] -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide (Compound N
o. 1.68) 1) 3-Nitro-2- (4-tolyl) thiophene Synthesized in exactly the same manner as in Example 3 except that 4-tolylboric acid was used instead of 4-chlorophenylboric acid (yield: 78%). _{^{1 H-NMR (CDCl 3,}} δ value): 2.41 (s, 3H) , 7.23~7.27 (m, 3H), 7.3
7 (dd, J = 2.2, 8.1, 2H)), 7.64 (d, J = 5.9, 1H) 2) 3-Amino-2- (4-tolyl) thiophene In Example 3, 3-nitro-2- (4 Synthesis was performed in exactly the same manner except that 3-nitro-2- (4-tolyl) thiophene was used instead of (-chlorophenyl) thiophene (yield: 68%). ¹ H-NMR (CDCl ₃ , δ value): 2.37 (s, 3H), 3.79 (brs, 2H), 6.54 (d,
J = 5.1), 7.09 (d, J = 5.1,1H), 7.22 ((d, J = 8.1,2H), 7.41 (d, J
= 8.1,2H) 3) N- [3- {2- (4-tolyl)} thienyl] -3
-Trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide In Example 3 instead of 3-amino-2- (4-chlorophenyl) thiophene, 3-amino-2- (4-
It was synthesized in exactly the same manner except that (tolyl) thiophene was used (yield: 85%).

Example 5 N- [3- {2- (4-methoxyphenyl)} thienyl] -3-trifluoromethyl-
Synthesis of 1-methylpyrazole-4-carboxylic acid amide (Compound No. 1.64) 1) 3-Nitro-2- (4-methoxyphenyl) thiophene In Example 3, 4-methoxy was used instead of 4-chlorophenylboric acid It was synthesized in exactly the same manner except that phenylboric acid was used (yield: 96%). ¹ H-NMR (CDCl ₃ , δ value): 3.86 (s, 3H), 6.96 (d, J = 7.3, 2H), 7.2
0 (d, J = 5.1, 1H), 7.44 (d, J = 7.3, 2H), 7.63 (d, J = 5.1, 1H) 2) 3-Amino-2- (4-methoxyphenyl) thiophene Example 3 Was used in the same manner except that 3-nitro-2- (4-methoxyphenyl) thiophene was used in place of 3-nitro-2- (4-chlorophenyl) thiophene (yield: 79%). ¹ H-NMR (CDCl ₃ , δ value): 3.77 (brs, 2H), 3.83 ((s, 3H), 6.65
((d, J = 5.9,1H), 6.96 (d, J = 8.8,2H), 7.07 (d, J = 5.9,1H), 7.
43 (d, J = 8.8,2H) 3) N- [3- {2- (4-methoxyphenyl)} thienyl] -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide In Example 3 Instead of 3-amino-2- (4-chlorophenyl) thiophene, 3-amino-2- (4-
Synthesis was performed in exactly the same manner except that (methoxyphenyl) thiophene was used (yield: 75%).

Example 6 N- (2-isopropenyl-3)
Synthesis of (thienyl) -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide (Compound No.
1.71) 1) 3- (t-butoxycarbonylamino) thiophene-2-carboxylic acid methyl ester 10 g of 3-aminothiophene-2-carboxylic acid methyl ester and 7.72 g of triethylamine were treated with methylene chloride 5
After a solution of 13.9 g of di-t-butyl dicarbonate in 20 ml of methylene chloride was added dropwise to the solution dissolved in 0 ml,
A catalytic amount of 4-dimethylaminopyridine was added. 5 at room temperature
After stirring for an hour, the mixture was separated into two layers, washed with water, and dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the precipitated crystals were separated by filtration and the filtrate was purified by silica gel chromatography to obtain 4.2 g of the desired product as colorless crystals (yield: 75%). ¹ H-NMR (CDCl ₃ , δ value): 1.52 (s, 9H), 3.88 (s, 3H), 7.43 (d, J =
5.1,1H), 7.88 (d, J = 5.1,1H), 9.35 (brs, 1H) 2) 2- (1-hydroxy-1-methyl) ethyl-3-
5. (t-butoxycarbonylamino) thiophene 3M-ether solution of MeMgBr under nitrogen atmosphere
5 ml was diluted with 5 ml of THF, cooled to 10 ° C.,
A solution of 1 g of (t-butoxycarbonylamino) thiophen-2-carboxylic acid methyl ester in 5 ml of THF was added dropwise. After stirring at room temperature for 3 hours, the mixture was discharged into an aqueous ammonium chloride solution, extracted with ethyl acetate, washed with brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure,
The desired product was obtained as a yellow oil (yield: quantitative). ¹ H-NMR (CDCl ₃ , δ value): 1.50 (s, 9H), 1.65 (s, 6H), 7.02 (d, J =
5.1,1H), 7.27 (d, J = 5.1,1H), 8.09 (brs, 1H) 3) 3-t-butoxycarbonylamino-2-isopropenylthiophene 2- (1-hydroxy-1-methyl) ethyl- 3- (t
-Butoxycarbonylamino) thiophene (1.8 g), acetic anhydride (1.4 g), potassium hydrogen sulfate (0.06 g) in DMF
Added to 10 ml and heated at 60 ° C. for 2 hours. Add water,
After extraction with ethyl acetate, the extract was washed with brine and dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel chromatography to obtain the target compound (1.04).
g were obtained as an orange oil (yield: 60%). ¹ H-NMR (CDCl ₃ , δ value): 1.50 (s, 9H), 2.11 (s, 3H), 5.18 ((s, 1
H), 5.27 (m, 1H), 6.71 (brs, 1H), 7.13 (d, J = 5.9,1H), 7.56
(d, J = 5.9,1H) 4) 3-Amino-2-isopropenylthiophene hydrochloride A solution obtained by dissolving 0.3 g of 3- (t-butoxycarbonylamino) -2-isopropenylthiophene in 7 ml of methylene chloride was used. After cooling to 0 ° C., 3 ml of 4N hydrogen chloride in dioxane was gradually added, and this was used as it was in the next reaction. 5) N- (2-isopropenyl-3-thienyl) -3-
Trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide The above solution was cooled to 0 ° C., 5 ml of pyridine was added, and 3-trifluoromethyl-1-methylpyrazole-
0.27 g of 4-carboxylic acid chloride was added to methylene chloride 5
The solution dissolved in ml was dropped. After stirring for 1 hour at room temperature,
After washing with 5% hydrochloric acid, saturated sodium bicarbonate and saturated saline in this order, the extract was dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography to obtain 0.12 g of the desired product as crystals (yield: 30).
%).

Example 7 Synthesis of N- [3- {2- (4-trifluoromethylphenyl)} thienyl] -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide (Compound No. 1. 77) 1) 3-Nitro-2- (4-trifluoromethylphenyl) thiophene Synthesized in exactly the same manner as in Example 3 except that 4-trifluoromethylphenylboric acid was used instead of 4-chlorophenylboric acid. (Yield: quantitative). ¹ H-NMR (CDCl ₃ , δ value): 7.35 (d, J = 5.9, 1H), 7.61 (d, J = 8.1, 2
H), 7.69-7.76 (m, 3H) 2) 3-Amino-2- (4-trifluoromethylphenyl) thiophene In Example 3, 3-nitro-2- (4-chlorophenyl) thiophene was used instead of 3-nitro-2- (4-chlorophenyl) thiophene ¹ H-NMR (CDCl ₃ , δ value): 4.00 (brs, 2H), synthesized by exactly the same method except that -2- (4-trifluoromethylphenyl) thiophene was used. 6.67 (d, J = 5.1,1H),
7.18 (d, J = 5.1,1H), 7.64 (s, 1H) 3) N- [3- {2- (4-trifluoromethylphenyl)} thienyl] -3-trifluoromethyl-1-methylpyrazole- 4-Carboxylic amide Synthesized in exactly the same manner as in Example 3 except that 3-amino-2- (4-trifluoromethylphenyl) thiophene was used instead of 3-amino-2- (4-chlorophenyl) thiophene. (Yield: 58%).

Example 8 N- [3- {2- (3-chlorophenyl)} thienyl] -3-trifluoromethyl-1
Synthesis of -methylpyrazole-4-carboxylic acid amide (Compound No. 1.75) 1) 3-Nitro-2- (3-chlorophenyl) thiophene Instead of 4-chlorophenylboric acid in Example 3, 3-chlorophenylboric acid (Yield: 84%). ¹ H-NMR _(CDCl, ^δ values): 7.31 (d, J = 5.9,1H), 7.36~7.46 (m, 3
H), 7.48 (s, 1H), 7.66 (d, J = 5.9,1H) 2) 3-amino-2- (3-chlorophenyl) thiophene In Example 3, 3-nitro-2- (4-chlorophenyl) thiophene Was synthesized in exactly the same manner as above except that 3-nitro-2- (3-chlorophenyl) thiophene was used (yield: 71%). ¹ H-NMR (CDCl ₃ , δ value): 3.84 (brs, 2H), 6.65 (d, J = 5.1, 1H),
7.14 (d, J = 5.1,1H), 7.21 (dd, J = 1.5,8.8,1H), 7.35 (dt, J =
1.5,8.8,1H), 7.41 (dd, J = 1.5,8.8,1H), 7.51-7.53 (m, 1H) 3) N- [3- {2- (3-chlorophenyl)} thienyl] -3-tri Fluoromethyl-1-methylpyrazole-4-carboxylic acid amide Except that in Example 3, 3-amino-2- (3-chlorophenyl) thiophene was used instead of 3-amino-2- (4-chlorophenyl) thiophene. It was synthesized in a similar manner (yield: 79%).

Example 9 Synthesis of N- {3- (2-phenyl) thienyl} -4-trifluoromethyl-2-methylthiazole-5-carboxylic acid amide (Compound No. 1.
62) 1) 3-Nitro-2-phenylthiophene Synthesized in exactly the same manner as in Example 3 except that phenylboric acid was used instead of 4-chlorophenylboric acid (yield: 85%) ¹ H-NMR ( CDCl ₃ , δ value): 7.27 (d, J = 5.1, 1H), 7.42 to 7.51 (m, 5
H), 7.65 (d, J = 5.1, 1H) 2) 3-Amino-2-phenylthiophene Instead of 3-nitro-2- (4-chlorophenyl) thiophene in Example 3, 3-nitro-2-phenylthiophene (Yield: 81%). ¹ H-NMR (CDCl ₃ , δ value): 3.82 (brs, 2H), 6.66 (d, J = 5.1, 1H),
7.12 (d, J = 5.1,1H), 7.22 ~ 7.29 (m, 1H), 7.42 ((dt, J = 1.5,
7.3,2H), 7.52 (dd, J = 1.5,7.3,2H) 3) N- {3- (2-phenyl) thienyl} -4-trifluoromethyl-2-methylthiazole-5-carboxylic amide 3- To a solution of 0.5 g of amino-2-phenylthiophene and 0.70 g of pyridine dissolved in 30 ml of methylene chloride, 0.79 g of 4-trifluoromethyl-2-methylthiazole-5-carboxylic acid chloride was added to 10 ml of methylene chloride with stirring. The dissolved solution was added dropwise. After stirring at room temperature for 1.5 hours, the mixture was washed successively with 5% hydrochloric acid, saturated sodium hydrogen carbonate and saturated saline, and then dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography to obtain 0.59 g of the desired product as colorless crystals (yield: 51%).

Example 10 N- {3- (2-phenyl)
Synthesis of thienyl} -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide (Compound No.
1.60) 0.2 g of 3-amino-2- (4-chlorophenyl) thiophene and 0.35 g of pyridine in 20 ml of methylene chloride
3-trifluoromethyl-1 under stirring to the solution dissolved in
-Methylpyrazole-4-carboxylic acid chloride 0.2
A solution of 9 g dissolved in 5 ml of methylene chloride was added dropwise.
After stirring at room temperature for 2 hours, the mixture was washed successively with 5% hydrochloric acid, saturated sodium hydrogen carbonate and saturated saline, and then dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography to obtain 0.28 g of the desired product as colorless crystals (yield: 66%).

Example 11 N- {3- (2-phenyl)
Synthesis of thienyl} -2-chlorobenzoic acid amide (Compound No. 1.96) A solution prepared by dissolving 0.18 g of 3-amino-2-phenylthiophene and 0.35 g of pyridine in 20 ml of methylene chloride was stirred under stirring with 2-chloro. A solution prepared by dissolving 0.18 g of benzoic acid chloride in 5 ml of methylene chloride was added dropwise. After stirring at room temperature for 1 hour, the mixture was washed sequentially with 5% hydrochloric acid, saturated sodium hydrogen carbonate and saturated saline, and then dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography to obtain 0.14 g of the desired product as colorless crystals (yield: 47%).

Example 12 N- {3- (2-phenyl)
Synthesis of thienyl} -2-chloronicotinamide (Compound No. 1.97) 2-Chloro-2-phenylthiophene (0.2 g) and pyridine (0.35 g) dissolved in methylene chloride (20 ml) were stirred in a solution of 2-chloroamine. A solution prepared by dissolving 0.20 g of nicotinic acid chloride in 5 ml of methylene chloride was added dropwise. After stirring at room temperature for 1 hour, the mixture was washed sequentially with 5% hydrochloric acid, saturated sodium hydrogen carbonate and saturated saline, and then dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography to obtain 0.11 g of the desired product as colorless crystals (yield: 39%).

Example 13 N- [2-｛(1S) -1-
Methylpropyl) {-3-thienyl] -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide (Compound No. 1.2, Method A) 1) 3-Amino-2-{(1S ) -1-Methylpropyl) {thiophene 2-{(1S) -1-methylpropyl} tetrahydrothiophen-3-one (1.7 g) and hydroxylamine hydrochloride (1.1 g) were dissolved in ethanol (50 ml). And barium hydroxide octahydrate (3.4 g).
The mixture was refluxed for 5 hours. After cooling and filtration, the solvent was distilled off under reduced pressure, ethyl ether was added, washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain an oxime compound. Ethyl ether (50 ml) was added thereto, and a methanol solution of 6.5 N-hydrogen chloride (1.7 ml) was added, and the mixture was stirred at room temperature for 3 hours, and then left at room temperature for 12 hours. After neutralization with a saturated aqueous solution of sodium hydrogen carbonate, the mixture was extracted with ethyl ether and washed with saturated saline. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 0.44 g of the desired product as a yellow oil (yield: 26%). 2) N- [2-{(1S) -1-methylpropyl)}-
3-thienyl] -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide In Example 3, instead of 3-amino-2- (4-chlorophenyl) thiophene, 3-amino-2-{(1S)
It was synthesized in exactly the same manner except that (-1-methylpropyl)} thiophene was used (yield: 75%).

Example 14 Synthesis of N- {2- (1,3-dimethylbutyl) -3-thienyl} -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide (Compound No. 1.13) , Method B) 1) 2- (1-hydroxy-1,3-dimethylbutyl)
-3-t-butoxycarbonylaminothiophene solution of 2-methylpropylmagnesium bromide in tetrahydrofuran (2.9 g of 2-methylpropylbromide,
0.47 g of magnesium, 20 ml of tetrahydrofuran
Was cooled to 10 ° C., and 2-acetyl-3-t-
A solution of butyloxycarbonylaminothiophene (1 g) in tetrahydrofuran (10 ml) was added dropwise at 15 ° C. or lower, and the mixture was stirred at room temperature for 2 hours, and then a saturated aqueous ammonium chloride solution was added under cooling. The mixture was extracted with ethyl acetate, washed with saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 1.2 g of the desired product (yield: 98%). 2) 3-amino-2- (1,3-dimethylbutyl) thiophene 2- (1-hydroxy-1,3-dimethylbutyl) -3
-T-butoxycarbonylaminothiophene (1.2 g) was dissolved in methylene chloride (10 ml), and triethylsilane (0.44 g) and trifluoroacetic acid (4.3 g) were added. After stirring at room temperature for 20 hours, saturated sodium bicarbonate was added. , Extraction (ethyl acetate), washing (saturated saline), and drying (anhydrous magnesium sulfate). After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography to obtain 0.43 g of the desired product as crystals. 3) N- {2- (1,3-dimethylbutyl) -3-thienyl} -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide In Example 3, 3-amino-2- (4- 3-Amino-2- (1,3-
It was synthesized in exactly the same manner except that dimethylbutyl) thiophene was used (yield: 41%).

Example 15 N- ｛2-isopropyl-3
Synthesis of -thienyl} -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide (Compound No.
1.1, Method C) 1) 3-Amino-2-isopropylthiophene 2- (1-hydroxy-1-methyl) ethyl-3-t-butoxycarbonylaminothiophene which is an intermediate of Example 6 (0.9 g) ) Was dissolved in methylene chloride (10 ml), triethylsilane (0.41 g) and trifluoroacetic acid (4 g) were added, and the mixture was stirred at room temperature for 20 hours, neutralized with saturated sodium hydrogen carbonate, extracted with ethyl acetate, and saturated saline. Washed with water and dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography to obtain 0.29 g of the desired product as crystals (yield: 62).
%). 2) N- {2-isopropyl-3-thienyl} -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide In Example 3, 3 was replaced with 3-amino-2- (4-chlorophenyl) thiophene. It was synthesized in exactly the same manner except that -amino-2-isopropylthiophene was used (yield: 53%).

Example 16 N-Δ2-isopropyl-3
Synthesis of -thienyl} -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide (Compound No.
1.1, Method D) 1 g of the compound of Example 6 (Compound No. 1.71) was dissolved in methanol (10 ml), and 5% Pd / carbon (0.2
g) was added, and catalytic reduction was carried out at room temperature over 8 hours under normal pressure. After filtration and washing with methanol, the filtrate was concentrated under reduced pressure, and the obtained oily substance was sludged with hexane to obtain 0.8 g of the desired product as crystals (yield: 79%).

Other examples of the compounds of the general formula (1) synthesized in the same manner as in the examples are summarized in the following Tables 20 to 62 (Tables 20 to 62). Tables 20 to 62
In Tables 20 to 62, R ^{3 in} A2 of Ar
Are all methyl groups.

[0084]

Embedded image

[0085]

[Table 20]

[0086]

[Table 21]

[0087]

[Table 22]

[0088]

[Table 23]

[0089]

[Table 24]

[0090]

[Table 25]

[0091]

[Table 26]

[0092]

[Table 27]

[0093]

[Table 28]

[0094]

[Table 29]

[0095]

[Table 30]

[0096]

[Table 31]

[0097]

[Table 32]

[0098]

[Table 33]

[0099]

[Table 34]

[0100]

[Table 35]

[0101]

[Table 36]

[0102]

[Table 37]

[0103]

[Table 38]

[0104]

[Table 39]

[0105]

[Table 40]

[0106]

[Table 41]

[0107]

[Table 42]

[0108]

[Table 43]

[0109]

[Table 44]

[0110]

[Table 45]

[0111]

[Table 46]

[0112]

[Table 47]

[0113]

[Table 48]

[0114]

[Table 49]

[0115]

[Table 50]

[0116]

[Table 51]

[0117]

[Table 52]

[0118]

[Table 53]

[0119]

[Table 54]

[0120]

[Table 55]

[0121]

Embedded image

[0122]

[Table 56]

[0123]

[Table 57]

[0124]

Embedded image

[0125]

[Table 58]

[0126]

[Table 59]

[0127]

[Table 60]

[0128]

Embedded image

[0129]

[Table 61]

[0130]

[Table 62]

Next, formulation examples and test examples of the fungicide for agricultural and horticultural use according to the present invention will be shown. Formulation Example 1 Powder 3 parts of the compound of Compound No. 1.2, 20 parts of diatomaceous earth, and 77 parts of clay were uniformly ground and mixed to obtain 100 parts of a powder.

Formulation Example 2 wettable powder 25 parts of compound of compound number 1.13, diatomaceous earth 72
Parts, 1 part of sodium ligninsulfonate and 2 parts of sodium alkylbenzenesulfonate were uniformly pulverized and mixed to obtain 100 parts of a wettable powder.

Formulation Example 3 Wettable powder 50 parts of compound No. 1.24, 30 parts of clay, 10 parts of white carbon, 5 parts of sodium lauryl phosphate and 5 parts of sodium alkylnaphthalenesulfonate were mixed, and wettable powder 100 Got a part.

Formulation Example 4 Wettable powder 50 parts of the compound of the compound No. 1.61, 10 parts of sodium ligninsulfonate, 5 parts of sodium alkylnaphthalenesulfonate, 10 parts of white carbon and 25 parts of diatomaceous earth were mixed and pulverized, and hydrated. 100 parts of the agent were obtained.

Formulation Example 5 Emulsion 10 parts of Compound No. 1.77, cyclohexane 1
0 parts, 60 parts of xylene and 20 parts of Solpol (a surfactant manufactured by Toho Chemical Co., Ltd.) were uniformly dissolved and mixed to obtain 100 parts of an emulsion.

Formulation Example 6 Flowable agent 40 parts of compound No. 1.13, 3 parts of carboxymethylcellulose, 2 parts of sodium ligninsulfonate,
1 part of dioctylsulfosuccinate sodium salt and 54 parts of water were wet-pulverized with a sand grinder to obtain 100 parts of a flowable.

Next, the efficacy of the compound of the present invention as a fungicide for agricultural and horticultural use will be described with reference to test examples. Test Example 1 Kidney Gray Mold Control Test (1) According to Formulation Example 3, a kidney bean (variety: vineless top crop) was grown in a greenhouse in a plastic pot having a diameter of 7.5 cm by two until the cotyledon was developed. Dilute the prepared wettable powder to a predetermined concentration (active ingredient concentration 200 ppm),
50 ml was sprayed per 4 pots. After the drug solution dries, the fungi grown on PDA medium (MBC resistant, RS
Conidia suspension (1 × 10 ⁵ / m)
l) is spray-inoculated on cotyledons, and the temperature is 20 to 23 ° C and the humidity is 95%.
It was kept in the above greenhouse for 7 days. Seven days after the inoculation, the area occupied by the gray mold spot per kidney leaf was examined according to the following index. The results are shown in Tables 63 to 72 (Tables 63 to 72). The average value of each treated section and the untreated section was defined as the disease severity. Control value (%) = (1−Severity of treated group / Severity of untreated group) × 100

Test Example 2 Test for control of kidney bean gray mold (2) Formulation example 3 was applied to a kidney bean (cultivar: vineless top crop) grown in a greenhouse in a plastic pot having a diameter of 7.5 cm by two until the cotyledon was developed. The wettable powder prepared according to the above is diluted to a predetermined concentration (active ingredient concentration: 200 ppm),
50 ml was sprayed per 4 pots. After the drug solution was dried, a conidial spore suspension (1 × 10 ⁵ cells / ml) prepared from a gray mold fungus (MBC resistant / dicarboximide drug resistant, RR bacteria) cultured on a PDA medium was placed on the cotyledons. They were spray-inoculated and kept in a greenhouse at 20 to 23 ° C and a humidity of 95% or more for 7 days. Seven days after the inoculation, the area occupied by the gray mold spot per kidney leaf was examined according to the following index. The results are shown in Tables 63 to 72 (Tables 63 to 72). The average value of each treated section and the untreated section was defined as the disease severity. Control value (%) = (1−Severity of treated group / Severity of untreated group) × 100

Test Example 3 Cucumber Powdery Mildew Control Test In a greenhouse, a 1.5 cm plastic pot was placed in a plastic pot having a diameter of 7.5 cm.
A wettable powder prepared according to Formulation Example 3 was diluted to a predetermined concentration (active ingredient concentration: 200 ppm) in cucumber (cultivar: Sagamihanjiro) grown two by two until the leaf stage, and sprayed at 50 ml per three pots. did. After the drug solution dries, a conidia spore suspension (1 × 10 ⁶ / ml) prepared by suspending cucumber powdery mildew conidia in water containing a small amount of a spreading agent is sprayed and inoculated into a greenhouse. I kept it for 7 days. 7 days after inoculation, cucumber 1
The area occupied by powdery mildew spots per leaf was investigated according to the following index. The results are shown in Tables 63 to 72 (Tables 63 to 63).
It is shown in Table 72). The average value of each treated section and the untreated section was defined as the disease severity. Control value (%) = (1−Severity of treated group / Severity of untreated group) × 100

Test Example 4 Control Test for Wheat Powdery Mildew (EBI Resistant Bacteria) Into a greenhouse, 15 to 20 wheat (cultivar: Chihoku) grown in a plastic pot of 6 cm in diameter until the 1.5 leaf stage was prepared. The wettable powder prepared according to Example 3 was diluted to a predetermined concentration (active ingredient concentration: 200 ppm) and sprayed 50 ml per 3 pots. After the chemical solution dries, sprinkle with wheat powdery mildew (EBI resistant bacteria) conidia and then
It left in the room of ° C. Seven days after the inoculation, the area occupied by the mildew spot on the first leaf of wheat was examined according to the following index. The results are shown in Tables 63 to 72 (Tables 63 to 72). The average value of each treated section and the untreated section was defined as the disease severity. Control value (%) = (1−Severity of treated group / Severity of untreated group) × 100

Test Example 5 Wheat Leaf Rust Control Test Wheat (cultivar: Agriculture and Forestry 6) grown in a greenhouse in plastic pots having a diameter of 6 cm by 15 to 20 each until the 1.5-leaf stage
No. 4), the wettable powder prepared according to Formulation Example 3 was diluted to a predetermined concentration (active ingredient concentration: 200 ppm), and sprayed 50 ml per 3 pots. After the chemical solution dries, spray euspores of wheat leaf rust and leave them in a humidified state for 2 days.
Transferred to room temperature. Ten days after the inoculation, the area occupied by the spot of leaf rust on the first leaf of wheat was examined according to the following index.
The results are shown in Tables 63 to 72 (Tables 63 to 72). The average value of each treated section and the untreated section was defined as the disease severity. Control value (%) = (1−Severity of treated group / Severity of untreated group) × 100

[0142]

[Table 63] The numerical values in the table represent the control value. --- represents an untested sample.

[0143]

[Table 64]

[0144]

[Table 65]

[0145]

[Table 66]

[0146]

[Table 67]

[0147]

[Table 68]

[0148]

[Table 69]

[0149]

[Table 70]

[0150]

[Table 71]

[0151]

[Table 72] Control compound 1: Procymidone, trade name = Sumirex, chemical name = N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide Control compound 2: triadimefon, trade name = biletone Chemical name = 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -2-butanone Control compound 3: JP-A-5-221994 In the gazette (compound of No. 10.1), chemical name = N- (2-isopropylphenyl) -5-chloro-1,3-dimethylpyrazole-4-carboxylic acid amide Control compound 4: JP-A-5-221994 No. 9.2, Chemical name = N- (2-propylphenyl) -2-methyl-4-trifluoromethylthiazole-5-carbo Acid amide

[0152]

Industrial Applicability The compounds represented by the general formula (1) of the present invention show excellent control effects against various diseases such as gray mold, powdery mildew and rust of various crops, and are now becoming more serious. It is also effective as a fungicide for agricultural and horticultural use, since it has an effect on drug-resistant bacteria.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI A01N 43/78 A01N 43/78 D C07D 409/12 C07D 409/12 417/12 417/12 (72) Inventor: Kan Takahashi Chiba Prefecture 1144 Togo, Mobara-shi, Mitsui Toatsu Chemicals Co., Ltd. (72) Inventor Shunichi Inami, 1144 Togo, Mobara-shi, Chiba Pref. Mitsui Toatsu Kagaku Co., Ltd. (72) Within Toatsu Chemicals Co., Ltd. (72) Inventor Junro Kishi 1144 Togo, Mobara City, Chiba Prefecture Inside Mitsui Toatsu Chemicals Co., Ltd. (72) Inventor Hitoshi Shimodori 1144 Togo, Togo, Mobara City, Chiba Prefecture Mitsui Toatsu Chemical Co., Ltd. In-company (72) Inventor Naofumi Tomura 1144 Togo, Mobara-shi, Chiba Examiner, Mitsui Toatsu Chemicals Co., Ltd.Examiner Tamotsu Tominaga (56) References JP-A-3-127787 (JP, A) JP-A-54-140725 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 333/36 A01N 43/10 A01N 43/40 101 A01N 43/56 A01N 43/60 A01N 43/78 C07D 409/12 C07D 417/12 CA (STN) REGISTRY (STN)

Claims (18)

(57) [Claims] 1. A compound represented by the general formula (1): [Wherein Q represents a hydrogen atom, a methyl group, a trifluoromethyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, a methylthio group, a methylsulfoxy group, a methylsulfonyl group, a nitro group or an amino group. R is a linear or branched alkyl group having 1 to 12 carbon atoms,
A straight-chain or branched halogenoalkyl group having 2 to 12 carbon atoms, a straight-chain or branched alkenyl group having 2 to 10 carbon atoms,
10 straight-chain or branched halogenoalkenyl groups, alkylthioalkyl groups having 2 to 10 carbon atoms, alkyloxyalkyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, halogeno substitution having 3 to 10 carbon atoms A cycloalkyl group or a phenyl group which may be substituted by 1 to 3 substituents, wherein the substituents of the phenyl group include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkenyl having 2 to 4 carbon atoms. Group, C2-4 alkynyl group, C3-6 cycloalkyl group, C1-4 alkoxy group, C1-4 halogenoalkoxy group, C1-4 alkylthio group, carbon An alkylsulfoxy group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, an acyl group having 2 to 4 carbon atoms, and an alkoxycarbonyl having 2 to 4 carbon atoms , An amino group or an amino group substituted with an alkyl group having 1 to 3 carbon atoms,, R and -NHC
The OArs are adjacent to each other, and Ar is the following (A1)
To (A8) (Chemical Formula 2) (In the formula, R ¹ is a trifluoromethyl group, a difluoromethyl group, a methyl group, an ethyl group, a chlorine atom, a bromine atom or an iodine atom, and R ² is a hydrogen atom, a methyl group, a trifluoromethyl group or an amino group. And R ³ has 1 carbon atom
And n is an integer of 0 to 2).] A substituted thiophene derivative represented by the formula: 2. Q is a hydrogen atom, and R is a group having 1 to 1 carbon atoms.
A straight-chain or branched alkyl group having 2 carbon atoms, a straight-chain or branched halogenoalkyl group having 1 to 12 carbon atoms,
The substituted thiophene derivative according to claim 1, which is 10 cycloalkyl groups. 3. The substituted thiophene derivative according to claim 2, wherein Ar is (A2). 4. The substituted thiophene derivative according to claim 3, wherein R is a branched alkyl group having 3 to 12 carbon atoms. 5. The method according to claim 5, wherein the substituted thiophene derivative is N- ｛2-
The substituted thiophene derivative according to claim 4, which is (1,3-dimethylbutyl) -3-thienyl} -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide. 6. Q is a hydrogen atom, and R is a phenyl group which may be substituted by 1 to 3 substituents, wherein the substituent of the phenyl group is a hydrogen atom, an alkyl having 1 to 4 carbon atoms. Group, alkenyl group having 2 to 4 carbon atoms, alkynyl group having 2 to 4 carbon atoms, cycloalkyl group having 3 to 6 carbon atoms, alkoxy group having 1 to 4 carbon atoms, halogenoalkoxy group having 1 to 4 carbon atoms, carbon An alkylthio group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
Alkylsulfonyl group, alkylsulfonyl group having 1 to 4 carbon atoms, halogen atom, cyano group, acyl group having 2 to 4 carbon atoms, alkoxycarbonyl group having 2 to 4 carbon atoms, amino group, or 1 to 3 carbon atoms The substituted thiophene derivative according to claim 1, which is an amino group substituted with an alkyl group. 7. A compound of the general formula (1) [Wherein Q represents a hydrogen atom, a methyl group, a trifluoromethyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, a methylthio group, a methylsulfoxy group, a methylsulfonyl group, a nitro group or an amino group. R is a linear or branched alkyl group having 1 to 12 carbon atoms,
A straight-chain or branched halogenoalkyl group having 2 to 12 carbon atoms, a straight-chain or branched alkenyl group having 2 to 10 carbon atoms,
10 straight-chain or branched halogenoalkenyl groups, alkylthioalkyl groups having 2 to 10 carbon atoms, alkyloxyalkyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, halogeno substitution having 3 to 10 carbon atoms A cycloalkyl group or a phenyl group which may be substituted by 1 to 3 substituents, wherein the substituents of the phenyl group include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkenyl having 2 to 4 carbon atoms. Group, C2-4 alkynyl group, C3-6 cycloalkyl group, C1-4 alkoxy group, C1-4 halogenoalkoxy group, C1-4 alkylthio group, carbon An alkylsulfoxy group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, an acyl group having 2 to 4 carbon atoms, and an alkoxycarbonyl having 2 to 4 carbon atoms , An amino group or an amino group substituted with an alkyl group having 1 to 3 carbon atoms,, R and -NHC
The OArs are adjacent to each other, and Ar is the following (A1)
To (A8) (Chemical Formula 4) (In the formula, R ¹ is a trifluoromethyl group, a difluoromethyl group, a methyl group, an ethyl group, a chlorine atom, a bromine atom or an iodine atom, and R ² is a hydrogen atom, a methyl group, a trifluoromethyl group or an amino group. And R ³ has 1 carbon atom
And n is an integer of 0 to 2).] A fungicide for agricultural and horticultural use containing a substituted thiophene derivative represented by the formula (1) as an active ingredient. 8. Q is a hydrogen atom, and R has 1 to 1 carbon atoms.
A straight-chain or branched alkyl group having 2 carbon atoms, a straight-chain or branched halogenoalkyl group having 1 to 12 carbon atoms,
The fungicide for agricultural and horticultural use according to claim 7, which is 10 cycloalkyl groups. 9. The fungicide for agricultural and horticultural use according to claim 8, wherein Ar is (A2). 10. The fungicide for agricultural and horticultural use according to claim 9, wherein R is a branched alkyl group having 3 to 12 carbon atoms. 11. The method according to claim 11, wherein the substituted thiophene derivative is N- ｛2-
The agricultural and horticultural fungicide according to claim 10, which is (1,3-dimethylbutyl) -3-thienyl} -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide. 12. Q is a hydrogen atom, R is a phenyl group optionally substituted by 1 to 3 substituents,
The substituent of the phenyl group is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, 1-4 alkoxy groups, halogenoalkoxy groups having 1-4 carbon atoms, alkylthio groups having 1-4 carbon atoms, 1-4 carbon atoms
4 alkylsulfoxy groups, alkylsulfonyl groups having 1 to 4 carbon atoms, halogen atoms, cyano groups, acyl groups having 2 to 4 carbon atoms, alkoxycarbonyl groups having 2 to 4 carbon atoms, amino groups, or 1 to 4 carbon atoms The fungicide for agricultural and horticultural use according to claim 7, which is an amino group substituted with the alkyl group of (3). 13. A compound of the general formula (1) [Wherein Q represents a hydrogen atom, a methyl group, a trifluoromethyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, a methylthio group, a methylsulfoxy group, a methylsulfonyl group, a nitro group or an amino group. R is a linear or branched alkyl group having 1 to 12 carbon atoms,
A straight-chain or branched halogenoalkyl group having 2 to 12 carbon atoms, a straight-chain or branched alkenyl group having 2 to 10 carbon atoms,
10 straight-chain or branched halogenoalkenyl groups, alkylthioalkyl groups having 2 to 10 carbon atoms, alkyloxyalkyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, halogeno substitution having 3 to 10 carbon atoms A cycloalkyl group or a phenyl group which may be substituted by 1 to 3 substituents, wherein the substituents of the phenyl group include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkenyl having 2 to 4 carbon atoms. Group, C2-4 alkynyl group, C3-6 cycloalkyl group, C1-4 alkoxy group, C1-4 halogenoalkoxy group, C1-4 alkylthio group, carbon An alkylsulfoxy group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, an acyl group having 2 to 4 carbon atoms, and an alkoxycarbonyl having 2 to 4 carbon atoms , An amino group or an amino group substituted with an alkyl group having 1 to 3 carbon atoms,, R and -NHC
The OArs are adjacent to each other, and Ar is the following (A1)
From (A8) (Chemical formula 6) (In the formula, R ¹ is a trifluoromethyl group, a difluoromethyl group, a methyl group, an ethyl group, a chlorine atom, a bromine atom or an iodine atom, and R ² is a hydrogen atom, a methyl group, a trifluoromethyl group or an amino group. And R ³ has 1 carbon atom
And n is an integer of 0 to 2).] A method for controlling plant diseases using a substituted thiophene derivative represented by the formula: 14. Q is a hydrogen atom, and R is a group having 1 to 1 carbon atoms.
12 straight-chain or branched alkyl groups, straight-chain or branched halogenoalkyl groups having 1 to 12 carbon atoms, or 3 carbon atoms
The method for controlling plant diseases according to claim 13, which is a cycloalkyl group of 10 to 10. 15. The method for controlling plant diseases according to claim 14, wherein Ar is (A2). 16. The method for controlling plant diseases according to claim 15, wherein R is a branched alkyl group having 3 to 12 carbon atoms. 17. The method according to claim 17, wherein the substituted thiophene derivative is N- ｛2-
The method for controlling plant diseases according to claim 16, which is (1,3-dimethylbutyl) -3-thienyl} -3-trifluoromethyl-1-methylpyrazole-4-carboxylic acid amide. 18. Q is a hydrogen atom, R is a phenyl group optionally substituted by 1 to 3 substituents,
The substituent of the phenyl group is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, 1-4 alkoxy groups, halogenoalkoxy groups having 1-4 carbon atoms, alkylthio groups having 1-4 carbon atoms, 1-4 carbon atoms
4 alkylsulfoxy groups, alkylsulfonyl groups having 1 to 4 carbon atoms, halogen atoms, cyano groups, acyl groups having 2 to 4 carbon atoms, alkoxycarbonyl groups having 2 to 4 carbon atoms, amino groups, or 1 to 4 carbon atoms 14. The method for controlling plant diseases according to claim 13, which is an amino group substituted with an alkyl group.