WO2004035560A1 - Pyrrole derivative, intermediate, and agricultural or horticultural bactericide - Google Patents

Abstract

An agricultural or horticultural bactericide characterized by containing as an active ingredient at least one of pyrrole derivatives represented by the formula (1): (1) [wherein R1 represents hydrogen, C1-6 alkyl, etc.; Q represents oxygen, sulfur, or a group represented by the formula (2): =N-O-R2 (2) (wherein R2 represents hydrogen, C1-6 alkyl, etc.); and A represents a group represented by the formula (3), group represented by the formula (4), or group represented by the formula (5): (3) (4) (5) (wherein R3 represents hydrogen, halogeno, etc.; R4 represents hydrogen, chlorine, bromine, iodine, etc.; R5 represents hydrogen, halogeno, etc.; X represents sulfur or oxygen; and m is an integer of 0 to 2)] and salts of the derivatives. Also provided is an intermediate for the derivatives.

Description

 Specification

 Pyrrole derivatives and intermediates and fungicides for agricultural and horticultural use

Technical field:

 The present invention relates to a novel pipal derivative, an agricultural / horticultural fungicide containing the compound as an active ingredient, and a novel intermediate for producing the compound. Background technology:

 In the cultivation of agricultural and horticultural crops, a large number of control agents are used for crop diseases, but their control efficacy is insufficient, or their use is limited by the emergence of drug-resistant pathogens. From the viewpoint of causing phytotoxicity and contamination of the plant, and toxicity to humans and fish, and environmental impacts, it is not always a satisfactory control agent. Therefore, there is a strong demand for a drug that can be safely used with few such disadvantages.

 The pyrrole compound according to the present invention is described as a synthetic intermediate of a 4,5-dioctylpyrrolyl derivative having a bactericidal activity (see, for example, US Pat. No. 3,876,660). See the book.) In addition, it is described as a synthetic intermediate of a pyrrolyl acrylate compound having a bactericidal activity, but it is not described that these intermediate compounds have a bactericidal activity (for example, European Patent Application Publication No. 20/20). 6, 52, 3). DISCLOSURE OF THE INVENTION:

An object of the present invention is to provide a pyrrole derivative which can be industrially advantageously synthesized, can be used as a fungicide for agricultural and horticultural use with certain effects and can be used safely, and a useful intermediate for producing the pyrrole derivative. The present invention relates to the formula (1)

Wherein a hydrogen atom, C ^ ₆ alkyl group, C i ₆ alkoxy C i ₆ alkyl group, 〇 Bok ₆ § Rukirukaruponiru group. Represents an alkyl sulfonyl Le group - DOO ₆ alkoxy Cal Poni group, DOO ₆ alkyl force Lupo two Ruokishi ₁ - ₆ alkyl or C i. Q represents an oxygen atom, a sulfur atom or a group represented by the formula (2).

= N- 0-R ₂ (2)

In the formula, R ₂ represents a hydrogen atom, a C 6 alkyl group or a C ₆ alkoxyC ₆ alkyl group. A represents a group represented by the formula (3), a group represented by the formula (4), or a group represented by the formula (5).

式中 H₃は、 ハロゲン原子、 Ci-6アルキル基、 C_{2 6}アルケニル基、 ニトロ基、 シァノ 基または C^ ₆ハロアルキル基または式 (6) で表される基を表す。 ~^-R₆ ( 式中 R₆は、 水素原子、 Ci— 6アルキル基、 ₆トリアルキルシリル基を表す。

In the formula, H ₃ represents a halogen atom, a Ci-6 alkyl group, a C ₂₆ alkenyl group, a nitro group, a cyano group, a C ₆ haloalkyl group or a group represented by the formula (6). ~ ^ -R ₆ (wherein R ₆ represents a hydrogen atom, a Ci-6 alkyl group, or a ₆ trialkylsilyl group.

R ₄ represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a Ci ₆ alkyl group or a C ^ ₆ haloalkyl group. R ₅ represents a hydrogen atom, a halogen atom, C ^ ₆ alkyl group or Ci-6 Haroa alkyl group.

 X represents a sulfur atom or an oxygen atom. m is 0 or a pyrrole derivative representing an integer of 1-2. Equation (7)

(Wherein, R ₃ , R ₄ , R ₅ , X and m have the same meanings as in claim 1, and R ₇ represents a hydrogen atom or a C ^ e alkyl group.) .

Equation (8)

(Wherein, R ₃ , R ₄ , R ₅ , X and m have the same meaning as in claim 1, and R ₈ represents a hydrogen atom or a C ₆ alkyl group.)

 Equation (9)

_{(Wherein, R 3, R 4, R} 5, X及Pi m have the same meanings as claim 1, R ₉ is a hydrogen atom or d_ represents an _alkyl group.) In the production intermediate represented.

Equation (1)

(Wherein, R ₁ Q and A represent the same meaning as in claim 1)

Is a fungicide for agricultural and horticultural use containing one or more of a pyrrole derivative or a salt thereof represented by Embodiment of the invention:

は水素原子；メチル、 ェチル、 プロピル、 ブチル等の Ci ₆アルキル基；メトキシメ チル、 メトキシェチル、 エトキシメチル等のじ ₆アルコキシ d— 6アルキル基；ァセチル、 プロピオニル等の C！― ₆アルキル力ルポニル基；メトキシカルポニル、 エトキシカルボニル 等の C^ ₆アルキコシカルポニル基；ァセチルォキシメチル、 プロピルォキシメチル等の C ！ - 6アルキル力ルポ二ルォキシ C i _ ₆ァルキル基；またはメチルスルホニル、 ェチルスルホ ニル等の C ₆アルキルスルホ二ル基を表わす。 In the definition of equation (1)

Is a hydrogen atom; Ci ₆ alkyl groups such as methyl, ethyl, propyl, and butyl; ₆ alkoxy d-6 alkyl groups such as methoxymethyl, methoxyethyl, and ethoxymethyl; C! - ₆ alkyl force Ruponiru group; methoxy Cal Poni Le, C ^ ₆ alkyl Koshika Lupo alkenyl groups such as ethoxycarbonyl; § cetyl O carboxymethyl, propyl O carboxymethyl C, such as methyl ! - 6 alkyl force Lupo two Ruokishi C i _ ₆ Arukiru group; or methylsulfonyl, represent C ₆ alkyl sulfonyl Le group such Echirusuruho chloride.

Q represents an oxygen atom, a sulfur atom or a group represented by the formula (2). = N-0-R ₂ (2) In the formula, R ₂ is a hydrogen atom; a C-e alkyl group such as methyl, ethyl, propyl, and butyl; or a C ₆ alkoxy C ₆ alkyl group such as methoxymethyl, methoxyethyl, and X-toxmethyl. Represents

 A represents a group represented by the formula (3), a group represented by the formula (4), or a group represented by the formula (5).

~ ^^ R ₆ (6)

X represents an oxygen atom or a sulfur atom.

R ₃ is a halogen atom such as a fluorine, chlorine, bromine or iodine atom; a C ₆ alkyl group such as methyl, ethyl, propyl or butyl; a Ci-6 alkynyl group such as vinyl or propenyl; a nitro group ; it represents a or triflate Ruo Russia methyl, difluoromethyl, pentafluoroethyl full O Roe Flip ₆ eight-necked alkyl groups such as chill; Shiano group.

In the formula (6), R ₆ is hydrogen; such as methyl, ethyl and propyl. ₆ alkyl groups; Represents a C i ₆ trialkylsilyl group such as trimethylsilyl and triethylsilyl groups.

R ₄ is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom; a C ₆ alkyl group such as methyl, ethyl, propyl, and butyl; or a C ₆ octyl group such as trifluoromethyl, difluoromethyl, and pentafluoroethyl. Represents an alkyl group.

R _s is a hydrogen atom; a fluorine, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom; methyl, Echiru, propyl, C i _ ₆ alkyl groups such as butyl, or triflate Ruo Russia methyl, Jifurorome chill, pen evening Furuoroechiru etc. It represents a C ₆ eight-necked alkyl group.

m represents an integer of 0 1 or 2. When m is 2, R ₃ may be the same or different. In addition, the salt of the compound according to the present invention refers to an agriculturally / horticulturally acceptable salt, and is not particularly limited as long as it is an agriculturally / 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, and salts of acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and acetic acid. No.

 The method for producing the pyrrole derivative represented by the formula (1) in the present invention will be described. The pyrrole derivative represented by the formula (1) can be produced, for example, by the following method, but the production method of the compound is not limited to these production methods. However, for example, it can be manufactured as follows. Manufacturing method (1)

The following formula (10)

 In the formula, represents the same meaning as described above. ) Is represented by the following formula (11)

^Y Y ^{A 1} )

 Q

(Wherein Q and A have the same meanings as described above, and Y represents a leaving group such as a halogen atom.). The pyrrole derivative of the present invention represented by (1) can be produced.

This reaction can be carried out in the presence or absence of a solvent. The solvent that can be used is not particularly limited as long as it is a solvent inert to the reaction. For example, hydrocarbon solvents such as pentane, hexane, heptane, benzene, toluene, and xylene, dichloromethane, 1,2-dichloroethane, and chloroform Halogen solvents such as form and tetrachlorosilane, nitrile solvents such as acetonitrile and propionnitrile, ether solvents such as getyl ether, dioxane and tetrahydrofuran, and non-protons such as NN dimethylformamide and dimethyl sulfoxide A polar solvent, water, and a mixed solvent system in which two or more of these solvents are mixed. The amount of the acylating agent to be used is generally 1 to 5 mol, preferably 1 to 2 mol, per 1 mol of compound (10).

 Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium carbonate, pyridine, triethylamine, N, N-dimethylaniline, Organic bases such as N-methylpyrrolidine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] indene-7-ene and the like. The amount of the base to be used is generally 1 to 10 moles, preferably 1 to 3 moles, per 1 mole of the amine compound (10). The temperature of this reaction is in the range of −78 ° C. to 200 ° C., preferably −20 ° C. to 100 ° C. The reaction time varies depending on the amount and temperature of the reagents, but ranges from 30 minutes to 24 hours. After completion of the reaction, if purification of the product is necessary, the product can be easily purified by a known and conventional production method such as distillation, recrystallization or column chromatography.

 The method for producing the intermediate represented by the formula (7-2) in the present invention will be described. The intermediate represented by the formula (7-2) can be produced, for example, by the following method, but the production method of the compound is not limited to these production methods.

(Wherein, R ₃ , R ₅ , R ₇ , X and m represent the same meaning as in claim 3). The brominated compounds represented by the formulas (13) and (14) can be produced by reacting the compound represented by the formula (12) with bromine by light irradiation. The reaction temperature of the reaction is usually in the range of 120 to 200, and the reaction time is usually in the range of 1 to 100 hours. The amount of bromine to be subjected to the reaction is usually 1 to 3 mol per 1 mol of the compound represented by the formula (12). The reaction is carried out in a solvent, if necessary. Examples of the solvent used include halogenated carbons such as chloroform and tetrahydrocarbon, and aliphatic hydrocarbons such as hexane and heptane. And aromatic hydrocarbons such as benzene, toluene and the like, and mixtures thereof. After completion of the reaction, the reaction solution is subjected to a post-treatment operation such as concentration to isolate the desired product. The target substance can be cleaved by recrystallization, chromatography or the like.

 The compound represented by the formula (15) can be produced by reacting the brominated compound represented by the formula (13) with NMO (N-methylmorpholine-1-N-oxide). The reaction temperature of the reaction is usually in the range of 120 to 200 ° C., and the reaction time is usually in the range of 1 to 100 hours. The amount of NMO to be subjected to the reaction is usually 1 to 5 mol per 1 mol of the compound represented by the formula (13). The reaction is carried out in a solvent as necessary. Examples of the solvent used include ethers such as tetrahydrofuran and dioxane, halogenated hydrocarbons such as chloroform and carbon tetrachloride, hexane, heptane and the like. Aliphatic hydrocarbons, aromatic hydrocarbons such as benzene and toluene, amides such as N, N-dimethylformamide, acetonitrile, and mixtures thereof. After completion of the reaction, the reaction solution is subjected to a post-treatment operation such as concentration, and the target product is isolated. The target product can be purified by recrystallization, chromatography and the like. Further, the compound represented by the formula (15) can be produced by hydrolyzing a brominated compound represented by the formula (14) in hydrous pyridine. The reaction temperature of the reaction is usually in the range of 0 to 200 ° C, and the reaction time is usually in the range of 1 to 100 hours. The concentration of the water-containing pyridine to be subjected to the reaction is usually 20 to 80%, and 10 to 100 ml per 1 mol of the compound represented by the formula (14). use. The reaction is carried out in a solvent, if necessary. Examples of the solvent used include ethers such as tetrahydrofuran and dioxane, halogenated carbons such as chloroform, tetrachloromethane carbon and the like, and hexane. And aliphatic hydrocarbons such as heptane, aromatic hydrocarbons such as benzene and toluene, amides such as N, N-dimethylformamide, and mixtures thereof. After completion of the reaction, the reaction solution is subjected to a post-treatment operation such as concentration to isolate the target compound. The target product can be purified by recrystallization, chromatography and the like. The compound represented by the formula (7-1) can be produced by reacting the compound represented by the formula (15) with DAST (getylaminosulfur trifluoride). The reaction temperature of the reaction is usually in the range of 120 to 70, and the reaction time is usually in the range of 1 to 100 hours. The amount of DAST used for the reaction is usually 1 to 1 mol of the compound represented by the formula (15).

~ 5 moles. The reaction is carried out in a solvent as necessary, and examples of the solvent used include ethers such as tetrahydrofuran and dioxane, and solvents such as chloroform and carbon tetrachloride. π-genated hydrocarbons, aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, amides such as Ν and Ν-dimethylformamide, acetonitrile, and mixtures thereof. can give. After completion of the reaction, the reaction solution is subjected to a post-treatment operation such as concentration to isolate the target compound. The target product can be purified by recrystallization, chromatography and the like. The compound represented by the formula (7-1) can be produced by hydrolyzing the compound represented by the formula (7-1) with a base (eg, potassium hydroxide) aqueous solution. The reaction temperature of the reaction is usually in the range of 120 to 100 ° C, and the reaction time is usually in the range of 1 to 100 hours. The amount of the base used in the reaction is usually 1 to 10 mol per 1 mol of the compound represented by the formula (7-1). Agriculture is in the range of 0.1 to 1 ON. The reaction is carried out in a solvent as necessary. Examples of the solvent used include ethers such as tetrahydrofuran and dioxane, halogenated hydrocarbons such as chloroform and carbon tetrachloride, and fats such as hexane and heptane. Examples include aromatic hydrocarbons, aromatic hydrocarbons such as benzene and toluene, amides such as N, N-dimethylformamide, aliphatic alcohols such as methanol and ethanol, and mixtures thereof. After completion of the reaction, the reaction solution is subjected to post-treatment operations such as neutralization and concentration to isolate the desired product. The target can be purified by recrystallization, chromatography or the like.

 A method for producing the intermediate represented by the formula (8-2) in the present invention will be described. The intermediate represented by the formula (8-2) can be produced, for example, by the following method, but the production method of the compound is not limited to these production methods.

(式中、 R ₃、 R ₅、 R ₈、 X及び mは請求項 4と同一の意味を表わす)。

(Wherein, R ₃ , R ₅ , R ₈ , X and m represent the same meaning as in claim 4).

 The brominated compounds represented by the formulas (17) and (18) can be produced by reacting the compound represented by the formula (16) with bromine by light irradiation. The reaction temperature of the reaction is usually in the range of 120 to 200 ° C, and the reaction time is usually in the range of 1 to 100 hours. The amount of bromine to be subjected to the reaction is usually 1 to 3 mol per 1 mol of the compound represented by the formula (16). The reaction is carried out in a solvent as necessary. Examples of the solvent used include halogenated hydrocarbons such as chloroform and carbon tetrachloride, aliphatic hydrocarbons such as hexane and heptane, and the like. Examples thereof include aromatic hydrocarbons such as benzene and toluene, and mixtures thereof. After completion of the reaction, the reaction solution is subjected to a post-treatment operation such as concentration to isolate the desired product. The target compound can be purified by recrystallization, chromatography or the like.

 The compound represented by the formula (19) can be produced by reacting the brominated compound represented by the formula (17) with NMO. The reaction temperature of the reaction is usually in the range of 120 to 200 ° C, and the reaction time is usually in the range of 1 to 100 hours. The amount of NMO supplied to the reaction is usually 1 to 5 mol per 1 mol of the compound represented by the formula (17). The reaction is carried out in a solvent as necessary. Examples of the solvent used include ethers such as tetrahydrofuran and dioxane, halogenated hydrocarbons such as chloroform and carbon tetrachloride, hexane and heptane. Aliphatic hydrocarbons such as benzene, aromatic hydrocarbons such as benzene and toluene, amides such as N, N-dimethylformamide, acetonitrile, and mixtures thereof. After completion of the reaction, the reaction solution is subjected to a post-treatment operation such as concentration to isolate the desired product. The target compound can be purified by recrystallization, chromatography or the like.

Further, the compound represented by the formula (19) can be produced by hydrolyzing a brominated compound represented by the formula (18) in hydrous pyridine. The reaction temperature of the reaction is usually in the range of 0 to 200 ° C, and the reaction time is usually in the range of 1 to 100 hours. The concentration of the water-containing pyridine to be subjected to the reaction is usually 20 to 80%, and 10 to 100 ml per 1 mol of the compound represented by the formula (18). use. The reaction is carried out in a solvent as necessary. Examples of the solvent used include ethers such as tetrahydrofuran and dioxane, halogenated hydrocarbons such as chloroform and carbon tetrachloride, and hexane and heptane. Examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons such as benzene and toluene, amides such as N, N-dimethylformamide, and mixtures thereof. After completion of the reaction, the reaction solution is subjected to a post-treatment operation such as concentration to isolate the target compound. The target product can be purified by recrystallization, chromatography and the like. The compound represented by the formula (8-1) can be produced by reacting the compound represented by the formula (19) with DAST. The reaction temperature of the reaction is usually in the range of −20 to 70 ° C., and the reaction time is generally in the range of 1 to 100 hours. The amount of DAST used in the reaction is usually 1 to 5 mol per 1 mol of the compound represented by the formula (19). The reaction is carried out in a solvent as necessary. Examples of the solvent used include tetrahydrofuran and dioxane. Ethers such as chloromethane, halogenated hydrocarbons such as carbon tetrachloride, aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, N, N-dimethylpho Examples include amides such as lumamide, acetonitrile, and mixtures thereof. After completion of the reaction, the reaction solution is subjected to a post-treatment operation such as concentration to isolate the desired product. The target substance can be purified by recrystallization, chromatography or the like.

 The compound represented by the formula (8-2) can be produced by hydrolyzing the compound represented by the formula (8-1) with an aqueous base (for example, aqueous hydroxide). The reaction temperature of the reaction is usually in the range of −20 to 100, and the reaction time is usually in the range of 1 to 100 hours. The amount of the base used for the reaction is usually 1 to 10 mol per 1 mol of the compound represented by the formula (8-1), and the concentration is within the range of 0.1 to 1 ON. is there. The reaction is carried out in a solvent, if necessary. Examples of the solvent used include ethers such as tetrahydrofuran and dioxane, halogenated carbons such as chloroform, tetrahydrofuran and tetrachlorosilane, hexane, and the like. Examples thereof include aliphatic hydrocarbons such as heptane, aromatic hydrocarbons such as benzene and toluene, amides such as N, N-dimethylformamide, aliphatic alcohols such as methanol and ethanol, and mixtures thereof. After completion of the reaction, the reaction solution is subjected to post-treatment operations such as neutralization and concentration to isolate the desired product. The target can be purified by recrystallization, chromatography or the like.

 The method for producing the intermediate represented by the formula (9-1-2) in the present invention will be described. The intermediate represented by the formula (9-12) can be produced, for example, by the following method, but the production method of the compound is not limited to these production methods.

(9-2) Wherein R ₃ , R ₅ , R ₉ , X and m have the same meaning as in claim 5. The brominated compounds represented by the formulas (21) and (22) can be produced by reacting the compound represented by the formula (20) with bromine by light irradiation. The reaction temperature of the reaction is usually in the range of 120 to 200, and the reaction time is usually in the range of 1 to 100 hours. The amount of bromine to be subjected to the reaction is usually 1 to 3 mol per 1 mol of the compound represented by the formula (20). The reaction is carried out in a solvent, if necessary. Examples of the solvent used include halogenated hydrocarbons such as chloroform and tetrachloroaniline, and aliphatic hydrocarbons such as hexane and heptane. , Benzene, aromatic hydrocarbons such as toluene, and mixtures thereof. After completion of the reaction, the reaction solution is subjected to a post-treatment operation such as concentration to isolate the desired product. The target compound can be purified by recrystallization, chromatography or the like.

 The compound represented by the formula (23) can be produced by reacting the brominated compound represented by the formula (21) with NMO. The reaction temperature of the reaction is usually in the range of 120 to 200 ° C, and the reaction time is usually in the range of 1 to 100 hours. The amount of NMO used in the reaction is usually 1 to 5 mol per 1 mol of the compound represented by the formula (21). The reaction is carried out in a solvent, if necessary. Examples of the solvent used include ethers such as tetrahydrofuran and dioxane, halogenated hydrocarbons such as chloroform, carbon tetrachloride and the like, hexane and heptane. Examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons such as benzene and toluene, amides such as N, N-dimethylformamide, acetonitrile, and mixtures thereof. After completion of the reaction, the reaction solution is subjected to a post-treatment operation such as concentration to isolate the desired product. The target compound can be purified by recrystallization, chromatography or the like.

Further, the compound represented by the formula (23) can be produced by hydrolyzing a brominated compound represented by the formula (22) in hydrous pyridine. The reaction temperature of the reaction is usually in the range of 0 to 200, and the reaction time is usually in the range of 1 to 100 hours. The concentration of the water-containing pyridine to be subjected to the reaction is usually 20 to 80%, and 10 to 100 ml per 1 mol of the compound represented by the formula (22). use. The reaction is carried out in a solvent, if necessary. Examples of the solvent used include ethers such as tetrahydrofuran and dioxane, halogenated hydrocarbons such as chloroform, carbon tetrachloride and the like, hexane, heptane and the like. Examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons such as benzene and toluene, amides such as N, N-dimethylformamide, and mixtures thereof. After completion of the reaction, the reaction solution is subjected to a post-treatment operation such as concentration to isolate the target compound. The target product can be purified by recrystallization, chromatography and the like. The compound represented by the formula (9-11) can be produced by reacting the compound represented by the formula (23) with DAST. The reaction temperature of the reaction is usually in the range of 120 to 70 ° C, and the reaction time is usually in the range of 1 to 100 hours. The amount of DAST used in the reaction is usually 1 to 5 mol per 1 mol of the compound represented by the formula (23). The reaction is necessary The solvent used is, for example, ethers such as tetrahydrofuran and dioxane, halogenated hydrocarbons such as chloroform, carbon tetrachloride and the like, and aliphatic hydrocarbons such as hexane and heptane. , Aromatic hydrocarbons such as benzene and toluene, amides such as N, N-dimethylformamide, acetonitrile and mixtures thereof. After completion of the reaction, the reaction solution is subjected to a post-treatment operation such as concentration to isolate the desired product. The target substance can be purified by recrystallization, chromatography or the like.

 The compound represented by the formula (9-1) can be produced by hydrolyzing the compound represented by the formula (9-1) with an aqueous base (eg, potassium hydroxide) solution. The reaction temperature of the reaction is usually in the range of 20 to 100 ° C, and the reaction time is usually in the range of 1 to 100 hours. The amount of the base used in the reaction is usually 1 to 10 mol per 1 mol of the compound represented by the formula (9-1), and the concentration is in the range of 0.1 to 10 N. . The reaction is carried out in a solvent as necessary. Examples of the solvent used include ethers such as tetrahydrofuran and dioxane, halogenated hydrocarbons such as chloroform and carbon tetrachloride, hexane, heptane and the like. Aliphatic hydrocarbons, aromatic hydrocarbons such as benzene and toluene, amides such as N, N-dimethylformamide, aliphatic alcohols such as methanol and ethanol, and mixtures thereof. After completion of the reaction, the reaction solution is subjected to post-treatment operations such as neutralization and concentration to isolate the desired product. The target can be purified by recrystallization, chromatography and the like.

(Agricultural and horticultural fungicides)

 The compound of the present invention (the compound represented by the formula (1) or a salt thereof) can be used for a wide variety of filamentous fungi, for example, algae (Oomy cetes), ascomycetes (Ascomy cetes), Incomplete fungi (Deuter omy cetes) ヽ Excellent bactericidal activity against bacteria belonging to Basidiomycetes (Basidi omy cetes). The composition containing the compound of the present invention as an active ingredient can be used for controlling various diseases that occur during the cultivation of agricultural and horticultural crops including flowers, lawns, and pastures by seed treatment, foliage application, soil application, or water application. Can be. For example,

 Sugar beet brown spot (Cer cos po r a b e t i c o 1 a)

 Laccasey brown spot (Mycos phae re l l a a r a c h i d i s

 Black rot (Myco s phae r e l l a b e r k e 1 e y i) Cucumber powdery mildew (Sphae r o t he c a f u 1 i g i n e a)

 Vines;) hei (Mycos phae reel 1 ame1onis)

 Sclerotium (Sc l e ro t l n l a s c 1 e r o t i o rum)

 Gray mold (Bot r y t i s c i n e r e a)

Scab (CI adospori um cucume ri num) Tomato gray mold (B otr V tiscinerea)

 Leaf mold (C I ado s po r i um f u 1 v um)

Eggplant Gray mold (Botrytiscinenerea)

 Black blight (Co ryne s po r a me 1 o n g e n a e)

 Ery s i p h e c i cho r ac e a rum

Strawberry gray blight (B o t r v t i s c i n e r e a)

 Powdery mildew (S ohae r o t he c a h umu 1 i)

Onion gray rot (Botrytisa1 1ii)

 Gray scab (B o t r y t i s c i n e r e a)

Singen sclerotium (Scl erot inias scllerot iorum)

 Gray mold (Bot r y t i s c i n e r e a)

 Apple powdery mildew (Podo s phae r a l euc o t r i cha)

 Scab (V e n t u r i a i n a e q u a 1 i s)

 Monilia disease (Moni 1 i n i a m a 1 i)

 Oyster powdery mildew (Phy l l ac t i n i a k a k i c o 1 a)

 Anthracnose (Gloe o s po r i um k a k i)

 Corn Leaf Spot (Cercosporakaki)

 Peach .Australia scab (Mo n i 1 i n i a f r u c t i c o 1 a)

 Grape Gray mold (Botrytiscinenerea)

 Powdery mildew (U n c i n u 1 a n e c a t o r)

 晚 Rot (G 1 ome r e 1 1 a c i n R u 1 a t a)

 Pear Scab (V e n t u r i a n a s h i c o 1 a)

 Scab (Gymn o s p o r a n g i um a s i a t i c um)

 Black spot (Al t e rna r i a k i kuch i ana)

 Cyan ring spot (P e st a 1 o t i a t h e a e)

 Anthracnose (Col 1 e t o t r i c h um t he ae— s i nen s i s)

 Blue mold (Penic i 1 1 i um i t a 1 i c um)

 Green mold (Penic i 1 1 i um d i R i t a t um)

 '' Gray mold (B o t r y t i s c i n e r e a)

 Ery s i p h e g r am ini s f .s p.hor de i) Naked scab (U s t i 1 a g o n u da)

 Fusarium head blight of wheat (G i b b e r e 1 1 az e a e)

 Leaf rust (Puc e i n i a r e c ond i t a)

Spot disease (C och 1 i obo lussativus) Eye spot disease (P s eudocer co s po re 1 1 a her po tric ho ides)

 Fusarium wilt (Le p t o s phae r i a no d o r um)

 Powdery mildew (Erysiph eRraminisifs.s.triticci) Scarlet snow rot (Microne ctrriel l1annivalis)

Rice blast (Py r i cu l a r i a o r y z a e)

 ktt ^ (Rh i z oc t on i a s o 1 a n i

 Idiot disease (G i b b e r e 1 l a f u j i k u r o i),

 Sesame leaf blight (C o c h 1 i o b o 1 u s n i yabe anu s),

Tobacco sclerotium (Scl erot iinis scl erotiorum)

 Powdery mildew (Ery s i p h e c i cho r ac e a rum)

Tulip gray mold (Botry tiscsinerae)

Bentgrass snow rot, Bacterial sclerotium (Scl erotini ni abore ali s),

Orchard-class powdery mildew (ErysipheRramininis)

Soybean purpura (Cercosporakakikukuhiiί),

Potatoes. Tomato blight (Phy t oph t ho rainfest an s), Kiyu ¹ J downy mildew (P s eudope r ono s po racubensis), grape downy mildew (P la smop aravitico 1 a)

 It can be used for pest control. '

 In recent years, various pathogens have developed resistance to benzimidazole fungicides and dicarpoxyimide fungicides, which have led to a lack of efficacy of these drugs. ing. The compound of the present invention is a drug having an excellent bactericidal effect not only on pathogenic bacteria sensitive to such drugs but also on resistant bacteria.

 For example, Botrytiscinerea, sugar beet (Cercos po rabetico 1 a), and apple scab ( Venturiainaegua 1 is) and the pear scab (Venturianashico 1 a) are also effective in the same manner as the susceptible bacteria.

 Furthermore, the compound of the present invention is also effective against gray mold fungi (Botryticiscinera) which is resistant to dicarpoxyimide fungicides (eg, vinclozolin, procymidone, iprodione) as well as susceptible bacteria.

 Diseases more preferably applied include sugar beet brown spot, wheat powdery mildew, rice blast, apple scab, gray mold of cucumber, brown spot of laccasei, and the like.

The compound of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to underwater contacts such as ship bottoms and fish nets. Some of the compounds of the present invention exhibit insecticidal and acaricidal activity.

 The fungicide of the present invention contains one or more of the compounds of the present invention as an active ingredient.

 When the compound of the present invention is actually applied, it can be used in a pure form without adding other components, and can be in a form that can be taken by a general pesticide for the purpose of using it as a pesticide, that is, a wettable powder, a granule, a powder, It can also be used in the form of emulsions, water-soluble agents, suspensions, wettable powders and the like.

 Additives and carriers that can be added to the pesticide formulation include, for solid formulations, vegetable powders such as soybean flour and wheat flour, diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, and clay. And organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate.

 For liquid dosage forms, kerosene, xylene and petroleum-based aromatic hydrocarbons, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, trichloroethylene, methylisobutyl Ketones, mineral oils, vegetable oils, water, etc. can be used as solvents.

 Further, in order to obtain a uniform and stable form in these preparations, a surfactant may be added as necessary. The surfactant that can be added is not particularly limited, and examples thereof include an alkylphenyl ether to which polyoxyethylene is added, an alkyl ether to which polyoxyethylene is added, a higher fatty acid ester to which polyoxyethylene is added, Nonionic surfactants such as sorbitan higher fatty acid esters to which polyoxyethylene has been added, tristyryl phenyl ether to which polyoxyethylene has been added, sulfate salts of alkyl phenyl ether to which polyoxyethylene has been added, alkylbenzene sulfonic acid Salts, sulfates of higher alcohols, alkylnaphthalenesulfonates, polycarboxylates, ligninsulfonates, formaldehyde condensates of alkylnaphthalenesulfonates, copolymers of isobutylene-maleic anhydride, etc. It is below.

 The wettable powders, emulsions, flowables, aqueous solvents, and granule wettable powders thus obtained are diluted to a predetermined concentration with water to obtain solutions, suspensions or emulsions. It is used as it is sprayed on plants.

 The amount of the active ingredient is usually preferably from 0.01 to 90% by weight, more preferably from 0.05 to 85% by weight, based on the whole composition (formulation).

 The formulated fungicidal composition of the present invention is applied to a plant, a seed, a water surface or soil as it is or after being diluted with water or the like. The application rate varies depending on the weather conditions, formulation, application magnetism, application method, application site, target disease, target crop, etc., but usually 1 to 100 g, preferably 100 to 100 g of active ingredient per hectare. Is from 100 to 100 g.

When applying wettable powders, emulsions, suspensions, aqueous solvents, granular wettable powders, etc. with water, the application concentration should be 1 to 100 pm, preferably 10 to 250 ppm. Yes, In the case of granules and powders, apply directly without dilution. It goes without saying that the compound of the present invention alone is sufficiently effective, but it can also be used as a mixture with one or more of various fungicides, insecticides and acaricides, or synergists.

 Representative examples of fungicides, insecticides, acaricides, and plant growth regulators that can be used by mixing with the compound of the present invention are shown below. Fungicide:

 Captan, Folpet, Thiuram, Ziram, Zineb, Maneb, Mancozeb, Propineb, Polycarbamate, Chlorothalonil, Kin 1 Zen, Capyahor, Iprodione, Prosimidon, Vinclozolin, Fluoroimide, Cymoxanil, Mepronil, Flotranyl, Pentoloxy Xin, Josetyl aluminum, Propamocarb, Triazimephone, Triazimenol

 , Propiconazole, diclobutrazole, bitertanol, hexaconazole, microbutanyl, flusilazole, methconazole, etaconazole, flutrimazole, sip mouth conazole, epoxyconazole, flutriafene, benconazole, diniconazole, Cyproconazoles, fenarimol, triflumizol, prochloraz, imazalil, ぺ furazoate, tridemorph, fenpropimorph, triforine, butiobate, pyriphenox, anilazine, polyoxin, metalaxyl, piprozilol, propyrazol, pyrazole Lunitrin, blasticidin S, kasugamycin, validamycin, dihydrostreptomycin sulfate, benomyl, Carbendazim, Thiophanetmethyl, Himexazole, Basic Copper Chloride, Basic Copper Sulfate, Fentin Acetate, Trifenyl Tin Hydroxide, Diethofencalp, Metasulfocalp, Quinomethionate, Pina Pacryl, Lecithin, Baking Soda, Dithianon, Zinocap , Phenaminosulf, diclomedine, guazatine, dozine, IBP, edifenphos, mepanipirim, fermzone, triclamide, metasulfocarp, fluazinam, etoquinolak, dimethomorph, pyroquilon, teclofuram, fusaride, fenadipool, thiavenda Tricyclazole, vinclozolin, simoxanil, cyclobutanyl, guatatin, propamocalp hydrochloride, oxolinic acid, hydroxyisoxazole Iminokutajin acetates. Insecticide · Acaricide:

 Organophosphorus and carbamate pesticides:

Fenthion, Fenitrothion, Diazinon, Chlorpyrifos, ESP, Bamidothione, Fentritol, Dimethate, Formothion, Marathon, Trichlorfon, Thiometone, Hosmet, Dichlorvos, Acephate, EPBP, Methylparathion, Saxithimeton, Saxithimeton , Cyanofos, isoxathion, pyridafenthion, hosalon, methidathion, sulprophos, chlorfenvinphos, tetrachlorvinphos, Dimethylvinphos, propaphos, isofenphos, ethylthiomethone, profenophos, piraclofos, monocrotophos, azinfosmethyl, aldicarb, mesomil, thiodicarb, carpofuran, carbosulfan, benfracarb, flatiocarp, proboxil,

BPMC, MTMC, MIPC, Kyrubiril, Pirimicarb, Etiofencalp, Phenoxycarp, EDDPP etc. Pyrethroid insecticides:

 Permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatrin, pyrethrin, arethrin, tetramethrin, resmethrin, dimethrin, propasulin, phenothrin, protrin, fulvalinate, cyfluthrin, cyhalothrin, flucitrinate, etofenproline, cyclophentoline, cyclofentoline Silafluofen, brofenprox, acrinasulin, etc. Benzoylurea and other insecticides:

 Difluvenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, methoprene, benzepin, diafentiuron, acetamiprid, imidacloprid , Ditenviram, fipronil, cartap, thiocyclam, bensultap, nicotine sulfate, rotenone, methaldehyde, machine oil, microbial pesticides such as BT and entomopathogenic virus. Nematicide:

 Fenamiphos, phosthiazate, etc. Acaricide:

 Chlorbenzilate, Phenylsoprolate, Dicofol, Amitraz, BPPS, Benzomate, Hexitiazox, Fenbutatin Oxide, Polynactin, Quinomethionate, CPCBS, Tetradihon, Avermectin, Milbemectin, Clofuentezin, Sihexaben, Pyreben Fenpyroximate, tebufenpyrad, pyrimidifen, phenothocalp, dienochlor and the like. Plant growth regulator:

Gibberellins (eg Gibberellin A3, Gibberellin A4, Gibberellin A7) I AA, NA A. BEST MODE FOR CARRYING OUT THE INVENTION:

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

Example 1

 4-Methyl-1-3-bromomethylthiophene 2-Production of methyl rubonate

4-90% 3-methylthiophene-2-methyl carboxylate 6.90 g (36.2 mmo 1) was dissolved in 70 ml of carbon tetrachloride, and 0.07 g of 2,2'-azobis (isobutyronitrile) was dissolved. (0.43 mmo 1), and a solution of 12.14 g (76.0 mmo 1) of bromine in 10 ml of carbon tetrachloride was added dropwise under light irradiation. After stirring for 3 hours, the reaction solution was concentrated under reduced pressure. The obtained residue was separated and purified by silica gel chromatography (n-hexane: ethyl acetate = 9: 1), and the desired 4-chloro-3-bromomethylthiophene-2-methyl methyl sulfonate was 9.76 g. Got. Yield 100%. Example 2

 (4) Preparation of 3-methyl-3-formylthiophene-2-methyl sulfonate

 9.76 g (36.2 mmo 1) of 4-chloro-3-bromomethylthiophene-2-methyl carponate was dissolved in 100 ml of acetonitrile, and 4-methylmorpholine TV—8.49 g (72.5 mmo) 1) was added and reacted at room temperature. After 3 hours, the reaction solution was poured into water, extracted with ethyl acetate, the organic layer was washed with brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained residue was separated and purified by silica gel chromatography (n-hexane: ethyl acetate = 9: 1) to obtain 5.00 g of the desired methyl 4-chloro-3-formylthiophene-2-carboxylate. . Yield 67.5%. mp. 72—74. Example 3

Production of 4-chloro-3-difluoromethylthiophene

4-Monochloro-3-formylthiophene 2-Fe-methyl ruponate 1.00 g (4.89 mmol) fc V, iV-Getylaminosulfur trifluoride 2.36 g (14.6 mmo 1) and 60 ° C Was reacted. After 3 hours, the reaction solution was diluted with chloroform, poured into water, and neutralized with aqueous potassium carbonate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained residue was separated and purified by silica gel chromatography (n-hexane: ethyl acetate = 9: 1) to obtain the desired 4-chloro-3-difluoromethylthiophene-2-methyl carboxylate 1. 00 g was obtained. Yield 90.1%. mp. 44—47. Example 4

 Production of 4-chloro-mouth 3-difluoromethylthiophene-2-carboxylic acid

Dissolve 1.00 g (4.41 mMol) of 4-methyl-3-carboxylate in 10 ml of methanol and add an aqueous solution of potassium hydroxide [0.27 g of potassium hydroxide (4. 8 lmmo 1) · water 2ml] and reacted at room temperature. One hour later, the reaction solution was poured into water, neutralized with 2 N hydrochloric acid, and extracted with a black hole form. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 0.94 g of 4-chloro-3-difluoromethylthiophene-2-carboxylic acid as a crude product. . Yield 100%. mp. 180-182 ° C ₀ Example 5

Preparation of 2- (4-chloro-1--3-fluoromethylthenoyl) pyrrol

3 ml of thionyl chloride was added to 1.56 g (7.34 mMol) of 4-chloro-1-3-fluoromethylthiophene-2-carboxylic acid, and the mixture was heated under reflux. After 1 hour, excess thionyl chloride was distilled off to obtain 4-chloro-1-difluoromethylthiophene-12-hydroxysulfonic acid chloride as a crude product. In a separate container, 0.59 g (8.79 mmo 1) of pyrrole was dissolved in 15 ml of dry tetrahydrofuran, and 5 ml of a 3.0 M getyl ether solution of ethyl magnesium bromide was added dropwise at 0 ° C under a nitrogen atmosphere. . After heating and refluxing for 30 minutes, the mixture was cooled to 10 ° C., and a solution of 4-chloro-3-difluoromethylthiophene-12-force sulfonic acid chloride in dry tetrahydrofuran 5 ml of furan was added dropwise under a nitrogen atmosphere. After stirring at room temperature for 2 hours, an aqueous solution of saturated sodium chloride was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained residue was separated and purified by silica gel chromatography (n-hexane: ethyl acetate = 9: 1) to obtain the desired 2- (4-chloro-3-3-difluoromethyltenoilyl) pyrrolide. 0.76 g was obtained. Yield 39.6%, mp. 127-129 ° C. Specific examples of the compound of the present invention including the above Examples are described in Tables 1 to 3.

Compound number i (R ₃ ) _m R _{4 5} XQ Physical constant

1-1 H H H H S o m.p. 130--133

1-2 H H H F S o m.p. 136— 138

1-3 H H H Me s 〇

1-4 HHH CF ₃ so mp 93-95 ° C

1-5 H 4-F H H s o

 1-6 H 4-F H F s o

 1-7 H 4- CI H H s o m.p. 125- 128 ° C

1-8 H 4-Cl H F s o m.p. 127-1291:

1-9 H 4-Cl CI F s o

 1-10 H 4-Cl CI CI s o

 1-11 H 4-Cl H Me s o

 1-12 H 4-Cl Me F s o

 1-13 H 4-Cl Me Me s o

1-14 H 4-Cl H CF ₃ so mp 118- 120 ° C

1-15 H 4-Cl CF ₃ F s 0

 1-16 H H H H s NOH

^{_{1-17 HHHF s NOH n D 16 -}} 4 1.5882

1-18 Me H H H s o

1-19 Me HHF son _D ²²⁸ 1.6006

1-20 Me H H H s NOH

 1-21 Me H H F s NOMe

 1-22 Me 4-Cl H H s NOH

 1-23 Me 4-Cl H F s NOH

 1-24 Me 4-Cl H F s NOMe

 1-25 Me 4-Cl H H s O

 1-26 Me 4-Cl H F s O m.p. 78-80 ° C

1-27 Me 4-Cl H H s NOMe

 1-28 Me 4-Cl H F s NOEt

 1-29 Me 4-Cl H H s NOEt

 1-30 Me 4-Cl H F s NOn-Pr

 1-31 H 4-Br H H s O

1-32 H 4-Br HF s O mp 195-196 ° C zz

(s'HI) ZT '(ΖΗ8 · Ϊ: 09 "1

SZ / 6 '(ZH ん ζ = Γ'Ρ'Ηΐ) ん n'(∞'ΕΚ) · n―εΐ7 / (∞'Ηΐ) n 8-9-68 · 9 '( ^ζ Η8 '1'ΗΙ) 56 · 9'(∞'Ηΐ) ΖGe 9-S · 9 ^ "l ( ^s jq'HI) ∑: n · 6'0» 'ΗΙ) 8ε · n -0n' (s 'HI) OS'Otsu'(∞'ΗΙ) ΗΙ8.9-8.9 '(ζΗΓε5 = ί Ηΐ) 08 · 9'0 "' ΗΙ) ε7-9-9ΐ7.9: S-1

niCT0/C00Zdf/X3d

niCT0 / C00Zdf / X3d

Compound number Ri (R ₃ ) _m R ₄ R ₅ XQ Physical constant

2-1 H H H H s o

 2-2 H H H F s 〇 m.p. 114-115 ° C

2-3 H H H Me s 〇

2-4 HHH CF ₃ so

 2-5 H H H Me s o

 2-6 H H Me F s o

 2-7 H H Me Me s o

2-8 HHH CF ₃ so

2-9 HH CF ₃ F s 〇

 2-10 Me H H Hs o

_{^{2-11 Me HHF son D 20 - 7}} 1.5971

2-12 H 4-Cl H H s o

 2-13 H 4-Cl H F s o m.p. 96-91V,

2-14 H 4-Br H H s o

 2-15 H 4-Br H F s 0

 2-16 H 4-Me H H s o

 2-17 H 4-Me H F s 〇

2-18 H 4,5-Cl ₂ HH so

2-19 H 4,5-Cl ₂ HF so

2-20 H 4,5-Bi- ₂ HH so

2-21 H 4,5-Br ₂ HF so

 2-22 H H H F s s

 2-23 H H H H 〇 o

 2-24 H H H F 〇 〇 m.p. 108--109

2-25 H H H Me 〇 〇

 2-26 H H Me F o o

2-27 HHH CF ₃ oo

2-28 HH CF ₃ F 0 o

 2-29 H 5-Br H F s o m.p. 116-117T:

2-30 H 5-C1 H F s o m.p. 106-107 ° C

2-31 H H H F s s m.p. 61-62 ° C

2-32 n-Pr HHF son _D ^{20 1} 1.5742

2-33 H 5-C1 H F o 0 m.p. 118-119 ° C

2-34 H 5-Br HF 0 o mp 124-126t Table 2 continued

化合物番号 Ri R₄ R₅ X Q 物理恒数

Compound number Ri R ₄ R ₅ XQ Physical constant

3-1 H H H H s o

3-2 HHHF son _D ²⁰ - ⁷ 1.5999

3-3 H H H Me s o

3-4 HHH CF ₃ so

 3-5 H H H Me s 〇

 3-6 H H Me F s o

 3-7 H H Me Me s o

3-8 HHH CF ₃ so

3-9 HH CF ₃ F so

 3-10 Me H H Hs o

 3-11 Me H H F s o

 3-12 H 2-C1 H H s o

 3-13 H 2-C1 H F s o

 3-14 H 5-C1 H H s o

 3-15 H 5-C1 H F s o m.p. no-lire

3-16 H 2-Br H H s o

 3-17 H 2-Br H F s o

 3-18 H 5-Br H H s 〇

 3-19 H 5-Br H F s 〇 m.p. 103-104 ° C

3-20 H 2-Me H H s o

 2-21 H 2-Me H F s o

 3-22 H 5-Me H H s o

 3-23 H 5-Me H F s o m.p. 98-99T

3-24 H 5-CHF ₂ HF so mp 114-115 ° C

3-25 H 5-CH = CH ₂ HF so mp 114-115 ° C

3-26 H 5-CN H F s 〇 m.p. 139-141 ° C

3-27 H 5-C≡CSiMe ₃ HF so mp 105-106 ° C

3-28 H 5-C≡CH H F s o m.p. 154-155 ° C

3-29 Me 5-Br H F s o m.p. 72-73T

3-30 H H H H o o

 3-31 H H H F 〇 0

 3-32 H H H Me o o

 3-33 H H Me F o o

3-34 HHH CF ₃ oo

3-35 HH CF ₃ F oo (Agriculture and horticultural fungicides)

 Next, some examples of the germicidal composition of the present invention will be described. However, the additives and the addition ratio are not limited to these examples, but can be changed in a wide range. Parts in Formulation Examples indicate parts by weight. Formulation Example 1 wettable powder

 Compound of the present invention 40 parts

 Cre 1 4 8

 Dioctyl sulfosuccinate sodium salt 4 parts

 Lignin sulfonic acid sodium salt 8 parts

 If the above are uniformly mixed and finely pulverized, a wettable powder with an active ingredient of 40% is obtained. Formulation Example 2 Emulsion

 10 parts of the compound according to the present invention

 Solbesso 2 0 0 5 3 parts

 Cyclohexanone 2 6 parts

 Dodecylbenzenesulfonic acid calcium salt 1 part

 Polyoxyethylene alkylaryl ether 10 parts

 By mixing and dissolving the above, an emulsion containing 10% of the active ingredient is obtained. Formulation Example 3 Suspension

 10 parts of the compound according to the present invention

 Sodium lignin sulfonate 4 parts

 Sodium dodecylbenzenesulfonate 1 part

 Xanthan gum 0.2 parts

 Water 8 4 .8 咅 | 5

 The above ingredients are mixed and wet-pulverized to a particle size of 1 micron or less to obtain a suspension containing 10% of the active ingredient. Industrial applicability:

Test examples show that the compounds according to the present invention are useful as active ingredients for various plant disease controlling agents. The control effect was determined by visually observing the diseased state of the test plant at the time of the survey, that is, the degree of growth of the diseased flora that appeared on the leaves, stems, and the like, and comparing it with the untreated one to determine the control effect. Test example 1 Apple scab control test (prevention test) Emulsions of Formulation Example 2 were applied to apples grown in unglazed pots (variety “Kunimitsu”, 3-4 leaf stage) at a concentration of 100 ppm of the active ingredient. After air-drying at room temperature, conidia of apple scab (Venturiainaequa 1 is) were inoculated and kept in a high-humidity constant temperature room (20 ° C) where light and dark were repeated every 12 hours for 2 weeks. The appearance of lesions on the leaves was compared with that of no treatment, and the control effect was determined. As a result, the following compounds showed excellent control values of 75% or more. The compound numbers correspond to the compound numbers in Tables 1 and 2.

 Compound No .: 1-2, 1-8 Test Example 2 Test for controlling bean gray mold (prevention test)

 The flowers of the kidney beans (variety “Nagauzura”) cultivated in the seedling raising bat were excised and immersed in the liquid medicine of Formulation Example 2 adjusted to a concentration of 100 ppm of the active ingredient. After immersion, it was air-dried at room temperature and spray-inoculated with a spore suspension of kidney bean fungus (Botrytiscinneaea). The inoculated flowers were placed on untreated bean leaves and kept in a high humidity constant temperature room (20 ° C) where light and dark were repeated every 12 hours for 7 days. The lesion diameter on leaves was compared with that of untreated leaves, and the control effect was determined. As a result, the following compounds exhibited excellent control values of 75% or more. The compound numbers correspond to the compound numbers in Tables 1 and 2.

 Compound number: 1-1, 1-8

Claims

Equation (1)

Wherein a hydrogen atom, C ₆ alkyl group, C ^ ₆ alkoxy C ^ ₆ alkyl group, C -6 § Rukirukaruponiru group, Ci ₆ alkoxy Cal Poni Le group, Ci ₆ alkyl force Lupo two Ruokishi 〇 _ ₆ alkyl group or Ci-6 alkyl represents a sulfonyl group. Q represents an oxygen atom, a sulfur atom or a group represented by the formula (2). = N-0-R ₂ (2)  to In the formula, R ₂ represents a hydrogen atom, a Ci ₆ alkyl group or a d ₆ alkoxy C ^ ₆ alkyl group.  0  A represents a group represented by the formula (3), a group represented by the formula (4), or a group represented by the formula (5).

Wherein R ₃ represents a halogen atom, C ^ ₆ alkyl group, C _{2 6} alkenyl group, a nitro group, Shiano group, C ^ e haloalkyl group or a group represented by the formula (6). ~ & R ₆ (6) In the formula, R ₆ represents a hydrogen atom, a Ci ₆ alkyl group or a d-6 trialkylsilyl group. R ₄ is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, - represents an _alkyl group or ₆ haloalkyl group. R ₅ represents a hydrogen atom, a halogen atom, C ^ _e alkyl grave or ₆ lambda lower alkyl group. X represents a sulfur atom or an oxygen atom. m represents 0 or an integer of 1-2. ] Pyrrole derivatives and salts. 2. Equation (1)

 (Wherein, Q and A have the same meaning as in claim 1), characterized in that they contain, as an active ingredient, one or more of a pyrrole derivative represented by the following formula or a salt thereof. Fungicide for agricultural and horticultural use. 3. Equation (7)

(Wherein, R ₃ , R ₄ , R ₅ , X and m have the same meanings as in claim 1, and R ₇ represents a hydrogen atom or a C ₆ alkyl group).  4. Equation (8)

(Wherein, R ₃ , R ₄ , R ₅ , X and m have the same meanings as in claim 1, and R ₈ represents a hydrogen atom or a _6- alkyl group).  5. Equation (9)

(Wherein, R ₃ , R ₄ , R ₅ , X and m have the same meaning as in claim 1, and R ₉ represents a hydrogen atom or an alkyl group.)