JP2023137573A - Bactericidal composition including thiazole carboxylic acid hydrazide compound - Google Patents

Abstract

To provide a bactericidal composition with an excellent control effect on plant diseases.SOLUTION: A bactericidal composition contains a thiazole carboxylic acid hydrazide compound represented by formula (I) [where each symbol is as set forth in the specifications] or a salt thereof as an active ingredient. The bactericidal composition has an excellent control effect on plant diseases.SELECTED DRAWING: None

Description

The present invention relates to novel thiazolecarboxylic acid hydrazide compounds or salts thereof, and fungicidal compositions containing them as active ingredients.

Patent Document 1 describes substitutions that further enhance resistance to abiotic stress (e.g., cold, heat, drought, salt, flood), promote plant growth, and/or contribute to increased plant yield. Heteroarylcarbonyl hydrazide compounds are described. As compounds in which the substituted heteroaryl is thiazole, compounds of general formulas (Ia19) to (Ia23) and general formula (Io20) in which the 2-position of thiazole is H, a pyridyl group, or a chloro group are described, and specific examples As compounds D1-1 to D1-681, D2-1 to D2-681, D3-1 to D3-681, D4-1 to D4-681, D5-1 to D5-681, and D6-1 to D6-681 is listed.

However, Patent Document 1 does not describe the thiazolecarboxylic acid hydrazide compound of the following formula (I), ie, the 2-amino-5-thiazolecarboxylic acid hydrazide compound, with any specific examples. Naturally, Patent Document 1 describes the compound of formula (IA), i.e., 2-amino-5- in which the terminal nitrogen atom of the hydrazide is monosubstituted with methyl, ethyl, n-propyl, propargyl, allyl, or cyclopropyl. Thiazole carboxylic acid hydrazide compounds are also not described with specific examples. Furthermore, Patent Document 1 does not include any specific description regarding the effect of the substituted heteroarylcarboxylic acid hydrazide compound on controlling plant diseases.

Patent Document 2 describes a 2-halogeno-5-thiazolecarboxylic acid hydrazide compound as a plant disease control agent, but the 2-amino-5-thiazolecarboxylic acid hydrazide compound represented by the following formula (I) is Not listed.

International Publication No. 2017/012965 Japanese Patent Application Publication No. 9-31069

The present inventors have discovered that although the substituted heteroarylcarbonyl hydrazide compound described in Patent Document 1 has a low environmental impact, it cannot exhibit sufficient control effects against plant diseases even at high doses. In addition, existing agricultural and horticultural fungicides have problems such as insufficient effectiveness in controlling plant diseases depending on the application situation, emergence of drug-resistant bacteria, and environmental burden (impact on surrounding plants and other ecosystems). There are concerns. Therefore, an object of the present invention is to provide a novel fungicidal composition that exhibits an excellent control effect on plant diseases regardless of the application situation.

As a result of intensive studies to solve the above problems, the present inventors found that a composition containing a compound of the following formula (I) having a 2-amino-5-thiazolecarboxylic acid hydrazide structure or a salt thereof as an active ingredient is harmful. It has been found that this method has an excellent control effect against various plant diseases. Then, the present invention was completed based on the finding that the compound of the following formula (IA) or a salt thereof has a particularly excellent control effect on various plant diseases.

In addition, the present inventors have discovered that a thiazolecarboxylic acid hydrazide compound or a salt thereof having the following specific chemical structure,
・Contains a compound that has a preventive control effect against plant diseases;
・Contains a compound that has a therapeutic control effect against plant diseases;
・Contains a compound that has both preventive and therapeutic effects on plant diseases;
・There is little impact on the appearance of the plants to which it is applied,
I found out.
That is, the present invention provides formula (I):

［式中、Ｒ^１は（Ｃ_１－Ｃ_３）－アルキル、シアノ、Ｈ、又は（Ｃ_１－Ｃ_３）－ハロアルキルであり、
Ｒ^２はＨ又は（Ｃ_１－Ｃ_３）－アルキルであり、
Ｒ^３は（Ｃ_１－Ｃ_３）－アルキル、（Ｃ_３－Ｃ_４）－アルキニル、（Ｃ_２－Ｃ_４）－アルケニル、（Ｃ_３－Ｃ_４）－シクロアルキル、（Ｃ_２－Ｃ_４）－ハロアルケニル、少なくとも１個のＺで置換された（Ｃ_１－Ｃ_３）－アルキル、又はＨであり、
Ｒ^２とＲ^３が一緒になって、Ｒ^２とＲ^３に結合した窒素原子と３～５員環を形成してもよく、
Ｚはシアノ、ハロゲン、（Ｃ_１－Ｃ_３）－アルコキシ、（Ｃ_３）－シクロアルキル、又は（Ｃ_１－Ｃ_３）－アルキルチオであり、
Ｒ^４はハロゲン、（Ｃ_１－Ｃ_３）－アルキル、（Ｃ_１－Ｃ_３）－ハロアルキル、ニトロ、シアノ、（Ｃ_１－Ｃ_３）－アルキルチオ、又は（Ｃ_１－Ｃ_３）－ハロアルキルチオであり、
ｎは１から５の整数である］で表されるチアゾールカルボン酸ヒドラジド化合物又はその塩（以下、化合物（Ｉ）ともいう）を有効成分とする殺菌組成物（以下、本組成物ともいう）、化合物（Ｉ）の有効量を、植物体、植物病原菌又は土壌に施用する工程を含む有害な植物病害を防除する方法に関する。
また本発明は、従来、具体的に知られておらず、種々の植物病害に対して特に優れた防除効果を有する化合物群である式（ＩＡ）：

[wherein R ¹ is (C ₁ -C ₃ )-alkyl, cyano, H, or (C ₁ -C ₃ )-haloalkyl,
R ² is H or (C ₁ -C ₃ )-alkyl;
R ³ is (C ₁ -C ₃ )-alkyl, (C ₃ -C ₄ )-alkynyl, (C ₂ -C ₄ )-alkenyl, (C ₃ -C ₄ )-cycloalkyl, (C ₂ -C ₄ )-haloalkenyl, (C ₁ -C ₃ )-alkyl substituted with at least one Z, or H;
R ² and R ³ may be taken together to form a 3- to 5-membered ring with the nitrogen atom bonded to R ² and R ³ ,
Z is cyano, halogen, (C ₁ -C ₃ )-alkoxy, (C ₃ )-cycloalkyl, or (C ₁ -C ₃ )-alkylthio,
R ⁴ is halogen, (C ₁ -C ₃ )-alkyl, (C ₁ -C ₃ )-haloalkyl, nitro, cyano, (C ₁ -C ₃ )-alkylthio, or (C ₁ -C ₃ )-haloalkylthio and
A bactericidal composition (hereinafter also referred to as the present composition) containing as an active ingredient a thiazolecarboxylic acid hydrazide compound or its salt (hereinafter also referred to as compound (I)) represented by n is an integer from 1 to 5; The present invention relates to a method for controlling harmful plant diseases, which includes the step of applying an effective amount of compound (I) to plants, plant pathogens, or soil.
Furthermore, the present invention relates to a group of compounds of the formula (IA), which have not been specifically known in the past and have particularly excellent control effects against various plant diseases:

［式中、Ｒ^１Ａはメチル、シアノ、又はＨであり、
Ｒ^３Ａはメチル、エチル、ノルマルプロピル、プロパルギル、アリル、又はシクロプロピルであり、
Ｒ^４Ａはハロゲン、（Ｃ_１－Ｃ_２）－アルキル、Ｃ_１－ハロアルキル、ニトロ、シアノ、（Ｃ_１）－アルキルチオ、又は（Ｃ_１）－ハロアルキルチオであり、
ｎは１から５の整数である］で表されるチアゾールカルボン酸ヒドラジド化合物又はその塩（以下、化合物（ＩＡ）ともいう）に関する。

[wherein R ^1A is methyl, cyano, or H,
R ^3A is methyl, ethyl, normal propyl, propargyl, allyl, or cyclopropyl;
R ^4A is halogen, (C ₁ -C ₂ )-alkyl, C ₁ -haloalkyl, nitro, cyano, (C ₁ )-alkylthio, or (C ₁ )-haloalkylthio;
n is an integer from 1 to 5] or a salt thereof (hereinafter also referred to as compound (IA)).

The present composition exhibits superior control effects against plant diseases compared to similar conventional compounds, and is useful as a fungicidal composition such as a fungicide for agricultural and horticultural use.

In compound (I) and compound (IA), the number of R ⁴ or R ^4A that is a substituent of phenyl may be one or two or more, and in the case of two or more, R ⁴ or R ^4A may be the same or different.
In compound (I) and compound (IA), examples of halogen or halogen as a substituent include fluorine, chlorine, bromine, or iodine atoms. The number of halogen atoms as a substituent may be one or more, and in the case of two or more, each halogen atom may be the same or different. Furthermore, the halogen as a substituent may be substituted at any position.

In compound (I) and compound (IA), the expression "C _P -C _T " means that the number of carbon atoms is P to T. For example, the notation "C ₁ -C ₃ " means that the number of carbon atoms is 1 to 3.

Examples of (C ₁ -C ₃ )-alkyl include straight-chain or branched alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, propyl, or isopropyl. Examples of (C ₁ -C ₂ )-alkyl include linear alkyl groups having 1 to 2 carbon atoms such as methyl or ethyl.
(C ₃ -C ₄ )-alkynyl can be any of the following, for example 1-propynyl, propargyl (also simply 2-propynyl), 1-butynyl, 2-butynyl, 3-butynyl or 1-methyl-2-propynyl. Mention may be made of straight-chain or branched alkynyl groups having 3 to 4 carbon atoms and having at least one triple bond in position.
(C ₂ -C ₄ )-alkenyl is, for example, vinyl (also simply referred to as ethenyl), allyl (also simply referred to as 2-propenyl), 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1,3-butadien-2-yl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl or 2- Examples include straight-chain or branched alkenyl groups having 2 to 4 carbon atoms and having at least one double bond at any position, such as ethyl-2-vinyl. In addition, if there is a geometric isomer, it may be only one of the E-form or the Z-form, or a mixture of the E-form and the Z-form in any ratio, and there are no particular limitations as long as the number of carbon atoms is within the specified range. It never happens.
(C ₃ -C ₄ )-cycloalkyl includes, for example, a cycloalkyl group having 3 to 4 carbon atoms such as cyclopropyl or cyclobutyl. (C ₃ )-Cycloalkyl includes, for example, a cycloalkyl group having 3 carbon atoms such as cyclopropyl.

(C ₁ -C ₃ )-Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, chlorofluoromethyl, 1-fluoroethyl, 2 -Fluoroethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 1-chloroethyl, 2-chloroethyl, 1,1-dichloroethyl, 2,2 -dichloroethyl, 2,2,2-trichloroethyl, 1-chloro-1-fluoroethyl, 2-chloro-2-fluoroethyl, 1-fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 2-fluoro- 2-propyl, 1,1-difluoropropyl, 2,2-difluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, perfluoropropyl, perfluoroisopropyl, 2,2,3,3 , 3-pentafluoropropyl or 1,1,1,3,3,3-hexafluoroisopropyl, etc., having 1 to 3 carbon atoms partially or completely substituted with 1 to 7 identical or different halogen atoms straight-chain or branched alkyl groups. (C ₁ )-Haloalkyl is, for example, 1 to 3 identical or Mention may be made of alkyl groups having one carbon atom that are partially or completely substituted with different halogen atoms.
(C ₂ -C ₄ )-Haloalkenyl is, for example, 2-fluorovinyl, 2,2-difluorovinyl, trifluorovinyl, 2-chlorovinyl, 2,2-dichlorovinyl, 2-bromovinyl, 2,2- Dibromovinyl, 3-fluoroallyl, 3,3-difluoroallyl, 2,3,3-trifluoroallyl, 3,3-difluoro-1-propenyl, 3,3,3-trifluoro-1-propenyl, 3- Chloroallyl, 3,3-dichloroallyl, 3,3-dichloro-1-propenyl, 3,3,3-trichloro-1-propenyl, 3,3-dichloro-3-fluoro-1-propenyl, 3-chloro-3 ,3-difluoro-1-propenyl, 3-bromoallyl, 3,3-dibromoallyl, 2-fluoro-1-methylvinyl, 2,2-difluoro-1-methylvinyl, 2-chloro-1-methylvinyl, 2 ,2-dichloro-1-methylvinyl, 2-bromo-1-methylvinyl, 2,2-dibromo-1-methylvinyl, 4,4,4-trifluoro-1-butenyl, 4,4,4-tri Fluoro-2-butenyl, 4,4-difluoro-3-butenyl, 3,3-difluoro-1-methyl-2-propenyl, 2-fluoro-1-ethylvinyl, 2,2-difluoro-1-ethylvinyl, 2- Chloro-1-ethylvinyl, 2,2-dichloro-1-ethylvinyl, 2-bromo-1-ethylvinyl, 2,2-dibromo-1-ethylvinyl, 2-fluoro-1-methyl-1-propenyl, 2-chloro- 1-Methyl-1-propenyl or 2-bromo-1-methyl-1-propenyl, which has at least one double bond at any position and is substituted with one or more same or different halogen atoms. Examples include linear or branched alkenyl groups having 2 to 4 carbon atoms. In addition, if there is a geometric isomer, it may be only one of the E-form or the Z-form, or a mixture of the E-form and the Z-form in any ratio, and there are no particular limitations as long as the number of carbon atoms is within the specified range. It never happens.

(C ₁ -C ₃ )-Alkyl substituted with at least one Z is, for example, cyanomethyl, 1-cyanoethyl, 2-cyanoethyl, 1-cyanopropyl, 2-cyanopropyl, 3-cyanopropyl, dicyanomethyl, 2 , 2-dicyanoethyl, methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, 1-methoxyethyl, 1-ethoxyethyl, 1-propoxyethyl, 1-isopropoxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-Propoxyethyl, 2-isopropoxyethyl, 1-methoxypropyl, 1-ethoxypropyl, 1-propoxypropyl, 1-isopropoxypropyl, 2-methoxypropyl, 2-ethoxypropyl, 2-propoxypropyl, 2-iso Propoxypropyl, 3-methoxypropyl, 3-ethoxypropyl, 3-propoxypropyl, 3-isopropoxypropyl, 1-methoxy-2-propyl, 1-ethoxy-2-propyl, 1-propoxy-2-propyl, 1- Isopropoxy-2-propyl, 2-methoxy-2-propyl, 2-ethoxy-2-propyl, 2-propoxy-2-propyl, 2-isopropoxy-2-propyl, dimethoxymethyl, diethoxymethyl, 2,2 -dimethoxyethyl, 2,2-diethoxyethyl, methylthiomethyl, ethylthiomethyl, propylthiomethyl, isopropylthiomethyl, 1-methylthioethyl, 1-ethylthioethyl, 1-propylthioethyl, 1-isopropylthioethyl, 2-Methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl, 2-isopropylthioethyl, 1-methylthiopropyl, 1-ethylthiopropyl, 1-propylthiopropyl, 1-isopropylthiopropyl, 2-methylthiopropyl , 2-ethylthiopropyl, 2-propylthiopropyl, 2-isopropylthiopropyl, 3-methylthiopropyl, 3-ethylthiopropyl, 3-propylthiopropyl, 3-isopropylthiopropyl, 1-methylthio-2-propyl, 1-ethylthio-2-propyl, 1-propylthio-2-propyl, 1-isopropylthio-2-propyl, 2-methylthio-2-propyl, 2-ethylthio-2-propyl, 2-propylthio-2-propyl, 2 -isopropylthio-2-propyl, dimethylthiomethyl, diethylthiomethyl, 2,2-dimethylthioethyl, 2,2-diethylthioethyl, cyclopropylmethyl, 1-cyclopropylethyl, 2-cyclopropylethyl, 1- Cyclopropylpropyl, 2-cyclopropylpropyl, 3-cyclopropylpropyl, 2-cyclopropyl-2-propyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, chlorodifluoromethyl, dichlorofluoro Methyl, chlorofluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 1-chloroethyl, 2- Chloroethyl, 1,1-dichloroethyl, 2,2-dichloroethyl, 2,2,2-trichloroethyl, 1-chloro-1-fluoroethyl, 2-chloro-2-fluoroethyl, 1-fluoropropyl, 2- Fluoropropyl, 3-fluoropropyl, 2-fluoro-2-propyl, 1,1-difluoropropyl, 2,2-difluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, perfluoropropyl , perfluoroisopropyl, 2,2,3,3,3-pentafluoropropyl or 1,1,1,3,3,3-hexafluoroisopropyl, etc., at least one carbon substituted with Z at any position Examples include straight-chain or branched alkyl groups having 1 to 3 atoms. The number of substitutions for Z may be one or more, and in the case of two or more, the types of Z may be the same or different, and the types of Z are preferably the same. Moreover, the substitution position of Z may be any position.

(C ₁ -C ₃ )-Alkoxy includes, for example, a straight or branched alkoxy group having 1 to 3 carbon atoms such as methoxy, ethoxy, propoxy or isopropoxy.

Examples of (C ₁ -C ₃ )-alkylthio include linear or branched alkylthio groups having 1 to 3 carbon atoms, such as methylthio, ethylthio, propylthio, or isopropylthio. (C ₁ )-Alkylthio includes, for example, a linear alkylthio group having one carbon atom, such as methylthio.
(C ₁ -C ₃ )-Haloalkylthio is, for example, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chloromethylthio, dichloromethylthio, trichloromethylthio, chlorodifluoromethylthio, dichlorofluoromethylthio, 2-fluoroethylthio, 2,2- Difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloroethylthio, 2,2-dichloroethylthio, 2,2,2-trichloroethylthio, perfluoroethylthio, perfluoropropylthio, perfluoroethylthio Fluoroisopropylthio, 3,3,3-trifluoropropylthio, 2,2,3,3,3-pentafluoropropylthio, 1,1,1,3,3,3-hexafluoroisopropylthio or 2-fluoro Examples include straight-chain or branched alkylthio groups having 1 to 3 carbon atoms and substituted with 1 to 7 identical or different halogen atoms, such as -2-propylthio. (C ₁ )-Haloalkylthio means 1 to 3 identical or different halogen atoms, such as fluoromethylthio, difluoromethylthio, trifluoromethylthio, chloromethylthio, dichloromethylthio, trichloromethylthio, chlorodifluoromethylthio, dichlorofluoromethylthio, etc. Examples include substituted linear alkylthio groups having one carbon atom.

R ² and R ³ together may form a 3- to 5-membered ring with the nitrogen atom bonded to R ² and R ³ , which ring may be saturated or unsaturated. For example, saturated rings include aziridine, azetidine or pyrrolidine, and unsaturated rings include pyrrole or dihydropyrrole.

The salts of compound (I) or compound (IA) include all agriculturally acceptable salts, such as alkali metal salts (e.g., sodium salts, potassium salts, etc.), alkaline earth metal salts, etc. salts (e.g. magnesium salts, calcium salts, etc.), inorganic acid salts (e.g. hydrochlorides, perchlorates, sulfates, nitrates, etc.) or organic acid salts (e.g. acetates, methanesulfonates, para-toluenesulfonates). salt, oxalate, etc.).

Compound (I) exists in various isomers, such as optical isomers and geometric isomers, and the present invention may include both each isomer and a mixture of isomers. Note that Compound (I) also includes various isomers other than those described above within the scope of common technical knowledge in the technical field. Furthermore, various isomers can be separately produced using common technical knowledge and general experimental methods in the relevant technical field.

Furthermore, depending on the type of isomer, it may have a chemical structure different from the described structural formula, but a person skilled in the art will be able to fully recognize that they are in an isomer relationship, and therefore within the scope of the present invention. It is clear that there is.

Next, a method for producing compound (I) will be explained. Compound (I) includes Compound (IA), and therefore the following description also includes a method for producing Compound (IA).
Compound (I) can be produced according to Production Method 1 (Reaction A to Reaction K) shown below and the usual salt production method, but the method for obtaining the compound is limited to these methods. isn't it. For example, the compound (I) of the present invention can be converted into a substituent on phenyl by various substituent conversion reactions well known in the art (e.g., alkylation reaction, haloalkylation reaction, cross-coupling reaction such as Suzuki coupling reaction). , Sandmeyer type reaction, halogenation reaction, oxidation reaction, reduction reaction, etc.). Furthermore, if necessary, protection and deprotection reactions commonly used in this field may be applied in the production of the compounds of the present invention. When carrying out the reaction, if necessary, the reaction may be carried out under an inert gas atmosphere such as nitrogen or argon, or a salt reagent may be used.

Manufacturing method 1
[Reaction A]
Reaction A is a method for obtaining a compound of formula (I) by deprotecting the Boc group from a compound of formula (XX-a). The Boc group is a tert-butoxycarbonyl group.

The symbols in the formula are as described above.

Reaction A is performed under known conditions used for deprotection of Boc groups, e.g. Greene's PROTECTIVE GROUPS in ORGANIC SYNTHESIS (John Wikey and Sons, 2007, Peter G. M. Wuts, Theodora W. . Greene) This can be done by any method. More specifically, it can be carried out, for example, by reacting with an acid such as trifluoroacetic acid or hydrogen chloride in the presence of a solvent, or by reacting with trimethylsilyl triflate in the presence of a solvent and a base such as 2,6-lutidine. can.

[Reaction B] and [Reaction C]
Reaction B is a method in which a compound of formula (II) and a compound of formula (III) are reacted to obtain a compound of formula (XX-b). Reaction C is a method in which a compound of formula (II-a) and a compound of formula (III) are reacted to obtain a compound of formula (XX-b).

where A is NH ₂ or NH(Boc) and R ^2a is H, (C ₁ -C ₃ )-alkyl or Boc. When R ^2a is (C ₁ -C ₃ )-alkyl, R ^2a and R ³ together form a nitrogen atom bonded to R ^2a and R ³ and a 3- to 5-membered ring (for example, aziridine, azetidine, pyrrolidine, dihydropyrrole or pyrrole). L is a leaving group, such as halogen, alkoxy, aryloxy, alkylcarbonyloxy, arylcarbonyloxy, and the like. Other symbols are as described above.

Reaction B can usually be carried out in the presence of a dehydration condensation agent and a solvent, with the addition of a base if necessary. The compound of formula (III) can be used in an amount of 0.5 to 3 equivalents, preferably 0.8 to 1.5 equivalents, per 1 equivalent of the compound of formula (II) (equivalents are molar equivalents, and the same applies below) ).

As the dehydration condensing agent, a carbodiimide condensing agent such as N,N'-dicyclohexylcarbodiimide (DCC), 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (EDC) or its hydrochloride; 1. Imidazole condensing agents such as 1'-carbonyldiimidazole (CDI); 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM) ); triazine condensing agents such as 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate (PyBOP); 1-[bis(dimethylamino)methylene]-1H- uronium-based condensing agents such as 1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU); such as 2-methyl-6-nitrobenzoic anhydride (MNBA); Acid anhydrides; 2-halopyridinium salts such as 2-chloro-1-methylpyridinium p-toluenesulfonate; propylphosphonic anhydride (cyclic trimer) (T3P); diphenylphosphoric azide (DPPA); etc. However, it is not limited to these. If necessary, common additives used together with dehydration condensation agents such as 1-hydroxybenzotriazole (HOBt) may be added. The dehydration condensation agent can be used in an amount of 0.5 to 5 equivalents, preferably 1 to 2 equivalents, per equivalent of the compound of formula (II), and the additive can be used in an amount of 0.5 to 5 equivalents, preferably 1 to 2 equivalents, per equivalent of the compound of formula (II). 2 to 5 equivalents, preferably 1 to 2 equivalents can be used.

Bases include, for example, carbonates such as sodium carbonate and potassium carbonate; bicarbonates such as sodium bicarbonate and potassium bicarbonate; metal hydroxides such as sodium hydroxide and potassium hydroxide; sodium hydride and hydrogen Metal hydrides such as potassium hydride; amines such as triethylamine and N,N-diisopropylethylamine; pyridines such as pyridine, 4-dimethylaminopyridine, and 2,6-lutidine; alkalis such as sodium acetate and potassium acetate One or more metal carboxylates can be appropriately selected and used as a mixture. The base can be used in an amount of 0.5 to 10 equivalents, preferably 1 to 5 equivalents, per 1 equivalent of the compound of formula (II).
The solvent may be any solvent inert to the reaction, such as aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; carbon tetrachloride, methyl chloride, chloroform, dichloromethane, dichloroethane, and trichloroethane. , hexane, cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether, dimethoxyethane; esters such as methyl acetate, ethyl acetate; dimethyl sulfoxide, sulfolane, N,N-dimethylacetamide , N,N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, propionitrile; ketones such as acetone, methyl ethyl ketone; protic polar solvents such as methanol, ethanol; water ; One or more types can be appropriately selected from the following.

The reaction temperature for reaction B is about -20°C to 150°C, preferably about 0°C to 100°C, and the reaction time is usually about 0.5 to 48 hours, preferably about 1 to 24 hours.

Reaction C can be carried out in the presence of a solvent and optionally with the addition of a base. The compound of formula (III) can be used in an amount of 0.5 to 3 equivalents, preferably 0.8 to 1.5 equivalents, per equivalent of the compound of formula (II-a).

Bases include, for example, carbonates such as sodium carbonate and potassium carbonate; bicarbonates such as sodium bicarbonate and potassium bicarbonate; metal hydroxides such as sodium hydroxide and potassium hydroxide; sodium hydride and hydrogen Metal hydrides such as potassium chloride; amines such as triethylamine and N,N-diisopropylethylamine; pyridines such as pyridine, 4-dimethylaminopyridine, and 2,6-lutidine; alkalis such as sodium acetate and potassium acetate One or more metal carboxylates can be appropriately selected and used as a mixture. The base can be used in an amount of 0.1 to 10 equivalents, preferably 0.5 to 5 equivalents, per 1 equivalent of the compound of formula (II-a).
The solvent may be any solvent inert to the reaction, such as aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; carbon tetrachloride, methyl chloride, chloroform, dichloromethane, dichloroethane, and trichloroethane. , hexane, cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether, dimethoxyethane; esters such as methyl acetate, ethyl acetate; dimethyl sulfoxide, sulfolane, N,N-dimethylacetamide , N,N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, polar aprotic solvents such as propionitrile; ketones such as acetone, methyl ethyl ketone; protic polar solvents such as methanol, ethanol; water ; One or more types can be appropriately selected from the following.

The reaction temperature for reaction C is about -20°C to 150°C, preferably about 0°C to 100°C, and the reaction time is usually about 0.5 to 48 hours, preferably about 1 to 24 hours.

The compound of formula (II) used in reaction B and reaction C can be produced according to reaction 1-1 below or a known method, or a commercially available product may be used. The compound of formula (III) can be produced according to Reaction 2-2, Reaction 2-4 or Reaction 2-6 below.
The compound of formula (II-a) used in reaction C can be produced from the compound of formula (II) according to known methods, or a commercially available product may be used.

[Reaction D]
Reaction D is a method of deprotecting the Boc group of the compound of formula (XX-c) and obtaining the compound of formula (I-a) via the compound of formula (XX-d) or formula (XX-e). . In addition, reaction D involves directly converting the compound of formula (I-a) from the compound of formula (XX-c) without isolating the compound of formula (XX-d), the compound of formula (XX-e), or a mixture thereof. You can also get it.

The symbols in the formula are as described above.
Reaction D can be carried out according to reaction A above.

[Reaction E] and [Reaction F]
Reaction E is a method in which a compound of formula (XX-f) is reacted with a compound of formula (IV-a) or a compound of formula (IV-b) to obtain a compound of formula (XX-g). Reaction F is a method of reducing a compound of formula (XX-g) to obtain a compound of formula (XX-h). Furthermore, reactions E and F can also be carried out continuously without isolating the compound of formula (XX-g).

In the formula, R ^3a is H, (C ₁ -C ₂ )-alkyl, (C ₂ -C ₃ )-alkynyl, (C ₂ -C ₃ )-alkenyl, (C ₂ -C ₃ )-haloalkenyl, or (C ₁ -C ₂ )-alkyl substituted with Z, and R ^3b is H or methyl. R ^3a and R ^3b may be taken together to form a 3-4 membered carbocycle (e.g. cyclopropyl or cyclobutyl), Y ¹ is alkyl and Y ² is hydrogen or The symbols are as described above.

Reaction E can be carried out by adding an acid, a base, or a dehydrating agent as necessary, and a solvent may be used. The compound of formula (IV-a) or formula (IV-b) is usually used in an amount of 1 to 5 equivalents per equivalent of the compound of formula (XX-f), and may be used in excess if there is no problem with the reaction.

The acid may be either an inorganic acid or an organic acid, and examples of the inorganic acid include hydrochloric acid and sulfuric acid, and examples of the organic acid include acetic acid, methanesulfonic acid, and paratoluenesulfonic acid.
Bases include, for example, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide; carbonates such as sodium carbonate and potassium carbonate; bicarbonates such as sodium bicarbonate and potassium bicarbonate; water Metal hydroxides such as sodium oxide and potassium hydroxide; Metal hydrides such as sodium hydride and potassium hydride; Amines such as triethylamine and N,N-diisopropylethylamine; Pyridine, 4-dimethylaminopyridine, Examples include pyridines such as 2,6-lutidine; alkali metal carboxylates such as sodium acetate and potassium acetate; and the like.
Examples of the dehydrating agent include anhydrous magnesium sulfate, anhydrous sodium sulfate, and molecular sieves.

The solvent may be any solvent as long as it is inert to the reaction; for example, aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; aromatic hydrocarbons such as toluene and xylene; dioxane, tetrahydrofuran, One or more of ethers such as diethyl ether and dimethoxyethane; esters such as methyl acetate and ethyl acetate; aprotic polar solvents such as acetonitrile; protic polar solvents such as methanol and ethanol; water; Two or more types can be selected as appropriate.

The reaction temperature for reaction E is about -20°C to 150°C, preferably about 0°C to 120°C, and the reaction time is usually about 0.5 to 48 hours, preferably about 1 to 24 hours.

The compound of formula (IV-a) or formula (IV-b) used in reaction E can be produced according to a known method, or a commercially available product may be used.

Reaction F can usually be carried out in the presence of a reducing agent and a solvent, with addition of an acid as necessary. Alternatively, hydrogenation can be carried out in a hydrogen atmosphere using palladium on carbon as a catalyst.

Examples of the reducing agent include sodium borohydride, sodium cyanoborohydride, sodium triacetoxyborohydride, and 2-picoline-borane complex. The reducing agent can be used in an amount of 0.5 to 10 equivalents, preferably 1 to 5 equivalents, per equivalent of the compound of formula (XX-g). The acid to be added may be either an inorganic acid or an organic acid, and examples of the inorganic acid include hydrochloric acid, and examples of the organic acid include acetic acid and trifluoroacetic acid. The acid can be used in an amount of 1 to 10 equivalents per equivalent of the compound of formula (XX-g).

The solvent used when using a reducing agent may be any solvent as long as it is inert to the reaction, such as aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; carbon tetrachloride, chloride, etc. Aliphatic hydrocarbons such as methyl, chloroform, dichloromethane, dichloroethane, trichloroethane, hexane, cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether, dimethoxyethane; esters such as methyl acetate, ethyl acetate; methanol, One or more types can be appropriately selected from protic polar solvents such as ethanol; water; and the like.

The solvent used in the reaction using palladium on carbon as a catalyst in a hydrogen atmosphere may be any solvent as long as it is inert to the reaction, such as ethers such as dioxane, tetrahydrofuran, diethyl ether, and dimethoxyethane; acetic acid. One or more types can be appropriately selected from esters such as methyl and ethyl acetate; alcohols such as methanol, ethanol, and isopropanol; and water. Moreover, it can also be carried out under pressurized conditions if necessary.

The reaction temperature for reaction F is about -20°C to 150°C, preferably about 0°C to 100°C, and the reaction time is usually about 0.5 to 48 hours, preferably about 1 to 24 hours.

[Reaction G]
Reaction G is a method of deprotecting the Boc group of a compound of formula (XX-ga) to obtain a compound of formula (XX-gb).

The symbols in the formula are as described above.
Reaction G can be carried out according to reaction A above.

[Reaction H] and [Reaction I]
Reaction H is a method of reacting a compound of formula (II) with a compound of formula (V) to obtain a compound of formula (XX-g). Reaction I is a method of reacting a compound of formula (II-a) with a compound of formula (V) to obtain a compound of formula (XX-g).

The symbols in the formula are as described above.
Reaction H can be carried out according to reaction B above. The compound of formula (V) can be used in an amount of 0.5 to 3 equivalents, preferably 0.8 to 1.5 equivalents, per equivalent of the compound of formula (II).

Reaction I can be carried out according to reaction C above. The compound of formula (V) can be used in an amount of 0.5 to 3 equivalents, preferably 0.7 to 1.5 equivalents, per 1 equivalent of the compound of formula (II-a).

The compound of formula (V) used in Reaction H and Reaction I can be produced according to Reaction 2-5 below or a known method, or a commercially available product may be used.

[Reaction J]
Reaction J is a method for obtaining a compound of formula (XX-j) by reacting a compound of formula (XX-i) with a compound of formula (VI).

In the formula, L ¹ is a leaving group such as halogen, trifluoromethanesulfonyloxy, methanesulfonyloxy, paratoluenesulfonyloxy, etc., and R ^3c is (C ₁ -C ₃ )-alkyl, (C ₃ -C ₄ )-alkynyl, (C ₂ -C ₄ )-alkenyl, (C ₂ -C ₄ )-haloalkenyl, (C ₃ -C ₄ )-cycloalkyl, or (C ₁ -) substituted with at least one Z C ₃ )-alkyl, and the other symbols are as described above.

Reaction J can be carried out usually in the presence of a base and a solvent, optionally adding a phase transfer catalyst. The compound of formula (VI) can be used in an amount of 1 to 5 equivalents, preferably 1 to 3 equivalents, per 1 equivalent of the compound of formula (XX-i).

Bases include, for example, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide; carbonates such as sodium carbonate and potassium carbonate; bicarbonates such as sodium bicarbonate and potassium bicarbonate; water Metal hydroxides such as sodium oxide and potassium hydroxide; Metal hydrides such as sodium hydride and potassium hydride; Amines such as triethylamine and N,N-diisopropylethylamine; Pyridine, 4-dimethylaminopyridine, Appropriate selection of one or more of pyridines such as 2,6-lutidine; organic lithium compounds such as n-butyllithium and lithium diisopropylamide; alkali metal carboxylates such as sodium acetate and potassium acetate; , can be used in combination. The base can be used in an amount of 1 to 10 equivalents, preferably 1 to 5 equivalents, relative to the compound of formula (XX-i).
The solvent may be any solvent inert to the reaction, such as aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; carbon tetrachloride, methyl chloride, chloroform, dichloromethane, dichloroethane, and trichloroethane. , hexane, cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether, dimethoxyethane; esters such as methyl acetate, ethyl acetate; methanol, ethanol, propanol, tert-butanol, etc. alcohols; polar aprotic solvents such as dimethyl sulfoxide, sulfolane, N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, propionitrile; polar aprotic solvents such as acetone, methyl ethyl ketone One or more types can be appropriately selected from ketones; water; and the like.
Examples of the phase transfer catalyst include quaternary ammonium salts such as tetrabutylammonium bromide, benzyltriethylammonium chloride, and tetrabutylammonium hydrogen sulfate; crown ethers such as 18-crown-6-ether; and the like. The phase transfer catalyst can be used in an amount of 0.1 to 3 equivalents based on the compound of formula (XX-i).

The reaction temperature for reaction J is about -20°C to 150°C, preferably about 0°C to 100°C, and the reaction time is usually about 10 minutes to 48 hours, preferably about 1 to 24 hours.

The compound of formula (VI) used in reaction J can be produced according to a known method, or a commercially available product may be used.

[Reaction K]
Reaction K is a method for obtaining a compound of formula (XX-b) by reacting a compound of formula (II-b) with a compound of formula (VII).

The symbols in the formula are as described above.

Reaction K can be carried out according to the above reaction J. The compound of formula (VII) can be used in an amount of 1 to 5 equivalents, preferably 1 to 2 equivalents, per 1 equivalent of the compound of formula (II-b).

The compound of formula (II-b) used in reaction K can be produced according to reaction 1-3 below or a known method, or a commercially available product may be used. The compound of formula (VII) used in reaction K can be produced according to a known method, or a commercially available product may be used.

The compounds used in Production Method 1 (Reactions A to Reactions K) were prepared according to the following Production Method 2 (Reactions 1-1 to 1-3 and Reactions 2-1 to 2-6) and ordinary salt production methods. However, these compounds are not limited to these methods, and these compounds may be produced according to known methods, or commercially available products may be used.

Manufacturing method 2
[Reaction 1-1], [Reaction 1-2] and [Reaction 1-3]
Reaction 1-1 is a method of hydrolyzing a compound of formula (1) to obtain a compound of formula (II). Reaction 1-2 is a method for protecting the amino group of a compound of formula (1-a) with a Boc group to obtain a compound of formula (I-b). Reaction 1-3 is a method in which a compound of formula (II) or a compound of formula (II-a) is reacted with a compound of formula (2) to obtain a compound of formula (II-b).

The symbols in the formula are as described above.
Reaction 1-1 can be carried out according to general ester hydrolysis conditions, for example, the method described in International Publication No. 2009/100171, Bioorganic & Medicinal Chemistry 2001, 9, 7-17.

The compound of formula (1) used in reaction 1-1 can be reacted with the following reaction 1-2 or with a known method, such as the method described in WO 2018/041563 and US Patent Application Publication No. 2008/312255. It can be manufactured according to the same method, or a commercially available product can be used.

Reaction 1-2 is performed under general reaction conditions for protecting an amino group with a Boc group, such as Greene's PROTECTIVE GROUPS in ORGANIC SYNTHESIS (John Wikey and Sons, 2007, Peter G. M. Wuts, Theodora W. Greene ) can be carried out according to the method described in .

The compound of formula (1-a) used in reaction 1-2 is produced according to a known method, for example, the method described in International Publication No. 2018/041563 and US Patent Application Publication No. 2008/312255. or a commercially available product may be used.

Reaction 1-3 can be carried out according to reaction B or reaction C above. The compound of formula (2) can be used in an amount of 1 to 5 equivalents, preferably 1 to 3 equivalents, per equivalent of the compound of formula (II) or the compound of formula (II-a).

The compound of formula (2) used in reaction 1-3 can be prepared according to known methods, for example, European Journal of Organic Chemistry, 2003, 4757-4764, Synthetic Communications, 2017, 47, 1231-123. 8. It can be manufactured according to the method, or a commercially available product may be used.

[Reaction 2-1] to [Reaction 2-6]
Reaction 2-1 is a method in which a compound of formula (10) is reacted with a compound of formula (3) to obtain a compound of formula (11). Reaction 2-2 is a method for reducing the compound of formula (11) to obtain the compound of formula (III). Reactions 2-1 and 2-2 can also be carried out consecutively without isolating the compound of formula (11).
Reaction 2-3 is a method for obtaining a compound of formula (11-b) by reacting a compound of formula (11-a) with a compound of formula (VI).
Reaction 2-4 is a method for obtaining a compound of formula (III) by reacting a compound of formula (VII) with a compound of formula (3).
Reaction 2-5 is a method in which a compound of formula (III-a) is reacted with a compound of formula (IV-a) or a compound of formula (IV-b) to obtain a compound of formula (V). Reaction 2-6 is a method of reducing the compound of formula (V) to obtain the compound of formula (III-b). Reactions 2-5 and 2-6 can also be carried out consecutively without isolating the compound of formula (V).

The symbols in the formula are as described above.

Reaction 2-1 can be carried out according to general hydrazonation conditions using an aldehyde and hydrazine, for example, the method described in Tetrahedron Letters, 2013, 54, 896-899. The compound of formula (3) can be used in an amount of 0.7 to 5 equivalents, preferably 1 to 2 equivalents, per 1 equivalent of the compound of formula (10).

The compound of formula (10) used in reaction 2-1 can be produced according to a known method, or a commercially available product may be used.

Reaction 2-2 can be carried out under general conditions for reducing hydrazone to hydrazine, for example, according to the method described in US Patent Application Publication No. 2016/002251, Chemical Reviews, 2019, 119, 11857-11911. . Further, the 2-picoline/borane complex can be used for reduction by adding an acid such as hydrochloric acid as necessary.

Reaction 2-3 is performed under known hydrazone alkylation conditions, for example, Organic Letters, 2014, 16, 5940-5943, Chemistry-A European Journal, 2019, 25, 976-980, Journal of Organic Chemistry try, 2006, 71, 7113-7116, etc.

Reaction 2-4 is a known alkylation reaction of hydrazine, for example, the method described in US Patent Application Publication No. 2012/0157386, Organic Letters, 2014, 16, 4782-4785, International Publication No. 2018/221679, etc. This can be done in accordance with the above.

Reaction 2-5 can be carried out according to reaction E, and reaction 2-6 can be carried out according to reaction F.

Compound (I), which is the active ingredient of the present composition, is useful as an active ingredient of an agricultural and horticultural fungicide that can control plant diseases with a low dose. Compound (I) includes compound (IA), and therefore, the following description also includes compound (IA).
Compound (I) is effective against plant pathogenic fungi belonging to, for example, Oomycetes, Phytomyxea, Zygomycota, Ascomycetes, Basidiomycetes, Deuteromycetes, etc. It is possible to control plant diseases caused by this. Among them, it is particularly effective for controlling plant diseases derived from plant pathogenic fungi belonging to the Oomycetes and Phytomyxea.

Specific examples of the plant pathogenic fungi include the following.
As oomycetes, Phytophthora ( Phytophthora infestans ) such as potato or tomato late blight fungus ( Phytophthora infestans ) and tomato gray blight fungus ( Phytophthora capsici ) ; Bacteria of the genus Plasmopara such as grape downy mildew ( Plasmopara viticol a); Bacteria of the genus Pythium such as Pythium graminicola and wheat brown snow rot fungus (Pythium iwayamai ) , Aphanomyces bacteria such as radish root necking disease and spinach root rot disease, and Albugo macrospora bacteria such as spinach white rust disease.
Plasmodiophora brassicae, which causes cabbage clubroot and cabbage clubroot, Polymyxa betae, which transmits beet necrotic yellow vein virus, and potato powder. Examples include Spongospora, such as Spongospora subterranea, and Olpidium virulentus, which transmits Mirafiori lettuce bigvein virus.
As ascomycetes, bacteria of the genus Erysiphe such as wheat powdery mildew ( Erysiphe graminis ); bacteria of the genus Sphaerotheca such as cucumber powdery mildew ( Sphaerotheca fuliginea ) and strawberry powdery mildew ( Sphaerotheca humuli ); Uncinula genus bacteria such as grape powdery mildew ( Uncinula necator ); Podosphaera genus bacteria such as apple powdery mildew ( Podosphaera leucotricha ); pea brown spot fungus ( Mycosphaerella pinodes ), apple black spot fungus ( Mycosphaerella ) pomi ), Mycosphaerella musicola , Mycosphaerella nawae , Mycosphaerella fragariae; Venturia inaequalis , Venturia inaequalis , and Mycosphaerella fragariae . Bacteria of the genus Venturia , such as Venturia nashicola ; Bacteria of the genus Pyrenophora, such as Pyrenophora teres and Pyrenophora graminea; Pyrenophora fungi, Pyrenophora graminea ; Pyrenophora fungi, Pyrenophora graminea; Sclerotinia sclerotiorum, such as Sclerotinia sclerotiorum, Cabbage sclerotiorum, Chinese cabbage sclerotia, Capsicum sclerotia , Pepper sclerotiorum or Onion sclerotiorum, Wheat snow rot large grain sclerotiorum ( Sclerotinia borealis ) , Sclerotinia microorganisms such as Sclerotinia minor and Sclerotinia trifoliorum on alfalfa; Sclerotinia microorganisms such as Botryolinia arachidis ; Cochliobolus species such as Cochliobolus miyabeanus ; Didymella species such as Didymella bryoniae ; Gibberella species such as Gibberella fujikuroi Bacteria of the genus Elsinoe, such as Elsinoe ampelina and Elsinoe fawcettii ; Diaporthe citri , and Diaporthe sp. Bacteria of the genus Diaporthe ; Bacteria of the genus Monilinia such as Monilinia mali and Monilinia fructicola ; Bacteria of the genus Glomerella such as Glomerella cingulata , etc. can be mentioned.
Examples of basidiomycetes include Rhizoctonia fungi such as rice sheath blight fungus ( Rhizoctonia solani ); Ustilago fungi such as wheat naked smut fungus ( Ustilago nuda ); oat crown rust fungus ( Puccinia coronata ), Bacteria of the genus Puccinia such as Puccinia recondita and Puccinia striiformis ; Bacteria of the genus Phakopsora such as Phakopsora pachyrhizi ; small grain fungi of wheat or barley snow rot Examples include Typhula genus bacteria such as Typhula incarnata , Typhula ishikariensissis .
Deuteromycetes include Septoria genus bacteria such as Septoria nodorum and Septoria tritici ; grape botrytis, citrus botrytis, cucumber botrytis, and tomato botrytis. Disease fungi, botrytis fungus of strawberry, botrytis fungus of eggplant, botrytis fungus of green bean, botrytis fungus of azuki bean, botrytis fungus of pea, botrytis fungus of groundnut, botrytis fungus of pepper, botrytis fungus of botrytis, botrytis fungus of lettuce, botrytis fungus of onion Botrytis cinerea, various Botrytis cinerea such as Botrytis Botrytis, Botrytis Botrytis , Carnation Botrytis, Rose Botrytis, Pansy Botrytis or Sunflower Botrytis, Botrytis allii , Onion Botrytis Bacteria of the genus Botrytis that cause leaf blight ( Botrytis squamosa , Botrytis byssoidea , Botrytis tulipae ); Fusarium such as Fusarium graminearum and Fusarium oxysporum Bacteria of the genus Pyricularia such as (Fusarium) and rice blast fungus ( Pyricularia oryzae ); Bacteria of the genus Cercospora such as Cercospora beticola and Cercospora kakivola ; Bacteria of the Colletotrichum genus , such as cucumber anthracnose ( Colletotrichum orbiculare ) ; Alternaria fungi such as Alternaria solani ), cabbage or Chinese cabbage black spot fungus ( Alternaria brassicae ), cabbage black sooty fungus ( Alternaria brassicola ), onion or allium black spot fungus ( Alternaria porri ); cabbage root rot fungus ( Phoma ) lingam ); Pseudocercosporella , such as Pseudocercosporella herpotrichoides ; Pseudocercospora , such as Pseudocercospora vitis . Fungi; Rhynchosporium genus bacteria such as barley cloud fungus ( Rhynchosporium secalis ); Cladosporium genus bacteria such as peach scab fungus (Cladosporium carpophilum ); such as Phomopsis sp. bacteria of the genus Phomopsis ; bacteria of the genus Gloeosporium , such as Gloeosporium kaki ; bacteria of the genus Fulvia, such as Fulvia fulva ; Examples include bacteria of the genus Corynespora , such as Corynespora cassiicola .

Since compound (I) can control the various plant pathogenic fungi mentioned above, the present composition can preventatively or therapeutically control various diseases. In particular, this composition can be used to treat various diseases that are problematic in the field of agriculture and horticulture, such as rice blast caused by Piricularia fungus, bakanae disease caused by Fusarium fungus, sesame leaf blight caused by Cochliobolus fungus, and sheath blight caused by Rhizoctonia fungi; Powdery mildew caused by fungi, Fusarium head blight or crown rot disease, Rust caused by Puccinium fungus, Brown snow rot caused by Pythium fungus, Naked smut caused by Ustilago fungus, Eye spot disease caused by Pseudocircosporella fungus, Septoria fungus Diseases of wheat such as leaf blight or rot blight caused by Fusarium fungi, Fusarium head blight caused by Phaeosperia fungi, rust caused by Puccinia fungi, sooty blight caused by Cetophaeria fungi, and sesame leaf blight caused by Cochliobolus bacterium. Corn diseases such as root rot caused by Pythium fungi, and smut caused by Ustilago fungi; smut caused by Ustilago fungi, leaf scorch caused by Stagonospora fungi, rust caused by Puccinia fungi, top rot caused by Gibberella fungi, and smut caused by Caldariomyces fungi. Diseases of grass crops such as sooty mildew, leaf blight caused by Pseudocercospora, and other sugarcane diseases; powdery mildew caused by Oedium, rust caused by Phacopsora, downy mildew caused by Peronospora, late blight caused by Phytophthora, and Colletotrichum. Diseases of leguminous crops such as anthracnose caused by fungi, sclerotia caused by Sclerotinia, gray mold caused by Botrytis, root rot or damping off caused by Fusarium, yellowing caused by Fusarium, and downy mildew caused by Peronospora. Diseases of cruciferous crops such as black spot caused by Alternaria fungi, root rot caused by Phoma fungi, clubroot caused by Plasmodiophora fungi, and root necking disease caused by Aphanomyces fungi; downy mildew caused by Bremia fungi, and root rot caused by Phytophthora fungi. Diseases of Asteraceae crops such as late blight, gray mold caused by Botrytis, sclerotia caused by Sclerotinia, and rust caused by Aesidium; ring spot caused by Alternaria, leaf mold caused by Fulvia, late blight caused by Phytophthora, Tomato diseases such as gray mold caused by Botrytis, powdery mildew caused by Oedium, downy mildew caused by Fusarium, and sooty mold caused by Pseudocercospora; summer late blight caused by Alternaria, late blight caused by Phytophthora, and Sclerotinia. Diseases of solanaceous crops such as potato diseases such as Sclerotinia caused by Sclerotinia and dry rot caused by Fusarium; anthracnose caused by Colletotrichum, powdery mildew caused by Sphaeroteca, vine blight caused by Didymera, and Pseudoperonospora. Diseases of Cucurbitaceae crops such as downy mildew caused by Peronospora, late blight caused by Phytophthora, brown spot caused by Corynespora, and vine crack caused by Fusarium; downy mildew caused by Peronospora, late blight caused by Phytophthora, gray mold caused by Botrytis, Diseases of allium crops such as sclerotia caused by Sclerotinia fungi and rust caused by Puccinia fungi; black leaf blight or black spot caused by Alternaria fungi, gray mold caused by Botrytis fungus, and sclerotia caused by Sclerotinia fungi. Diseases of Umbelliferae crops such as powdery mildew caused by Erysiphe bacteria and leaf spot caused by Circospora bacteria; diseases of Liliaceae crops such as leaf blight caused by Botrytis bacteria, late blight caused by Phytophthora bacteria, and stem blight caused by Homopsis bacteria; Diseases of Polygonaceae crops such as rotary mildew, powdery mildew caused by Erysiphe bacterium, and damping-off caused by Rhizoctonia bacterium; Diseases of crops in the Convolvulaceae family; downy mildew caused by Peronospora fungi, late blight caused by Phytophthora fungi, gray mold caused by Botrytis fungi, sclerotia caused by Sclerotinia fungi, powdery mildew caused by Oedium fungi, brown spot caused by Circospora fungi, etc. Diseases of family crops: Black rot caused by Yersinoe bacterium, late rot caused by Colletotrichum fungus, powdery mildew caused by Erysiphe fungus, downy mildew caused by Plasmopara fungus, gray mold caused by Botrytis fungus, brown spot caused by Pseudocircospora fungus, and deer. Diseases of grape family crops such as branch blight caused by M. portae; diseases of strawberries such as powdery mildew caused by Sphaerotheca, gray mold caused by Botrytis, anthracnose caused by Glomerella, and dry rot caused by Fusarium; monilia caused by M. Monilinia. Powdery mildew caused by Podosphaera, leaf spot caused by Alternaria, scab caused by Venturia, anthracnose caused by Glomerella, brown spot caused by Diplocarpon, ring spot caused by Botryosphaeria, and Stigophialia. Diseases of apples such as sooty spot caused by Gloeodes, black spot caused by Mycosphaerella; scab caused by Venturia, black spot caused by Alternaria, powdery mildew caused by Factinia, and late blight caused by Phytophthora. , diseases of pears such as fruit rot caused by Fusarium fungi; diseases of Rosaceae crops such as peach diseases such as gray rot caused by Monilinia fungi, scab caused by Cladosporium fungi, and homopsis rot caused by Homopsis fungi; Diseases of citrus crops such as citrus diseases such as black spot caused by fungi, scab caused by Yersinoe bacterium, and Fusarium damping off caused by Fusarium fungi; anthracnose caused by Gloeosporium fungi, defoliation caused by Circospora fungi, and phylacti Diseases of persimmonaceous crops such as powdery mildew caused by Mycobacterium Niia and sooty spot caused by Mycobacterium Tygophiara; anthracnose caused by Mycobacterium Colletotrichum, ring spot caused by Mycobacterium Pestaloothiopsis, red rot caused by Pseudomonas, and blast caused by Mycobacterium Camellia. It is effective in controlling plant diseases such as diseases of Camellia family crops such as;
In addition, Fusarium fungus or crown rot disease, Colletotrichum fungus anthracnose, Tilletia fungus smut, Ustilago fungus streak disease, Cephalosporium bacterium streak disease, Septoria fungus blight, etc. Diseases of wheat such as sesame leaf blight caused by Bipolaris bacteria, anthracnose caused by Colletotrichum bacteria, and seedling damping off caused by Fusarium bacteria; red rot caused by Glomerella bacteria, black rot caused by Ceratocystis bacteria, Diseases of grass crops such as sugarcane diseases such as downy mildew caused by Sclerospora; purpura caused by Circospora, downy mildew caused by Peronospora, damping off caused by Fusarium, brown spot caused by Septoria, and Diaporte. Diseases of leguminous crops such as soybean diseases such as black spot, anthracnose caused by Colletotrichum, and downy mildew caused by Septogloeum; , diseases of cabbage such as bacterial black spot caused by Pseudomonas, black rot caused by Xanthomonas, and root rot caused by Fungus Forma; diseases of radish such as black spot caused by Alternaria, yellow chlorosis caused by Fusarium, and black rot caused by Xanthomonas. Diseases of cruciferous crops such as Chinese cabbage diseases such as black spot caused by Alternaria fungus, black rot caused by Xanthomonas fungus, and yellowing disease caused by Verticillium fungus; ring spot disease caused by Alternaria fungus, and scab caused by Clavibacter fungus. Tomato diseases such as bacterial spot disease caused by Xanthomonas; diseases of eggplant such as brown spot caused by Alternaria and brown spot caused by Homopsis; scab caused by Streptomyces and silver spot caused by Helmintosporium. Diseases of solanaceous crops, such as potato diseases such as powdery scab caused by Spongospora; diseases of cucumbers such as black spot caused by Alternaria, bacterial spot caused by Pseudomonas, and bacterial brown spot caused by Xanthomonas. Diseases of Cucurbitaceae crops; diseases of Alliumaceae crops such as black spot caused by Alternaria fungi, gray rot or mycelial rot caused by Botrytis fungi, dry rot caused by Fusarium fungi, downy mildew caused by Peronospora fungi, etc. ; Carrot diseases such as black leaf blight or black spot caused by Alternaria fungi, and bacterial leaf spot caused by Xanthomonas; leaf blight caused by Septoria fungi, sclerotia caused by Sclerotinia fungi, and bacterial leaf blight caused by Pseudomonas bacterium; Diseases of Umbelliferae crops such as celery diseases; Diseases of Chenopodiaceae crops such as spinach diseases such as downy mildew caused by Peronospora, wilt caused by Fusarium fungi, and anthracnose caused by Colletotrichum; is also valid.
Furthermore, it is also effective in controlling soil diseases caused by plant pathogenic bacteria such as Fusarium, Pythium, Rhizoctonia, Verticillium, Plasmodiophora, and Thielabiopsis.

Even when Compound (I) is applied to plants, there are few changes in the appearance of the plants (such as yellowing and leaf withering), so this composition containing Compound (I) as an active ingredient has no environmental burden. has light characteristics.
Furthermore, since Compound (I) has excellent rain resistance, residual effect, and permeability, the present composition containing Compound (I) as an active ingredient can be applied to plants. Harmful fungi above ground can be controlled for a certain period of time.

In order to control various plant diseases, the present composition can be applied to plants, plant pathogens, or soil.
The plant body refers to above-ground parts of a plant such as a tree trunk, stem, leaves, flowers, and fruits, and underground parts of a plant such as seeds, tubers, rhizomes, roots, seedlings, and transplanted seedlings.
The soil refers to agricultural land such as fields, paddy fields, orchards, and non-agricultural land such as lawns and forests where plants are cultivated.

The plants to which this composition is applied are not particularly limited as long as they are useful for agriculture and horticulture, but include, for example, grass crops (rice, wheat, barley, oats, rye, corn, sugarcane, etc.), legume crops ( soybean, kidney bean, adzuki bean, pea, groundnut, etc.), cruciferous crops (cabbage, Chinese cabbage, radish, turnip, broccoli, cauliflower, napa, canola, etc.), Asteraceae crops (lettuce, burdock, Chinese chrysanthemum, etc.), Solanaceae crops (potatoes, eggplants, tomatoes, green peppers, tobacco, chili peppers, etc.), Cucurbitaceae crops (cucumbers, pumpkins, melons, watermelons, etc.), Alliumaceae crops (green onions, chives, rakkyo, garlic, onions, etc.), Umbelliferae crops (celery) , carrots, parsley, etc.), Liliaceae crops (lilies, tulips, asparagus, etc.), Polygonaceae (buckwheat, etc.), Convolvulaceae (sweet potatoes, etc.), Chenopodiaceae crops (spinach, sugar beets, etc.), Vitaceae crops (grapes, etc.) ), Rosaceae crops (roses, strawberries, apples, pears, peaches, loquats, almonds, etc.), Rutaceae crops (mandarin oranges, lemons, oranges, citrus, etc.), Persimmonaceae crops (persimmons, etc.), Camellia family crops (cha, etc.) ), Oleaceae crops (olive, jasmine, etc.), Malvaceae crops (cotton, cacao, okra, etc.), Musaceae crops (bananas, etc.), Zingiberaceae crops (ginger etc.), Rubiaceae crops (coffee, etc.), or Pineappleaceae crops Examples include crops (pineapples, bromeliads, etc.), crops of the Lomoaceae family (statices), crops of the Caryophyllaceae family (carnations), crops of the Viola family (pansies), and crops of the Asteraceae family (sunflowers).

The plants include plants grown using genetic recombination technology or gene editing technology, such as plants endowed with environmental stress tolerance, herbicide tolerance, pest tolerance, disease regime, etc., or plants with growth, fertility traits, Includes plants whose quality and yield have been modified.

The present composition is usually prepared by mixing compound (I) with a solid carrier or a liquid carrier, and adding surfactants and other formulation auxiliaries as necessary to form powders, granules, hydrated granules, etc. It can be formulated and used in various forms such as wettable powders, aqueous suspensions, oily suspensions, aqueous solutions, emulsions, liquids, pastes, aerosols, microdispersions, and microcapsules. As long as it is compatible with the purpose, it can be made into any formulation commonly used in the field. The solid carrier, the liquid carrier, the surfactant, and the formulation adjuvant include diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, a mixture of kaolinite and sericite, clay, sodium carbonate, baking soda, Solid carriers such as mirabilite, zeolite, starch; water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, N,N-dimethylformamide, dimethylacetamide, N-methyl- Liquid carrier such as 2-pyrrolidone, alcohol; fatty acid salt, benzoate, alkyl sulfosuccinate, dialkyl sulfosuccinate, polycarboxylate, alkyl sulfate ester salt, alkyl sulfate, alkylaryl sulfate, alkyl diglycol ether Sulfate, alcohol sulfate ester salt, alkyl sulfonate, alkylaryl sulfonate, aryl sulfonate, lignin sulfonate, alkyldiphenyl ether disulfonate, polystyrene sulfonate, alkyl phosphate ester salt, alkylaryl phosphate salt, styryl aryl phosphate, polyoxyethylene alkyl ether sulfate salt, polyoxyethylene alkylaryl ether sulfate, polyoxyethylene alkylaryl ether sulfate salt, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkylaryl Anionic surfactants and spreading agents such as phosphate ester salts and salts of naphthalene sulfonic acid formalin condensates; sorbitan fatty acid esters, glycerin fatty acid esters, fatty acid polyglycerides, fatty acid alcohol polyglycol ethers, acetylene glycol, acetylene Alcohol, oxyalkylene block polymer, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene styryl aryl ether, polyoxyethylene glycol alkyl ether, polyethylene glycol, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, Nonionic surfactants and spreading agents such as polyoxyethylene glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxypropylene fatty acid ester; olive oil, kapok oil, castor oil, coir oil, camellia oil, coconut oil, sesame oil Examples include vegetable oils and mineral oils such as corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, tung oil, and liquid paraffin. Each component of these auxiliary agents may be used alone or in combinations of two or more, as long as it does not depart from the purpose of the present invention. In addition to the above-mentioned auxiliary agents, those known in the field may be selected and used as appropriate, such as bulking agents, thickeners, anti-settling agents, anti-freezing agents, dispersion stabilizers, chemical damage reducers, etc. Various commonly used adjuvants such as antifungal agents and antifungal agents can also be used. The compounding ratio of compound (I) and various auxiliary agents is 0.001:99.999 to 95:5, preferably 0.005:99.995 to 90:10. When actually using these preparations, they can be used as is, or diluted to a specified concentration with a diluent such as water, and various spreading agents (surfactants, vegetable oil, mineral oil, etc.) may be added as necessary. and can be used.

Although the application of the present composition cannot be absolutely defined due to differences in weather conditions, formulation form, target crop, application time, application location, type and occurrence of plant diseases, etc., the application method generally used is: The present composition or a diluted product thereof can be applied by spraying, soil treatment, seed treatment, etc. Generally, in the case of spraying treatment, the appropriate amount of the composition to be applied can be about 10 to 100,000 g per hectare. In the case of soil treatment, the appropriate application amount can be about 0.01 to 1,000 g of the composition per hectare. In the case of seed treatment, the appropriate amount of the composition to be applied can be about 0.001 to 100 g, preferably about 0.01 to 1 g, per 1 kg of seeds.

The above-mentioned spraying treatment is a treatment method for controlling plant pathogenic bacteria by spraying an effective amount of the present composition onto the surfaces of plant trunks, buds, stems, leaves, flowers, panicles, and fruits, or onto plant pathogenic bacteria. Examples include foliage spraying, tree trunk spraying, etc.
The above-mentioned soil treatment is a method of treating soil with the present composition in order to infiltrate and transfer an effective amount of compound (I) from the roots of the plant into the inside of the plant in order to protect crops from damage caused by plant pathogens. be. For example, irrigation treatment (drinking the present composition into the soil for growing plants), soil mixing treatment (mixing the present composition with the soil for growing plants), planting hole treatment, treatment at the base of plants or between plants (spraying or irrigation) ), mixing treatment with soil used for cultivation soil, seedling raising boxes, seedling raising trays, paper pots, seedling beds, etc.
The seed treatment is a treatment method for controlling plant pathogens by applying the present composition directly or in the vicinity of seeds, bulbs, etc. of crops in order to protect crops from damage caused by plant pathogens. Examples include coating treatment, powder coating treatment, dipping treatment, and the like.
Other examples include seedling treatment (irrigation or immersion), immersion treatment of bulbs, tubers, scales, roots, etc., and hydroponic treatment such as mixing with a hydroponic culture nutrient solution. The treatment may be performed on the whole plant or a portion thereof (stems, buds, flowers, ears, fruits, trunks, seeds, bulbs, tubers, scales, roots, etc.).

The present composition can be mixed or used in combination with other ingredients selected from other agricultural and horticultural chemicals, fertilizers, phytotoxicity reducers, etc. In this case, even more excellent effects and actions may be exhibited.
The above-mentioned mixing or combination means using the present composition and other components simultaneously, separately, or at intervals of time.
Other agricultural and horticultural chemicals include herbicides, insecticides, acaricides, nematicides, soil insecticides, fungicides, antiviral agents, attractants, antibiotics, plant hormones, and plant growth regulators. Can be mentioned. In particular, mixed fungicidal compositions that are used in combination with this composition and one or more active ingredient compounds of other fungicides improve the application range, timing of chemical treatment, pesticidal activity, etc. in a favorable direction. Sometimes. The active ingredient compounds of this composition and other fungicides may be prepared separately and mixed together at the time of spraying, or both may be prepared and used together. The present invention also includes such mixed fungicides.

The mixing ratio of Compound (I) and the active ingredient compounds of other fungicides is generally determined depending on differences in weather conditions, formulation form, target crop, application time, application location, type and occurrence of plant diseases, etc. Although not possible, the ratio can generally be 1:300 to 300:1, preferably 1:100 to 100:1. Further, the appropriate application amount can be 0.1 to 70,000 g, preferably 1 to 30,000 g of the total active ingredient compound per hectare. The present invention also includes a method for controlling plant diseases by applying such a mixed fungicidal composition.

When applying the fungicidal composition containing compound (I), other agricultural and horticultural agents such as fungicides, insecticides, acaricides, nematicides, soil insecticides, antiviral agents, attractants, It is also possible to further treat with herbicides, plant growth regulators, etc.

The active ingredient compound (common name) of the fungicide in the other agricultural and horticultural chemicals mentioned above can be appropriately selected from the following compound group, for example. Even if there is no particular description, if salts, alkyl esters, various structural isomers such as optical isomers, etc. exist in these compounds, they are naturally included.

Anilinopyrimidine compounds such as mepanipyrim, pyrimethanil, cyprodinil;
Triazolopyrimidine compounds such as ametoctradin;
Pyridinamine compounds such as fluazinam;
triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, myclobutanil, cyproconazole ( cyproconazole), tebuconazole, hexaconazole, furconazole-cis, prochloraz, metconazole, epoxiconazole, tetraconazole, oxpoconazole fumarate, prothioconazole, triadimenol, flutriafol, difenoconazole, fluquinconazole, fenbuconazole , bromuconazole, diniconazole, tricyclazole, simeconazole, pefurazoate, ipconazole, imibenconazole, azaconazole, triticonazole ), azole compounds such as imazalil, ipfentrifluconazole, mefentrifluconazole;
Quinoxaline compounds such as quinomethionate;
Dithiocarbamate compounds such as maneb, zineb, mancozeb, polycarbamate, metiram, propineb, thiram;
Organochlorine compounds such as fthalide, chlorothalonil, and quintozene;
Imidazole compounds such as benomyl, thiophanate-methyl, carbendazim, thiabendazole, fuberiazole;
Cyanoacetamide compounds such as cymoxanil;
metalaxyl, metalaxyl-M (also known as mefenoxam), oxadixyl, ofurace, benalaxyl, benalaxyl-M, also known as chiralaxyl, chiralaxyl )), acylamino acid compounds such as furalaxyl, valifenalate;
Cyprofuram, carboxin, oxycarboxin, thifluzamide, boscalid, fenhexamid, isotianil, tiadinil, pyraziflumid Anilide compounds such as;
Sulfamide compounds such as dichlofluanid;
Such as cupric hydroxide, oxine copper, anhydrous copper sulfate, copper nonylphenolsulfonate, copper 8-hydroxyquinoline, dodecylbenzenesulfonic acid bisethylenediamine copper complex (II) (also known as DBEDC). Copper-based compounds;
Organophosphorus compounds such as fosetyl-Al, tolclofos-Methyl, edifenphos, iprobenfos;
Phthalimides such as captan, captafol, folpet;
Dicarboximide compounds such as procymidone, iprodione, vinclozolin;
Benzanilide compounds such as flutolanil, mepronil, benodanil;
Amides such as carpropamid, diclocymet, silthiopham, fenoxanil;
benzovindiflupyr, bixafen, fluindapyr, fluxapyroxad, furametpyr, isopyrazam, penflufen, penthiopyrad, pidiflu Pyrazole carboxamides such as pydiflumetofen, sedaxane, isoflucypram, inpyrfluxam, pyrapropoyne;
Benzamide compounds such as fluopicolide, fluopyram, zoxamide, fluopimomide;
Furanilide compounds such as fenfuram;
Thiophenamide compounds such as isofetamid;
piperazine compounds such as triforine;
Pyridine compounds such as pyrifenox, pyrisoxazole, aminopyrifen;
Pyrimidine compounds such as fenarimol, ferimzone, nuarimol;
piperidine compounds such as fenpropidin;
Morpholine compounds such as fenpropimorph and tridemorph;
Organotin compounds such as fentin hydroxide and fentin acetate;
Urea-based compounds such as pencycuron;
Carboxylic acid amide compounds such as dimethomorph, flumorph, pyrimorph, iprovalicarb, benthiavalicarb-isopropyl, mandipropamid;
Phenyl carbamate compounds such as diethofencarb;
Cyanopyrrole compounds such as fludioxonil and fenpiclonil;
azoxystrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, picoxystrobin, oryzastrobin, dimoxystrobin ( dimoxystrobin, pyraclostrobin, fluoxastrobin, Enestroburin, Pyraoxystrobin, Pyrametostrobin, coumoxystrobin, enoxast Strobilurin compounds such as enoxastrobin, fenaminstrobin, flufenoxystrobin, triclopyricarb, mandestrobin;
Oxazole compounds such as famoxadone, oxathiapiprolin;
Thiazole carboxamides such as ethaboxam;
Imidazolinone compounds such as fenamidone;
Benzene sulfonamides such as flusulfamide;
Oxime ether compounds such as cyflufenamide;
Anthraquinone compounds such as dithianon;
Crotonic acid compounds such as meptyldinocap;
Antibiotics such as validamycin, kasugamycin, streptomycin, polyoxins;
Guanidine compounds such as iminoctadine, dodine; Quinoline compounds such as tebufloquin, quinoxyfen, quinofumelin, ipflufenoquin;
Thiazolidine compounds such as flutianil;
Carbamate compounds such as propamocarb hydrochloride, pyribencarb, tolprocarb;
Tetrazole compounds such as picarbutrazox, methyltetraprole;
Sulfonamide compounds such as amisulbrom, cyazofamiid;
Allyl phenyl ketone compounds such as metrafenone and pyriofenone;
Benzothiazole compounds such as probenazole, dichlobentiazox;
Phenylpyrazole compounds such as fenpyrazamine;
Dithiolane compounds such as isoprothiolane;
Picolinamide compounds such as fenpicoxamide, florylpicoxamide;
Sulfur-based compounds such as sulfur and lime sulfur agents;
Other compounds include pyroquilon, diclomezine, chloropicrin, dazomet, metam-sodium, proquinazid, spiroxamine, dipymetitrone, etc. ;
Microbial fungicides such as Bacillus amyloliqefaciens strain QST713, Bacillus amyloliqefaciens strain FZB24, Bacillus amyloliqefaciens strain MBI600, Bacillus amyloliqefaciens strain D747, Pseudomonas fluorescens, Bacillus subtilis, Trichoderma atroviride SKT-1; and Tea tree oil. Like plant extract.

The active ingredient compound (common name) of the insecticide, nematicide, acaricide, or soil insecticide among the other agricultural and horticultural chemicals mentioned above may be appropriately selected from the following compound groups, for example. can. Even if there is no particular description, if salts, alkyl esters, various structural isomers such as optical isomers, etc. exist in these compounds, they are naturally included.

profenofos, dichlorvos, fenamiphos, fenitrothion, EPN ((RS)-(O-ethyl O-4-nitrophenyl phenylphosphonothioate)), diazinon, chlorpyrifos, chlorpyrifos chlorpyrifos-methyl, acephate, prothiofos, fosthiazate, cadusafos, disulfoton, isoxathion, isofenphos, ethion, etrimfos ), quinalphos, dimethylvinphos, dimethoate, sulprofos, thiometon, vamidothion, pyraclofos, pyridaphenthion, pirimiphos-methyl , propaphos, phosalone, formothion, malathion, tetrachlorvinphos, chlorfenvinphos, cyanophos, trichlorfon, methidathion ), phenthoate, oxydeprofos (also known as ESP), azinphos-methyl, fenthion, heptenophos, methoxychlor, parathion, phosphocarb, demeton -S-methyl, monocrotophos, methamidophos, imicyafos, parathion-methyl, terbufos, phosphamidon, phosmet ), organic phosphate compounds such as phorate;
carbaryl, propoxur, aldicarb, carbofuran, thiodicarb, methomyl, oxamyl, ethiofencarb, pirimicarb, fenobucarb, Carbosulfan, benfuracarb, bendiocarb, furathiocarb, isoprocarb, metolcarb, xylylcarb, XMC (3,5-xylyl methylcarbamate), phenothiocarb Carbamate compounds such as (fenothiocarb);
Cartap, thiocyclam, thiocyclam oxalate, thiocyclam hydrochloride, bensultap, thiosultap, monosultap; also known as thiosultap monosodium (thiosultap- Nelystoxin derivatives such as thiosultap-disodium, polythialan;
Organochlorine compounds such as dicofol, tetradifon, endosulfan, dienochlor, dieldrin;
Organometallic compounds such as fenbutatin oxide, cyhexatin;
Fenvalerate, permethrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, theta-cypermethrin, beta-cypermethrin Permethrin, deltamethrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, tefluthrin, kappa-tefluthrin, ethos fenprox, flufenprox, cyfluthrin, beta-cyfluthrin, fenpropathrin, flucythrinate, fluvalinate, cycloprothrin (cycloprothrin), pyrethrins, esfenvalerate, tetramethrin, resmethrin, protrifenbute, bifenthrin, kappa-bifenthrin, acrinathrin ( acrinathrin, allethrin, tau-fluvalinate, tralomethrin, profluthrin, metofluthrin, epsilon-metofluthrin, heptafluthrin, Pyrethroid compounds such as phenothrin, flumethrin, momfluorothrin, epsilon-momfluorothrin, silafluofen, chloroprallethrin;
Diflubenzuron, chlorfluazuron, teflubenzuron, flufenoxuron, lufenuron, novaluron, triflumuron, hexaflumuron, bistrifluron Benzoylurea compounds such as (bistrifluron), noviflumuron, and fluazuron;
Juvenile hormone-like compounds such as methoprene, pyriproxyfen, fenoxycarb, diofenolan;
Pyridazinone compounds such as pyridaben;
Pyrazole compounds such as fenpyroximate, fipronil, ethiprole, acetoprole, pyrafluprole, pyriprole, cyenopyrafen, flufiprole ;
Pyrazole carboxamides such as pyflubumide, tebufenpyrad, tolfenpyrad;
Pyridylpyrazole compounds such as chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole, tyclopyrazoflor;
Neonic drugs such as imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, nidinotefuran, dinotefuran, nithiazine Noid compounds;
Hydrazine compounds such as tebufenozide, methoxyfenozide, chromafenozide, halofenozide;
Pyridine-based compounds such as pyridalyl and flonicamid; Tetronic acid-based compounds such as spirodiclofen and spiromesifen;
Tetramic acid compounds such as spirotetramat and spiropidion;
Strobilurin compounds such as fluacrypyrim, pyriminostrobin;
Pyrimidinamines such as flufenerim, pyrimidifen;
Organosulfur compounds such as malathion;
Urea-based compounds such as flufenoxuron;
Triazine compounds such as cyromazine;
Hydrazone compounds such as hydramethylnon;
Diamide compounds such as flubendiamide, broflanilide, cyhalodiamide;
Thiourea compounds such as diafenthiuron and chloromethiuron;
Formamidine compounds such as amitraz, chlordimeform, chloromebuform;
Pyridine azomethine compounds such as pymetrozine and pyrifluquinazone;
isoxazoline compounds such as afoxolaner, fluralaner, fluxametamide, sarolaner;
Other compounds include buprofezin, hexythiazox, triazamate, chlorfenapyr, indoxacarb, acequinocyl, etoxazole, 1,3-dichloropropene. (1,3-dichloropropene), benclothiaz, bifenazate, propargite, clofentezine, metaflumizone, cyflumetofen, fenazaquin, amidoflumet, sulfluramid, hydramethylnon, metaldehyde, sulfoxaflor, fluensulfone, verbutin, dicloromezotiaz, triflumezopyrim, fluhexafone (fluhexafon), thioxazafen (tioxazafen), afidopyropen (afidopyropen), flometoquin (flometoquin), flupyradifurone (flupyradifurone), fluazaindolizine (fluazaindolizine), acinonapyr (acynonapyr), benzpyrimoxan (benzpyrimoxan), flupyrimin, Compounds such as oxazosulfyl.
Moreover, the composition of the present invention may be applied in combination with the following compounds.
Bacillus thuringiensis aizawai, Bacillus thuringiensis kurstaki, Bacillus thuringiensis israelensis, Bacillus thuringiensis japonensis, Bacillus thuringiensis tenebrionis or crystal protein toxins produced by Bacillus thuringiensis, entomopathogenic viral agents, entomopathogenic fungal agents, nematode pathogenic fungal agents, etc. microbial pesticides;
Antibiotics like abamectin, emamectin benzoate, ivermectin, milbemectin, milbemycin oxime, lepimectin, spinosad, spinetoram and semi-synthetic antibiotics;
Natural products such as azadirachtin, rotenone, ryanodine;
repellents such as DEET;
Physical control agents such as paraffin oil and mineral oil.

Desirable embodiments of the present invention are as follows. However, the present invention is not limited to these.
[1] A sterilizing composition containing a compound represented by formula (I) or a salt thereof.
[2] A method for controlling harmful plant diseases, comprising the step of applying an effective amount of the compound represented by formula (I) or a salt thereof to plants, plant pathogens, or soil.
[3] A compound represented by formula (IA) or a salt thereof.
[4] An agricultural and horticultural fungicide containing the compound or salt thereof according to [3] above.
[5] A method for controlling harmful plant diseases, including the step of applying the compound or its salt according to [3] above to plants, plant pathogens, or soil.

Next, examples of the present invention will be described, but the present invention is not limited thereto.

[Synthesis example]
Synthesis of 2-amino-4-methyl-N-(2,4-difluorobenzyl)-N'-methylthiazole-5-carbohydrazide (Compound No. 17) (1) 1-Boc-1-methylhydrazine (6 2,4-difluorobenzaldehyde (5.00 g) dissolved in a small amount of methanol was added to a solution of triethylamine (5.89 mL) in methanol (180 mL) and stirred at room temperature for 2.5 hours. Thereafter, 2-picoline borane (5.65 g, 85%) was added under ice cooling, followed by slow addition of 3N aqueous hydrochloric acid (58.64 mL), and the mixture was stirred at room temperature for 3 hours to obtain a reaction solution. The reaction solution was quenched using saturated aqueous sodium bicarbonate solution. The quenched reaction solution was made basic using an aqueous sodium hydroxide solution, and then extracted using ethyl acetate. The organic layer was washed with a saturated aqueous sodium bicarbonate solution, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting residue was purified by column chromatography (eluent: ethyl acetate/heptane) to obtain oily tert-butyl 2-(2,4-difluorobenzyl)-1-methylhydrazine-1-carboxylate (8. 10g) was obtained.
¹ H NMR (CDCl ₃ /300MHz):δ(ppm)= 7.33 (dd, 1H), 6.90-6.79 (m, 2H), 3.99 (s, 2H), 2.97 (s, 3H), 1.47 (s, 9H) ).

(2) Bioorganic & Medicinal Chemistry 2001, 9, 7-17. To a solution of 2-[(tert-butoxycarbonyl)amino]-4-methylthiazole-5-carboxylic acid (0.57 g) in tetrahydrofuran (22 mL), under ice-cooling, was added oxalyl chloride (0.56 g), A catalytic amount of N,N-dimethylformamide was added and stirred at 40°C for 3 hours to obtain a reaction solution. Thereafter, the reaction solution was concentrated under reduced pressure to obtain 2-[(tert-butoxycarbonyl)amino]-4-methylthiazole-5-carboxylic acid chloride. Next, a solution of tert-butyl 2-(2,4-difluorobenzyl)-1-methylhydrazine-1-carboxylate (0.50 g) in tetrahydrofuran (3 mL) was added with sodium hydride (0.08 g, 60%) and stirred at the same temperature for 15 minutes to obtain a reaction solution. A solution of the prepared carboxylic acid chloride in tetrahydrofuran (20 mL) was added to the reaction solution, and the mixture was stirred at room temperature for 3 hours to obtain a reaction solution. A saturated aqueous sodium hydrogen carbonate solution was added to the reaction solution to quench it under ice cooling. Subsequently, the quenched reaction solution was extracted using ethyl acetate, and the organic layer was washed successively with an aqueous sodium hydroxide solution and saturated brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting residue was purified by column chromatography (eluent: ethyl acetate/heptane) to give gummy tert-butyl 2-{2-[(tert-butoxycarbonyl)amino]-4-methylthiazole-5- Carbonyl}-2-(2,4-difluorobenzyl)-1-methylhydrazine-1-carboxylate (0.53 g) was obtained.
¹ H NMR (CDCl ₃ /300MHz):δ(ppm)= 9.45 (brs, 1H), 7.61-7.53 (m, 1H), 6.93-6.79 (m, 2H), 5.08-4.73 (m, 2H), 3.09 (s, 3H), 2.67 (s, 3H), 1.54 (s, 9H), 1.24 (brs, 9H).

(3) tert-butyl 2-{2-[(tert-butoxycarbonyl)amino]-4-methylthiazole-5-carbonyl}-2-(2,4-difluorobenzyl)-1-methylhydrazine-1-carboxy Trifluoroacetic acid (0.84 mL) was added to a solution of Rate (0.53 g) in dichloromethane (4.20 mL) under ice cooling, and the mixture was stirred overnight at room temperature to obtain a reaction solution. Thereafter, a saturated aqueous sodium hydrogen carbonate solution was slowly added to the reaction solution under ice cooling to quench it. The quenched reaction solution was extracted using ethyl acetate. The organic layer was washed with a saturated aqueous sodium bicarbonate solution, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained residue was purified by column chromatography (eluent: ethanol/ethyl acetate/heptane) to obtain the target product (0.21 g) as a solid.
^1H NMR (acetone-d ₆ /300MHz):δ(ppm)= 7.44 (dt, 1H), 7.06-6.97 (m, 2H), 6.48 (brs, 2H), 4.89 (s, 2H), 4.53 (q , 1H), 2.61 (d, 3H), 2.52 (s, 3H).

Next, representative examples of compound (I) are specifically listed in Table 1. These compounds can be synthesized based on the above production method, the above synthesis example, and methods known in the technical field.
In the table, No. is compound No. shows. For compounds described as NMR in the physical properties column of Table 1, 1H-NMR spectrum data are shown in Table 2. The abbreviations used in the R ¹ , R ² , R ³ , and R ⁴ columns in Table 1 each represent the following substituents. Me represents a methyl group, Et represents an ethyl group, n-Pr represents a normal propyl group, c-Pr represents a cyclopropyl group, CN represents a cyano group, NO ₂ represents a nitro group, di represents two groups, and tri represents three groups.
In addition, in the case of a salt of compound (I), the type of the salt is shown in the physical properties column of Table 1. For example, in the physical properties column of Table 1, a compound described as HCl salt represents a hydrochloride, and a compound described as TsOH salt represents a para-toluenesulfonate. For example, compound no. 78 is compound no. 3 hydrochloride, compound no. 79 is compound no. 12 hydrochloride, and compound no. 80 is compound No. 17 hydrochloride. Compound no. 81 is compound no. para-toluene sulfonate of Compound No. 3, compound no. 82 is compound no. 12 para-toluene sulfonate, and Compound No. 83 is compound no. 17 para-toluenesulfonate.

In the ¹ H-NMR data in Table 2, s is a singlet, brs is a broad singlet, d is a doublet, t is a triplet, and q is a quartet. ), m indicates a multiplet (multiple line).

The positions of the substituents shown in the ^R4 column in Table 1 indicate the positions of the substituents as follows.

例えば、Ｒ^４欄において「２-Ｍｅ」並びにｎ欄において１と記載された化合物は、上記の化学構造式に付与した置換基位置で１つのＲ^４基で置換されている、即ち、ベンゼン環の２位のみがメチルで置換されている「ｎ＝１」の化合物であることを表す。

For example, a compound described as "2-Me" in the R ⁴ column and 1 in the n column is substituted with one R ⁴ group at the substituent position given in the above chemical structure, that is, a benzene ring. represents a compound where only the 2nd position of is substituted with methyl, where n=1.

¹ H-NMR data [measured by ¹ H-nuclear magnetic resonance spectroscopy; δ is the chemical shift value (ppm)] is shown in Table 2.

[Test example]
Preparation of drug solution containing compound (I):
Compound (I) and acetone or dimethyl sulfoxide were mixed to dissolve compound (I). After dissolving Compound (I), water was added to dilute the active ingredient Compound (I) to a predetermined concentration (400 ppm, 200 ppm, or 100 ppm) to obtain a drug solution. This chemical solution was used in Test Examples 1 to 2 below.

Test Example 1: Bactericidal effect test against tomato late blight (preventive effect test)
Tomatoes were grown in vinyl pots with a diameter of 6 cm, and when they reached the 4.5 to 5.5 leaf stage, 10 ml of the chemical solution was sprayed with a spray gun. After the chemical solution had dried (on the day of treatment), a spore suspension of Phytophthora infestans was spray inoculated and placed in an inoculation box at a temperature of 20° C. and a humidity of 95% or higher for 16 hours. Thereafter, the plants were placed in a constant temperature room at 20° C., and the lesion area ratio was investigated 3 days after inoculation, and the control rate was calculated according to the following formula. As a result, each composition containing the following compounds (active ingredient concentration: 400 ppm or 200 ppm) showed a control rate of 90% or more against tomato late blight. Compounds with underlined compound numbers have a control rate of 90% or more against tomato late blight at an active ingredient concentration of 200 ppm, and other compounds have a control rate of 90% or more against tomato late blight at an active ingredient concentration of 400 ppm. % or more.
[Formula for calculating control rate]
Control rate (%) = 100 - (X/Y) x 100
X: Lesion area rate of test compound (%), Y: Lesion area rate of untreated area (%)
Compound: No. 1 , 3 , 2, 4, 5, 6, 9, 10, 11, 12, 14, 16, 17, 20, 22, 23, 24, 25, 26, 30, 34, 35, 36, 37
Furthermore, each composition containing the following compounds (active ingredient concentration: 100 ppm) showed a control rate of 90% or more against tomato late blight.
Compound: No. 1, 2, 4, 6, 9, 10, 11, 12, 14, 15, 16, 17, 20, 21, 22, 24, 25, 26, 30, 34, 35, 36, 37

Test Example 2: Bactericidal effect test against cucumber downy mildew (preventive effect test)
Cucumbers were grown in vinyl pots with a diameter of 6 cm, and when they reached the 1.2 to 1.5 leaf stage, 10 ml of a chemical solution prepared with the compound of the present invention was sprayed with a spray gun. After the chemical solution had dried (on the day of treatment), a spore suspension of cucumber downy mildew (Pseudoperonospora cubensis) was spray inoculated and placed in an inoculation box at a temperature of 20° C. and a humidity of 95% or higher for 24 hours. Thereafter, the plants were placed in a constant temperature room at 20° C., and the lesion area ratio was investigated 7 days after inoculation, and the control rate was calculated using the same formula as in Test Example 1 above. As a result, each composition containing the following compounds (active ingredient concentration: 400 ppm) showed a control rate of 90% or more against cucumber downy mildew.
Compound: No. 2, 4, 5, 6, 8, 9, 10, 11, 12, 14, 16, 17, 20, 21, 22, 23, 24, 25, 26, 28, 29, 30, 34, 35, 36, 37

Next, formulation examples of the present composition will be described, but the blending ratio, dosage form, etc. are not limited to the described examples.
Formulation example 1
(1) 20 parts by weight of the compound of formula (I), (2) 72 parts by weight of clay, and (3) 8 parts by weight or more of sodium ligninsulfonate are uniformly mixed to prepare a wettable powder.
Formulation example 2
(1) 5 parts by weight of the compound of formula (I) (2) 95 parts by weight or more of talc are uniformly mixed to form a powder.
Formulation example 3
(1) Compound of formula (I) 20 parts by weight (2) N,N'-dimethylacetamide 20 parts by weight (3) Polyoxyethylene alkylphenyl ether 10 parts by weight (4) Xylene 50 parts by weight or more uniformly Mix and dissolve to form an emulsion.

Formulation example 4
(1) Clay 68 parts by weight (2) Sodium ligninsulfonate 2 parts by weight (3) Polyoxyethylene alkylaryl sulfate 5 parts by weight (4) Finely divided silica A mixture of 25 parts by weight or more of each component and the formula (I) compound at a weight ratio of 4:1 to form a wettable powder.
Formulation example 5
(1) Compound of formula (I) 50 parts by weight (2) Oxylated polyalkylphenyl phosphate-triethanolamine 2 parts by weight (3) Silicone 0.2 part by weight (4) Water 47.8 parts by weight or more Further, (5) 5 parts by weight of sodium polycarboxylate (6) 42.8 parts by weight of anhydrous sodium sulfate are added to the stock solution which is uniformly mixed and pulverized, mixed uniformly, granulated, and dried to form a granule wettable powder. .
Formulation example 6
(1) Compound of formula (I) 5 parts by weight (2) Polyoxyethylene octylphenyl ether 1 part by weight (3) Phosphate of polyoxyethylene 0.1 part by weight (4) Granular calcium carbonate 93.9 parts by weight ( 1) to (3) are uniformly mixed in advance, diluted with an appropriate amount of acetone, and then sprayed onto (4) to remove the acetone to form granules.

Formulation example 7
(1) 2.5 parts by weight of the compound of formula (I) (2) 2.5 parts by weight of N-methyl-2-pyrrolidone (3) 95.0 parts by weight or more of soybean oil are uniformly mixed and dissolved. Ultra low volume formulation.
Formulation example 8
(1) Compound of formula (I) 20 parts by weight (2) Oxylated polyalkylphenol phosphate-triethanolamine 2 parts by weight (3) Silicone 0.2 part by weight (4) Xanthan gum 0.1 part by weight (5) Ethylene glycol 5 parts by weight (6) Water 72.7 parts by weight or more are uniformly mixed and pulverized to obtain an aqueous suspension.

Claims (3)

Formula (I):

[wherein R ¹ is (C ₁ -C ₃ )-alkyl, cyano, H, or (C ₁ -C ₃ )-haloalkyl]
R ² is H or (C ₁ -C ₃ )-alkyl;
R ³ is (C ₁ -C ₃ )-alkyl, (C ₃ -C ₄ )-alkynyl, (C ₂ -C ₄ )-alkenyl, (C ₃ -C ₄ )-cycloalkyl, (C ₂ -C ₄ )-haloalkenyl, (C ₁ -C ₃ )-alkyl substituted with at least one Z, or H;
R ² and R ³ may be taken together to form a 3- to 5-membered ring with the nitrogen atom bonded to R ² and R ³ ,
Z is cyano, halogen, (C ₁ -C ₃ )-alkoxy, (C ₃ )-cycloalkyl, or (C ₁ -C ₃ )-alkylthio,
R ⁴ is halogen, (C ₁ -C ₃ )-alkyl, (C ₁ -C ₃ )-haloalkyl, nitro, cyano, (C ₁ -C ₃ )-alkylthio, or (C ₁ -C ₃ )-haloalkylthio and
n is an integer from 1 to 5] A sterilizing composition containing a thiazolecarboxylic acid hydrazide compound or a salt thereof as an active ingredient. Formula (I):

[wherein R ¹ is (C ₁ -C ₃ )-alkyl, cyano, H, or (C ₁ -C ₃ )-haloalkyl,
R ² is H or (C ₁ -C ₃ )-alkyl;
R ³ is (C ₁ -C ₃ )-alkyl, (C ₃ -C ₄ )-alkynyl, (C ₂ -C ₄ )-alkenyl, (C ₃ -C ₄ )-cycloalkyl, (C ₂ -C ₄ )-haloalkenyl, (C ₁ -C ₃ )-alkyl substituted with at least one Z, or H;
R ² and R ³ may be taken together to form a 3- to 5-membered ring with the nitrogen atom bonded to R ² and R ³ ,
Z is cyano, halogen, (C ₁ -C ₃ )-alkoxy, (C ₃ )-cycloalkyl, or (C ₁ -C ₃ )-alkylthio,
R ⁴ is halogen, (C ₁ -C ₃ )-alkyl, (C ₁ -C ₃ )-haloalkyl, nitro, cyano, (C ₁ -C ₃ )-alkylthio, or (C ₁ -C ₃ )-haloalkylthio and
A method for controlling harmful plant diseases, which comprises applying an effective amount of a thiazolecarboxylic acid hydrazide compound or a salt thereof represented by [n is an integer from 1 to 5] to plants, plant pathogens, or soil. Formula (IA):

[wherein R ^1A is methyl, cyano, or H,
R ^3A is methyl, ethyl, normal propyl, propargyl, allyl, or cyclopropyl;
R ^4A is halogen, (C ₁ -C ₂ )-alkyl, C ₁ -haloalkyl, nitro, cyano, C ₁ -alkylthio, or C ₁ -haloalkylthio;
n is an integer from 1 to 5] A thiazolecarboxylic acid hydrazide compound or a salt thereof.