JP4550405B2 - Bactericidal composition containing a carboxylic acid amide derivative - Google Patents

Description

  The present invention relates to a bactericidal composition containing a carboxylic acid amide derivative.

WO2001 / 60783 and WO2003 / 27059 describe that an acid amide derivative having a certain chemical structure is useful as an active ingredient of a pest control agent. However, it does not describe that these compounds have a bactericidal action.
International Publication WO 01/60783 International Publication WO 03/27059

  Many of the bactericidal compositions that have been provided so far have insufficient preventive or therapeutic effects, insufficient residual effects, or depending on the application situation against plant diseases. It has some practical problems such as insufficient control effect. Accordingly, there is a need for a bactericidal composition that overcomes these problems.

  As a result of researches to solve the above-mentioned problems, the present inventors have found that bactericidal compositions containing a carboxylic acid amide derivative of the following formula (I) have various harmful fungi such as oomycetes, ascomycetes, It has been found that it has excellent preventive and therapeutic effects against various diseases caused by basidiomycetes and incomplete fungi, and at the same time has practically satisfactory residual effects, thereby completing the present invention.

  That is, the present invention relates to the formula (I):

（式中、ＡはＸで置換されてもよいフェニル、Ｘで置換されてもよいナフチル、Ｘで置換されてもよいベンゾジオキソラニル又はＸで置換されてもよいベンゾジオキサニルであり、Ｂは置換されてもよいフェニル又は置換されてもよいピリジルであり、Ｒ₁及びＲ₂は各々アルキルであり、またＲ₁とＲ₂は一緒になって３〜６員飽和炭素環を形成してもよく、Ｘはハロゲン、アルキル、ハロアルキル、アルケニル、ハロアルケニル、アルキニル、ハロアルキニル、アルコキシ、ハロアルコキシ、アルケニルオキシ、ハロアルケニルオキシ、アルキニルオキシ、ハロアルキニルオキシ、Ｙで置換されたフェニル、Ｙで置換されたフェノキシ、Ｙで置換されたピリジル又はＹで置換されたピリジルオキシであり、Ｙはハロゲン、アルキル、ハロアルキル、アルケニル、ハロアルケニル、アルキニル、ハロアルキニル、アルコキシ又はハロアルコキシである）で表されるカルボン酸アミド誘導体又はその塩を有効成分として含有する殺菌性組成物に関する。また、本発明は、前記誘導体又はその塩の有効量を施用して種々の有害菌類或は種々の有害菌類に起因する各種病害を防除する方法、前記誘導体又はその塩の有効量を施用して作物を保護する或は作物の収穫量を向上させる方法などに関する。

(Wherein A is phenyl optionally substituted with X, naphthyl optionally substituted with X, benzodioxolanyl optionally substituted with X, or benzodioxanyl optionally substituted with X; B is optionally substituted phenyl or optionally substituted pyridyl, R ₁ and R ₂ are each alkyl, and R ₁ and R ₂ together form a 3-6 membered saturated carbocycle. X is halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxy, haloalkoxy, alkenyloxy, haloalkenyloxy, alkynyloxy, haloalkynyloxy, phenyl substituted with Y, Y Substituted phenoxy, pyridyl substituted with Y or pyridyloxy substituted with Y, where Y is halogen, alkyl, halo Kill, alkenyl, haloalkenyl, alkynyl, haloalkynyl, relates alkoxy or haloalkoxy a is) carboxylic acid amide derivative represented by or fungicidal composition containing a salt thereof as an active ingredient. Further, the present invention provides a method for controlling various diseases caused by various harmful fungi or various harmful fungi by applying an effective amount of the derivative or a salt thereof, and applying an effective amount of the derivative or a salt thereof. The present invention relates to a method for protecting crops or improving crop yields.

  A bactericidal composition containing a carboxylic acid amide derivative of the formula (I) or a salt thereof as an active ingredient (hereinafter abbreviated as the composition of the present invention) can control harmful fungi at a low dose, for example, for agricultural and horticultural use It is useful as a bactericidal composition.

  Number of X substitutions in phenyl in A which may be substituted with X, naphthyl which may be substituted with X, benzodioxolanyl which may be substituted with X or benzodioxanyl which may be substituted with X May be 1 or 2 or more, and in the case of 2 or more, they may be the same or different. Further, the replacement position may be any position.

  Examples of the optionally substituted phenyl or optionally substituted pyridyl substituent in B include halogen, alkyl, haloalkyl, alkoxy, haloalkoxy and the like, and the number of these substituents is 1 or 2 or more. There may be two or more, and they may be the same or different. The substitution position may be any position, but it is desirable to have a substituent at the ortho position of the aminocarbonyl group. In this case, it may have either a substituent only at the ortho position of the aminocarbonyl group or may have a substituent other than that.

  In X, phenyl substituted with Y, phenoxy substituted with Y, pyridyl substituted with Y or pyridyloxy substituted with Y, the number of substitution of Y may be 1 or 2 or more They may be the same or different. Further, the replacement position may be any position.

  The number of substitutions of halogen as a substituent contained in X or Y may be 1 or 2 or more, and in the case of 2 or more, they may be the same or different. Further, the replacement position may be any position.

  Specific examples of the halogen or the halogen moiety contained in the substituent of the optionally substituted phenyl or the substituted pyridyl in B, or the halogen or the halogen moiety contained in X or Y include fluorine, chlorine, Examples include bromine or iodine atoms.

The alkyl or alkyl moiety contained in the substituent of the optionally substituted phenyl or optionally substituted pyridyl in B, or the alkyl or alkyl moiety contained in R ₁ , R ₂ , X or Y is linear It may be in the form of a branched or branched one, and specific examples thereof include those of C _1-6 such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl and hexyl.

The alkenyl or alkenyl moiety contained in X or Y may be either linear or branched, and specific examples thereof include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl and 1,3-butadienyl. C _2-6 such as 1-hexenyl and the like.

The alkynyl or alkynyl moiety contained in X or Y may be either linear or branched, and specific examples thereof include ethynyl, 2-butynyl, 2-pentynyl, 3-methyl-1-butynyl, 2- Examples thereof include those of C _2-6 such as pentene-4-ynyl and 3-hexynyl.

  The salt of the carboxylic acid amide derivative of the formula (I) includes any one that is agriculturally acceptable, for example, alkali metal salts such as sodium salt and potassium salt; magnesium salt and calcium salt Alkaline earth metal salts such as; ammonium salts such as dimethylamine and triethylamine salts; inorganic acid salts such as hydrochloride, perchlorate, sulfate and nitrate; organic such as acetate and methanesulfonate Examples include acid salts.

  The carboxylic acid amide derivative of the formula (I) includes various isomers such as optical isomers and geometric isomers, and the present invention includes both isomers and isomer mixtures. The present invention also includes various isomers other than those described above within the scope of technical common sense in the technical field. In addition, depending on the type of isomer, the chemical structure may be different from that of the formula (I). However, since those skilled in the art can sufficiently recognize that they are related to isomers, the scope of the present invention It is clear that it is within.

  The carboxylic acid amide derivative of the formula (I) or a salt thereof can be produced according to the method disclosed in WO2001 / 60783 or WO2003 / 27059. More specifically, it can be produced according to the following reactions [A] to [K] and usual salt production methods.

In the reaction [A], A, B, R ₁ and R ₂ are as described above, Z is hydroxy, alkoxy or halogen, and the halogen includes fluorine, chlorine, bromine or iodine atoms.

Reaction [A] can be normally performed in presence of a base and a solvent.
Examples of the base include alkali metals such as sodium and potassium; alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tertiary butoxide; carbonates such as sodium carbonate and potassium carbonate; sodium bicarbonate and bicarbonate. Bicarbonates such as potassium; metal hydroxides such as sodium hydroxide and potassium hydroxide; metal hydrides such as sodium hydride and potassium hydride; amines such as monomethylamine, dimethylamine and triethylamine; One or two or more kinds can be appropriately selected from pyridines such as pyridine and 4-dimethylaminopyridine. The base can be used in an amount of 1 to 3 mol, desirably 1 to 2 mol per mol of the compound of formula (II).

  The solvent may be any solvent as long as it is inert to the reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; carbon tetrachloride, methyl chloride, chloroform, dichloromethane, dichloroethane, trichloroethane, Aliphatic hydrocarbons such as hexane and cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether and dimethoxyethane; esters such as methyl acetate and ethyl acetate; dimethyl sulfoxide, sulfolane, dimethylacetamide, dimethylformamide, N A polar aprotic solvent such as methylpyrrolidone or pyridine; a nitrile such as acetonitrile, propionitrile, or acrylonitrile; a ketone such as acetone or methylethylketone; It can be appropriately selected or more species.

Reaction [A] can be carried out in the presence of a dehydrating condensing agent, if necessary. Examples of the dehydrating condensing agent include N, N′-dicyclohexylcarbodiimide, chlorosulfonyl isocyanate, N, N′-carbonyldiimidazole, trifluoroacetic anhydride and the like.
The reaction [A] can be carried out usually at 0 to 100 ° C., preferably 0 to 50 ° C., and the reaction time can be usually about 0.5 to 48 hours, preferably about 1 to 24 hours.

During reaction (B), B, in which R ₁ and R ₂ are as defined above, A ₁ is phenyl substituted with X _1, naphthyl substituted by X _1, benzodioxolanyl substituted by X ₁ or a benzodioxanyl substituted by X _1, a ₂ is substituted with phenyl, naphthyl substituted with X _2, benzodioxolanyl or X ₂ substituted with X ₂ substituted by X ₂ benzo Dioxanyl, X ₁ is chlorine, bromine or iodine atoms, X ₂ is phenyl substituted with Y, phenoxy substituted with Y, pyridyl substituted with Y or pyridyl substituted with Y Oxy (Y is as described above).

The reaction [B] can usually be performed in the presence of a catalyst, a base, a solvent and an inert gas.
The catalyst may be one or more of palladium complexes such as tetrakis (triphenylphosphine) palladium (0), bis (dibenzylideneacetone) palladium (0), tris (dibenzylideneacetone) dipalladium (0), etc. Can be appropriately selected.
Examples of the base include carbonates such as sodium carbonate, potassium carbonate, and calcium carbonate; bicarbonates such as sodium bicarbonate and potassium bicarbonate; metal hydroxides such as sodium hydroxide and potassium hydroxide, and the like. Or 2 or more types can be selected suitably. The base can be used in an amount of 1 to 20 times mol, preferably 1 to 10 times mol for the compound of formula (I-1).

The solvent may be any solvent as long as it is inert to the reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; carbon tetrachloride, methyl chloride, chloroform, dichloromethane, dichloroethane, trichloroethane, Aliphatic hydrocarbons such as hexane and cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether and 1,2-dimethoxyethane; esters such as methyl acetate and ethyl acetate; dimethyl sulfoxide, sulfolane, dimethylacetamide, Polar aprotic solvents such as dimethylformamide, N-methylpyrrolidone and pyridine; Nitriles such as acetonitrile, propionitrile and acrylonitrile; Ketones such as acetone and methyl ethyl ketone; Methanol Ethanol, propanol, tert- alcohols such as butanol; water one or more of such may be suitably selected.
For example, nitrogen gas or argon gas can be used as the inert gas.
The reaction [B] can be carried out usually at 0 to 150 ° C., preferably 15 to 100 ° C., and the reaction time is usually about 0.5 to 96 hours, preferably about 1 to 48 hours.

  The compound of the formula (II) used in the reaction [A] can be produced according to the following reactions [C] to [E].

In the reaction [C], A, R ₁ and R ₂ are as described above. In the reaction [C], a salt of the compound (II) can be produced according to a post-treatment of the reaction or a normal salt formation reaction.

Reaction [C] can be normally performed in presence of an oxidizing agent and a solvent.
Examples of the oxidizing agent include potassium ferricyanide. The oxidizing agent can be used in an amount of 1 to 10 times mol, preferably 1 to 5 times mol, of the compound of formula (IV).

The solvent may be any solvent as long as it is inert to the reaction. For example, ethers such as dioxane, tetrahydrofuran, diethyl ether and dimethoxyethane; esters such as methyl acetate and ethyl acetate; dimethyl sulfoxide, sulfolane, Polar aprotic solvents such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone and pyridine; nitriles such as acetonitrile, propionitrile and acrylonitrile; ketones such as acetone and methyl ethyl ketone; one or two from water More than one species can be selected as appropriate.
The reaction [C] can usually be carried out at 20 to 150 ° C., preferably 50 to 100 ° C., and the reaction time is usually about 0.5 to 30 hours, preferably about 1 to 20 hours.

In the reaction [D], A, R ₁ and R ₂ are as described above. In the reaction [D], a salt of the compound (II) can be produced according to a post-treatment of the reaction or a normal salt formation reaction.

The cyclization reaction of reaction [D] can usually be performed in the presence of a base and a solvent.
Examples of the base include alkali metals such as sodium and potassium; alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tertiary butoxide; metal hydrides such as sodium hydride and potassium hydride, and the like. Or 2 or more types can be selected suitably. The base can be used in an amount of 1 to 3 times mol, preferably 1 to 1.5 times mol, of the compound of formula (V).

The solvent may be any solvent that is inert to the reaction, for example, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; ethers such as dioxane, tetrahydrofuran, diethyl ether and dimethoxyethane; One or more kinds can be appropriately selected from alcohols such as methanol, ethanol, propanol and tert-butanol; nitriles such as acetonitrile, propionitrile and acrylonitrile.
The cyclization reaction of reaction [D] can be usually carried out at 0 to 150 ° C., preferably 30 to 100 ° C., and the reaction time is usually about 0.5 to 24 hours, preferably about 1 to 12 hours. Can do.

The hydrolysis reaction [D] can be carried out according to a general hydrolysis reaction, and can usually be carried out in the presence of an acid or a base and a solvent.
Examples of the acid include hydrogen chloride and sulfuric acid. Examples of the base include metal hydroxides such as sodium hydroxide and potassium hydroxide.

The solvent may be any solvent as long as it is inert to the reaction. For example, alcohols such as methanol, ethanol, propanol and tert-butanol; nitriles such as acetonitrile, propionitrile and acrylonitrile; acetone and methyl ethyl ketone 1 type or 2 types or more can be suitably selected from water etc .;
The hydrolysis reaction (D) can be carried out usually at 0 to 100 ° C., preferably 20 to 80 ° C., and the reaction time is usually about 0.1 to 12 hours, preferably about 0.1 to 1 hour. Can do.

In the reaction [E], A, R ₁ and R ₂ are as described above. In the reaction [E], a salt of the compound (II) can be produced according to a post-treatment of the reaction or a normal salt formation reaction.

  Examples of the reduction reaction of the reaction [E] include catalytic reduction, reduction with a metal hydride (sodium borohydride, lithium aluminum hydride, etc.), reduction with triphenylphosphine or sulfide, and the like. The catalytic reduction can usually be carried out by reacting with hydrogen, formic acid, ammonium formate, alcohol, cyclohexane, triethylammonium formate, ammonium chloride and the like in the presence of a catalyst. As said catalyst, 1 type (s) or 2 or more types can be suitably selected from platinum, platinum oxide, platinum black, Raney nickel, palladium, palladium-carbon, rhodium, rhodium-alumina, iron, copper, etc., for example.

Reaction [E] can be normally performed in presence of a solvent. The solvent may be any solvent as long as it is inert to the reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane and cyclohexane; dioxane, tetrahydrofuran, Ethers such as diethyl ether and dimethoxyethane; esters such as methyl acetate and ethyl acetate; polar aprotic solvents such as dimethyl sulfoxide, sulfolane, dimethylacetamide, dimethylformamide, N-methylpyrrolidone and pyridine; acetonitrile, Nitriles such as propionitrile and acrylonitrile; Ketones such as acetone and methyl ethyl ketone; Alcohols such as methanol, ethanol, propanol and tert-butanol; One or two or more can be appropriately selected from water, etc.
The reaction [E] can be carried out usually at 0 to 150 ° C., preferably 0 to 80 ° C., and the reaction time can be usually about 0.5 to 96 hours, preferably about 0.5 to 48 hours.

  The compound of the formula (V) used in the reaction [D] can be produced according to the following reaction [F].

In the reaction [F], A, R ₁ and R ₂ are as described above.

  Reaction [F] can be performed in presence of a solvent as needed. The solvent may be any solvent that is inert to the reaction, for example, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene; carbon tetrachloride, chloroform, dichloromethane, dichloroethane, trichloroethane, hexane. Aliphatic hydrocarbons such as cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether and dimethoxyethane; esters such as methyl acetate and ethyl acetate; alcohols such as methanol, ethanol, propanol and tert-butanol 1 type or 2 or more types can be appropriately selected from nitriles such as acetonitrile, propionitrile and acrylonitrile; ketones such as acetone and methyl ethyl ketone.

The methyl iodide in the reaction [F] can be used in an amount of 1 to 10 times mol, preferably 1 to 3 times mol for the compound of formula (VII). Further, when methyl iodide is used in excess, it can also serve as a solvent.
The reaction [F] can be carried out usually at 0 to 100 ° C., preferably 10 to 50 ° C., and the reaction time can be usually about 0.5 to 48 hours, preferably about 1 to 24 hours.

  The compound of the formula (VI) used in the reaction [E] can be produced according to the following reaction [G].

In the reaction [G], A, R ₁ and R ₂ are as described above, and U is each atom of chlorine or bromine.

  Reaction [G] can be performed in presence of an azidating agent. As the azidating agent, one or two or more kinds can be appropriately selected from, for example, sodium azide, potassium azide, trimethylsilyl azide and the like.

Reaction [G] can be normally performed in presence of a solvent. The solvent may be any solvent as long as it is inert to the reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene; carbon tetrachloride, methyl chloride, chloroform, dichloromethane, dichloroethane, trichloroethane. Aliphatic hydrocarbons such as hexane and cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether and dimethoxyethane; esters such as methyl acetate and ethyl acetate; dimethyl sulfoxide, sulfolane, dimethylacetamide, dimethylformamide, Polar aprotic solvents such as N-methylpyrrolidone and pyridine; nitriles such as acetonitrile, propionitrile and acrylonitrile; ketones such as acetone and methyl ethyl ketone; methanol; Ethanol, propanol, tert- alcohols such as butanol; water one or more of such may be suitably selected.
The reaction [G] can be carried out usually at 0 to 150 ° C., preferably 20 to 90 ° C., and the reaction time is usually about 0.1 to 96 hours, preferably about 0.5 to 12 hours.

  The compound of the formula (VII) used in the reaction [F] can be produced according to the following reaction [H].

In the reaction [H], A, R ₁ and R ₂ are as described above.

The reaction [H] can be carried out according to a general hydrazone synthesis reaction, and can be carried out in the presence of a dehydrating agent and / or a catalyst as necessary.
Examples of the dehydrating agent include molecular sieves. The dehydrating agent is usually used in an amount of 1 to 30 times, preferably 5 to 10 times the weight of the compound of the formula (IV).
Examples of the catalyst include titanium tetrachloride.

The dimethylhydrazine in the reaction [H] is usually used in an amount of 1 to 30 times mol, preferably 5 to 10 times mol, of the compound of the formula (IV).
The reaction [H] can be usually carried out at 20 to 150 ° C., preferably 50 to 120 ° C., and the reaction time can be usually about 5 to 200 hours, preferably about 24 to 120 hours.

  The compound of the formula (VIII) used in the reaction [G] can be produced according to the following reaction [I].

In the reaction [I], A, R ₁ , R ₂ and U are as described above.

  Reaction [I] can be performed in presence of a chlorinating agent or a brominating agent. As the chlorinating agent, for example, one or two or more kinds can be appropriately selected from chlorine, N-chlorosuccinimide, and the like. As the brominating agent, for example, bromine, N-bromosuccinimide, phenyltrimethylammonium tribromide, etc. One type or two or more types can be appropriately selected.

Reaction [I] can be normally performed in presence of a solvent. The solvent may be any solvent as long as it is inert to the reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene; carbon tetrachloride, methyl chloride, chloroform, dichloromethane, dichloroethane, trichloroethane. Aliphatic hydrocarbons such as hexane and cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether and dimethoxyethane; esters such as methyl acetate and ethyl acetate; dimethyl sulfoxide, sulfolane, dimethylacetamide, dimethylformamide, One or two or more polar aprotic solvents such as N-methylpyrrolidone and pyridine; organic acids such as acetic acid and propionic acid; and water can be appropriately selected.
Reaction [I] can be carried out in the presence of a base or an acid, if necessary.
Examples of the base include lithium diisopropylamide. The base can be used in an amount of 1 to 2 moles, preferably 1 to 1.2 moles based on the compound of the formula (IV).

The acid can be appropriately selected from one or more of organic acids such as acetic acid and propionic acid; aluminum chloride. The acid can usually be used in catalytic amounts. Moreover, a solvent and an acid can be combined by using an organic acid as a solvent in excess.
The reaction [I] can be carried out usually at -100 to 150 ° C, preferably at -78 to 110 ° C, and the reaction time is usually about 0.1 to 48 hours, preferably about 0.5 to 24 hours. However, when carried out in the presence of a base, it can usually be carried out at -100 to 0 ° C, preferably -78 to -20 ° C, and the reaction time is usually about 0.1 to 12 hours, preferably about 0.5 to 6 hours. When it is carried out in the presence of an acid, it can be usually carried out at 0 to 150 ° C., preferably 20 to 110 ° C., and the reaction time is usually about 0.1 to 48 hours, preferably 1 to It can be about 24 hours.

  The compound of formula (IV) used in the reaction [C], [H] or [I] is a known compound, or according to the following reaction [J] or [K] or a method analogous thereto. Can be manufactured.

In the reaction [J], R ₁ and R ₂ are as described above, Xa is a hydrogen atom, chlorine atom or alkyl, Xa ′ is a chlorine atom or alkyl, and Xb, Xc, Xd, Xe, G ₁ And G ₂ are each a hydrogen atom, a fluorine atom or a chlorine atom, V is a bromine atom or an iodine atom, and j is 0 or 1.

The 1st process of reaction [J] can be normally performed in presence of a base and a solvent.
The base can be appropriately selected from organic lithium compounds such as lithium diisopropylamide. The base can be used in an amount of 1 to 2 mol, preferably 1 to 1.5 mol based on the compound of the formula (IX-1) or (IX-2).
The solvent may be any solvent as long as it is inert to the reaction. For example, one or more solvents can be appropriately selected from ethers such as dioxane, tetrahydrofuran and diethyl ether.

Examples of the chlorinating agent used in the first step of the reaction [J] include N-chlorosuccinimide.
The formula: Xa′-I used in the first step of the reaction [J] can be used in an amount of 1 to 10 times mol, preferably 1 to 5 times mol for the compound of the formula (IX-1) or (IX-2). Moreover, the chlorinating agent used at the 1st process of reaction [J] can be used 1-5 times mole with respect to the compound of Formula (IX-1) or (IX-2), Preferably 1-3 times mole can be used.

The 1st process of reaction [J] can be performed in presence of inert gas as needed. The inert gas can be appropriately selected from, for example, nitrogen gas and argon gas.
The first step of the reaction [J] can be carried out usually at −100 to 50 ° C., preferably −70 to 25 ° C., and the reaction time is usually about 1 to 48 hours, preferably about 1 to 20 hours. can do.

The 2nd process of reaction [J] can be normally performed in presence of a base and a solvent.
The base can be appropriately selected from one or more of organic lithium compounds such as methyl lithium and n-butyl lithium. The base can be used in an amount of 1 to 2 mol, preferably 1 to 1.5 mol based on the compound of the formula (IX-1), (IX-2), (X-1) or (X-2).
The solvent may be any solvent as long as it is inert to the reaction. For example, one or more solvents can be appropriately selected from ethers such as dioxane, tetrahydrofuran and diethyl ether.

The compound of the formula (XI) used in the second step of the reaction [J] is 1 to 3 times the compound of the formula (IX-1), (IX-2), (X-1) or (X-2) Mole, preferably 1 to 1.5 times mol can be used.
The 2nd process of reaction [J] can be performed in presence of inert gas as needed. The inert gas can be appropriately selected from, for example, nitrogen gas and argon gas.
The second step of the reaction [J] can be carried out usually at −100 to 50 ° C., preferably −70 to 25 ° C., and the reaction time is usually about 1 to 48 hours, preferably about 1 to 20 hours. can do.

In the reaction [K], R ₁ , R ₂ , Xa, Xa ′, Xb, Xc, Xd, Xe, V, and j are as described above.

The 1st process of reaction [K] can be normally performed in presence of a base and a solvent.
The base can be appropriately selected from one or more of organic lithium compounds such as methyl lithium and n-butyl lithium. The base can be used in an amount of 1 to 2 mol, preferably 1 to 1.5 mol based on the compound of the formula (IX-1), (IX-2), (X-1) or (X-2).
The solvent may be any solvent as long as it is inert to the reaction. For example, one or more solvents can be appropriately selected from ethers such as dioxane, tetrahydrofuran and diethyl ether.

The formula (XII) used in the first step of the reaction [K] is 1 to 3 moles compared to the compound of the formula (IX-1), (IX-2), (X-1) or (X-2), Desirably, it can be used at 1 to 1.5 moles.
The 1st process of reaction [K] can be performed in presence of inert gas as needed. The inert gas can be appropriately selected from, for example, nitrogen gas and argon gas.
The first step of the reaction [K] can be usually carried out at −100 to 50 ° C., preferably −70 to 25 ° C., and the reaction time is usually about 1 to 48 hours, preferably about 1 to 20 hours. can do.

The 2nd process of reaction [K] can be normally performed in presence of an oxidizing agent and a solvent.
The oxidizing agent can be appropriately selected from one or more of pyridinium chlorochromate and manganese dioxide. The oxidizing agent can be used in an amount of 1 to 10 times mol, preferably 1 to 3 times mol, of the compound of formula (XIII-1) or (XIII-2).

The solvent may be any solvent as long as it is inert to the reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; carbon tetrachloride, methyl chloride, chloroform, dichloromethane, dichloroethane, trichloroethane, One type or two or more types can be appropriately selected from aliphatic hydrocarbons such as hexane and cyclohexane.
The second step of the reaction [K] can be usually carried out at 0 to 150 ° C., preferably 20 to 100 ° C., and the reaction time is usually about 0.5 to 24 hours, preferably about 1 to 12 hours. Can do.

  The composition of the present invention is useful as a bactericidal composition capable of controlling harmful fungi at a low dose, and particularly useful as a bactericidal composition for agriculture and horticulture. When used as an agricultural and horticultural bactericidal composition, the composition of the present invention is a harmful fungus belonging to, for example, oomycetes, ascomycetes, basidiomycetes, incomplete fungi (Deuteromycetes), etc. It is particularly effective for controlling harmful fungi belonging to Ascomycetes and Deuteromycetes.

Specific examples of the harmful fungi include the following.
As oomycetes, potato or Phytophthora infestans , Phytophthora genus such as Phytophthora capsici, Pseudoperonospora cubensis Pseudoperonospora ( Pseudoperonospora cubensis ) Pseudoperonospora ); Plasmopara genus such as Plasmopara viticol ; Pythium graminicola ; Pythium genus such as wheat brown snow rot Pythium iwayamai ; Etc.

As ascomycetes, Erysiphe such as wheat powdery mildew (Erysiphe graminis) (Erysiphe) genus; cucumber powdery mildew (Sphaerotheca fuliginea), Sphaerotheca (Sphaerotheca) such as strawberry powdery mildew (Sphaerotheca humuli) genus; grape udon Unshinyura such as this fungus (Uncinula necator) (Uncinula) genus; Podosufaera such as apple powdery mildew (Podosphaera leucotricha) (Podosphaera) genus; pea褐紋fungus (Mycosphaerella pinodes), apple black spot fungus (Mycosphaerella pomi), banana black Sigatoka fungus (Mycosphaerella musicola), oysters circle star deciduous fungus (Mycosphaerella nawae), Mikosufaerera (Mycosphaerella) species such as the strawberry bull's-eye fungus (Mycosphaerella fragariae); apple scab (Venturia inaequalis), pear scab (Venturia nashicola) Venturia such as (Venturia Genus; barley net plaques fungi (Pyrenophora teres), Pirenohora (Pyrenophora) such as barley Madaraha fungi (Pyrenophora graminea) genus; sclerotinia such as beans Sclerotinia sclerotiorum (Sclerotinia sclerotiorum) (Sclerotinia) genus; rice Gomaha Cochliobolus genus, such as Cochliobolus miyabeanus ; Didymella genus, such as Didymella bryoniae ; Gibberella genus, such as Gibberella zeae ; grape black痘病bacteria (Elsinoe ampelina), Erushinoe such as citrus scab pathogen (Elsinoe fawcettii) (Elsinoe) genus; (. Diaporthe sp) citrus black spot fungus (Diaporthe citri), Diaporuse such as grape branch膨病bacteria (Diaporthe ) Genus; like apple Monilinia mali and Monilinia fructicola Such Monirinia (Monilinia) genus; Guromerera (Glomerella) such as grape evening Rot Fungus (Glomerella cingulata) genus; and the like.

As basidiomycetes, Rhizoctonia genus such as rice rot ( Rhizoctonia solani ); Ustilago genus such as Ustilago nuda ; Puccinia coronata , wheat red rust fungus (Puccinia r econdita), Pukushinia (Puccinia), such as wheat yellow rust (Puccinia striiformis) genus; and the like.

As Deuteromycetes, wheat glume blotch fungus (Septoria nodorum), Septoria (Septoria) such as wheat leaf blotch fungi (Septoria tritici) genus; Botrytis (Botrytis) genus, such as grape Botrytis cinerea (Botrytis cinerea); Pyricularia Pyricularia (Pyricularia) species, such as the fungus (Pyricularia oryzae); sugar beet brown spot fungus (Cercospora beticola), Sakosupora (Cercospora), such as oysters angle plaques fungus (Cercospora kakivola) genus; as cucumber anthracnose fungi (Colletotrichum orbiculare) The genus Colletotrichum ; Alternaria alternata apple pathotype, Alternaria alternata Japanese pear pathotype, Alternaria alternata Japanese pear pathogen or Alternaria solani , Alternaria brassicae Alternaria, such as a) (Alternaria) genus; wheat Memonbyo Shu de circo spot these (Pseudocercosporella) genera, such as (Pseudocercosporella herpotrichoides); grape brown spot fungus (Pseudocercospora vitis) oxalic de Sir Kos Paula like (Pseudocercospora) Genus; Lincomycin spot tumefaciens, such as barley scald pathogen (Rhynchosporium secalis) ( Rhynchosporium) genus; Cladosporium (Cladosporium) species such as peach scab (Cladosporium carpophilum);. Momohomopushisu rot (Phomopsis sp Homopushisu (Phomopsis), such as a) the genus; as oysters anthracnose fungus (Gloeosporium kaki) such Glo Eos poly um (Gloeosporium) genus; Fulvia (Fulvia) genus, such as tomato leaf mold fungus (Fulvia fulva); Korinesupora such as cucumber brown spot pathogen (Corynespora cassiicola) (Corynespora) genus; and the like.

  Since the composition of the present invention can control various harmful fungi described above, it can control various diseases preventively or therapeutically. In particular, the composition of the present invention has various diseases that are problematic in the field of agriculture and horticulture, such as rice blast, sesame leaf blight, leaf blight or seedling blight; wheat powdery mildew, red mold, red rust , Yellow rust, net blotch disease, leafy leaf disease, snow rot, naked ear disease, eye spot disease, cloud shape disease, leaf blight or dry blight; citrus black spot or scab; apple monilia , Powdery mildew, black spot disease, spot deciduous disease or black spot disease; pear black star disease or black spot disease; peach ash star disease, black star disease or fomoposis rot disease; grape black mildew, late rot, brown spot Disease, branch rot, powdery mildew or downy mildew; oyster anthracnose, round leaf deciduous or horny spot disease; cucurbit anthracnose, powdery mildew, vine blight, brown spot or downy mildew Ring tomato ring disease, gray blight, leaf mold or blight; banana black sigatoka disease; sugar beet brown blight; pea brown blight; cruciferous vegetables Black Spot disease; potato late blight or early blight; strawberry powdery mildew or bull's-eye disease; is effective for controlling various diseases, such as, various Botrytis or rot in crops.

  The composition of the present invention is also effective for preventive or therapeutic control of soil diseases caused by phytopathogenic fungi such as Fusarium, Psium, Rhizoctonia, Verticillium, and Plasmodiophora.

The composition of the present invention is also effective in controlling various harmful harmful fungi against drugs such as benzimidazole, strobilurin, dicarboximide, phenylamide, and ergosterol biosynthesis inhibitor.
Furthermore, since the composition of the present invention has excellent osmotic transfer properties, by applying a pest control agent containing the composition of the present invention to the soil, simultaneously with the control of pests in the soil, the foliage part It can also control harmful fungi.

  The composition of the present invention is usually prepared by mixing a carboxylic acid amide derivative of the formula (I) or a salt thereof and various agricultural adjuvants into a powder, granule, granule wettable powder, wettable powder, aqueous suspension. , Oily suspensions, aqueous solvents, emulsions, solutions, pastes, aerosols, microdispersions and the like. It can be in any formulation form used. Adjuvants used in the formulation include solid carriers such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite and sericite, clay, sodium carbonate, sodium bicarbonate, sodium sulfate, zeolite, starch, etc. Solvents such as water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, N, N-dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, alcohol; Fatty acid salts, benzoates, alkylsulfosuccinates, dialkylsulfosuccinates, polycarboxylates, alkylsulfate esters, alkylsulfates, alkylarylsulfates, alkyldiglycol ether sulfates, alcohols Lucol sulfate, alkyl sulfonate, alkyl aryl sulfonate, aryl sulfonate, lignin sulfonate, alkyl diphenyl ether disulfonate, polystyrene sulfonate, alkyl phosphate ester, alkyl aryl phosphate, styryl Aryl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl aryl phosphate Salts, anionic surfactants such as naphthalene sulfonic acid formalin condensate and spreading agents; sorbitan fatty acid esters, glycerin fatty acid esters, fatty acid polyglycols Ride, fatty acid alcohol polyglycol ether, acetylene glycol, acetylene alcohol, oxyalkylene block polymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl aryl ether, polyoxyethylene glycol alkyl ether, polyethylene glycol, poly Nonionic surfactants and spreading agents such as oxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxypropylene fatty acid ester; olive oil, kapok oil , Castor oil, palm oil, camellia oil, palm oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil Rapeseed oil, linseed oil, tung oil, vegetable oils, and the like or a mineral oil such as liquid paraffin. Each component of these adjuvants can be used by appropriately selecting one or two or more types without departing from the object of the present invention. In addition to the above-mentioned adjuvants, it can be used by appropriately selecting from those known in the art. For example, a bulking agent, a thickening agent, an anti-settling agent, an antifreezing agent, a dispersion stabilizer, a phytotoxicity reduction. Various commonly used adjuvants such as agents and antifungal agents can also be used. The compounding ratio of the carboxylic acid amide derivative of the formula (I) or a salt thereof and various adjuvants is 0.001: 99.999 to 95: 5, preferably 0.005: 99.995 to 90:10. In actual use of these preparations, use them as they are or dilute them to a predetermined concentration with a diluent such as water, and add various spreading agents (surfactants, vegetable oils, mineral oils, etc.) as necessary. Can be used.

  Application of the composition of the present invention cannot be defined unconditionally due to differences in weather conditions, formulation forms, target crops, application timing, application location, types and occurrences of harmful fungi, types and occurrences of diseases, etc. In the case of treatment, it can be applied at an active ingredient concentration of 0.1 to 10,000 ppm, preferably 1 to 2,000 ppm. The appropriate amount of application is 0.1 to 50,000 g of the carboxylic acid amide derivative of the formula (I) or a salt thereof per hectare. Desirably, it can be about 1 to 30,000 g. In the case of soil treatment, generally 10 to 100,000 g, preferably 200 to 20,000 g of the carboxylic acid amide derivative of the formula (I) or a salt thereof can be applied per hectare.

  Application of various preparations of the composition of the present invention, or dilutions thereof, is generally performed by application methods such as spraying (eg spraying, spraying, misting, atomizing, dusting, water surface application, etc.), soil application. (Mixing, irrigation, etc.), surface application (application, powder coating, coating, etc.) can be performed. It can also be applied by the so-called ultra low volume application method (ultra low volume). In this method, it is possible to contain 100% of the active ingredient.

  The composition of the present invention can be mixed with or used in combination with other agricultural chemicals, fertilizers, safeners, etc. In this case, there are cases where more excellent effects and functions are exhibited. Other pesticides include herbicides, insecticides, acaricides, nematicides, soil insecticides, fungicides, antiviral agents, attractants, antibiotics, plant hormones, plant growth regulators, etc. . In particular, a mixed bactericidal composition in which a carboxylic acid amide derivative of the formula (I) or a salt thereof and one or more active ingredient compounds of other bactericides are used in combination or in combination, The timing, control activity, etc. may be improved in a preferred direction. In addition, the carboxylic acid amide derivative of formula (I) or a salt thereof and the active ingredient compound of other fungicide may be used by mixing them separately, even if they are mixed at the time of spraying. May be. The present invention also includes such a mixed bactericidal composition.

  The mixing ratio of the carboxylic acid amide derivative of formula (I) or a salt thereof and the active ingredient compound of other fungicide is the weather conditions, formulation form, target crop, application time, application place, type and occurrence of harmful fungi, Although it cannot be defined unconditionally due to differences in disease type or occurrence status, it is generally 1: 300 to 300: 1, preferably 1: 100 to 100: 1. In addition, the appropriate amount of application can be 0.1 to 70,000 g, preferably 1 to 30,000 g as the total amount of active ingredient compounds per hectare. The present invention also includes a method for controlling harmful fungi by applying such a mixed bactericidal composition.

In the above-mentioned other pesticides, as an active ingredient compound of a fungicide (generic name; including partial application, or Japan Plant Protection Association test code), for example, mepanipyrim, pyrimethanil, cyprodinil Pyrimidinamine compounds such as (Cyprodinil);
Pyridinamine compounds such as Fluazinam;
Triadimefon, Bitertanol, Triflumizole, Etaconazole, Propiconazole, Penconazole, Flusilazole, Microbutanil, Cyproconazole Cyproconazole, terbuconazole, hexaconazole, furconazole-cis, prochloraz, metconazole, epoxiconazole, tetraconazole , Oxpoconazole fumarate, Sipconazole, Prothioconazole, Triadimenol, Flutriafol, Difenoconazole Fluquinconazole (Fluquinconazole), fenbuconazole (Fenbuconazole), azole compounds such as bromuconazole (Bromuconazole), diniconazole (Diniconazole);

Quinoxaline compounds such as quinomethionate;
Dithiocarbamate compounds such as Maneb, Zineb, Mancozeb, Polycarbamate, Metiram, Propineb;
Organochlorine compounds such as Fthalide, Chlorothalonil, Quintozene;
Imidazole compounds such as Benomyl, Thiophanate-Methyl, Carbendazim, Cyazofamid;
Cyanoacetamide compounds such as Cymoxanil;
Phenylamide compounds such as Metalaxyl, Metalaxyl M, Oxadixyl, Offurace, Benalaxyl, Furalaxyl, Cyprofuram;
Sulfenic acid compounds such as Dichlofluanid;
Copper compounds such as cuprichydroxide and organic copper (Oxine Copper);
Isoxazole compounds such as hymexazol;

Organophosphorus such as fosetyl-aluminum, turfos-methyl, S-benzyl O, O-diisopropyl phosphorothioate, O-ethyl S, S-diphenyl phosphorodithioate, aluminum ethyl hydrogen phosphonate Compound;
N-halogenothioalkyl compounds such as Captan, Captafol, Folpet;
Dicarboximide compounds such as Procymidone, Iprodione, Vinclozolin;
Benzanilide compounds such as Flutolanil, Mepronil, Zoxamid, Tiadinil;
Piperazine compounds such as Triforine;
Pyridine compounds such as Pyrifenox;
Carbinol compounds such as Fenarimol and Flutriafol;
Piperidine compounds such as Fenpropidine;
Morpholine compounds such as Fenpropimorph;
Organotin compounds such as Fentin Hydroxide and Fentin Acetate;

Urea compounds such as Pencycuron;
Synamic acid compounds such as Dimethomorph and Flumorph;
Phenyl carbamate compounds such as Dietofencarb;
Cyanopyrrole compounds such as fludioxonil and fenpiclonil;
Azoxystrobin, Kresoxim-Methyl, Metominofen, Trifloxystrobin, Picoxystrobin, Oryzastrobin, Dimoxystrobin Strobilurin-based compounds such as Fluoxastrobin and Fluacrypyrin;
Oxazolidinone compounds such as Famoxadone;
Thiazole carboxamide compounds such as ethaboxam;
Silylamide compounds such as Silthiopham;
Amino acid amide carbamate compounds such as Iprovalicarb, benchthiavalicarb;

An imidazolidine-based compound such as fenamidone;
Hydroxyanilide compounds such as Fenhexamid;
Benzenesulfonamide compounds such as Flusulfamid;
Oxime ether compounds such as cyflufenamid;
Phenoxyamide-based compounds such as phenoxanil;
Triazole compounds such as Simeconazole;
Antibiotics such as polyoxins;

  Other compounds include Isoprothiolane, Tricyclazole, Pyroquilon, Diclomezine, Probenazole, Quinoxyfen, Propamocarb Hydrochloride, Spiroxamine Spiroxamine (Spiroxamine) (Chloropicrin), Dazomet, Carbam sodium salt (Metam-sodium), Nicobifen, Metrafenone, MTF-753 (Pentiopyrad), UBF-307, Diclocymet, Proquinazid ) And the like.

Preferred embodiments of the present invention are as follows. However, the present invention is not limited to these.
(1) Carboxylic acid amide in which A is phenyl substituted with X, naphthyl substituted with X, benzodioxolanyl substituted with X, or benzodioxanyl substituted with X in the formula (I) A bactericidal composition containing a derivative or a salt thereof as an active ingredient.
(2) In the formula (I), a carboxylic acid amide derivative or a salt thereof in which the optionally substituted phenyl of B or the optionally substituted pyridyl has a substituent at the ortho position of the aminocarbonyl group is effective. Bactericidal composition contained as an ingredient.
(3) In the formula (I), a carboxylic acid amide derivative in which the optionally substituted phenyl or the optionally substituted pyridyl of B is substituted with halogen, alkyl, haloalkyl, alkoxy or haloalkoxy A bactericidal composition containing salt as an active ingredient.
(4) In the above formula (I), the optionally substituted phenyl of B or the optionally substituted pyridyl has a substituent at the ortho position of the aminocarbonyl group, and the substituent is halogen, alkyl, haloalkyl A bactericidal composition comprising a carboxylic acid amide derivative which is alkoxy or haloalkoxy or a salt thereof as an active ingredient.
(5) A method for controlling harmful fungi by applying an effective amount of the carboxylic acid amide derivative or salt thereof of (1) to (4).
(6) A method for controlling plant diseases by applying an effective amount of the carboxylic acid amide derivatives or salts thereof of (1) to (4).
(7) A method for protecting crops by applying an effective amount of the carboxylic acid amide derivative or the salt thereof according to (1) to (4).
(8) A method for improving crop yield by applying an effective amount of the carboxylic acid amide derivative or salt thereof of (1) to (4).

Next, examples of the present invention will be described, but the present invention is not limited thereto. First, synthesis examples of the carboxylic acid amide derivative of the formula (I) or a salt thereof are described.
Synthesis example 1
Synthesis of N-[(4'-Bromo-2'-methyl-1,1-dimethyl) phenacyl] -2-trifluoromethylbenzamide (Compound No. 1-9 described later)
(1) 0.78 g of phenyltrimethylammonium tribromide was added to a mixture of 0.5 g of 4-bromo-2-methylisobutyrophenone and 15 ml of tetrahydrofuran, and reacted at room temperature for 2 hours. After completion of the reaction, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain 0.65 g of oily α-bromo-4-bromo-2-methylisobutyrophenone. The NMR spectrum data of this product is as follows.
¹ H-NMR δppm (Solvent: CDCl ₃ / 400MHz)
1.91 (s, 6H), 2.23 (s, 3H), 7.33 (d, 1H), 7.40 (s, 1H), 7.53 (d, 1H)

(2) 0.26 g of sodium azide was added to a mixture of 0.65 g of α-bromo-4-bromo-2-methylisobutyrophenone and 15 ml of dimethyl sulfoxide, and reacted at 50 ° C. for 1 hour. After completion of the reaction, the reaction mixture was poured into water, extracted with ether and washed with water. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 0.56 g of oily α-azido-4-bromo-2-methylisobutyrophenone. The NMR spectrum data of this product is as follows.
¹ H-NMR δppm (Solvent: CDCl ₃ / 400MHz)
1.59 (s, 6H), 2.30 (s, 3H), 7.32 (d, 1H), 7.38 (d, 1H), 7.43 (s, 1H)

  (3) To a mixture of 0.56 g of α-azido-4-bromo-2-methylisobutyrophenone, 7 ml of tetrahydrofuran and 0.2 ml of water, 0.62 g of triphenylphosphine was added and reacted at room temperature for 23 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure. The residue was made weakly acidic by adding water and then hydrochloric acid, and then washed with ethyl acetate. The aqueous layer was neutralized with aqueous sodium hydroxide solution and extracted with methylene chloride. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 0.43 g of oily α-amino-4-bromo-2-methylisobutyrophenone.

(4) 0.25 g of triethylamine was added to a mixture of 0.43 g of α-amino-4-bromo-2-methylisobutyrophenone and 10 ml of tetrahydrofuran, and then a mixture of 0.27 g of 2-trifluoromethylbenzoyl chloride and 8 ml of tetrahydrofuran was cooled on ice. Added in. After completion of dropping, the reaction was allowed to proceed at room temperature for 1.5 hours. After completion of the reaction, the reaction mixture was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/4) to obtain 0.50 g of the desired product having a melting point of 137-139 ° C. The NMR spectrum data of this product is as follows.
¹ H-NMR δppm (Solvent: CDCl ₃ / 400MHz)
1.75 (s, 6H), 2.36 (s, 3H), 6.55 (s, 1H), 7.14 (d, 1H), 7.32 (d, 1H), 7.38 (d, 1H), 7.46 (s, 1H), 7.54 (m, 2H), 7.68 (d, 1H)

Synthesis example 2
Synthesis of N-[[4 '-(4 "-Fluorophenyl) -1,1-dimethyl] phenacyl] -2,3-difluorobenzamide (Compound No. 1-12 described later)
(1) Using 2.0 g of 4-bromoisobutyrophenone, N-[(4′-bromo-1,1-dimethyl) phenacyl] -2,3-3- having a melting point of 122 to 123 ° C. in the same manner as in Synthesis Example 1 2.67 g of difluorobenzamide was obtained. The NMR spectrum data of this product is as follows.
¹ H-NMR δppm (Solvent: CDCl ₃ / 400MHz)
1.73 (s, 6H), 7.13 (m, 1H), 7.30 (m, 2H), 7.50 (d, 2H), 7.59 (t, 1H), 7.89 (d, 2H)

(2) N-[(4′-bromo-1,1-dimethyl) phenacyl] -2,3-difluorobenzamide 0.3 g, 4-fluorophenylboronic acid 0.15 g, sodium carbonate 0.33 g, water 4 ml, tetrakis (tri Phenylphosphine) palladium (36 mg) and 1,2-dimethoxyethane (10 ml) were mixed, the inside of the reaction vessel was replaced with nitrogen, and the mixture was reacted for 1 hour under reflux. After completion of the reaction, the reaction mixture was poured into water, diluted with weak hydrochloric acid to weakly acid, and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/4) to obtain 0.28 g of the desired product having a melting point of 116 to 117 ° C. The NMR spectrum data of this product is as follows.
¹ H-NMR δppm (Solvent: CDCl ₃ / 400MHz)
1.84 (s, 6H), 7.13 (m, 3H), 7.29 (m, 1H), 7.43 (d, 1H), 7.55 (m, 4H), 7.64 (t, 1H), 8.11 (d, 2H)

Synthesis example 3
Synthesis of 2-chloro-N-[[4 '-(3 "-chloro-5" -trifluoromethyl-2 "-pyridinyloxy) -1,1-dimethyl] phenacyl] benzamide (Compound No. 1-41)
(1) Prepared from 0.31 g of magnesium, 1.82 g of 2-bromopropane and 25 ml of anhydrous ether in a mixture of 2.95 g of 4- (3'-chloro-5'-trifluoromethyl-2'-pyridinyloxy) benzonitrile and 20 ml of anhydrous ether The prepared Grignard reagent was added dropwise. After completion of the dropwise addition, the mixture was reacted for 20 hours under reflux. After completion of the reaction, the reaction mixture was poured into ice water, and 6N sulfuric acid was added to make it weakly acidic, followed by stirring for 0.5 hour. The mixture was extracted with ethyl acetate, the organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/19) to give 4- (3′-chloro-5′-trifluoromethyl-2′-pyridinyloxy) iso 0.85 g of butyrophenone was obtained. The NMR spectrum data of this product is as follows.
¹ H-NMR δppm (Solvent: CDCl ₃ / 400MHz)
1.23 (d, 6H), 3.53 (m, 1H), 7.26 (d, 2H), 8.0 (s, 1H), 8.06 (d, 2H), 8.27 (d, 2H)

(2) Using 0.85 g of 4- (3′-chloro-5′-trifluoromethyl-2′-pyridinyloxy) isobutyrophenone, 0.16 g of the desired product having a melting point of 184 to 185 ° C. was obtained in the same manner as in Synthesis Example 1. It was. The NMR spectrum data of this product is as follows.
¹ H-NMR δppm (Solvent: CDCl ₃ / 400MHz)
1.82 (s, 6H), 7.03 (s, 1H), 7.17 (d, 2H), 7.26 (d, 1H), 7.35 (m, 2H), 7.43 (d, 1H), 7.97 (s, 1H), 8.13 (d, 2H), 8.23 (s, 1H)

Synthesis example 4
N- [2-[(2,2-difluoro-4-methyl-1,3-benzodioxolan-5-yl) carbonyl] -2-propyl] -2-trifluoromethylbenzamide (Compound No. 3-19 described later) )
(1) To a mixture of 8.77 g of diisopropylamine and 150 ml of tetrahydrofuran was added dropwise 52.7 ml of n-butyllithium (1.56M n-hexane solution) at −20 ° C. in a nitrogen atmosphere, and the mixture was stirred at the same temperature for 30 minutes. After adding 15.0 g of 5-bromo-2,2-difluoro-1,3-benzodioxolane dropwise at -50 ° C. or lower, the mixture was stirred at the same temperature for 30 minutes. After dropwise addition of 19.7 ml of methyl iodide at −70 ° C. or lower, the mixture was warmed to room temperature and reacted for 15 hours. After completion of the reaction, the reaction mixture was poured into water, made weakly acidic with hydrochloric acid and extracted with diethyl ether. The organic layer was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: n-hexane) to obtain 12.54 g of oily 5-bromo-2,2-difluoro-4-methyl-1,3-benzodioxolane. The NMR spectrum data of this product is as follows.
¹ H-NMR δppm (Solvent: CDCl ₃ / 400MHz)
2.34 (s, 3H), 6.79 (d, 1H), 7.27 (d, 1H)

(2) A mixture of 12.54 g of 5-bromo-2,2-difluoro-4-methyl-1,3-benzodioxolane and 150 ml of diethyl ether was mixed with n-butyllithium (1.56M n- Hexane solution (35.2 ml) was added dropwise, followed by stirring at the same temperature for 30 minutes. After dropwise addition of 5.4 g of isobutyraldehyde at −70 ° C. or lower, the mixture was warmed to room temperature and reacted for 15 hours. After completion of the reaction, the reaction mixture was poured into water, made weakly acidic with hydrochloric acid and extracted with diethyl ether. The organic layer was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/9) to give oily 1- (2,2-difluoro-4-methyl-1,3-benzodioxolane-5- Yl) -2-methylpropanol 10.65g was obtained. The NMR spectrum data of this product is as follows.
¹ H-NMR δppm (Solvent: CDCl ₃ / 400MHz)
0.84 (d, 3H), 1.02 (d, 3H), 1.94 (m, 1H), 2.29 (s, 3H), 4.57 (m, 1H), 6.90 (d, 1H), 7.14 (d, 1H)

(3) 1- (2,2-difluoro-4-methyl-1,3-benzodioxolan-5-yl) -2 at room temperature in a mixture of 11.7 g of pyridinium chlorochromate, 5.94 g of sodium acetate and 100 ml of dichloromethane -A mixture of 10.65 g of methylpropanol and 35 ml of dichloromethane was added and reacted at the same temperature with stirring for 2 hours. After completion of the reaction, the reaction mixture was filtered through celite, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/19) to give oily 5- (2,2-difluoro-4-methyl-1,3-benzodioxolanyl) 8.64 g of 2-propyl ketone was obtained. The NMR spectrum data of this product is as follows.
¹ H-NMR δppm (Solvent: CDCl ₃ / 400MHz)
1.16 (d, 6H), 2.40 (s, 3H), 3.35 (m, 1H), 6.94 (d, 1H), 7.39 (d, 1H)

(4) 5- (2,2-difluoro-4-methyl-1,3-benzodioxolanyl) 2-propyl ketone 13.64 g of phenyltrimethylammonium tribromide was added to a mixture of 8.64 g of ketone and 86 ml of tetrahydrofuran. Reacted for hours. After completion of the reaction, the reaction mixture was filtered and the filtrate was concentrated under reduced pressure to give oily 2-bromo-2-propyl 5- (2,2-difluoro-4-methyl-1,3-benzodioxolanyl) ketone 11.4. g was obtained.
To a mixture of 2-bromo-2-propyl 5- (2,2-difluoro-4-methyl-1,3-benzodioxolanyl) ketone 11.4 g and dimethyl sulfoxide 69.6 ml was added sodium azide 4.64 g, For 2 hours. After completion of the reaction, the reaction mixture was poured into water, extracted with diethyl ether and washed with water. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/19) to give oily 2-azido-2-propyl 5- (2,2-difluoro-4-methyl-1, 9.6 g of 3-benzodioxolanyl) ketone was obtained. The NMR spectrum data of this product is as follows.
¹ H-NMR δppm (Solvent: CDCl ₃ / 400MHz)
1.57 (s, 6H), 2.27 (s, 3H), 6.94 (d, 1H), 7.38 (d, 1H)

(5) A mixture of 9.6 g of 2-azido-2-propyl 5- (2,2-difluoro-4-methyl-1,3-benzodioxolanyl) ketone, 90 ml of methanol and 1.0 g of 5% palladium carbon The reaction was allowed to proceed at room temperature for 15 hours. After completion of the reaction, the reaction mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure to give oily 2-amino-2-propyl 5- (2,2-difluoro-4-methyl-1,3-benzodioxolanyl) ketone. 8.78 g was obtained.
To a mixture of 0.39 g of 2-amino-2-propyl 5- (2,2-difluoro-4-methyl-1,3-benzodioxolanyl) ketone and 14 ml of tetrahydrofuran was added 0.23 g of triethylamine, and then 2-trifluoro Methylbenzoyl chloride (0.38 g) was added dropwise under ice cooling, and after completion of the addition, the reaction was allowed to proceed at room temperature for 2 hours. After completion of the reaction, the reaction mixture was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 3/7) to obtain 0.55 g of the desired product having a melting point of 106 to 108 ° C. The NMR spectrum data of this product is as follows.
¹ H-NMR δppm (Solvent: CDCl ₃ / 400MHz)
1.72 (s, 6H), 2.36 (s, 3H), 6.46 (s, 1H), 6.89 (d, 1H), 7.17 (dd, 1H), 7.34 (d, 1H), 7.52 to 7.56 (m, 1H) , 7.66 (dd, 1H)

Next, typical examples of the carboxylic acid amide derivative of the formula (I) or a salt thereof are specifically shown in Tables 1 to 5. These compounds can be synthesized based on the above synthesis examples or the various production methods described above.
In the table, No. represents a compound No., Me represents a methyl group, and Et represents an ethyl group. In addition, the abbreviations X1 to X9 used in the table each represent the following substituents. In addition, the notation “4-O-X1” in the table indicates that X1 is substituted through the oxygen atom at the 4-position, and other similar descriptions are also based on this.

Below, the test example of this invention composition is described. In each test, the control index followed the following criteria.
[Control index] [Disease severity: Visual observation]
5: No lesion or sporulation is observed.
4: The lesion area, lesion length, number of lesions or spore formation area is less than 10% of the untreated area.
3: The lesion area, lesion length, number of lesions or sporulation area is less than 40% of the untreated area.
2: The lesion area, lesion length, number of lesions, or sporulation area is less than 70% of the untreated area.
1: The lesion area, the lesion length, the number of lesions, or the spore formation area is 70% or more of the untreated section.

Test Example 1 (Wheat powdery mildew prevention effect test)
Cultivate wheat (variety: Norin 61) in a 7.5cm diameter plastic pot, and when it reaches the 1.5 leaf stage, 10ml of a chemical solution prepared by adjusting the carboxylic acid amide derivative of formula (I) or a salt thereof to a predetermined concentration. It sprayed with the spray gun. After the chemical solution was dried (on the day of treatment), conidial spores of powdery mildew were inoculated and kept in a constant temperature room at 20 ° C. The spore formation area was investigated 6 to 7 days after the inoculation, and the control index was determined according to the above evaluation criteria. Compound Nos. 1-1, 1-2, 1-3, 1-5, 1-6, 1-9, 1-10, 1-11, 1-14, 1-15, 1-16, 1- 17, 1-21, 1-22, 1-31, 1-39, 1-44, 1-46, 1-51, 1-56, 3-7, 3-12, 3-13, 3-16, When tested on 3-17, 3-19, 3-20, 3-23, 4-5, 4-6, 4-7, 4-8, 4-9, 4-10 or 5-2, all The compound showed an effect of controlling index 4 or 5 at 500 ppm. Further, when the compounds No. 1-20 or 1-54 were tested, all compounds showed an effect of controlling index 4 or 5 at 250 ppm.

Test Example 2 (Cucumber powdery mildew prevention effect test)
Cucumber (variety: Sagamihanjiro) is cultivated in a 7.5cm diameter plastic pot, and when the 1.5 leaf stage is reached, 10ml of a medicinal solution in which the carboxylic acid amide derivative of formula (I) or a salt thereof is adjusted to a predetermined concentration. It sprayed with the spray gun. After the chemical solution was dried (on the day of treatment or the next day), a conidial spore suspension of powdery mildew was sprayed and kept in a constant temperature room at 20 ° C. The spore formation area was investigated 6 to 7 days after the inoculation, and the control index was determined according to the above evaluation criteria. Compound Nos. 1-2, 1-3, 1-4, 1-5, 1-6, 1-9, 1-12, 1-14, 1-17, 1-22, 3-6, 3- When tested on 12, 3-13, 3-16, 3-17, 3-19, 3-23, 4-5 or 4-6, all compounds showed an effect with a control index of 4 or 5 at 500 ppm. .

Test example 3 (rice blast prevention effect test)
Rice (variety: Nipponbare) is cultivated in a 7.5cm diameter plastic pot, and when the 1.5 leaf stage is reached, 10ml of a chemical solution prepared by adjusting the carboxylic acid amide derivative of formula (I) or a salt thereof to a predetermined concentration is spray gun. It was sprayed with. After the chemical solution was dried (on the day of treatment or the next day), the conidial spore suspension of blast fungus was spray-inoculated, kept in an inoculation box at 20 ° C. for 24 hours, and then kept in a constant temperature room at 20 ° C. The number of lesions was investigated 5 to 7 days after the inoculation, and the control index was determined according to the evaluation criteria. When tested for Compound No. 1-9, 1-47, 1-49, 1-50, 1-53, 1-55, 1-57, 1-58, 2-10 or 4-5, The compound showed an effect of controlling index 4 or 5 at 500 ppm.

Test Example 4 (Rice blight prevention effect test)
Rice (variety: Nipponbare) is cultivated in a 7.5cm diameter plastic pot, and when the 5th leaf stage is reached, 10ml of chemical solution adjusted to the prescribed concentration of the carboxylic acid amide derivative of formula (I) or its salt with a spray gun Scattered. After the chemical solution was dried (the day after the treatment), the filamentous fungus mycelium pieces previously grown on the potato / glucose agar medium were sandwiched and inoculated in the leaf sheath, and kept in a 28 ° C. inoculation box. The lesion length (mm) was investigated 7 days after the inoculation, and the control index was determined according to the above evaluation criteria. When the compounds No. 1-14, 1-45 or 1-52 were tested, all the compounds showed an effect of controlling index 4 or 5 at 500 ppm.

Test Example 5 (Oat Crown Rust Prevention Effect Test)
Cultivate oats (variety: advance) in a 7.5cm diameter plastic pot, and when the two-leaf stage is reached, use a spray gun to add 10ml of the medicinal solution adjusted to the prescribed concentration of the carboxylic acid amide derivative of formula (I) or its salt. Scattered. After the chemical solution was dried (on the day of treatment), conidial spores of the rust fungus were sprinkled and inoculated in a constant temperature room at 20 ° C. The number of lesions was investigated 9 to 10 days after the inoculation, and the control index was determined according to the evaluation criteria. When tested for Compound No. 1-1 or 1-48, all compounds showed an effect of controlling index 4 or 5 at 500 ppm.

Test Example 6 (Green beans mildew prevention effect test)
Growing green beans (variety: at Taishokin) in a 15cm diameter plastic pot, and when the true leaf is fully developed, use a spray gun to prepare 10ml of a chemical solution with the carboxylic acid amide derivative of formula (I) or its salt adjusted to a predetermined concentration. Scattered. After the drug solution was dried (the day after the treatment), a gray mold fungus spore suspension (potato / glucose broth diluted to 50% with water) was inoculated and kept in a constant temperature room at 20 ° C. The lesion length (mm) was examined 3 days after the inoculation, and the control index was determined according to the above evaluation criteria. The compound No. 3-15 was tested and showed an effect of controlling index 4 at 500 ppm.

  Next, formulation examples of the composition of the present invention will be described, but the blending amount, dosage form and the like are not limited to the description examples.

Formulation Example 1
(1) Compound of formula (I) 20 parts by weight (2) Clay 72 parts by weight (3) Sodium lignin sulfonate 8 parts by weight or more is uniformly mixed to obtain a wettable powder.

Formulation Example 2
(1) Compound of formula (I) 5 parts by weight (2) Talc 95 parts by weight or more is uniformly mixed to obtain 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 make emulsion.

Formulation Example 4
(1) Clay 68 parts by weight (2) Lignin sulfonic acid soda 2 parts by weight (3) Polyoxyethylene alkylaryl sulfate 5 parts by weight (4) Fine powder silica A mixture of 25 parts by weight or more of each component of formula (I) The compound is mixed at a weight ratio of 4: 1 to obtain a wettable powder.

Formulation Example 5
(1) 50 parts by weight of the compound of the formula (I) (2) Oxylated polyalkylphenyl phosphate-triethanolamine 2 parts by weight (3) 0.2 part by weight of silicone (4) 47.8 parts by weight or more of water (5) 5 parts by weight of sodium polycarboxylate (6) 42.8 parts by weight of anhydrous sodium sulfate are added to the stock solution that is uniformly mixed and pulverized. .

Formulation Example 6
(1) Compound of formula (I) 5 parts by weight (2) Polyoxyethylene octylphenyl ether 1 part by weight (3) Polyoxyethylene phosphate ester 0.1 part by weight (4) Granular calcium carbonate 93.9 parts by weight ( 1) to (3) are mixed uniformly in advance and diluted with an appropriate amount of acetone, and then sprayed on (4) to remove the acetone and form granules.

Formulation Example 7
(1) Compound of formula (I) 2.5 parts by weight (2) N-methyl-2-pyrrolidone 2.5 parts by weight (3) Soybean oil 95.0 parts by weight Use as an ultra low volume formulation.

Formulation Example 8
(1) Compound of formula (I) 20 parts by weight (2) Oxidated polyalkylphenol phosphate-triethanolamine 2 parts by weight (3) Silicone 0.2 parts by weight (4) Xanthan gum 0.1 parts 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 (8)

Formula (I):

(Wherein A is phenyl optionally substituted with X, naphthyl optionally substituted with X, benzodioxolanyl optionally substituted with X, or benzodioxanyl optionally substituted with X; B is phenyl optionally substituted with halogen, alkyl, haloalkyl, alkoxy or haloalkoxy or pyridyl optionally substituted with alkyl, haloalkyl, alkoxy or haloalkoxy , and R ₁ and R ₂ are each alkyl R ₁ and R ₂ together may form a 3- to 6-membered saturated carbocycle, and X is halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxy, haloalkoxy, alkenyl Substituted with oxy, haloalkenyloxy, alkynyloxy, haloalkynyloxy, Y Yenyl, Y-substituted phenoxy, Y-substituted pyridyl or Y-substituted pyridyloxy, where Y is halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxy or haloalkoxy The bactericidal composition which contains the carboxylic acid amide derivative represented by this, or its salt as an active ingredient. The bactericidal composition according to claim 1, wherein A is phenyl substituted with X, naphthyl substituted with X, benzodioxolanyl substituted with X, or benzodioxanyl substituted with X. The bactericidal composition according to claim 1, wherein the optionally substituted phenyl of B or the optionally substituted pyridyl has a substituent at the ortho position of the aminocarbonyl group. The bactericidal composition according to claim 1, wherein the optionally substituted phenyl or optionally substituted pyridyl of B is substituted with halogen, alkyl, haloalkyl, alkoxy or haloalkoxy. A method for controlling harmful fungi by applying an effective amount of the carboxylic acid amide derivative of the formula (I) or a salt thereof according to claim 1. A method for controlling plant diseases by applying an effective amount of the carboxylic acid amide derivative of the formula (I) or a salt thereof according to claim 1. A method for protecting a crop by applying an effective amount of the carboxylic acid amide derivative of the formula (I) or a salt thereof according to claim 1 to control harmful fungi or to control plant diseases . A method for improving the crop yield by applying an effective amount of the carboxylic acid amide derivative of the formula (I) or a salt thereof according to claim 1 to control harmful fungi or plant diseases .