JP2011001356A - Amide compound and use thereof in controlling plant disease - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound exhibiting an excellent effect on controlling plant diseases.SOLUTION: This amide compound represented by formula (1) and the salt thereof exhibit an excellent effect on controlling plant diseases (in the formula, Rand Reach represents a halogen, a cyano group, a nitro group or the like).

Description

  The present invention relates to an amide compound and its use for controlling plant diseases.

  Conventionally, many compounds have been developed and used for controlling plant diseases.

  An object of the present invention is to provide a compound having an excellent plant disease control effect.

  As a result of intensive studies to find a compound having an excellent plant disease control effect, the present inventors have found that the amide compound represented by the following formula (1) has an excellent plant disease control effect and completed the present invention. did. That is, the present invention is as follows.

〔式中、
Ｒ¹及びＲ²は相互に同一又は相異なり、水素、群Ｃより選ばれる１以上の基で置換されていてもよいＣ１〜Ｃ５鎖式炭化水素基、群Ｄより選ばれる１以上の基で置換されていてもよいＣ３〜Ｃ１０シクロアルキル基、群Ｅより選ばれる１以上の基で置換されていてもよいフェニル基、ハロゲン、シアノ基、ニトロ基、−Ｏ−Ｒ⁵基、−Ｓ−Ｒ⁵基、−Ｃ（＝Ｏ）−Ｒ⁵基、−Ｃ（＝Ｏ）−ＯＲ⁵基、−ＯＣ（＝Ｏ）−Ｒ⁵基、−ＮＲ⁵Ｒ⁶基、−Ｃ（＝Ｏ）−ＮＲ⁵Ｒ⁶基又は−ＮＲ⁵−Ｃ（＝Ｏ）−Ｒ⁶基を表し、
Ｒ⁵及びＲ⁶は相互に同一又は相異なり、水素、群Cより選ばれる１以上の基で置換されていてもよいＣ１〜Ｃ１０鎖式炭化水素基、群Ｄより選ばれる１以上の基で置換されていてもよいＣ３〜Ｃ１０シクロアルキル基又は群Ｅより選ばれる１以上の基で置換されていてもよいフェニル基を表す。
但し、Ｒ¹及びＲ²のいずれか一方は水素を表し、他方は水素以外の基を表す。
なお、群Ｃは群Ｄより選ばれる１以上の基で置換されていてもよいＣ３〜Ｃ１０シクロアルキル基、ハロゲン、シアノ基、ハロゲンで置換されていてもよいＣ１〜Ｃ４アルコキシ基、ハロゲンで置換されていてもよいＣ１〜Ｃ４アルキルチオ基、ハロゲンで置換されていてもよいＣ１〜Ｃ４アルキルスルフィニル基、ハロゲンで置換されていてもよいＣ１〜Ｃ４アルキルスルホニル基、ハロゲンで置換されていてもよい（Ｃ１〜Ｃ４アルキル）カルボニル基、ハロゲンで置換されていてもよい（Ｃ１〜Ｃ４アルコキシ）カルボニル基及びハロゲンで置換されていてもよい（Ｃ１〜Ｃ４アルキル）カルボニルオキシ基からなる群を表し、
群ＤはＣ１〜Ｃ５アルキル基及びハロゲンからなる群を表し、
群Ｅはハロゲン、シアノ基、ニトロ基、ハロゲンで置換されていてもよいＣ１〜Ｃ１０鎖式炭化水素基、群Ｄより選ばれる１以上の基で置換されていてもよいＣ３〜Ｃ１０シクロアルキル基、ハロゲンで置換されていてもよいＣ１〜Ｃ４アルコキシ基、ハロゲンで置換されていてもよいＣ１〜Ｃ４アルキルチオ基、ハロゲンで置換されていてもよいＣ１〜Ｃ４アルキルスルフィニル基、ハロゲンで置換されていてもよいＣ１〜Ｃ４アルキルスルホニル基、ハロゲンで置換されていてもよい（Ｃ１〜Ｃ４アルキル）カルボニル基、ハロゲンで置換されていてもよい（Ｃ１〜Ｃ４アルコキシ）カルボニル基及びハロゲンで置換されていてもよい（Ｃ１〜Ｃ４アルキル）カルボニルオキシ基からなる群を表す。〕
で示されるアミド化合物（以下、本発明化合物と記す）又はその塩。 [1] Formula (1)

[Where,
R ¹ and R ² are the same or different from each other, and are hydrogen, a C1-C5 chain hydrocarbon group optionally substituted with one or more groups selected from group C, and one or more groups selected from group D. C3-C10 cycloalkyl group which may be substituted, phenyl group which may be substituted with one or more groups selected from group E, halogen, cyano group, nitro group, —O—R ⁵ group, —S— R ⁵ group, —C (═O) —R ⁵ group, —C (═O) —OR ⁵ group, —OC (═O) —R ⁵ group, —NR ⁵ R ⁶ group, —C (═O) Represents a —NR ⁵ R ⁶ group or —NR ⁵ —C (═O) —R ⁶ group,
R ⁵ and R ⁶ are the same or different from each other, and are hydrogen, a C1-C10 chain hydrocarbon group optionally substituted with one or more groups selected from group C, and one or more groups selected from group D. A C3-C10 cycloalkyl group which may be substituted or a phenyl group which may be substituted with one or more groups selected from group E.
However, ^one of R ¹ and R ² represents hydrogen, and the other represents a group other than hydrogen.
Group C is a C3-C10 cycloalkyl group which may be substituted with one or more groups selected from Group D, a halogen, a cyano group, a C1-C4 alkoxy group which may be substituted with halogen, or a halogen. An optionally substituted C1-C4 alkylthio group, an optionally substituted C1-C4 alkylsulfinyl group, an optionally substituted C1-C4 alkylsulfonyl group, and an optionally substituted halogen ( A group consisting of a (C1-C4 alkyl) carbonyl group, a (C1-C4 alkoxy) carbonyl group optionally substituted with halogen and a (C1-C4 alkyl) carbonyloxy group optionally substituted with halogen;
Group D represents a group consisting of a C1-C5 alkyl group and halogen,
Group E is halogen, cyano group, nitro group, C1-C10 chain hydrocarbon group which may be substituted with halogen, C3-C10 cycloalkyl group which may be substituted with one or more groups selected from group D C1-C4 alkoxy group optionally substituted with halogen, C1-C4 alkylthio group optionally substituted with halogen, C1-C4 alkylsulfinyl group optionally substituted with halogen, halogen-substituted May be a C1-C4 alkylsulfonyl group, a (C1-C4 alkyl) carbonyl group optionally substituted with halogen, a (C1-C4 alkoxy) carbonyl group optionally substituted with halogen, and a halogen-substituted A good (C1-C4 alkyl) carbonyloxy group is represented. ]
Or an salt thereof (hereinafter referred to as the present compound).

[2] The amide compound or a salt thereof according to [1], wherein R ¹ and R ² are the same or different from each other and are hydrogen or halogen.

[3] The amide compound or a salt thereof according to [1], wherein R ¹ and R ² are the same or different from each other and are hydrogen, fluorine, chlorine or bromine.

[4] A plant disease control agent comprising the amide compound or salt thereof according to any one of [1] to [3], and an inert carrier.

[5] A method for controlling plant diseases, comprising a step of applying an effective amount of the amide compound or salt thereof according to any one of [1] to [3] to a plant or soil where the plant grows.

[6] Use of the amide compound or salt thereof according to any one of [1] to [3] for controlling plant diseases.

  Since the compound of the present invention or a salt thereof has an excellent plant disease control effect, it is useful for plant disease control applications.

Various substituents used in the description of the present specification will be described below with examples.
“Halogen” means fluorine, chlorine, bromine and iodine.

Examples of the “C1-C5 chain hydrocarbon group optionally substituted with one or more groups selected from group C” include a cyclopropylmethyl group, a cyclopropylethyl group, a cyclopropylpropyl group, a cyclopropylbutyl group, A cyclopropylpentyl group,
Methyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, iodomethyl group, chlorodifluoromethyl group,
Ethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group, perfluoroethyl group, 2-chloroethyl group, 2,2,2-trichloroethyl group, 2-bromoethyl group, 2-iodoethyl group,
Propyl group, 3-fluoropropyl group, 3,3,3-trifluoropropyl group, perfluoropropyl group, isopropyl group, 2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl group, perfluoro Isopropyl group, 3-chloropropyl group, 3,3,3-trichloropropyl group, 3-bromopropyl group, 3-iodopropyl group,
Butyl group, 4-fluorobutyl group, 4,4,4-trifluorobutyl group, perfluorobutyl group, 4-chlorobutyl group, 4,4,4-trichlorobutyl group, 4-bromobutyl group, 4-iodobutyl group, s-butyl group, t-butyl group,
Pentyl group, 5-fluoropentyl group, 5,5,5-trifluoropentyl group, perfluoropentyl group, 5-chloropentyl group, 5,5,5-trichloropentyl group, 5-bromopentyl group, 5-iodo Pentyl group,
Cyanomethyl group, dicyanomethyl group, 2-cyanoethyl group, 2,2-dicyanoethyl group, 3-cyanopropyl group, 3,3-dicyanopropyl group, 4-cyanobutyl group, 4,4-dicyanobutyl group, 5-cyano Pentyl group, 5,5-dicyanopentyl group,
Methoxymethyl group, ethoxymethyl group, propoxymethyl group, isopropoxymethyl group, butoxymethyl group, isobutoxymethyl group, t-butoxymethyl group, 2-methoxyethyl group, 3-methoxypropyl group, 4-methoxybutyl group, 5-methoxypentyl group, 2-ethoxyethyl group, 3-ethoxypropyl group, 4-ethoxybutyl group, 5-ethoxypentyl group, 2-propoxyethyl group, 3-propoxypropyl group, 4-propoxybutyl group, 5- Propoxypentyl group, 2-butoxyethyl group, 3-butoxypropyl group, 4-butoxybutyl group, 5-butoxypentyl group,
Methylthiomethyl group, ethylthiomethyl group, propylthiomethyl group, isopropylthiomethyl group, butylthiomethyl group, isobutylthiomethyl group, t-butylthiomethyl group, 2-methylthioethyl group, 3-methylthiopropyl group, 4- Methylthiobutyl group, 5-methylthiopentyl group, 2-ethylthioethyl group, 3-ethylthiopropyl group, 4-ethylthiobutyl group, 5-ethylthiopentyl group, 2-propylthioethyl group, 3-propylthiopropyl group Group, 4-propylthiobutyl group, 5-propylthiopentyl group, 2-butylthioethyl group, 3-butylthiopropyl group, 4-butylthiobutyl group, 5-butylthiopentyl group,
Methanesulfinylmethyl group, ethanesulfinylmethyl group, propanesulfinylmethyl group, isopropanesulfinylmethyl group, butanesulfinylmethyl group, isobutanesulfinylmethyl group, t-butanesulfinylmethyl group, 2-methanesulfinylethyl group, 3-methanesulfinylpropyl group Group, 4-methanesulfinylbutyl group, 5-methanesulfinylpentyl group, 2-ethanesulfinylethyl group, 3-ethanesulfinylpropyl group, 4-ethanesulfinylbutyl group, 5-ethanesulfinylpentyl group, 2-propanesulfinylethyl group 3-propanesulfinylpropyl group, 4-propanesulfinylbutyl group, 5-propanesulfinylpentyl group, 2-butanesulfinylethyl group, 3-butanesulfy group Rupuropiru group, 4-Bed ethanesulfinyl butyl group, 5- butane sulfinyl point pen butyl group,
Methanesulfonylmethyl group, ethanesulfonylmethyl group, propanesulfonylmethyl group, isopropanesulfonylmethyl group, butanesulfonylmethyl group, isobutanesulfonylmethyl group, t-butanesulfonylmethyl group, 2-methanesulfonylethyl group, 3-methanesulfonylpropyl group Group, 4-methanesulfonylbutyl group, 5-methanesulfonylpentyl group, 2-ethanesulfonylethyl group, 3-ethanesulfonylpropyl group, 4-ethanesulfonylbutyl group, 5-ethanesulfonylpentyl group, 2-propanesulfonylethyl group 3-propanesulfonylpropyl group, 4-propanesulfonylbutyl group, 5-propanesulfonylpentyl group, 2-butanesulfonylethyl group, 3-butanesulfonylpropyl group, 4-butanesulfonylbutyl group , 5-butane sulfonyl pentyl group, and the like.

"C3-C10 cycloalkyl group optionally substituted with one or more groups selected from group D" means cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group , Cyclodecyl group, methylcyclopropyl group, 1,1-dimethylcyclopropyl group, ethylcyclopropyl group, propylcyclopropyl group, butylcyclopropyl group, pentylcyclopropyl group, 2-methylcyclohexyl group, 2-ethylcyclohexyl group, 2-propylcyclohexyl group, 2-butylcyclohexyl group, 2-pentylcyclohexyl group, 3-methylcyclohexyl group, 3-ethylcyclohexyl group, 3-propylcyclohexyl group, 3-butylcyclohexyl group, 3-pentylcyclohexyl 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4-butylcyclohexyl group, 4-pentylcyclohexyl group, fluorocyclopropyl group, chlorocyclopropyl group, 1,1-difluorocyclopropyl group, Examples include 1,1-dichlorocyclopropyl group, 2-fluorocyclohexyl group, 3-fluorocyclohexyl group, 4-fluorocyclohexyl group, 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, and the like.

Examples of the “phenyl group optionally substituted with one or more groups selected from group E” include phenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3 -Chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group,
2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, 2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group, 2-methylphenyl group, 3-methylphenyl group, 4- Methylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl Group, 4-isopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2-isobutylphenyl group, 3-isobutylphenyl group, 4-isobutylphenyl group, 2-t-butylphenyl Group, 3-t-butylphenyl group, 4-t-butylphenyl group, 2-pentylphenyl group, -Hexylphenyl group, 4-heptylphenyl group, 2-octylphenyl group, 3-nonylphenyl group, 4-decylphenyl group, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethyl Phenyl group, 2- (2,2,2-trifluoroethyl) phenyl group, 3- (3,3,3-trifluoropropyl) phenyl group, 4- (4,4,4-trifluorobutyl) phenyl group 2- (5,5,5-trifluoropentyl) phenyl group, 3- (6,6,6-trifluorohexyl) phenyl group, 4- (7,7,7-trifluoroheptyl) phenyl group, 2 -(8,8,8-trifluorooctyl) phenyl group, 3- (9,9,9-trifluorononyl) phenyl group, 4- (10,10,10-trifluorode) ) Phenyl group,
2-cyclopropylphenyl group, 3-cyclopropylphenyl group, 4-cyclopropylphenyl group, 2-cyclobutylphenyl group, 3-cyclopentylphenyl group, 4-cyclohexylphenyl group, 2-cycloheptylphenyl group, 3-cyclo Octylphenyl group, 4-cyclononylphenyl group, 2-cyclodecylphenyl group, 3- (methylcyclopropyl) phenyl group, 4- (1,1-dimethylcyclopropyl) phenyl group, 3- (fluorocyclopropyl) phenyl Group, 4- (chlorocyclopropyl) phenyl group, 2- (1,1-difluorocyclopropyl) phenyl group, 3- (1,1-dichlorocyclopropyl) phenyl group, 4- (2-fluorocyclohexyl) phenyl group 4- (2-chlorocyclohexyl) phenyl group,
2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-trifluoromethoxyphenyl group, 3-trifluoromethoxyphenyl group, 4-trifluoromethoxyphenyl group, 2-ethoxyphenyl group, 3- Propoxyphenyl group, 4-butoxyphenyl group,
2-methylthiophenyl group, 3-methylthiophenyl group, 4-methylthiophenyl group, 2-trifluoromethylthiophenyl group, 3-trifluoromethylthiophenyl group, 4-trifluoromethylthiophenyl group, 2-ethylthiophenyl group, 3 -Propylthiophenyl group, 4-butylthiophenyl group,
2-methanesulfinylphenyl group, 3-methanesulfinylphenyl group, 4-methanesulfinylphenyl group, 2-methanesulfinylphenyl group, 3-methanesulfinylphenyl group, 4-methanesulfinylphenyl group, 2-ethylsulfinylphenyl group, 3 -Propylsulfinylphenyl group, 4-butylsulfinylphenyl group,
2-methanesulfonylphenyl group, 3-methanesulfonylphenyl group, 4-methanesulfonylphenyl group, 2-methanesulfonylphenyl group, 3-methanesulfonylphenyl group, 4-methanesulfonylphenyl group, 2-ethylsulfonylphenyl group, 3 -Propylsulfonylphenyl group, 4-butylsulfonylphenyl group,
2-acetylphenyl group, 3-acetylphenyl group, 4-acetylphenyl group, 2-difluoroacetylphenyl group, 3-trifluoroacetylphenyl group, 4-dichloroacetylphenyl group, 2-trichloroacetylphenyl group, 3-propa Noylphenyl group, 4-butanoylphenyl group, 2-isobutanoylphenyl group, 3-pentanoylphenyl group, 4-pivaloylphenyl group,
2- (methoxycarbonyl) phenyl group, 3- (methoxycarbonyl) phenyl group, 4- (methoxycarbonyl) phenyl group, 2- (trifluoromethoxycarbonyl) phenyl group, 3- (trichloromethoxycarbonyl) phenyl group, 4- (Ethoxycarbonyl) phenyl group, 2- (propoxycarbonyl) phenyl group, 3- (isopropoxycarbonyl) phenyl group, 4- (butoxycarbonyl) phenyl group,
2-acetoxyphenyl group, 3-acetoxyphenyl group, 4-acetoxyphenyl group, 2-difluoroacetoxyphenyl group, 3-trifluoroacetoxyphenyl group, 4-trichloroacetoxyphenyl group, 2-propanoyloxyphenyl group, 3- Examples include butanoyloxyphenyl group, 4-isobutanoyloxyphenyl group, 2-pentanoyloxyphenyl group and 3-pivaloyloxyphenyl group.

  Examples of the “C1-C4 chain hydrocarbon group” include a methyl group, an ethyl group, an ethynyl group, a propyl group, an isopropyl group, an allyl group, a propargyl group, a butyl group, an isobutyl group, and a t-butyl group.

Examples of the “C1-C10 chain hydrocarbon group optionally substituted with one or more groups selected from group C” include a cyclopropylmethyl group, a cyclopropylethyl group, a cyclopropylpropyl group, a cyclopropylbutyl group, A cyclopropylpentyl group,
Methyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, iodomethyl group, chlorodifluoromethyl group,
Ethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group, perfluoroethyl group, 2-chloroethyl group, 2,2,2-trichloroethyl group, 2-bromoethyl group, 2-iodoethyl group, Chlorodifluoromethyl group,
Propyl group, 3-fluoropropyl group, 3,3,3-trifluoropropyl group, perfluoropropyl group, isopropyl group, 2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl group, perfluoro Isopropyl group, 3-chloropropyl group, 3,3,3-trichloropropyl group, 3-bromopropyl group, 3-iodopropyl group,
Butyl group, 4-fluorobutyl group, 4,4,4-trifluorobutyl group, perfluorobutyl group, 4-chlorobutyl group, 4,4,4-trichlorobutyl group, 4-bromobutyl group, 4-iodobutyl group, s-butyl group, t-butyl group,
Pentyl group, 5-fluoropentyl group, 5,5,5-trifluoropentyl group, perfluoropentyl group, 5-chloropentyl group, 5,5,5-trichloropentyl group, 5-bromopentyl group, 5-iodo Pentyl group,
Hexyl group, 6,6,6-trifluorohexyl group, 6-chlorohexyl group,
Heptyl group, 7,7,7-trifluoroheptyl group, 7-chloroheptyl group,
Octyl group, 8,8,8, -trifluorooctyl group, 8-chlorooctyl group,
Nonyl group, 9,9,9-trifluorononyl group, 9-chlorononyl group,
Decyl group, 10,10,10-trifluorodecyl group, 10-chlorodecyl group,
Cyanomethyl group, dicyanomethyl group, 2-cyanoethyl group, 2,2-dicyanoethyl group, 3-cyanopropyl group, 3,3-dicyanopropyl group, 4-cyanobutyl group, 4,4-dicyanobutyl group, 5-cyano Pentyl group, 5,5-dicyanopentyl group,
Methoxymethyl group, ethoxymethyl group, propoxymethyl group, isopropoxymethyl group, butoxymethyl group, isobutoxymethyl group, t-butoxymethyl group, 2-methoxyethyl group, 3-methoxypropyl group, 4-methoxybutyl group, 5-methoxypentyl group, 2-ethoxyethyl group, 3-ethoxypropyl group, 4-ethoxybutyl group, 5-ethoxypentyl group, 2-propoxyethyl group, 3-propoxypropyl group, 4-propoxybutyl group, 5- Propoxypentyl group, 2-butoxyethyl group, 3-butoxypropyl group, 4-butoxybutyl group, 5-butoxypentyl group,
Methylthiomethyl group, ethylthiomethyl group, propylthiomethyl group, isopropylthiomethyl group, butylthiomethyl group, isobutylthiomethyl group, t-butylthiomethyl group, 2-methylthioethyl group, 3-methylthiopropyl group, 4- Methylthiobutyl group, 5-methylthiopentyl group, 2-ethylthioethyl group, 3-ethylthiopropyl group, 4-ethylthiobutyl group, 5-ethylthiopentyl group, 2-propylthioethyl group, 3-propylthiopropyl group Group, 4-propylthiobutyl group, 5-propylthiopentyl group, 2-butylthioethyl group, 3-butylthiopropyl group, 4-butylthiobutyl group, 5-butylthiopentyl group,
Methanesulfinylmethyl group, ethanesulfinylmethyl group, propanesulfinylmethyl group, isopropanesulfinylmethyl group, butanesulfinylmethyl group, isobutanesulfinylmethyl group, t-butanesulfinylmethyl group, 2-methanesulfinylethyl group, 3-methanesulfinylpropyl group Group, 4-methanesulfinylbutyl group, 5-methanesulfinylpentyl group, 2-ethanesulfinylethyl group, 3-ethanesulfinylpropyl group, 4-ethanesulfinylbutyl group, 5-ethanesulfinylpentyl group, 2-propanesulfinylethyl group 3-propanesulfinylpropyl group, 4-propanesulfinylbutyl group, 5-propanesulfinylpentyl group, 2-butanesulfinylethyl group, 3-butanesulfy group Rupuropiru group, 4-Bed ethanesulfinyl butyl group, 5- butane sulfinyl point pen butyl group,
Methanesulfonylmethyl group, ethanesulfonylmethyl group, propanesulfonylmethyl group, isopropanesulfonylmethyl group, butanesulfonylmethyl group, isobutanesulfonylmethyl group, t-butanesulfonylmethyl group, 2-methanesulfonylethyl group, 3-methanesulfonylpropyl group Group, 4-methanesulfonylbutyl group, 5-methanesulfonylpentyl group, 2-ethanesulfonylethyl group, 3-ethanesulfonylpropyl group, 4-ethanesulfonylbutyl group, 5-ethanesulfonylpentyl group, 2-propanesulfonylethyl group 3-propanesulfonylpropyl group, 4-propanesulfonylbutyl group, 5-propanesulfonylpentyl group, 2-butanesulfonylethyl group, 3-butanesulfonylpropyl group, 4-butanesulfonylbutyl group And it includes 5-butane sulfonyl pentyl group.

  Examples of the “C1-C4 alkoxy group” include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, and a t-butoxy group.

  Examples of the “C1-C4 alkylthio group” include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, and a t-butylthio group.

  Examples of the “C1-C4 alkylsulfinyl group” include a methanesulfinyl group, an ethanesulfinyl group, a propanesulfinyl group, an isopropanesulfinyl group, a butanesulfinyl group, an isobutanesulfinyl group, and a t-butanesulfinyl group.

  Examples of the “C1-C4 alkylsulfonyl group” include a methanesulfonyl group, an ethanesulfonyl group, a propanesulfonyl group, an isopropanesulfonyl group, a butanesulfonyl group, an isobutanesulfonyl group, and a t-butanesulfonyl group.

Examples of the “C1-C4 alkoxy group optionally substituted with halogen” include a methoxy group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a chloromethoxy group, a dichloromethoxy group, a trichloromethoxy group, and a bromomethoxy group. , Dibromomethoxy group, iodomethoxy group, chlorodifluoromethoxy group,
Ethoxy group, 2-fluoroethoxy group, 2,2,2-trifluoroethoxy group, perfluoroethoxy group, 2-chloroethoxy group, 2,2,2-trichloroethoxy group, 2-bromoethoxy group, 2-iodo An ethoxy group,
Propoxy group, 3-fluoropropoxy group, 3,3,3-trifluoropropoxy group, perfluoropropoxy group, 2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropoxy group, perfluoroisopropoxy group Group, 3-chloropropoxy group, 3,3,3-trichloropropoxy group, 3-bromopropoxy group, 3-iodopropoxy group,
Butoxy group, 4-fluorobutoxy group, 4,4,4-trifluorobutoxy group, perfluorobutoxy group, 4-chlorobutoxy group, 4,4,4-trichlorobutoxy group, 4-bromobutoxy group and 4-iodo A butoxy group is mentioned.

Examples of the “C1-C4 alkylthio group optionally substituted with halogen” include, for example, methylthio group, fluoromethylthio group, difluoromethylthio group, trifluoromethylthio group, chloromethylthio group, dichloromethylthio group, trichloromethylthio group, bromomethylthio group , Dibromomethylthio group, iodomethylthio group, chlorodifluoromethylthio group,
Ethylthio group, 2-fluoroethylthio group, 2,2,2-trifluoroethylthio group, perfluoroethylthio group, 2-chloroethylthio group, 2,2,2-trichloroethylthio group, 2-bromoethyl A thio group, a 2-iodoethylthio group,
Propylthio group, 3-fluoropropylthio group, 3,3,3-trifluoropropylthio group, perfluoropropylthio group, 2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropylthio group, Fluoroisopropylthio group, 3-chloropropylthio group, 3,3,3-trichloropropylthio group, 3-bromopropylthio group, 3-iodopropylthio group,
Butylthio group, 4-fluorobutylthio group, 4,4,4-trifluorobutylthio group, perfluorobutylthio group, 4-chlorobutylthio group, 4,4,4-trichlorobutylthio group, 4-bromobutyl A thio group and a 4-iodobutylthio group are mentioned.

Examples of the “C1-C4 alkylsulfinyl group optionally substituted with halogen” include methanesulfinyl group, fluoromethanesulfinyl group, difluoromethanesulfinyl group, trifluoromethanesulfinyl group, chloromethanesulfinyl group, dichloromethanesulfinyl group, trichloromethane. Sulfinyl group, bromomethanesulfinyl group, dibromomethanesulfinyl group, iodomethanesulfinyl group, chlorodifluoromethanesulfinyl group,
Ethanesulfinyl group, 2-fluoroethanesulfinyl group, 2,2,2-trifluoroethanesulfinyl group, perfluoroethanesulfinyl group, 2-chloroethanesulfinyl group, 2,2,2-trichloroethanesulfinyl group, 2-bromoethanesulfinyl group Group, 2-iodoethanesulfinyl group,
Propanesulfinyl group, 3-fluoropropanesulfinyl group, 3,3,3-trifluoropropanesulfinyl group, perfluoropropanesulfinyl group, isopropanesulfinyl group, 2,2,2,2 ′, 2 ′, 2′-hexa Fluoroisopropanesulfinyl group, perfluoroisopropanesulfinyl group, 3-chloropropanesulfinyl group, 3,3,3-trichloropropanesulfinyl group, 3-bromopropanesulfinyl group, 3-iodopropanesulfinyl group,
Butanesulfinyl group, 4-fluorobutanesulfinyl group, 4,4,4-trifluorobutanesulfinyl group, perfluorobutanesulfinyl group, 4-chlorobutanesulfinyl group, 4,4,4-trichlorobutanesulfinyl group, 4-bromo Examples include butanesulfinyl group and 4-iodobutanesulfinyl group.

Examples of the “optionally substituted C1-C4 alkylsulfonyl group” include a methanesulfonyl group, a fluoromethanesulfonyl group, a difluoromethanesulfonyl group, a trifluoromethanesulfonyl group, a chloromethanesulfonyl group, a dichloromethanesulfonyl group, and trichloromethane. Sulfonyl group, bromomethanesulfonyl group, dibromomethanesulfonyl group, iodomethanesulfonyl group, chlorodifluoromethanesulfonyl group,
Ethanesulfonyl group, 2-fluoroethanesulfonyl group, 2,2,2-trifluoroethanesulfonyl group, perfluoroethanesulfonyl group, 2-chloroethanesulfonyl group, 2,2,2-trichloroethanesulfonyl group, 2-bromoethanesulfonyl Group, 2-iodoethanesulfonyl group,
Propanesulfonyl group, 3-fluoropropanesulfonyl group, 3,3,3-trifluoropropanesulfonyl group, perfluoropropanesulfonyl group, isopropanesulfonyl group, 2,2,2,2 ′, 2 ′, 2′-hexa Fluoroisopropanesulfonyl group, perfluoroisopropanesulfonyl group, 3-chloropropanesulfonyl group, 3,3,3-trichloropropanesulfonyl group, 3-bromopropanesulfonyl group, 3-iodopropanesulfonyl group,
Butanesulfonyl group, 4-fluorobutanesulfonyl group, 4,4,4-trifluorobutanesulfonyl group, perfluorobutanesulfonyl group, 4-chlorobutanesulfonyl group, 4,4,4-trichlorobutanesulfonyl group, 4-bromo A butanesulfonyl group and a 4-iodobutanesulfonyl group are mentioned.

Examples of the “(C1-C4 alkyl) carbonyl group optionally substituted with halogen” include an acetyl group, a fluoroacetyl group, a difluoroacetyl group, a trifluoroacetyl group, a chloroacetyl group, a dichloroacetyl group, a trichloroacetyl group, Bromoacetyl group, dibromoacetyl group, iodoacetyl group, chlorodifluoroacetyl group,
Propanoyl group, 3-fluoropropanoyl group, 3,3,3-trifluoropropanoyl group, perfluoropropanoyl group, 3-chloropropanoyl group, 3,3,3-trichloropropanoyl group, 3-bromopropanoyl group Noyl group, 3-iodopropanoyl group,
Butanoyl group, 4-fluorobutanoyl group, 4,4,4-trifluorobutanoyl group, perfluorobutanoyl group, 3,3,3,3 ′, 3 ′, 3′-hexafluoroisobutanoyl group, Perfluoroisobutanoyl group, 4-chlorobutanoyl group, 4,4,4-trichlorobutanoyl group, 4-bromobutanoyl group, 4-iodobutanoyl group, isobutanoyl group, 2,2,2,2 ′ , 2 ′, 2′-hexafluoroisobutanoyl group, perfluoroisobutanoyl group,
Pentanoyl group, 5-fluoropentanoyl group, 5,5,5-trifluoropentanoyl group, perfluoropentanoyl group, 5-chloropentanoyl group, 5,5,5-trichloropentanoyl group, 5-bromopenta Examples include a noyl group, a 5-iodopentanoyl group, and a pivaloyl group.

Examples of the “(C1-C4 alkoxy) carbonyl group optionally substituted with halogen” include a methoxycarbonyl group, a fluoromethoxycarbonyl group, a difluoromethoxycarbonyl group, a trifluoromethoxycarbonyl group, a chloromethoxycarbonyl group, and a dichloromethoxycarbonyl group. Group, trichloromethoxycarbonyl group, bromomethoxycarbonyl group, dibromomethoxycarbonyl group, iodomethoxycarbonyl group, chlorodifluoromethoxycarbonyl group,
Ethoxycarbonyl group, 2-fluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, perfluoroethoxycarbonyl group, 2-chloroethoxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, 2-bromo Ethoxycarbonyl group, 2-iodoethoxycarbonyl group,
Propoxycarbonyl group, 3-fluoropropoxycarbonyl group, 3,3,3-trifluoropropoxycarbonyl group, perfluoropropoxycarbonyl group, isopropoxycarbonyl group, 2,2,2,2 ′, 2 ′, 2′-hexa Fluoroisopropoxycarbonyl group, perfluoroisopropoxycarbonyl group, 3-chloropropoxycarbonyl group, 3,3,3-trichloropropoxycarbonyl group, 3-bromopropoxycarbonyl group, 3-iodopropoxycarbonyl group,
Butoxycarbonyl group, 4-fluorobutoxycarbonyl group, 4,4,4-trifluorobutoxycarbonyl group, perfluorobutoxycarbonyl group, 4-chlorobutoxycarbonyl group, 4,4,4-trichlorobutoxycarbonyl group, 4-bromo A butoxycarbonyl group, a 4-iodobutoxycarbonyl group, and a t-butoxycarbonyl group are mentioned.

Examples of the “(C1-C4 alkyl) carbonyloxy group optionally substituted with halogen” include, for example, an acetoxy group, a fluoroacetoxy group, a difluoroacetoxy group, a trifluoroacetoxy group, a chloroacetoxy group, a dichloroacetoxy group, and a trichloroacetoxy group Bromoacetoxy group, dibromoacetoxy group, iodoacetoxy group, chlorodifluoroacetoxy group,
Propanoyloxy group, 3-fluoropropanoyloxy group, 3,3,3-trifluoropropanoyloxy group, perfluoropropanoyloxy group, 3-chloropropanoyloxy group, 3,3,3-trichloropropanoyl An oxy group, a 3-bromopropanoyloxy group, a 3-iodopropanoyloxy group,
Butanoyloxy group, 4-fluorobutanoyloxy group, 4,4,4-trifluorobutanoyloxy group, perfluorobutanoyloxy group, isobutanoyloxy group, 3,3,3,3 ′, 3 ′ , 3′-hexafluoroisobutanoyloxy group, perfluoroisobutanoyloxy group, 4-chlorobutanoyloxy group, 4,4,4-trichlorobutanoyloxy group, 4-bromobutanoyloxy group, 4- Iodobutanoyloxy group, pentanoyloxy group, 5-fluoropentanoyloxy group, 5,5,5-trifluoropentanoyloxy group, perfluoropentanoyloxy group, 5-chloropentanoyloxy group, 5,5 , 5-trichloropentanoyloxy group, 5-bromopentanoyloxy group, 5-iodopentanoyloxy group and piva Yloxy group, and the like.

  Examples of the “C1-C5 alkyl group” include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, and a pentyl group.

Examples of the “C1-C10 chain hydrocarbon group optionally substituted with halogen” include a methyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, Bromomethyl group, dibromomethyl group, iodomethyl group, chlorodifluoromethyl group,
Ethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group, perfluoroethyl group, 2-chloroethyl group, 2,2,2-trichloroethyl group, 2-bromoethyl group, 2-iodoethyl group,
Propyl group, 3-fluoropropyl group, 3,3,3-trifluoropropyl group, perfluoropropyl group, isopropyl group, 2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl group, perfluoro Isopropyl group, 3-chloropropyl group, 3,3,3-trichloropropyl group, 3-bromopropyl group, 3-iodopropyl group,
Butyl group, 4-fluorobutyl group, 4,4,4-trifluorobutyl group, perfluorobutyl group, 4-chlorobutyl group, 4,4,4-trichlorobutyl group, 4-bromobutyl group, 4-iodobutyl group, s-butyl group, t-butyl group,
Pentyl group, 5-fluoropentyl group, 5,5,5-trifluoropentyl group, perfluoropentyl group, 5-chloropentyl group, 5,5,5-trichloropentyl group, 5-bromopentyl group and 5-iodo A pentyl group is mentioned.

As an aspect of this invention compound, the following amide compounds are mentioned, for example.
An amide compound in which R ¹ or R ² in formula (1) is a C1-C5 chain hydrocarbon group which may be substituted with halogen or halogen;
An amide compound in which R ¹ or R ² in formula (1) is a methyl group or halogen optionally substituted with halogen;
An amide compound in which R ¹ or R ² is a methyl group in formula (1);
An amide compound in which R ¹ or R ² is a trifluoromethyl group in formula (1);
An amide compound in which R ¹ or R ² is fluorine in formula (1);
An amide compound in which R ¹ or R ² is chlorine in formula (1);
as well as,
An amide compound in which R ¹ or R ² is bromine in formula (1).

〔式中、Ｒ¹及びＲ²は前記と同じ意味を表す。〕
該反応は、通常溶媒の存在下で行われる。
該反応に用いられる溶媒としては、例えばテトラヒドロフラン（以下、ＴＨＦと記す場合がある。）、エチレングリコールジメチルエーテル、ｔｅｒｔ−ブチルメチルエーテル（以下、ＭＴＢＥと記す場合がある。）等のエーテル類、ヘキサン、へプタン、オクタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、クロロベンゼン等のハロゲン化炭化水素類、酢酸ブチル、酢酸エチル等のエステル類、アセトニトリル等のニトリル類、Ｎ，Ｎ−ジメチルホルムアミド（以下、ＤＭＦと記す場合がある。）等の酸アミド類、ジメチルスルホキシド（以下、ＤＭＳＯと記す場合がある。）等のスルホキシド類及びこれらの混合物が挙げられる。
該反応に用いられる脱水縮合剤としては、１−エチル−３−（３−ジメチルアミノプロピル）カルボジイミド塩酸塩（以下、ＷＳＣと記す。）、ベンゾトリアゾール−１−イルオキシ）トリス（ジメチルアミノ）ホスホニウムヘキサフルオロホスフェート（以下、ＢＯＰ試薬と記す。）及び１，３−ジシクロヘキシルカルボジイミド等が挙げられる。
該反応には化合物（２）１モルに対して、化合物（３）が通常１〜３モルの割合、脱水縮合剤が通常１〜５モルの割合で用いられる。
該反応の反応温度は、通常０〜２００℃の範囲である。該反応の反応時間は通常１〜２４時間の範囲である。
該反応において、ＢＯＰ試薬を使用する場合は、必要に応じて塩基の存在下で反応を行う。かかる塩基としては、例えばトリエチルアミン、ジイソプロピルエチルアミン等の第３級アミン類及びピリジン、４−ジメチルアミノピリジン等の含窒素芳香族化合物類等が挙げられる。
該反応には化合物（２）１モルに対して、塩基が通常１〜１０モルの割合で用いられる。
反応終了後は、反応混合物に水を加えた後、有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、本発明化合物を単離することができる。単離された本発明化合物は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 1)
The compound of the present invention or a salt thereof can be produced by reacting the compound (3) or a salt thereof with the compound (2) in the presence of a dehydration condensing agent.

[Wherein, R ¹ and R ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as tetrahydrofuran (hereinafter sometimes referred to as THF), ethylene glycol dimethyl ether, tert-butyl methyl ether (hereinafter sometimes referred to as MTBE), hexane, Aliphatic hydrocarbons such as heptane and octane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorobenzene, esters such as butyl acetate and ethyl acetate, nitriles such as acetonitrile, N, Examples thereof include acid amides such as N-dimethylformamide (hereinafter sometimes referred to as DMF), sulfoxides such as dimethyl sulfoxide (hereinafter sometimes referred to as DMSO), and mixtures thereof.
Examples of the dehydrating condensing agent used in the reaction include 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (hereinafter referred to as WSC), benzotriazol-1-yloxy) tris (dimethylamino) phosphonium hexa Examples thereof include fluorophosphate (hereinafter referred to as BOP reagent) and 1,3-dicyclohexylcarbodiimide.
In the reaction, with respect to 1 mol of the compound (2), the compound (3) is usually used in a proportion of 1 to 3 mol, and the dehydrating condensing agent is usually used in a proportion of 1 to 5 mol.
The reaction temperature of the reaction is usually in the range of 0 to 200 ° C. The reaction time is usually in the range of 1 to 24 hours.
In the reaction, when a BOP reagent is used, the reaction is performed in the presence of a base as necessary. Examples of such bases include tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.
In the reaction, the base is usually used at a ratio of 1 to 10 mol per 1 mol of the compound (2).
After completion of the reaction, the compound of the present invention can be isolated by performing post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer. The isolated compound of the present invention can be further purified by chromatography, recrystallization and the like.

〔式中、Ｒ¹及びＲ²は前記と同じ意味を表す。〕
該反応は、通常溶媒の存在下で行われる。
該反応に用いられる溶媒としては、例えばＴＨＦ、エチレングリコールジメチルエーテル、ＭＴＢＥ等のエーテル類、ヘキサン、へプタン、オクタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、クロロベンゼン等のハロゲン化炭化水素類、酢酸ブチル、酢酸エチル等のエステル類、アセトニトリル等のニトリル類、ＤＭＦ等の酸アミド類、ＤＭＳＯ等のスルホキシド類及びこれらの混合物が挙げられる。
該反応に用いられる塩基としては、炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩類、トリエチルアミン、ジイソプロピルエチルアミン等の第３級アミン類及びピリジン、４−ジメチルアミノピリジン等の含窒素芳香族化合物類等が挙げられる。
該反応には化合物（４）１モルに対して、化合物（３）が通常１〜３モルの割合、塩基が通常１〜１０モルの割合で用いられる。
該反応の反応温度は通常−２０〜１４０℃の範囲である。該反応の反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、本発明化合物を単離することができる。単離された本発明化合物は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 2)
The compound of the present invention can be produced by reacting compound (3) or a salt thereof with compound (4) or a salt thereof in the presence of a base.

[Wherein, R ¹ and R ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, and MTBE, aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as toluene and xylene, and chlorobenzene. Examples thereof include halogenated hydrocarbons, esters such as butyl acetate and ethyl acetate, nitriles such as acetonitrile, acid amides such as DMF, sulfoxides such as DMSO, and mixtures thereof.
Examples of the base used in the reaction include alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine. Can be mentioned.
In the reaction, with respect to 1 mol of the compound (4), the compound (3) is usually used in a proportion of 1 to 3 mol, and the base is usually used in a proportion of 1 to 10 mol.
The reaction temperature is usually in the range of -20 to 140 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound of the present invention can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound of the present invention can be further purified by chromatography, recrystallization and the like.

〔式中、Ｒ¹及びＲ²は前記と同じ意味を表す。〕 (Production method 3)
The compound of the present invention can be produced, for example, from compound (5) according to the following scheme.

[Wherein, R ¹ and R ² represent the same meaning as described above. ]

Step (I-1)
Compound (6) can be produced by reacting compound (5) with compound (3) or a salt thereof in the presence of a dehydration condensing agent.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, and MTBE, aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as toluene and xylene, and chlorobenzene. Examples thereof include halogenated hydrocarbons, esters such as butyl acetate and ethyl acetate, nitriles such as acetonitrile, acid amides such as DMF, sulfoxides such as DMSO, and mixtures thereof.
Examples of the dehydrating condensing agent used in the reaction include WSC, BOP reagent, and 1,3-dicyclohexylcarbodiimide.
In the reaction, with respect to 1 mol of the compound (5), the compound (3) is usually used in a proportion of 1 to 3 mol, and the dehydrating condensing agent is usually used in a proportion of 1 to 5 mol.
The reaction temperature of the reaction is usually in the range of 0 to 200 ° C. The reaction time is usually in the range of 1 to 24 hours.
In the reaction, when a BOP reagent is used, the reaction is performed in the presence of a base as necessary. Examples of such bases include tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.
In the reaction, the base is usually used at a ratio of 1 to 10 mol per 1 mol of the compound (5).
After completion of the reaction, the compound (6) can be isolated by performing post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer. The isolated compound (6) can be further purified by chromatography, recrystallization and the like.

Step (I-2)
The compound of the present invention can be produced by reacting the compound (6) with an acid.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, sulfoxides such as DMSO, methanol, ethanol, 2-methylethanol and the like. Alcohols, acetones, ketones such as methyl ethyl ketone and methyl isobutyl ketone, water, and mixtures thereof.
Examples of the acid used in the reaction include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as trifluoroacetic acid, p-toluenesulfonic acid, and methanesulfonic acid.
In the reaction, the acid is usually used in an amount of 1 mol to excess with respect to 1 mol of the compound (6).
The reaction temperature of the reaction is usually in the range of 0 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound of the present invention can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound of the present invention can be further purified by chromatography, recrystallization and the like.

  The compound of the present invention can form an agriculturally acceptable salt. Such a salt of the compound of the present invention is usually a salt of the compound of the present invention and an acid. Examples of the salt with an acid include inorganic acid salts such as hydrochloride, hydrobromide, and sulfate, and organic acid salts such as methanesulfonate, formate, acetate, and trifluoroacetate.

〔式中、Ｒ¹及びＲ²は前記と同じ意味を表すし、ＨＸは酸を表す。〕
該反応は、溶媒の存在下又は溶媒の非存在下で行われる。
該反応に用いられる溶媒としては、例えばＴＨＦ、エチレングリコールジメチルエーテル、ＭＴＢＥ等のエーテル類、ヘキサン、へプタン、オクタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、水及びこれらの混合物が挙げられる。
該反応に用いられる酸としては、例えば塩酸、臭化水素酸、ヨウ化水素酸、硫酸等の無機酸、酢酸、トリフルオロ酢酸、ギ酸、ｐ−トルエンスルホン酸、メタンスルホン酸等の有機酸が挙げられる。
該反応には本発明化合物１モルに対して、酸が通常１〜１００モルの割合で用いられる。
該反応の反応温度は、通常０〜２００℃の範囲である。該反応の反応時間は通常１〜２４時間の範囲である。
反応終了後は、未反応の酸を除去して本発明化合物と酸との塩を単離することができる。 The salt of this invention compound and an acid can be manufactured by making this invention compound react with an acid.

[Wherein R ¹ and R ² represent the same meaning as described above, and HX represents an acid. ]
The reaction is performed in the presence of a solvent or in the absence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, and MTBE, aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as toluene and xylene, water, and the like. Of the mixture.
Examples of the acid used in the reaction include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, and sulfuric acid, and organic acids such as acetic acid, trifluoroacetic acid, formic acid, p-toluenesulfonic acid, and methanesulfonic acid. Can be mentioned.
In the reaction, an acid is usually used at a ratio of 1 to 100 mol with respect to 1 mol of the compound of the present invention.
The reaction temperature of the reaction is usually in the range of 0 to 200 ° C. The reaction time is usually in the range of 1 to 24 hours.
After completion of the reaction, the salt of the compound of the present invention and the acid can be isolated by removing the unreacted acid.

  The plant disease control agent of the present invention contains the compound of the present invention or a salt thereof and an inert carrier (solid carrier, liquid carrier or gas carrier). The plant disease control agent of the present invention is further mixed with a surfactant and other formulation adjuvants, wettable powder, granular wettable powder, flowable powder, granules, dry flowable powder, emulsion, aqueous liquid, oil, Formulated into smoking agents, aerosols, microcapsules and the like. These preparations contain the compound of the present invention or a salt thereof in a weight ratio of usually 0.1 to 99%, preferably 0.2 to 90%.

  Examples of the solid support include clays (for example, kaolin, diatomaceous earth, synthetic hydrous silicon oxide, wax clay, bentonite, acid clay, talc), and other inorganic minerals (for example, sericite, quartz powder, sulfur powder, activated carbon). , Calcium carbonate, hydrated silica) and the like. Examples of the liquid carrier include water, alcohols (eg, methanol, ethanol), ketones (eg, acetone, methyl ethyl ketone), aromatic hydrocarbons (eg, benzene, toluene, xylene, ethylbenzene, methylnaphthalene), fat Group hydrocarbons (eg, hexane, cyclohexanone, kerosene), esters (eg, ethyl acetate, butyl acetate), nitriles (eg, acetonitrile, isobutyronitrile), ethers (eg, dioxane, diisopropyl ether), Acid amides (for example, dimethylformamide, dimethylacetamide), halogenated hydrocarbons (for example, dichloroethane, trichloroethylene, carbon tetrachloride) and the like can be mentioned. Examples of the gaseous carrier include dimethyl ether and carbon dioxide.

  Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylene compounds thereof, polyoxyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives. Etc.

  Other formulation adjuvants include, for example, fixing agents, dispersants, thickeners, wetting agents, extenders and antioxidants, specifically casein, gelatin, polysaccharides (eg starch, arabic gum, cellulose derivatives, Alginic acid), lignin derivatives, bentonite, saccharides, synthetic water-soluble polymers (eg, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids), PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4) -Methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil, fatty acid or ester thereof, and the like.

The compound of the present invention or a salt thereof is used for controlling plant diseases by applying to plants or soil where plants grow. Examples of the method of applying the compound of the present invention or a salt thereof to the plant or the soil where the plant grows include, for example, a method of spraying foliage on the plant, a method of applying to the soil where the plant is cultivated, and a method of applying to the plant seed. It is done.
In the plant disease control method of the present invention, the plant disease control agent of the present invention is usually used.
In the case where the plant disease control agent of the present invention is used in a method of spraying foliage on a plant or a method of applying to a soil where plants are cultivated, the application amount of the plant disease control agent of the present invention is 1,000 m ^{2 at the} application site. The ratio of the present compound or its salt is usually 1 to 500 g, preferably 2 to 200 g. When the plant disease control agent of the present invention is formulated into an emulsion, wettable powder, suspension, etc., the concentration of the compound of the present invention or a salt thereof is usually 0.0005 to 2% by weight, preferably It is diluted with water so as to be 0.005 to 1% by weight. When the plant disease control agent of the present invention is formulated into a powder, granule or the like, the formulation is applied as it is without dilution.
When used in the method of applying the plant disease control agent of the present invention to plant seeds, the application amount of the plant disease control agent of the present invention is usually 0.001 to 1 kg of the compound of the present invention or a salt thereof per 1 kg of seed. The ratio is 100 g, preferably 0.01 to 50 g.

The plant disease control agent of the present invention can be mixed and / or used in combination with other fungicides, insecticides, acaricides, nematicides, herbicides, plant growth regulators, fertilizers or soil conditioners.
Examples of the active ingredient of such a bactericide include the following.

(1) Azole bactericidal active compounds propiconazole, prothioconazole, triadimenol, prochloraz, penconazole, zebolazole, tebuconazole diconazole, bromuconazole, epoxiconazole, difenoconazole, cyproconazole, metconazole, metconazole, metconazole ), Tetraconazole, microbutanil, fenbuconazole, hexaconazole, fluquinconazole, triticonazole, triticonazole. (Imazalil), flutriafol, simeconazole, ipconazole, etc .;

(2) Amine bactericidal active compounds fenpropimorph, tridemorph, fenpropidin, spiroxamine and the like;

(3) benzimidazole bactericidal active compounds carbendazim, benomyl, thiabendazole, thiophanate-methyl and the like;

(4) Dicarboximide bactericidal active compound procymidone, iprodione, vinclozolin and the like;

(5) Anilinopyrimidine bactericidal active compounds cyprodinil, pyrimethanil, mepanipyrim and the like;

(6) Phenylpyrrole bactericidal active compound fenpiclonil, fludioxonil and the like;

(7) strobilurin bactericidal active compounds cresoxim-methyl, azoxystrobin, trifloxystrobin, floxastrobin, picoxystrobin (picoxystrobibin) pyraclostrobin, dimoxystrobin, pyribencarb, methinostrobin, oryzatrobin, enestrobin, etc .;

(8) Phenylamide bactericidal active compounds metalaxyl, metalaxyl M or mefenoxam, benalaxyl, benalaxyl M or kiraxyl-ra

(9) Carboxylic acid amide bactericidal active compounds dimethomorph, iprovarialcarb, benchavaricarb-isopropyl, mandipropamide, varifenal

(10) Carboxylic acid bactericidal active compounds carboxin, mepronil, flutolanil, tifluzamide, furamethpyr, boscalid, penthipyrofylpentylpyrpentyl Bixafen,

(11) Other bactericidal active compounds dietophane carb; thiuram; fluazinam; mancozeb; chlorothalonil; captan; diclofluuride; folpette; Flusulfamide; fluorpicolide; focetyl; simoxanil; penclone; tolcrofosmethyl; carpropamide; diclocimet; phenoxanil; tricyclazole; pyroxilone; probenazole; ;I Oxolinic acid; oxytetracycline; streptomycin; basic copper chloride; cupric hydroxide; basic copper sulfate; organic copper;

〔式中、Ｘ¹は水素、またはハロゲンを表し、Ｘ²はメチル基、ジフルオロメチル基、又はトリフルオロメチル基を表し、Ｑは下記のいずれかの基

を表す。〕
で示されるピラゾールカルボン酸アミド化合物； Formula (8)

[Wherein, X ¹ represents hydrogen or halogen, X ² represents a methyl group, a difluoromethyl group, or a trifluoromethyl group, and Q represents any of the following groups:

Represents. ]
A pyrazolecarboxylic acid amide compound represented by:

〔式中、Ｘ³はメチル基、ジフルオロメチル基、またはエチル基を表し、Ｘ⁴はメトキシ基、またはメチルアミノ基を表し、Ｘ⁵はフェニル基、２−メチルフェニル基、または２，５−ジメチルフェニル基を表す。〕
で示されるα−アルコキシフェニル酢酸化合物； Formula (9)

[Wherein, X ³ represents a methyl group, a difluoromethyl group or an ethyl group, X ⁴ represents a methoxy group or a methylamino group, X ⁵ represents a phenyl group, a 2-methylphenyl group, or 2,5- Represents a dimethylphenyl group. ]
An α-alkoxyphenylacetic acid compound represented by:

〔式中、Ｘ⁶はメトキシ基、エトキシ基、プロポキシ基、２−プロペニルオキシ基、２−プロピニルオキシ基、３−ブテニルオキシ基、３−ブチニルオキシ基、メチルチオ基、エチルチオ基、または２−プロペニルチオ基を表し、Ｘ⁷は１−メチルエチル基、または１−メチルプロピル基を表し、Ｘ⁸は２−メチルフェニル基、または２，６−ジクロロフェニル基を表す。〕
で示されるピラゾリノン化合物。 Formula (10)

[Wherein, X ⁶ is a methoxy group, an ethoxy group, a propoxy group, a 2-propenyloxy group, a 2-propynyloxy group, a 3-butenyloxy group, a 3-butynyloxy group, a methylthio group, an ethylthio group, or a 2-propenylthio group. X ⁷ represents a 1-methylethyl group or a 1-methylpropyl group, and X ⁸ represents a 2-methylphenyl group or a 2,6-dichlorophenyl group. ]
A pyrazolinone compound represented by:

Examples of the active ingredient of such an insecticide include the following.
(1) Organophosphorus insecticidal active compounds: acephate, aluminum phosphide, butathiofos, cadusafos, chlorethoxyphos, chlorfenvinphos, chlorfenvinphos , Chlorpyrifos-methyl, Cyanophos (CYAP), Diazinon, DCIP (Dichlorodipropionether), Dichlorfenthion (ECP), Dichlorvos (DchloV) Dimethoate, dimethylvinphos, disulfoton, EPN, etion, ethoprofos, etrimfos, fentione: MPP, fenitrothion, EP fothiazate, formothion (formulation), hydrogen phosphide (isofenphos), isoxathion (isoxathion), malathion (mesulfenfos), DM thiothion , Monocrotophos, nared (BRP), oxydeprofos (ESP), parathion, fosarone, phosmet (PMP), pirimiphosentyl (pyrimimiphosentythiophene) ), Quinalphos, phentoate (PAP), profenofos, propopafos, prothiofos, pyrachlorfos, salithion, sulfilos ebupirimfos), temephos (temephos), tetrachlorvinphos bottle phosphite (tetrachlorvinphos), terbufos (terbufos), thiometon (thiometon), trichlorfon (trichlorphon: DEP), vamidothion (vamidothion), folate (phorate), cadusafos (cadusafos), and the like;

(2) Carbamate insecticidal active compounds alaniccarb, bendiocarb, benfuracarb, BPMC, carbaryl, carbofuran, carbosulfane, carbosulfane, carbosulfane Ethiofencarb, fenobucarb, phenothiocarb, phenoxycarb, furathiocarb, isoprocarb (MIPC), metholcarb, MIPC, etolcarb (Methiocarb), NAC, oxamyl (oxamyl), pirimicarb (pirimicarb), propoxur (propoxur: PHC), XMC, thiodicarb (thiodicarb), xylylcarb (xylylcarb), aldicarb (aldicarb) or the like;

(3) Synthetic Pyrethroid Insecticidal Compounds Acrinathrin, Allethrin, Benfluthrin, Beta-Cyfluthrin, Bifenthrin, Cycloprothrin, Cycloprothrin (Cyhalothrin), cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, fenvalerate Flunate, flufenprox, flumethrin, fluvalinate, halfenprox, imiprothrin, perthrin, threthrin, pelmethrin Resmethrin, sigma-cypermethrin, silafluofen, tefluthrin, tralomethrin, transfluthrin, transfluthrin, transfluthrin eteramethrin), phenothrin, cyphenothrin, alpha-cypermethrin, zeta-cypermethrin, lambda cithalthrin (lambda-thylmethrin) (Tau-flavinate), 2,3,5,6-tetrafluoro-4- (methoxymethyl) benzyl (EZ)-(1RS, 3RS; 1RS, 3SR) -2,2-dimethyl-3-prop-1- Enylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4-methylbenzyl (EZ)-(1RS, 3RS; 1RS, 3SR) -2,2- Methyl-3-prop-1-enylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4- (methoxymethyl) benzyl (1RS, 3RS; 1RS, 3SR) -2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate and the like;

(4) Nereistoxin insecticidal active compound cartap, bensultap, thiocyclam, monosultap, bisultap, etc .;

(5) Neonicotinoid insecticidal active compound imidacloprid, nitenpyram, acetamiprid, thiamethoxam, thiacloani, dinotefur, intefurandin

(6) Benzoylurea insecticidal active compound chlorfluazuron, bistrifluron, diafenthiuron, diflubenzuron, fluazuron, flucyclolon, flucyclofluron Phenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron, etc.

(7) Phenylpyrazole insecticidal active compounds acetoprole, etiprole, fipronil, vaniliprole, pyriprole, pyrafluprole, etc .;

(8) Bt toxin Live spores and produced crystal toxins derived from Bacillus thuringiensis, and mixtures thereof;

(9) Hydrazine insecticidal active compounds Chromafenozide, halofenozide, methoxyphenozide, tebufenozide and the like;

(10) Organochlorine compounds Aldrin, dieldrin, dienochlor, endosulfan, methoxychlor and the like;

(11) Other insecticides machine oil, nicotine sulfate (nicotine-sulfate);
Avermectin (avermectin-B), bromopropyrate, buprofezin, chlorphenapyr, cyromazine, D-D (1,3-Dichloropropene), D-D (1,3-Dichloropropene) fenazaquin, flupyrazofos, hydroprene, methoprene, indoxacarb, methoxadiazone, milbemyropymetropine, milbemycine Pyridalyl, pyriproxyfen, spinosad, sulfuramide, tolfenpyrad, triazemate, flubendiametic, flubendiamide , Benclothiaz, Calcium cyanamide, Calcium polysulfide, Chlordane, DDT, DSP, flufenerim, flurifammid , Formatenate, metham-ammonium, metham-sodium, methyl bromide, ninototefuran, potassium oleate, protastoleate profibutene, spiromesifen, sulfur, metaflumizone, spirotetramat, pyrifluinole, spinet tram, spinet tram

［式中、
Ｒ₁₀は、Ｍｅ、Ｃｌ、ＢｒまたはＦ、
Ｒ₂₀は、Ｆ、Ｃｌ、Ｂｒ、Ｃ１−Ｃ４ハロアルキル、またはＣ１−Ｃ４ハロアルコキシ、
Ｒ₃₀は、Ｆ、ＣｌまたはＢｒ、
Ｒ₄₀は、Ｈ、１以上のハロゲン；ＣＮ；ＳＭｅ；Ｓ（Ｏ）Ｍｅ；Ｓ（０）₂ＭｅおよびＯＭｅで置換されていてもよいＣ１−Ｃ４アルキル、Ｃ３−Ｃ４アルケニル、Ｃ３−Ｃ４アルキニル、または、Ｃ３−Ｃ５シクロアルキルアルキル、
Ｒ₅₀は、ＨまたはＭｅ、
Ｒ₆₀は、Ｈ、ＦまたはＣｌ、
Ｒ₇₀は、Ｈ、ＦまたはＣｌを表す。］で示される化合物、 Formula (11)

[Where:
R ₁₀ is Me, Cl, Br or F,
R ₂₀ is F, Cl, Br, C1-C4 haloalkyl, or C1-C4 haloalkoxy,
R ₃₀ is F, Cl or Br,
R ₄₀ is H, one or more halogen; CN; SMe; S (O) Me; C1-C4 alkyl, C3-C4 alkenyl, C3-C4 alkynyl optionally substituted with S (0) ₂ Me and OMe Or C3-C5 cycloalkylalkyl,
R ₅₀ is H or Me,
R ₆₀ is H, F or Cl,
R ₇₀ represents H, F or Cl. A compound represented by

［式中、Ｘは、Ｃｌ、ＢｒまたはＩを表す。］
で示される化合物。 Formula (12)

[Wherein X represents Cl, Br, or I. ]
A compound represented by

  Examples of the active ingredient of such an acaricide include, for example, acequinocyl, amitraz, benzoximate, bifenate, phenisobromolate, quinomethionate, chinomethionate, chlorobenzilate, CPCBS (chlorfenson), clofentezine, cyflumetofen, quercene, dioxol, etoxazole, fenbutatin phenothiophene Fenpyroximate, fluacrylpyrim, fluproxyfen, penthiridinepirpene, fenpyridine , Tetradiphon, spirodiclofen, spiromesifen, spirotetramat, amidoflumet, cienopyrafene ), And the like.

  Examples of the active ingredient of such a nematicide include DCIP, fostiazate, levamisole hydrochloride, methylisothiocyanate, morantartrate tartrate, and imiciafos.

  Examples of the active ingredient of such a plant growth regulator include ethephon, chlormequat-chloride, mepiquat-chloride, and the like.

  The plant disease control agent of the present invention can be used, for example, in agricultural lands such as fields, paddy fields, lawns, orchards. Examples of the “crop” in which the plant disease control agent of the present invention can be used include the following.

Agricultural crops: corn, rice, wheat, barley, rye, oats, sorghum, cotton, soybeans, peanuts, buckwheat, sugar beet, rapeseed, sunflower, sugarcane, tobacco, vegetables, solanaceous vegetables (eggplant, tomato, pepper, pepper, potato Cucumber, pumpkin, zucchini, watermelon, melon, etc., cruciferous vegetables (radish, turnip, horseradish, kohlrabi, cabbage, cabbage, mustard, broccoli, cauliflower, etc.), asteraceae (burdock, Shungiku, artichokes, lettuce, etc.), liliaceae vegetables (leek, onion, garlic, asparagus), celeryaceae vegetables (carrot, parsley, celery, red pepper, etc.), red crustacean vegetables (spinach, chard, etc.) (Perilla, mint, basil ), Strawberry, sweet potato, yam, taro, Jatropha, etc.,
Bridegroom,
Foliage plant,
Fruit trees; pears (apples, pears, Japanese pears, quince, quince, etc.), nuclear fruits (peaches, plums, nectarines, ume, sweet cherry, apricots, prunes, etc.), citrus (satsuma mandarin, orange, lemon, lime, grapefruit) ), Nuts (chestnut, walnut, hazel, almond, pistachio, cashew nut, macadamia nut, etc.), berries (blueberry, cranberry, blackberry, raspberry, etc.), grape, oyster, olive, loquat, banana, coffee, Date palm, coconut palm, etc.
Trees other than fruit trees: Cha, mulberry, flowering trees, street trees (ash, birch, dogwood, eucalyptus, ginkgo, lilac, maple, oak, poplar, redwood, fu, sycamore, zelkova, black bean, peach tree, Tsuga, rat, pine, Spruce, yew) etc.

  The “crop” includes crops to which traits such as resistance to herbicides, pest resistance, and disease resistance have been imparted by classical breeding methods or genetic recombination techniques.

  Examples of plant diseases in which the compound of the present invention or a salt thereof is effective include plant diseases caused by filamentous fungi, and specific examples include the following plant diseases.

Rice blast (Magnaporthe grisea), sesame leaf blight (Cochliobolus miyabeanus), blight (Rhizoctonia solani), idiot seedling (Gibberella fujikuroi);
Wheat diseases: powdery mildew (Erysiphe graminis), red mold (Fusarium graminearum, F. avenacerum, F. culmorum, Microdochium nivale), rust (Puccinia striiformis, P. graminis, P. recondita), red snow rot (Micronectriella nivale), Snowy rot granule nuclei (Typhula sp.), Bare scab (Ustilago tritici), Tuna scab (Tilletia caries), Eye rot (Pseudocercosporella herpotrichoides), Leaf blight (Mycosphaerella graminicola), Fu Blight (Stagonospora nodorum), macular disease (Pyrenophora tritici-repentis);
Barley diseases: powdery mildew (Erysiphe graminis), mildew (Fusarium graminearum, F. avenacerum, F. culmorum, Microdochium nivale), rust (Puccinia striiformis, P. graminis, P. hordei), naked scab ( Ustilago nuda), cloud disease (Rhynchosporium secalis), reticulum disease (Pyrenophora teres), spot disease (Cochliobolus sativus), leafy leaf disease (Pyrenophora graminea), Rhizoctonia solani (Rhizoctonia solani);
Citrus spot disease (Diaporthe citri), common scab (Elsinoe fawcetti), fruit rot (Penicillium digitatum, P. italicum), phytophthora disease (Phytophthora parasitica, Phytophthora citrophthora);
Monilinia mali, rot (Valsa ceratosperma), powdery mildew (Podosphaera leucotricha), spotted leaf (Alternaria alternata apple pathotype), black rot (Venturia inaequalis), anthracnose (Glomerella cingulata), plague (Phytophtora cactorum);
Pear black spot disease (Venturia nashicola, V. pirina), black spot disease (Alternaria alternata Japanese pear pathotype), red star disease (Gymnosporangium haraeanum);
Peach ash scab (Monilinia fructicola), black scab (Cladosporium carpophilum), Phomopsis sp. (Phomopsis sp.);

Grapes black rot (Elsinoe ampelina), late rot (Glomerella cingulata), powdery mildew (Uncinula necator), rust (Phakopsora ampelopsidis), black lot disease (Guignardia bidwellii), downy mildew (Plasmopara viticola);
Oyster anthracnose (Gloeosporium kaki), deciduous leaf disease (Cercospora kaki, Mycosphaerella nawae);
Colletotrichum lagenarium, powdery mildew (Sphaerotheca fuliginea), vine blight (Mycosphaerella melonis), vine split (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), plague (Phytophthora sp.) Seedling blight (Pythium sp.);
Tomato ring disease (Alternaria solani), leaf mold (Cladosporium fulvum), plague (Phytophthora infestans);
Eggplant brown spot (Phomopsis vexans), powdery mildew (Erysiphe cichoracearum);
Brassicaceae vegetable black spot (Alternaria japonica), white spot (Cercosporella brassicae);
Leek rust (Puccinia allii), soybean purpura (Cercospora kikuchii), black scab (Elsinoe glycines), sunspot (Diaporthe phaseolorum var. Sojae), rust (Phakopsora pachyrhizi), stem rot (Phytophthora sojae)
Green Bean Anthracnose (Colletotrichum lindemthianum)
Groundnut black rot (Cercospora personata), brown spot (Cercospora arachidicola), silkworm (Sclerotium rolfsii);
Pea powdery mildew (Erysiphe pisi);
Potato summer plague (Alternaria solani), plague (Phytophthora infestans), scarlet rot (Phytophthora erythroseptica), half body wilt (Verticillium albo-atrum, V. dahliae, V. nigrescens);
Strawberry powdery mildew (Sphaerotheca humuli);
Tea net blast (Exobasidium reticulatum); white spot (Elsinoe leucospila), ring spot (Pestalotiopsis sp.), Anthracnose (Colletotrichum theae-sinensis)
Tobacco red blight (Alternaria longipes), powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina), plague (Phytophthora nicotianae);

Sugar beet brown spot (Cercospora beticola), leaf rot (Thanatephorus cucumeris), root rot (Thanatephorus cucumeris), black root (Aphanomyces cochlioides);
Rose scab (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa);
Chrysanthemum brown spot (Septoria chrysanthemi-indici), white rust (Puccinia horiana);
Sunflower downy mildew (Plasmopara halstedii);
Onion white spot blight (Botrytis cinerea, B. byssoidea, B. squamosa), gray rot (Botrytis alli), sclerotia rot (Botrytis squamosa);
Various crops of gray mold (Botrytis cinerea), sclerotia (Sclerotinia sclerotiorum), seedling blight (Pythium aphanidermatum, P. debarianum, P. graminicola, P. irregulare, P. ultimum); Black soot disease (Alternaria brassicicola);
Shirah's dollar spot disease (Sclerotinia homeocarpa), Shiva brown patch disease and large patch disease (Rhizoctonia solani);
Viral diseases of various plants mediated by banana sigatoka disease (Mycosphaerella fijiensis, Mycosphaerella musicola, Pseudocercospora musae); and Polymixa spp. Or Olpidium spp.

  Hereinafter, although this invention is demonstrated in more detail by a manufacture example, a reference manufacture example, a formulation example, a test example, etc., this invention is not limited only to these examples.

  First, the manufacture example of this invention compound is shown.

２−アミノ−４−メチルチアゾール−５−カルボン酸０．４０ｇ、２−フルオロベンジルアミン０．２１ｇ、ＤＭＦ１．５ｍＬ及びトリエチルアミン０．１６ｇの混合物に、ＢＯＰ試薬０．７０ｇを加え、室温で１時間攪拌した。室温にて終夜放置し、反応混合物を飽和重曹水に注加した。その混合物を酢酸エチルで抽出し、水及び飽和食塩水で洗浄した。硫酸マグネシウムで乾燥し、減圧下で濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付して、２−アミノ−Ｎ−（２−フルオロベンジル）−４−メチルチアゾール−５−カルボン酸アミド（以下、本発明化合物（１）と記す。）を０．１７ｇ得た。
¹H-NMR (DMSO-d₆) δ［ppm］:2.34(3H, s), 4.40(2H, d, J=4.8Hz), 7.10-7.34(6H, m), 7.87(1H, t, J=4.8Hz) Production Example 1

To a mixture of 0.40 g of 2-amino-4-methylthiazole-5-carboxylic acid, 0.21 g of 2-fluorobenzylamine, 1.5 mL of DMF and 0.16 g of triethylamine, 0.70 g of BOP reagent was added, and the mixture was stirred at room temperature for 1 hour. Stir. The reaction mixture was allowed to stand at room temperature overnight and poured into a saturated aqueous sodium bicarbonate solution. The mixture was extracted with ethyl acetate and washed with water and saturated brine. Dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2-amino-N- (2-fluorobenzyl) -4-methylthiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (1)). 0.17 g was obtained.
¹ H-NMR (DMSO-d ₆ ) δ [ppm]: 2.34 (3H, s), 4.40 (2H, d, J = 4.8Hz), 7.10-7.34 (6H, m), 7.87 (1H, t, J = 4.8Hz)

２−アミノ−４−メチルチアゾール−５−カルボン酸０．４０ｇ、３−フルオロベンジルアミン０．２１ｇ、ＤＭＦ１．５ｍＬ及びトリエチルアミン０．１６ｇの混合物に、ＢＯＰ試薬０．７０ｇを加え、室温で１２時間攪拌した。室温にて終夜放置し、反応混合物を飽和重曹水に注加した。その混合物を酢酸エチルで抽出し、水及び飽和食塩水で洗浄した。硫酸マグネシウムで乾燥し、減圧下で濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付して、２−アミノ−Ｎ−（３−フルオロベンジル）−４−メチルチアゾール−５−カルボン酸アミド（以下、本発明化合物（２）と記す。）を０．１５ｇ得た。
¹H-NMR (DMSO-d₆) δ［ppm］:2.34(3H, s), 4.35(2H, d, J=5.4Hz), 7.00-7.37(6H, m), 7.92(1H, t, J=4.8Hz) Production Example 2

To a mixture of 0.40 g of 2-amino-4-methylthiazole-5-carboxylic acid, 0.21 g of 3-fluorobenzylamine, 1.5 mL of DMF and 0.16 g of triethylamine, 0.70 g of BOP reagent was added, and the mixture was stirred at room temperature for 12 hours. Stir. The reaction mixture was allowed to stand at room temperature overnight and poured into a saturated aqueous sodium bicarbonate solution. The mixture was extracted with ethyl acetate and washed with water and saturated brine. Dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2-amino-N- (3-fluorobenzyl) -4-methylthiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (2)). 0.15 g was obtained.
¹ H-NMR (DMSO-d ₆ ) δ [ppm]: 2.34 (3H, s), 4.35 (2H, d, J = 5.4Hz), 7.00-7.37 (6H, m), 7.92 (1H, t, J = 4.8Hz)

２−アミノ−４−メチルチアゾール−５−カルボン酸０．２４ｇ、２−クロロベンジルアミン０．２３ｇ、ＤＭＦ１．５ｍＬ及びトリエチルアミン０．１６ｇの混合物に、ＢＯＰ試薬０．７０ｇを加え、室温で１１．５時間攪拌した。室温にて終夜放置し、反応混合物を飽和重曹水に注加した。その混合物を酢酸エチルで抽出し、水及び飽和食塩水で洗浄した。硫酸マグネシウムで乾燥し、減圧下で濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付して、２−アミノ−Ｎ−（２−クロロベンジル）−４−メチルチアゾール−５−カルボン酸アミド（以下、本発明化合物（３）と記す。）を０．１２ｇ得た。
¹H-NMR (DMSO-d₆) δ［ppm］ :2.35(3H, s), 4.40(2H, d, J=4.1Hz), 7.25-7.67(6H, m), 8.01(1H, t, J=4.1Hz) Production Example 3

To a mixture of 0.24 g of 2-amino-4-methylthiazole-5-carboxylic acid, 0.23 g of 2-chlorobenzylamine, 1.5 mL of DMF and 0.16 g of triethylamine, 0.70 g of BOP reagent was added, and 11. Stir for 5 hours. The reaction mixture was allowed to stand at room temperature overnight and poured into a saturated aqueous sodium bicarbonate solution. The mixture was extracted with ethyl acetate and washed with water and saturated brine. Dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2-amino-N- (2-chlorobenzyl) -4-methylthiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (3)). 0.12 g was obtained.
¹ H-NMR (DMSO-d ₆ ) δ [ppm]: 2.35 (3H, s), 4.40 (2H, d, J = 4.1Hz), 7.25-7.67 (6H, m), 8.01 (1H, t, J = 4.1Hz)

２−アミノ−４−メチルチアゾール−５−カルボン酸０．２４ｇ、２−メチルベンジルアミン０．２０ｇ、ＤＭＦ１．５ｍＬ及びトリエチルアミン０．１６ｇの混合物に、ＢＯＰ試薬０．７０ｇを加え、室温で１１．５時間攪拌した。室温にて終夜放置し、反応混合物を飽和重曹水に注加した。その混合物を酢酸エチルで抽出し、水及び飽和食塩水で洗浄した。硫酸マグネシウムで乾燥し、減圧下で濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付して、２−アミノ−４−メチル−Ｎ−（２−メチルベンジル）−チアゾール−５−カルボン酸アミド（以下、本発明化合物（４）と記す。）を０．２４ｇ得た。
¹H-NMR (DMSO-d₆) δ［ppm］ :2.29(3H, s), 2.34(3H, s), 4.31(2H, d, J=4.6Hz), 7.14-7.35(6H, m), 7.91(1H, t, J=4.6Hz) Production Example 4

To a mixture of 0.24 g of 2-amino-4-methylthiazole-5-carboxylic acid, 0.20 g of 2-methylbenzylamine, 1.5 mL of DMF and 0.16 g of triethylamine, 0.70 g of BOP reagent was added, and 11. Stir for 5 hours. The reaction mixture was allowed to stand at room temperature overnight and poured into a saturated aqueous sodium bicarbonate solution. The mixture was extracted with ethyl acetate and washed with water and saturated brine. Dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography, and described as 2-amino-4-methyl-N- (2-methylbenzyl) -thiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (4)). ) Was obtained 0.24 g.
¹ H-NMR (DMSO-d ₆ ) δ [ppm]: 2.29 (3H, s), 2.34 (3H, s), 4.31 (2H, d, J = 4.6Hz), 7.14-7.35 (6H, m), 7.91 (1H, t, J = 4.6Hz)

２−アミノ−４−メチルチアゾール−５−カルボン酸０．３２ｇ、２−ブロモベンジルアミン塩酸塩０．４９ｇ、ＤＭＦ２ｍＬ及びトリエチルアミン０．４２ｇの混合物に、氷冷下にてＢＯＰ試薬０．９３ｇを加えた。その混合物を氷冷下にて5分間攪拌後、室温で４時間攪拌した。室温にて終夜放置し、反応混合物を飽和重曹水に注加した。その混合物を酢酸エチルで抽出し、飽和食塩水で洗浄した。硫酸ナトリウムで乾燥し、減圧下で濃縮した。得られた結晶をクロロホルムで洗浄し、２−アミノ−Ｎ−（２−ブロモベンジル）−４−メチルチアゾール−５−カルボン酸アミド（以下、本発明化合物（５）と記す。）を０．５０ｇ得た。
¹H-NMR (DMSO-d₆) δ［ppm］ :2.36(3H, s), 4.38(2H, d, J=5.9Hz), 7.17-7.38(5H, m), 7.58(1H, dd,J1=7.9Hz, J2=1.1Hz), 7.88(1H, t, J=5.9Hz) Production Example 5

To a mixture of 0.32 g of 2-amino-4-methylthiazole-5-carboxylic acid, 0.49 g of 2-bromobenzylamine hydrochloride, 2 mL of DMF and 0.42 g of triethylamine, 0.93 g of BOP reagent was added under ice cooling. It was. The mixture was stirred for 5 minutes under ice-cooling and then stirred at room temperature for 4 hours. The reaction mixture was allowed to stand at room temperature overnight and poured into a saturated aqueous sodium bicarbonate solution. The mixture was extracted with ethyl acetate and washed with saturated brine. Dried over sodium sulfate and concentrated under reduced pressure. The obtained crystals were washed with chloroform and 0.50 g of 2-amino-N- (2-bromobenzyl) -4-methylthiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (5)). Obtained.
¹ H-NMR (DMSO-d ₆ ) δ [ppm]: 2.36 (3H, s), 4.38 (2H, d, J = 5.9Hz), 7.17-7.38 (5H, m), 7.58 (1H, dd, J1 = 7.9Hz, J2 = 1.1Hz), 7.88 (1H, t, J = 5.9Hz)

２−アミノ−４−メチルチアゾール−５−カルボン酸０．３２ｇ、２−トリフルオロメチルベンジルアミン０．３９ｇ、ＤＭＦ２ｍＬ及びトリエチルアミン０．２１ｇの混合物に、氷冷下にてＢＯＰ試薬０．９３ｇを加えた。その混合物を氷冷下にて５分間攪拌後、室温で２．５時間攪拌した。室温にて終夜放置し、反応混合物を飽和重曹水に注加した。その混合物を酢酸エチルで抽出し、飽和食塩水で洗浄した。硫酸ナトリウムで乾燥し、減圧下で濃縮した。得られた結晶をクロロホルムで洗浄し、２−アミノ−４−メチル−Ｎ−（２−トリフルオロメチルベンジル）−チアゾール−５−カルボン酸アミド（以下、本発明化合物（６）と記す。）を０．４５ｇ得た。
¹H-NMR (DMSO-d₆) δ［ppm］:2.36(3H, s), 4.55(2H, d, J=5.4Hz), 7.28(2H, brs), 7.43-7.49(2H, m), 7.62-7.70(2H, m), 7.93(1H, t, J=5.4Hz) Production Example 6

To a mixture of 0.32 g of 2-amino-4-methylthiazole-5-carboxylic acid, 0.39 g of 2-trifluoromethylbenzylamine, 2 mL of DMF and 0.21 g of triethylamine, 0.93 g of BOP reagent was added under ice cooling. It was. The mixture was stirred under ice-cooling for 5 minutes and then at room temperature for 2.5 hours. The reaction mixture was allowed to stand at room temperature overnight and poured into a saturated aqueous sodium bicarbonate solution. The mixture was extracted with ethyl acetate and washed with saturated brine. Dried over sodium sulfate and concentrated under reduced pressure. The obtained crystals were washed with chloroform to give 2-amino-4-methyl-N- (2-trifluoromethylbenzyl) -thiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (6)). 0.45 g was obtained.
¹ H-NMR (DMSO-d ₆ ) δ [ppm]: 2.36 (3H, s), 4.55 (2H, d, J = 5.4Hz), 7.28 (2H, brs), 7.43-7.49 (2H, m), 7.62-7.70 (2H, m), 7.93 (1H, t, J = 5.4Hz)

２−アミノ−４−メチル−チアゾール−５−カルボン酸０．３２ｇのＤＭＦ溶液（１ｍＬ）、３−メチルベンジルアミン０．１７ｇのＤＭＦ溶液（１ｍＬ）、トリエチルアミン０．２１ｇの混合物に、氷冷下にてＢＯＰ試薬０．９３ｇを加えた。その混合物を氷冷下にて５分間攪拌した後、室温で４時間攪拌した。反応混合物を一晩室温で放置し、反応混合物を飽和重曹水１０ｍＬに注加した。酢酸エチルで抽出し、飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥して、減圧下で濃縮した。得られた残渣にクロロホルムを加え不溶物をろ過にて取り除き、ろ液は減圧下で濃縮した。残渣をシリカゲルカラムクロマトグラフィーに付した。得られた２−アミノ−４−メチル−Ｎ−（３−メチルベンジル）−チアゾール−５−カルボン酸アミドをクロロホルムとｔ−ブチルメチルエーテルで洗浄し、２−アミノ−４−メチル−Ｎ−（３−メチルベンジル）−チアゾール−５−カルボン酸アミド（以下、本発明化合物（７）と記す。）を０．２０ｇ得た。
¹Ｈ−ＮＭＲ （ＤＭＳＯ−ｄ₆） δ： ２．２８ （３Ｈ， ｓ）， ２．３４ （３Ｈ， ｓ）， ４．３１ （２Ｈ， ｄ， Ｊ ＝ ５．９ Ｈｚ）， ７．０２−７．０８ （３Ｈ， ｍ）， ７．１８ （１Ｈ， ｔ， Ｊ ＝ ７．８Ｈｚ）， ７．２０ （２Ｈ， ｂｒｓ）， ７．８４ （１Ｈ， ｔ， Ｊ ＝ ５．９ Ｈｚ）． Production Example 7

To a mixture of 0.32 g of 2-amino-4-methyl-thiazole-5-carboxylic acid in DMF (1 mL), 0.17 g of 3-methylbenzylamine in DMF (1 mL) and 0.21 g of triethylamine was added under ice cooling. 0.93 g of BOP reagent was added. The mixture was stirred for 5 minutes under ice cooling, and then stirred at room temperature for 4 hours. The reaction mixture was left overnight at room temperature, and the reaction mixture was poured into 10 mL of saturated aqueous sodium bicarbonate. The mixture was extracted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. Chloroform was added to the obtained residue, insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography. The resulting 2-amino-4-methyl-N- (3-methylbenzyl) -thiazole-5-carboxylic acid amide was washed with chloroform and t-butyl methyl ether to give 2-amino-4-methyl-N- ( 0.20 g of 3-methylbenzyl) -thiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (7)) was obtained.
¹ H-NMR (DMSO-d ₆ ) δ: 2.28 (3H, s), 2.34 (3H, s), 4.31 (2H, d, J = 5.9 Hz), 7.02- 7.08 (3H, m), 7.18 (1H, t, J = 7.8 Hz), 7.20 (2H, brs), 7.84 (1H, t, J = 5.9 Hz).

２−アミノ−４−メチル−チアゾール−５−カルボン酸０．２４ｇのＤＭＦ溶液（１ｍＬ）、２−フェニル−ベンジルアミン０．３１ｇのＤＭＦ溶液（１ｍＬ）、トリエチルアミン０．１６ｇの混合物に、氷冷下にてＢＯＰ試薬０．７２ｇを加えた。その混合物を氷冷下にて５分間攪拌した後、室温で１時間攪拌した。反応混合物を一晩室温で放置し、反応混合物を飽和重曹水１０ｍＬに注加した。酢酸エチルで抽出し、飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥して、減圧下で濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付した。得られた２−アミノ−４−メチル−Ｎ−（２−フェニル−ベンジル）−チアゾール−５−カルボン酸アミドをクロロホルムで洗浄し、２−アミノ−４−メチル−Ｎ−（２−フェニル−ベンジル）−チアゾール−５−カルボン酸アミド（以下、本発明化合物（８）と記す。）を０．２７ｇ得た。
¹Ｈ−ＮＭＲ （ＤＭＳＯ−ｄ₆） δ： ２．３１ （３Ｈ， ｓ）， ４．３０ （２Ｈ， ｄ， Ｊ ＝ ５．９ Ｈｚ）， ７．１８−７．４７（１１Ｈ， ｍ）， ７．７１ （１Ｈ， ｔ， Ｊ ＝ ５．９Ｈｚ） Production Example 8

To a mixture of 0.24 g of 2-amino-4-methyl-thiazole-5-carboxylic acid in DMF (1 mL), 0.31 g of 2-phenyl-benzylamine in DMF (1 mL) and 0.16 g of triethylamine, Below, 0.72 g of BOP reagent was added. The mixture was stirred for 5 minutes under ice-cooling and then stirred at room temperature for 1 hour. The reaction mixture was left overnight at room temperature, and the reaction mixture was poured into 10 mL of saturated aqueous sodium bicarbonate. The mixture was extracted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography. The resulting 2-amino-4-methyl-N- (2-phenyl-benzyl) -thiazole-5-carboxylic acid amide was washed with chloroform and 2-amino-4-methyl-N- (2-phenyl-benzyl). ) -Thiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (8)) was obtained in an amount of 0.27 g.
¹ H-NMR (DMSO-d ₆ ) δ: 2.31 (3H, s), 4.30 (2H, d, J = 5.9 Hz), 7.18-7.47 (11H, m), 7.71 (1H, t, J = 5.9 Hz)

２−アミノ−４−メチル−チアゾール−５−カルボン酸０．３２ｇのＤＭＦ溶液（１ｍＬ）、３−クロロ−ベンジルアミン０．３１ｇのＤＭＦ溶液（１ｍＬ）、トリエチルアミン０．２１ｇの混合物に、氷冷下にてＢＯＰ試薬０．９３ｇを加えた。その混合物を氷冷下にて５分間攪拌した後、室温で７時間攪拌した。反応混合物を一晩室温で放置し、反応混合物を飽和重曹水１０ｍＬに注加した。酢酸エチルで抽出し、飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥して、減圧下で濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付した。得られた２−アミノ−Ｎ−（３−クロロ−ベンジル）−４−メチル−チアゾール−５−カルボン酸アミドをクロロホルムで洗浄し、２−アミノ−Ｎ−（３−クロロ−ベンジル）−４−メチル−チアゾール−５−カルボン酸アミド（以下、本発明化合物（９）と記す。）をクロロホルムを０．４１ｇ得た。
¹Ｈ−ＮＭＲ （ＤＭＳＯ−ｄ₆） δ： ２．３４ （３Ｈ， ｓ）， ４．３４ （２Ｈ， ｄ， Ｊ ＝ ５．９ Ｈｚ）， ７．２３−７．３６（６Ｈ， ｍ）， ７．９３ （１Ｈ， ｔ， Ｊ ＝ ５．９Ｈｚ） Production Example 9

To a mixture of 0.32 g of 2-amino-4-methyl-thiazole-5-carboxylic acid in DMF (1 mL), 0.31 g of 3-chloro-benzylamine in DMF (1 mL) and 0.21 g of triethylamine, Below, 0.93 g of BOP reagent was added. The mixture was stirred under ice-cooling for 5 minutes and then stirred at room temperature for 7 hours. The reaction mixture was left overnight at room temperature, and the reaction mixture was poured into 10 mL of saturated aqueous sodium bicarbonate. The mixture was extracted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography. The resulting 2-amino-N- (3-chloro-benzyl) -4-methyl-thiazole-5-carboxylic acid amide was washed with chloroform and 2-amino-N- (3-chloro-benzyl) -4- 0.41 g of chloroform was obtained from methyl-thiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (9)).
¹ H-NMR (DMSO-d ₆ ) δ: 2.34 (3H, s), 4.34 (2H, d, J = 5.9 Hz), 7.23-7.36 (6H, m), 7.93 (1H, t, J = 5.9 Hz)

２−アミノ−４−メチル−チアゾール−５−カルボン酸０．３２ｇのＤＭＦ溶液（１ｍＬ）、３−トリフルオロメチル−ベンジルアミン０．３９ｇのＤＭＦ溶液（１ｍＬ）、トリエチルアミン０．２１ｇの混合物に、氷冷下にてＢＯＰ試薬０．９３ｇを加えた。その混合物を氷冷下にて５分間攪拌した後、室温で７時間攪拌した。反応混合物を一晩室温で放置し、反応混合物を飽和重曹水１０ｍＬに注加した。酢酸エチルで抽出し、飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥して、減圧下で濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付した。得られた２−アミノ−４−メチル−Ｎ−（３−トリフルオロメチル−ベンジル）−チアゾール−５−カルボン酸アミドにクロロホルムを加え不溶物を除去した後、ｔ−ブチルメチルエーテルで洗浄し、２−アミノ−４−メチル−Ｎ−（３−トリフルオロメチル−ベンジル）−チアゾール−５−カルボン酸アミド（以下、本発明化合物（１０）と記す。）を０．１５ｇ得た。
¹Ｈ−ＮＭＲ （ＤＭＳＯ−ｄ₆） δ： ２．３４ （３Ｈ， ｓ）， ４．４３ （２Ｈ， ｄ， Ｊ ＝ ６．０ Ｈｚ）， ７．２６（２Ｈ， ｓ）， ７．５３−７．６２（４Ｈ， ｍ）， ８．００ （１Ｈ， ｔ， Ｊ ＝ ６．０Ｈｚ） Production Example 10

To a mixture of 0.32 g of 2-amino-4-methyl-thiazole-5-carboxylic acid in DMF (1 mL), 0.39 g of 3-trifluoromethyl-benzylamine in DMF (1 mL) and 0.21 g of triethylamine, Under ice cooling, 0.93 g of BOP reagent was added. The mixture was stirred under ice-cooling for 5 minutes and then stirred at room temperature for 7 hours. The reaction mixture was left overnight at room temperature, and the reaction mixture was poured into 10 mL of saturated aqueous sodium bicarbonate. The mixture was extracted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography. Chloroform was added to the obtained 2-amino-4-methyl-N- (3-trifluoromethyl-benzyl) -thiazole-5-carboxylic acid amide to remove insolubles, and then washed with t-butyl methyl ether. 0.15 g of 2-amino-4-methyl-N- (3-trifluoromethyl-benzyl) -thiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (10)) was obtained.
¹ H-NMR (DMSO-d ₆ ) δ: 2.34 (3H, s), 4.43 (2H, d, J = 6.0 Hz), 7.26 (2H, s), 7.53- 7.62 (4H, m), 8.00 (1H, t, J = 6.0 Hz)

２−アミノ−４−メチル−チアゾール−５−カルボン酸０．３２ｇのＤＭＦ溶液（１ｍＬ）、３−メトキシ−ベンジルアミン０．３０ｇのＤＭＦ溶液（１ｍＬ）、トリエチルアミン０．２１ｇの混合物に、氷冷下にてＢＯＰ試薬０．９３ｇを加えた。その混合物を氷冷下にて５分間攪拌した後、室温で２時間攪拌した。反応混合物を一晩室温で放置し、反応混合物を飽和重曹水１０ｍＬに注加した。酢酸エチルで抽出し、飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥して、減圧下で濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付した。得られた２−アミノ−Ｎ−（３−メトキシ−ベンジル）−４−メチル−チアゾール−５−カルボン酸アミドをｔ−ブチルメチルエーテルで洗浄し、２−アミノ−Ｎ−（３−メトキシ−ベンジル）−４−メチル−チアゾール−５−カルボン酸アミド（以下、本発明化合物（１１）と記す。）を０．４５ｇ得た。
¹Ｈ−ＮＭＲ （ＤＭＳＯ−ｄ₆） δ： ２．３４ （３Ｈ， ｓ）， ３．７３ （３Ｈ， ｓ）， ４．３２ （２Ｈ， ｄ， Ｊ ＝ ５．９ Ｈｚ）， ６．７７−６．８６（３Ｈ， ｍ）， ７．２０−７．２３（３Ｈ， ｍ）， ７．８６ （１Ｈ， ｔ， Ｊ ＝ ５．９Ｈｚ） Production Example 11

To a mixture of 0.32 g of 2-amino-4-methyl-thiazole-5-carboxylic acid in DMF (1 mL), 0.30 g of 3-methoxy-benzylamine in DMF (1 mL) and 0.21 g of triethylamine, Below, 0.93 g of BOP reagent was added. The mixture was stirred for 5 minutes under ice cooling, and then stirred at room temperature for 2 hours. The reaction mixture was left overnight at room temperature, and the reaction mixture was poured into 10 mL of saturated aqueous sodium bicarbonate. The mixture was extracted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography. The resulting 2-amino-N- (3-methoxy-benzyl) -4-methyl-thiazole-5-carboxylic acid amide was washed with t-butyl methyl ether to give 2-amino-N- (3-methoxy-benzyl 0.45 g of -4-methyl-thiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (11)) was obtained.
¹ H-NMR (DMSO-d ₆ ) δ: 2.34 (3H, s), 3.73 (3H, s), 4.32 (2H, d, J = 5.9 Hz), 6.77- 6.86 (3H, m), 7.20-7.23 (3H, m), 7.86 (1H, t, J = 5.9 Hz)

２−（ｔ−ブトキシカルボニルアミノ）−Ｎ−（２−メトキシカルボニル−ベンジル）−４−メチル−チアゾール−５−カルボン酸アミド０．４２ｇをトリフルオロ酢酸１ｍＬに溶解させ、その混合物を室温で２時間攪拌した。反応混合物に酢酸エチル２０ｍＬを加え、１Ｎ水酸化ナトリウム水溶液で洗浄した。洗液は酢酸エチルで抽出し、先の酢酸エチルと合わせた。飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥し、減圧下で濃縮した。残渣をクロロホルムとｔ−ブチルメチルエーテルの混合液で洗浄して、２−アミノ−Ｎ−（２−メトキシカルボニル−ベンジル）−４−メチル−チアゾール−５−カルボン酸アミド（以下、本発明化合物（１２）と記す。）０．２２ｇを得た。
¹Ｈ−ＮＭＲ （ＤＭＳＯ−ｄ₆） δ： ２．３４ （３Ｈ， ｓ）， ３．８６ （３Ｈ， ｓ）， ４．６５ （２Ｈ， ｄ， Ｊ ＝ ５．９ Ｈｚ）， ７．２４ （２Ｈ， ｂｒｓ），
７．３７ （１Ｈ， ｄｄｄ， Ｊ₁ ＝ ７．８ Ｈｚ， Ｊ₂ ＝ ７．６ Ｈｚ， Ｊ₃ ＝ １．１ Ｈｚ）， ７．４２ （１Ｈ， ｄｄ， Ｊ₁ ＝ ７．８ Ｈｚ， Ｊ₂ ＝ １．３ Ｈｚ）， ７．５６ （１Ｈ， ｄｄｄ， Ｊ₁ ＝ ７．７ Ｈｚ， Ｊ₂ ＝ ７．６ Ｈｚ， Ｊ₃ ＝ １．３ Ｈｚ）， ７．７２ （１Ｈ， ｔ， Ｊ ＝ ５．９ Ｈｚ）， ７．８４（１Ｈ， ｄｄ， Ｊ₁ ＝ ７．７ Ｈｚ， Ｊ₂ ＝１．１ Ｈｚ）， Production Example 12

0.42 g of 2- (t-butoxycarbonylamino) -N- (2-methoxycarbonyl-benzyl) -4-methyl-thiazole-5-carboxylic acid amide is dissolved in 1 mL of trifluoroacetic acid and the mixture is dissolved at room temperature with 2 Stir for hours. 20 mL of ethyl acetate was added to the reaction mixture, and the mixture was washed with 1N aqueous sodium hydroxide solution. The washings were extracted with ethyl acetate and combined with the previous ethyl acetate. The extract was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was washed with a mixed solution of chloroform and t-butyl methyl ether to give 2-amino-N- (2-methoxycarbonyl-benzyl) -4-methyl-thiazole-5-carboxylic acid amide (hereinafter referred to as the present compound ( 12).) 0.22 g was obtained.
¹ H-NMR (DMSO-d ₆ ) δ: 2.34 (3H, s), 3.86 (3H, s), 4.65 (2H, d, J = 5.9 Hz), 7.24 ( 2H, brs),
7.37 (1H, ddd, J ₁ = 7.8 Hz, J ₂ = 7.6 Hz, J ₃ = 1.1 Hz), 7.42 (1H, dd, J ₁ = 7.8 Hz, J _{2 = 1.3 Hz), 7.56 (} 1H, ddd, J 1 = 7.7 Hz, J 2 = 7.6 Hz, J 3 = 1.3 Hz), 7.72 (1H, t, J = 5.9 Hz), 7.84 (1H, dd, J ₁ = 7.7 Hz, J ₂ = 1.1 Hz),

２−アミノ−４−メチル−チアゾール−５−カルボン酸０．３２ｇのＤＭＦ溶液（１ｍＬ）、２−エチル−ベンジルアミン０．３０ｇのＤＭＦ溶液（１ｍＬ）、トリエチルアミン０．２１ｇの混合物に、氷冷下にてＢＯＰ試薬０．９３ｇを加えた。その混合物を氷冷下にて５分間攪拌した後、室温で４．５時間攪拌した。反応混合物を一晩室温で放置し、反応混合物を飽和重曹水１０ｍＬに注加した。酢酸エチルで抽出し、飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥して、減圧下で濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付した。得られた２−アミノ−Ｎ−（２−エチル−ベンジル）−４−メチル−チアゾール−５−カルボン酸アミドをｔ−ブチルメチルエーテルで洗浄し、２−アミノ−Ｎ−（２−エチル−ベンジル）−４−メチル−チアゾール−５−カルボン酸アミド（以下、本発明化合物（１３）と記す。）を０．１５ｇ得た。
¹Ｈ−ＮＭＲ （ＤＭＳＯ−ｄ₆） δ： １．１７（３Ｈ， ｔ， Ｊ ＝ ７．６ Ｈｚ）， ２．３３ （３Ｈ， ｓ）， ２．６６（２Ｈ， ｑ， Ｊ ＝ ７．６ Ｈｚ）， ４．３７ （２Ｈ， ｄ， Ｊ ＝ ５．９ Ｈｚ）， ７．１１−７．２３（６Ｈ， ｍ）， ７．７７ （１Ｈ， ｔ， Ｊ ＝ ５．９Ｈｚ） Production Example 13

To a mixture of 0.32 g of 2-amino-4-methyl-thiazole-5-carboxylic acid in DMF (1 mL), 0.30 g of 2-ethyl-benzylamine in DMF (1 mL) and 0.21 g of triethylamine, Below, 0.93 g of BOP reagent was added. The mixture was stirred for 5 minutes under ice-cooling and then stirred at room temperature for 4.5 hours. The reaction mixture was left overnight at room temperature, and the reaction mixture was poured into 10 mL of saturated aqueous sodium bicarbonate. The mixture was extracted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography. The resulting 2-amino-N- (2-ethyl-benzyl) -4-methyl-thiazole-5-carboxylic acid amide was washed with t-butyl methyl ether to give 2-amino-N- (2-ethyl-benzyl). 0.15 g of -4-methyl-thiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (13)) was obtained.
¹ H-NMR (DMSO-d ₆ ) δ: 1.17 (3H, t, J = 7.6 Hz), 2.33 (3H, s), 2.66 (2H, q, J = 7.6) Hz), 4.37 (2H, d, J = 5.9 Hz), 7.11-7.23 (6H, m), 7.77 (1H, t, J = 5.9 Hz)

Ｎ−（３−アミノベンジル）−２−（ｔ−ブトキシカルボニルアミノ）−４−メチル−チアゾール−５−カルボン酸アミド０．９２ｇをトリフルオロ酢酸２ｍＬに溶解させ、その混合物を室温で２．５時間攪拌した。反応混合物に酢酸エチル３０ｍＬを加え、１Ｎ水酸化ナトリウム水溶液を加えてアルカリ性にし、酢酸エチル層を分取した。水層は酢酸エチルで抽出し、先の酢酸エチル層に合わせた。飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥した。減圧下で濃縮し、Ｎ−（３−アミノベンジル）−２−アミノ−４−メチル−チアゾール−５−カルボン酸アミド（以下、本発明化合物（１４）と記す。）０．３８ｇを得た。
¹Ｈ−ＮＭＲ （ＤＭＳＯ−ｄ₆） δ： ２．３４ （３Ｈ， ｓ）， ４．２１ （２Ｈ， ｄ， Ｊ ＝ ５．９ Ｈｚ）， ４．８８ （２Ｈ， ｂｒｓ）， ６．４１−６．４９（３Ｈ． ｍ）， ６．９３（１Ｈ， ｔ， Ｊ＝７．７Ｈｚ）， ７．１８ （２Ｈ， ｂｒｓ）， ７．７３ （１Ｈ， ｔ， Ｊ ＝ ５．４ Ｈｚ）． Production Example 14

0.92 g of N- (3-aminobenzyl) -2- (t-butoxycarbonylamino) -4-methyl-thiazole-5-carboxylic acid amide was dissolved in 2 mL of trifluoroacetic acid, and the mixture was stirred at room temperature for 2.5. Stir for hours. 30 mL of ethyl acetate was added to the reaction mixture, and a 1N sodium hydroxide aqueous solution was added to make the mixture alkaline, and the ethyl acetate layer was separated. The aqueous layer was extracted with ethyl acetate and combined with the previous ethyl acetate layer. The extract was washed with saturated brine and dried over sodium sulfate. Concentration under reduced pressure gave 0.38 g of N- (3-aminobenzyl) -2-amino-4-methyl-thiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (14)).
¹ H-NMR (DMSO-d ₆ ) δ: 2.34 (3H, s), 4.21 (2H, d, J = 5.9 Hz), 4.88 (2H, brs), 6.41- 6.49 (3H.m), 6.93 (1H, t, J = 7.7 Hz), 7.18 (2H, brs), 7.73 (1H, t, J = 5.4 Hz).

２−（ｔ−ブトキシカルボニルアミノ）−Ｎ−（３−シアノベンジル）−４−メチル−チアゾール−５−カルボン酸アミド０．３５ｇをトリフルオロ酢酸１ｍＬに溶解した。その混合物を室温で２時間攪拌した。反応混合物に酢酸エチル２０ｍＬを加え、１Ｎ水酸化ナトリウム水溶液を加えてアルカリ性にし、酢酸エチル層を分取した。水層は酢酸エチルで抽出し、先の酢酸エチル層に合わせた。飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥した。減圧下で濃縮し、２−アミノ−Ｎ−（３−シアノベンジル）−４−メチル−チアゾール−５−カルボン酸アミド（以下、本発明化合物（１５）と記す。）０．２２ｇを得た。
¹Ｈ−ＮＭＲ （ＤＭＳＯ−ｄ₆） δ： ２．３４（３Ｈ， ｓ）， ４．３９（２Ｈ， ｄ， Ｊ ＝ ５．６ Ｈｚ）， ７．２３−７．４２（２Ｈ， ｍ）， ７．５０−７．７０（４Ｈ， ｍ）， ７．９６ （１Ｈ， ｔ， Ｊ ＝ ５．６ Ｈｚ）． Production Example 15

0.35 g of 2- (t-butoxycarbonylamino) -N- (3-cyanobenzyl) -4-methyl-thiazole-5-carboxylic acid amide was dissolved in 1 mL of trifluoroacetic acid. The mixture was stirred at room temperature for 2 hours. 20 mL of ethyl acetate was added to the reaction mixture, and 1N sodium hydroxide aqueous solution was added to make the mixture alkaline, and the ethyl acetate layer was separated. The aqueous layer was extracted with ethyl acetate and combined with the previous ethyl acetate layer. The extract was washed with saturated brine and dried over sodium sulfate. Concentration under reduced pressure gave 0.22 g of 2-amino-N- (3-cyanobenzyl) -4-methyl-thiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (15)).
¹ H-NMR (DMSO-d ₆ ) δ: 2.34 (3H, s), 4.39 (2H, d, J = 5.6 Hz), 7.23-7.42 (2H, m), 7.50-7.70 (4H, m), 7.96 (1H, t, J = 5.6 Hz).

２−（ｔ−ブトキシカルボニルアミノ）−Ｎ−（３−カルバモイルベンジル）−４−メチル−チアゾール−５−カルボン酸アミド０．２７ｇをトリフルオロ酢酸１ｍＬに溶解した。その混合物を室温で２時間攪拌した。反応混合物を１Ｎ水酸化ナトリウム水溶液２０ｍＬに注加し、アルカリ性になったことを確認し、酢酸エチルで抽出した。硫酸ナトリウムで乾燥した後、減圧下で濃縮し、２−アミノ−Ｎ−（３−カルバモイルベンジル）−４−メチル−チアゾール−５−カルボン酸アミド（以下、本発明化合物（１７）と記す。）９５ｍｇを得た。
¹Ｈ−ＮＭＲ （ＤＭＳＯ−ｄ₆） δ： ２．３４（３Ｈ， ｓ）， ４．３８（２Ｈ， ｄ， Ｊ ＝ ５．６ Ｈｚ）， ７．１９−７．４３（５Ｈ， ｍ）， ７．７１−７．８３（３Ｈ， ｍ）， ７．９２ （１Ｈ， ｔ， Ｊ ＝ ５．６ Ｈｚ）． Production Example 17

0.27 g of 2- (t-butoxycarbonylamino) -N- (3-carbamoylbenzyl) -4-methyl-thiazole-5-carboxylic acid amide was dissolved in 1 mL of trifluoroacetic acid. The mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into 20 mL of 1N aqueous sodium hydroxide solution, confirmed to be alkaline, and extracted with ethyl acetate. After drying over sodium sulfate, the mixture was concentrated under reduced pressure to give 2-amino-N- (3-carbamoylbenzyl) -4-methyl-thiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (17)). 95 mg was obtained.
¹ H-NMR (DMSO-d ₆ ) δ: 2.34 (3H, s), 4.38 (2H, d, J = 5.6 Hz), 7.19-7.43 (5H, m), 7.71-7.83 (3H, m), 7.92 (1H, t, J = 5.6 Hz).

２−アミノ−４−メチル−チアゾール−５−カルボン酸０．３２ｇのＤＭＦ溶液（１ｍＬ）、２−メチルチオベンジルアミン０．３４ｇのＤＭＦ溶液（１ｍＬ）、トリエチルアミン０．２１ｇの混合物に、氷冷下にてＢＯＰ試薬０．９３ｇを加えた。その混合物を氷冷下にて５分間攪拌した後、室温で４．５時間攪拌した。反応混合物を室温で３日間放置した後、飽和重曹水１０ｍＬに注加し、酢酸エチルで抽出した。飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥して、減圧下で濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付した。得られた２−アミノ−４−メチル−Ｎ−（２−メチルチオベンジル）−チアゾール−５−カルボン酸アミドをクロロホルムで洗浄し、２−アミノ−４−メチル−Ｎ−（２−メチルチオベンジル）−チアゾール−５−カルボン酸アミド（以下、本発明化合物（１８）と記す。）を０．３１ｇ得た。
¹Ｈ−ＮＭＲ （ＤＭＳＯ−ｄ₆） δ： ２．３５ （３Ｈ， ｓ）， ２．４８ （３Ｈ， ｓ）， ４．３６ （２Ｈ， ｄ， Ｊ ＝ ５．９ Ｈｚ）， ７．１２−７．３０ （６Ｈ， ｍ）， ７．７７ （１Ｈ， ｔ， Ｊ ＝ ５．９ Ｈｚ）． Production Example 18

To a mixture of 0.32 g of 2-amino-4-methyl-thiazole-5-carboxylic acid in DMF (1 mL), 0.34 g of 2-methylthiobenzylamine in DMF (1 mL) and 0.21 g of triethylamine was added under ice cooling. 0.93 g of BOP reagent was added. The mixture was stirred for 5 minutes under ice-cooling and then stirred at room temperature for 4.5 hours. The reaction mixture was allowed to stand at room temperature for 3 days, poured into 10 mL of saturated aqueous sodium hydrogen carbonate, and extracted with ethyl acetate. The extract was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography. The obtained 2-amino-4-methyl-N- (2-methylthiobenzyl) -thiazole-5-carboxylic acid amide was washed with chloroform, and 2-amino-4-methyl-N- (2-methylthiobenzyl)- 0.31 g of thiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (18)) was obtained.
¹ H-NMR (DMSO-d ₆ ) δ: 2.35 (3H, s), 2.48 (3H, s), 4.36 (2H, d, J = 5.9 Hz), 7.12- 7.30 (6H, m), 7.77 (1H, t, J = 5.9 Hz).

２−アミノ−４−メチル−チアゾール−５−カルボン酸０．２４ｇのＤＭＦ溶液（０．７５ｍＬ）、２−ヨードベンジルアミン塩酸塩０．４４ｇのＤＭＦ溶液（０．７５ｍＬ）、トリエチルアミン０．３２ｇの混合物に、氷冷下にてＢＯＰ試薬０．７０ｇを加えた。その混合物を氷冷下にて５分間攪拌した後、室温で６時間攪拌した。反応混合物を室温で一晩放置した後、飽和重曹水１０ｍＬに注加し、酢酸エチルで抽出した。飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥して、減圧下で濃縮した。得られた残渣を酢酸エチルで洗浄し、２−アミノ−Ｎ−（２−ヨードベンジル）−４−メチル−チアゾール−５−カルボン酸アミド（以下、本発明化合物（１９）と記す。）を０．３５ｇ得た。
¹Ｈ−ＮＭＲ （ＤＭＳＯ−ｄ₆） δ： ２．３４（３Ｈ， ｓ）， ４．２８ （２Ｈ， ｄ， Ｊ ＝ ５．６ Ｈｚ）， ７．００（１Ｈ， ｔｄ， Ｊ₁＝７．７Ｈｚ， Ｊ₂＝１．６Ｈｚ）， ７．２２（１Ｈ， ｄｄ， Ｊ₁＝７．７Ｈｚ， Ｊ₂＝１．６Ｈｚ）， ７．２４（２Ｈ， ｂｒｓ）， ７．３６（１Ｈ， ｔｄ， Ｊ₁＝７．７Ｈｚ， Ｊ₂＝１．１Ｈｚ）， ７．８３（１Ｈ， ｄｄ， Ｊ₁＝７．７Ｈｚ， Ｊ₂＝１．１Ｈｚ）， ７．８８ （１Ｈ， ｔ， Ｊ ＝ ５．６ Ｈｚ）． Production Example 19

2-amino-4-methyl-thiazole-5-carboxylic acid 0.24 g in DMF solution (0.75 mL), 2-iodobenzylamine hydrochloride 0.44 g in DMF solution (0.75 mL), triethylamine 0.32 g To the mixture, 0.70 g of BOP reagent was added under ice cooling. The mixture was stirred for 5 minutes under ice-cooling and then stirred at room temperature for 6 hours. The reaction mixture was allowed to stand overnight at room temperature, then poured into 10 mL of saturated aqueous sodium hydrogen carbonate, and extracted with ethyl acetate. The extract was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was washed with ethyl acetate, and 2-amino-N- (2-iodobenzyl) -4-methyl-thiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (19)) was 0. .35 g was obtained.
¹ H-NMR (DMSO-d ₆ ) δ: 2.34 (3H, s), 4.28 (2H, d, J = 5.6 Hz), 7.00 (1H, td, J ₁ = 7. 7 Hz, J ₂ = 1.6 Hz), 7.22 ( ₁ H, dd, J ₁ = 7.7 Hz, J ₂ = 1.6 Hz), 7.24 (2 H, brs), 7.36 (1 H, td, J ₁ = 7.7 Hz, J ₂ = 1.1 Hz), 7.83 (1H, dd, J ₁ = 7.7 Hz, J ₂ = 1.1 Hz), 7.88 (1H, t, J = 5. 6 Hz).

２−アミノ−４−メチル−チアゾール−５−カルボン酸０．３２ｇのＤＭＦ溶液（１ｍＬ）、２−ニトロベンジルアミン塩酸塩０．４１ｇのＤＭＦ溶液（１ｍＬ）、トリエチルアミン０．４２ｇの混合物に、氷冷下にてＢＯＰ試薬０．９３ｇを加えた。その混合物を氷冷下にて５分間攪拌した後、室温で１．５時間攪拌した。反応混合物を室温で一晩放置した後、飽和重曹水１０ｍＬに注加し、酢酸エチルで抽出した。飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥して、減圧下で濃縮した。得られた残渣をクロロホルムで洗浄し、２−アミノ−４−メチル−Ｎ−（２−ニトロベンジル）−チアゾール−５−カルボン酸アミド（以下、本発明化合物（２０）と記す。）を０．４４ｇ得た。
¹Ｈ−ＮＭＲ （ＤＭＳＯ−ｄ₆） δ： ２．３２（３Ｈ， ｓ）， ４．６０ （２Ｈ， ｄ， Ｊ ＝ ５．９ Ｈｚ）， ７．２６（２Ｈ， ｂｒｓ）， ７．４８−７．５３（２Ｈ， ｍ）， ７．７０（１Ｈ， ｔｄ， Ｊ₁＝７．６Ｈｚ， Ｊ₂＝１．３Ｈｚ） ， ７．９１ （１Ｈ， ｔ， Ｊ ＝ ５．９ Ｈｚ）， ８．００（１Ｈ， ｄｄ， Ｊ₁＝７．７Ｈｚ， Ｊ₂＝１．２Ｈｚ） Production Example 20

To a mixture of 0.32 g of 2-amino-4-methyl-thiazole-5-carboxylic acid in DMF (1 mL), 0.41 g of 2-nitrobenzylamine hydrochloride in DMF (1 mL) and 0.42 g of triethylamine, Under cooling, 0.93 g of BOP reagent was added. The mixture was stirred for 5 minutes under ice-cooling and then stirred at room temperature for 1.5 hours. The reaction mixture was allowed to stand overnight at room temperature, then poured into 10 mL of saturated aqueous sodium hydrogen carbonate, and extracted with ethyl acetate. The extract was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was washed with chloroform, and 2-amino-4-methyl-N- (2-nitrobenzyl) -thiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (20)) was reduced to 0. 44 g was obtained.
¹ H-NMR (DMSO-d ₆ ) δ: 2.32 (3H, s), 4.60 (2H, d, J = 5.9 Hz), 7.26 (2H, brs), 7.48- 7.53 (2H, m), 7.70 (1H, td, J 1 = 7.6Hz, J 2 = 1.3Hz), 7.91 (1H, t, J = 5.9 Hz), 8. 00 (1H, dd, J ₁ = 7.7 Hz, J ₂ = 1.2 Hz)

２−アミノ−４−メチル−チアゾール−５−カルボン酸０．３２ｇのＤＭＦ溶液（１ｍＬ）、３−ニトロベンジルアミン塩酸塩０．４１ｇのＤＭＦ溶液（１ｍＬ）、トリエチルアミン０．４２ｇの混合物に、氷冷下にてＢＯＰ試薬０．９３ｇを加えた。その混合物を氷冷下にて５分間攪拌した後、室温で４時間攪拌した。反応混合物を室温で一晩放置した後、飽和重曹水１０ｍＬに注加し、酢酸エチルで抽出した。飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥して、減圧下で濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付して、得られた２−アミノ−４−メチル−Ｎ−（３−ニトロベンジル）−チアゾール−５−カルボン酸アミドをクロロホルムで洗浄し、２−アミノ−４−メチル−Ｎ−（３−ニトロベンジル）−チアゾール−５−カルボン酸アミド（以下、本発明化合物（２１）と記す。）を０．４８ｇ得た。
¹Ｈ−ＮＭＲ （ＤＭＳＯ−ｄ₆） δ： ２．３３（３Ｈ， ｓ）， ４．４５ （２Ｈ， ｄ， Ｊ ＝ ５．８ Ｈｚ）， ７．２５（２Ｈ， ｂｒｓ）， ７．６０（１Ｈ， ｔ， Ｊ＝７．８Ｈｚ） ， ７．７３０（１Ｈ， ｄ， Ｊ＝７．７Ｈｚ） ， ８．０５−８．０８（２Ｈ， ｍ）， ８．１２ （１Ｈ， ｔ， Ｊ ＝ １．９ Ｈｚ） Production Example 21

To a mixture of 0.32 g of 2-amino-4-methyl-thiazole-5-carboxylic acid in DMF (1 mL), 0.41 g of 3-nitrobenzylamine hydrochloride in DMF (1 mL) and 0.42 g of triethylamine, Under cooling, 0.93 g of BOP reagent was added. The mixture was stirred for 5 minutes under ice cooling, and then stirred at room temperature for 4 hours. The reaction mixture was allowed to stand overnight at room temperature, then poured into 10 mL of saturated aqueous sodium hydrogen carbonate, and extracted with ethyl acetate. The extract was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography, and the resulting 2-amino-4-methyl-N- (3-nitrobenzyl) -thiazole-5-carboxylic acid amide was washed with chloroform to give 2-amino 0.48 g of -4-methyl-N- (3-nitrobenzyl) -thiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (21)) was obtained.
¹ H-NMR (DMSO-d ₆ ) δ: 2.33 (3H, s), 4.45 (2H, d, J = 5.8 Hz), 7.25 (2H, brs), 7.60 ( 1H, t, J = 7.8 Hz), 7.730 (1H, d, J = 7.7 Hz), 8.05-8.08 (2H, m), 8.12 (1H, t, J = 1) .9 Hz)

２−アミノ−４−メチルチアゾール−５−カルボン酸０．３２ｇ、ＤＭＦ３ｍＬ、トリエチルアミン０．２４ｇ、ＢＯＰ試薬１．０６ｇ、および３−トリフルオロメトキシベンジルアミン０．３８ｇを混合し、その混合物を室温で３時間攪拌した。反応混合物を氷水に注加し、酢酸エチルで抽出した。飽和重曹水、飽和食塩水で順次洗浄した後、硫酸マグネシウムで乾燥し、減圧下で濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付して、２−アミノ−４−メチル−Ｎ−（３−トリフルオロメトキシベンジル）チアゾール−５−カルボン酸アミド（以下、本発明化合物（２２）と記す。）を０．３７ｇ得た。
１Ｈ−ＮＭＲ （ＤＭＳＯ−Ｄ６） δ： ２．３５ （３Ｈ， ｓ）， ４．３８ （２Ｈ， ｄ， Ｊ ＝ ５．９ Ｈｚ）， ７．２１−７．２５ （２Ｈ， ｍ）， ７．３１ （１Ｈ， ｄ， Ｊ ＝ ７．６ Ｈｚ）， ７．４４−７．４８ （１Ｈ， ｍ）， ７．５２ （２Ｈ， ｓ）， ８．１３ （１Ｈ， ｔ， Ｊ ＝ ５．９ Ｈｚ）． Production Example 22

A mixture of 0.32 g of 2-amino-4-methylthiazole-5-carboxylic acid, 3 mL of DMF, 0.24 g of triethylamine, 1.06 g of BOP reagent, and 0.38 g of 3-trifluoromethoxybenzylamine was mixed at room temperature. Stir for 3 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The extract was washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 2-amino-4-methyl-N- (3-trifluoromethoxybenzyl) thiazole-5-carboxylic acid amide (hereinafter referred to as the present compound (22)). 0.37 g was obtained.
1H-NMR (DMSO-D6) δ: 2.35 (3H, s), 4.38 (2H, d, J = 5.9 Hz), 7.21-7.25 (2H, m), 7. 31 (1H, d, J = 7.6 Hz), 7.44-7.48 (1H, m), 7.52 (2H, s), 8.13 (1H, t, J = 5.9 Hz) ).

  Next, reference production examples are shown.

２−（ｔ−ブトキシカルボニルアミノ）−４−メチル−チアゾール−５−カルボン酸アミドのトルエン溶液（１０ｍＬ）に塩化チオニル０．１６ｍＬを加え、８０℃で１時間４０分攪拌した。反応混合物を濃縮し、残渣に氷冷下にてテトラヒドロフラン１５ｍＬ、２−メトキシカルボニルベンジルアミン塩酸塩０．３０ｇ、トリエチルアミン０．３３ｇを順に加えた。室温にて１時間４０分攪拌を行い、反応混合物に水１０ｍＬを加えた。酢酸エチルで抽出し、飽和重曹水、１Ｎ塩酸、飽和食塩水の順で洗浄した。硫酸マグネシウムで乾燥し、減圧下で濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付して、２−（ｔ−ブトキシカルボニルアミノ）−Ｎ−（２−メトキシカルボニル−ベンジル）−４−メチル−チアゾール−５−カルボン酸アミド０．４７ｇを得た。
¹Ｈ−ＮＭＲ （ＣＤＣｌ₃） δ： １．５２（９Ｈ， ｓ）， ２．６０（３Ｈ， ｓ）， ３．９５（３Ｈ， ｓ）， ４．７５ （２Ｈ， ｄ， Ｊ ＝ ６．３ Ｈｚ） ， ７．０８ （１Ｈ， ｔ， Ｊ ＝ ６．３ Ｈｚ） ， ７．３７ （１Ｈ， ｄｄ， Ｊ₁ ＝ ７．６ Ｈｚ， Ｊ₂ ＝ ７．１ Ｈｚ）， ７．５２ （１Ｈ， ｄｄ， Ｊ₁ ＝ ７．６ Ｈｚ， Ｊ₂ ＝ ７．１ Ｈｚ）， ７．６１（１Ｈ， ｄ， Ｊ＝ ７．６ Ｈｚ）， ７．９９（１Ｈ， ｄ， Ｊ＝ ７．６ Ｈｚ）， １０．６８ （１Ｈ， ｂｒｓ） Reference production example 1

To a toluene solution (10 mL) of 2- (t-butoxycarbonylamino) -4-methyl-thiazole-5-carboxylic acid amide was added 0.16 mL of thionyl chloride, and the mixture was stirred at 80 ° C. for 1 hour and 40 minutes. The reaction mixture was concentrated, and 15 mL of tetrahydrofuran, 0.30 g of 2-methoxycarbonylbenzylamine hydrochloride and 0.33 g of triethylamine were sequentially added to the residue under ice cooling. The mixture was stirred at room temperature for 1 hour and 40 minutes, and 10 mL of water was added to the reaction mixture. The mixture was extracted with ethyl acetate, and washed successively with saturated aqueous sodium hydrogen carbonate, 1N hydrochloric acid, and saturated brine. Dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 0.47 g of 2- (t-butoxycarbonylamino) -N- (2-methoxycarbonyl-benzyl) -4-methyl-thiazole-5-carboxylic acid amide. Obtained.
¹ H-NMR (CDCl ₃ ) δ: 1.52 (9H, s), 2.60 (3H, s), 3.95 (3H, s), 4.75 (2H, d, J = 6.3) Hz), 7.08 (1H, t , J = 6.3 Hz), 7.37 (1H, dd, J 1 = 7.6 Hz, J 2 = 7.1 Hz), 7.52 (1H, _{dd, J 1 = 7.6 Hz,} J 2 = 7.1 Hz), 7.61 (1H, d, J = 7.6 Hz), 7.99 (1H, d, J = 7.6 Hz) , 10.68 (1H, brs)

２−（ｔ−ブトキシカルボニルアミノ）−４−メチル−チアゾール−５−カルボン酸２．５８ｇのＤＭＦ溶液（５ｍＬ）、３−アミノベンジルアミン１．３４ｇのＤＭＦ溶液（５ｍＬ）、トリエチルアミン１．４６ｇの混合物に、氷冷下にてＢＯＰ試薬４．６４ｇを加えた。その混合物を氷冷下にて５分間攪拌した後、室温で２０分間攪拌した。反応混合物を一晩室温で放置し、反応混合物を飽和重曹水１０ｍＬに注加した。酢酸エチルで抽出し、飽和食塩水で洗浄した後、硫酸ナトリウムで乾燥して、減圧下で濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付した。得られたＮ−（３−アミノベンジル）−２−（ｔ−ブトキシカルボニルアミノ）−４−メチル−チアゾール−５−カルボン酸アミドをクロロホルムで洗浄し、Ｎ−（３−アミノベンジル）−２−（ｔ−ブトキシカルボニルアミノ）−４−メチル−チアゾール−５−カルボン酸アミド０．９９ｇを得た。
¹Ｈ−ＮＭＲ （ＤＭＳＯ−ｄ₆） δ： １．４８（９Ｈ， ｓ）， ２．４４ （３Ｈ， ｓ）， ４．２４ （２Ｈ， ｄ， Ｊ ＝ ５．９Ｈｚ）， ４．９０（２Ｈ， ｂｒｓ）， ６．４２−６．５１（３Ｈ， ｍ）， ６．９４（１Ｈ， ｔ， Ｊ ＝ ７．７Ｈｚ）， ８．２２ （１Ｈ， ｔ， Ｊ ＝ ５．９Ｈｚ）， １１．４５（１Ｈ， ｂｒｓ） Reference production example 2

2- (t-butoxycarbonylamino) -4-methyl-thiazole-5-carboxylic acid 2.58 g in DMF solution (5 mL), 3-aminobenzylamine 1.34 g in DMF solution (5 mL), triethylamine 1.46 g To the mixture, 4.64 g of BOP reagent was added under ice cooling. The mixture was stirred under ice-cooling for 5 minutes and then stirred at room temperature for 20 minutes. The reaction mixture was left overnight at room temperature, and the reaction mixture was poured into 10 mL of saturated aqueous sodium bicarbonate. The mixture was extracted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography. The obtained N- (3-aminobenzyl) -2- (t-butoxycarbonylamino) -4-methyl-thiazole-5-carboxylic acid amide was washed with chloroform, and N- (3-aminobenzyl) -2- 0.99 g of (t-butoxycarbonylamino) -4-methyl-thiazole-5-carboxylic acid amide was obtained.
¹ H-NMR (DMSO-d ₆ ) δ: 1.48 (9H, s), 2.44 (3H, s), 4.24 (2H, d, J = 5.9 Hz), 4.90 (2H) , Brs), 6.42-6.51 (3H, m), 6.94 (1H, t, J = 7.7 Hz), 8.22 (1H, t, J = 5.9 Hz), 11.45 (1H, brs)

２−（ｔ−ブトキシカルボニルアミノ）−４−メチル−チアゾール−５−カルボン酸１．５８ｇのＤＭＦ溶液（３ｍＬ）、３−シアノベンジルアミン１．１９ｇのＤＭＦ溶液（３ｍＬ）、トリエチルアミン０．６４ｇの混合物に、氷冷下にてＢＯＰ試薬２．７９ｇを加えた。その混合物を氷冷下にて５分間攪拌した後、室温で２時間攪拌した。反応混合物を一晩室温で放置し、反応混合物を飽和重曹水５０ｍＬに注加した。酢酸エチルで抽出し、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥して、減圧下で濃縮した。得られた残渣を酢酸エチルで洗浄し、２−（ｔ−ブトキシカルボニルアミノ）−Ｎ−（３−シアノベンジル）−４−メチル−チアゾール−５−カルボン酸アミド０．７７ｇを得た。
¹Ｈ−ＮＭＲ （ＤＭＳＯ−ｄ₆） δ： １．４９（９Ｈ， ｓ）， ２．４５ （３Ｈ， ｓ）， ４．４３ （２Ｈ， ｄ， Ｊ ＝ ５．９Ｈｚ）， ７．５３−７．７１（４Ｈ， ｍ）， ８．４３ （１Ｈ， ｔ， Ｊ ＝ ５．９Ｈｚ）， １１．４０（１Ｈ， ｂｒｓ） Reference production example 3

2- (t-butoxycarbonylamino) -4-methyl-thiazole-5-carboxylic acid 1.58 g in DMF solution (3 mL), 3-cyanobenzylamine 1.19 g in DMF solution (3 mL), triethylamine 0.64 g To the mixture, 2.79 g of BOP reagent was added under ice cooling. The mixture was stirred for 5 minutes under ice cooling, and then stirred at room temperature for 2 hours. The reaction mixture was left overnight at room temperature, and the reaction mixture was poured into 50 mL of saturated aqueous sodium bicarbonate. The mixture was extracted with ethyl acetate, washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained residue was washed with ethyl acetate to obtain 0.77 g of 2- (t-butoxycarbonylamino) -N- (3-cyanobenzyl) -4-methyl-thiazole-5-carboxylic acid amide.
¹ H-NMR (DMSO-d ₆ ) δ: 1.49 (9H, s), 2.45 (3H, s), 4.43 (2H, d, J = 5.9 Hz), 7.53-7 .71 (4H, m), 8.43 (1H, t, J = 5.9 Hz), 11.40 (1H, brs)

２−（ｔ−ブトキシカルボニルアミノ）−Ｎ−（３−シアノベンジル）−４−メチル−チアゾール−５−カルボン酸アミドのＤＭＳＯ溶液（１ｍＬ）に炭酸カリウム２０ｍｇと過酸化水素０．１２ｍＬを加え、室温で１３時間攪拌した。そこに水酸化カリウム５２ｍｇを加え、４．５時間攪拌した。反応混合物に水を加え、酢酸エチルで抽出した。硫酸マグネシウムで乾燥し、減圧下で濃縮した。残渣をシリカゲルカラムクロマトに付して、２−（ｔ−ブトキシカルボニルアミノ）−Ｎ−（３−カルバモイルベンジル）−４−メチル−チアゾール−５−カルボン酸アミド０．２８ｇを得た。
¹Ｈ−ＮＭＲ （ＤＭＳＯ−ｄ₆） δ： １．４９（９Ｈ， ｓ）， ２．４５ （３Ｈ， ｓ）， ４．４３ （２Ｈ， ｄ， Ｊ ＝ ５．９Ｈｚ）， ７．１８（１Ｈ， ｂｒｓ）， ７．３７−７．４５（２Ｈ， ｍ）， ７．７２−７．７５（１Ｈ， ｍ）， ７．８２（２Ｈ， ｂｒｓ）， ８．３９ （１Ｈ， ｔ， Ｊ ＝ ５．９Ｈｚ）， １１．４８（１Ｈ， ｂｒｓ） Reference production example 4

To a DMSO solution (1 mL) of 2- (t-butoxycarbonylamino) -N- (3-cyanobenzyl) -4-methyl-thiazole-5-carboxylic acid amide was added 20 mg of potassium carbonate and 0.12 mL of hydrogen peroxide. Stir at room temperature for 13 hours. Thereto, 52 mg of potassium hydroxide was added and stirred for 4.5 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. Dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.28 g of 2- (t-butoxycarbonylamino) -N- (3-carbamoylbenzyl) -4-methyl-thiazole-5-carboxylic acid amide.
¹ H-NMR (DMSO-d ₆ ) δ: 1.49 (9H, s), 2.45 (3H, s), 4.43 (2H, d, J = 5.9 Hz), 7.18 (1H , Brs), 7.37-7.45 (2H, m), 7.72-7.75 (1H, m), 7.82 (2H, brs), 8.39 (1H, t, J = 5 .9Hz), 11.48 (1H, brs)

  Next, formulation examples are shown. In addition, a part shows a weight part.

Formulation Example 1
Each wettable powder is obtained by thoroughly grinding and mixing 50 parts of any one of the compounds (1) to (22) of the present invention, 3 parts of calcium lignin sulfonate, 2 parts of magnesium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide. Get.

Formulation Example 2
20 parts of any one of the compounds (1) to (22) of the present invention and 1.5 parts of sorbitan trioleate are mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and finely divided by a wet pulverization method. After pulverization, 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate is added thereto, and further 10 parts of propylene glycol is added and stirred to obtain each flowable preparation.

Formulation Example 3
Each powder agent is obtained by pulverizing and mixing well 2 parts of any one of the present compounds (1) to (22), 88 parts of kaolin clay and 10 parts of talc.

Formulation Example 4
Each emulsion is obtained by thoroughly mixing 5 parts of any one of the compounds (1) to (22) of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 75 parts of xylene. Get.

Formulation Example 5
After thoroughly mixing 2 parts of any one of the compounds (1) to (22) of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay, water is added. Knead well and granulate and dry to obtain each granule.

Formulation Example 6
10 parts of any one of the compounds (1) to (22) of the present invention; 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt; and 55 parts of water are mixed and pulverized by a wet pulverization method. Thus, each flowable preparation is obtained.

Formulation Example 7
40 parts of any one of the compounds (1) to (22) of the present invention, 5 parts of propylene glycol (manufactured by Nacalai Tesque), 5 parts of Soprophor FLK (manufactured by Rhodia Nikka), 0.2 part of anti-form C emulsion (Dow Corning), 0.3 part of Proxel GXL (manufactured by Arch Chemical), and 49.5 parts of ion-exchanged water are mixed to prepare a base slurry. 150 parts of glass beads (Φ = 1 mm) are put into 100 parts of the slurry, and pulverized for 2 hours while cooling with cooling water. After grinding, the glass beads are removed by filtration to obtain each flowable formulation.

Formulation Example 8
50 parts of any one of the compounds (1) to (22) of the present invention, 38.5 parts of NN kaolin clay (manufactured by Takehara Chemical Industries), 10 parts of Morwet D425, 1.5 parts of Morwer EFW (Akzo Nobel) And the mixture is pulverized with a jet mill to obtain each powder.

Next, test examples show that the compounds of the present invention are useful for controlling plant diseases.
The control effect is obtained by visually observing the area of the lesion on the test plant at the time of the survey, and comparing the area of the lesion on the plant treated with the compound of the present invention and the area of the lesion on the untreated plant. evaluated.

Test example 1
The plastic pot was filled with soil, tomato (variety: patio) was sown and grown in a greenhouse for 20 days. Each of the compounds (2), (3), (4), (5) and (6) of the present invention is made into a flowable formulation according to Formulation Example 6, and then diluted with water to a predetermined concentration (200 ppm). The foliage was sprayed so as to adhere well to the leaf surface of the seedling. After air-drying the diluted solution on the leaf surface to dryness, an aqueous suspension of Phytophthora infestans spores was spray-inoculated. After inoculation, the plant was first placed at 23 ° C. under high humidity for 1 day, followed by cultivation in an artificial weather room at 20 ° C. for 4 days, and then the lesion area was examined.
The lesion area in the plant which processed this invention compound (2), (3), (4), (5) and (6) was 30% or less of the lesion area in an untreated plant.

Test example 2
Tomato (variety: patio) was sown on a plastic sponge piece and hydroponically cultivated in a plastic cup for about 20 days. Each of the compounds (2), (3) and (4) of the present invention was made into a flowable formulation according to Formulation Example 6, and 0.4 mg per plant in terms of weight was put into the cup of the tomato hydroponics seedling. did. Further, after 7 days of hydroponics, spray inoculation with an aqueous suspension of Phytophthora infestans spores. After inoculation, the plant was first placed at 23 ° C. under high humidity for 1 day, followed by cultivation in an artificial weather room at 20 ° C. for 4 days, and then the lesion area was examined.
The lesion area in the plant which processed this invention compound (2), (3) and (4) was 30% or less of the lesion area in an untreated plant.

Test example 3
A plastic pot was filled with soil, rice (cultivar; Nipponbare) was sown, and grown in a greenhouse for 20 days. Thereafter, each of the compounds (9) and (10) of the present invention is made into a flowable preparation according to Preparation Example 6 and then diluted with water to a predetermined concentration (500 ppm) and sprayed on the foliage so as to adhere well to the rice leaf surface. did. After spraying, the plants were air-dried and placed for 6 days in contact with rice seedlings (variety: Nihonbare) afflicted with Magnaporthe oryzae at 24 ° C in the daytime and 20 ° C in the nighttime. did. As a result, the lesion area on the plant treated with the compounds (9) and (10) of the present invention was 30% or less of the lesion area on the untreated plant.

Test example 4
A plastic pot was filled with soil, seeded with wheat (variety: Shirogane), grown in a greenhouse for 9 days, and then sprinkled with spores of wheat red rust fungus (Puccinia redondita f. Sp. Tritici). After inoculation, it was placed in a dark and humid place at 23 ° C. for 1 day, and then air-dried to obtain a wheat rust-infected seedling. The compound (15) of the present invention was made into a flowable formulation according to Formulation Example 6, diluted with water to a predetermined concentration (500 ppm), and sprayed on the foliage so as to adhere well to the leaf surface of the wheat. After spraying, the plants were air-dried and placed under illumination for 6 days, and then the lesion area was examined. As a result, the lesion area in the plant treated with the compound (15) of the present invention was 30% or less of the lesion area in the untreated plant.

Test Example 5
A plastic pot was filled with soil, seeded with wheat (variety: Apogee), and grown in a greenhouse for 10 days. Each of the compounds (9), (10) and (14) of the present invention is made into a flowable preparation according to Preparation Example 6 and then diluted with water to a predetermined concentration (500 ppm) so that it adheres well to the leaves of the wheat. The foliage was sprayed on the ground. After spraying, the plants were air-dried and spray-inoculated with a water suspension of Septoria tritici spores after 3 or 4 days. After the inoculation, the area was first placed under a high humidity of 18 ° C. for 3 days and further under illumination for 14 to 18 days, and then the lesion area was examined. As a result, the lesion area in the plant which processed this invention compound (9), (10) and (14) was 30% or less of the lesion area in an untreated plant.

Test Example 6
The plastic pot was filled with soil, cucumber (variety: Sagamihanjiro) was sown and grown in a greenhouse for 12 days. The above-mentioned pot was spray-inoculated with a water suspension of Pseudoperonospola cubensis zoosporangium, placed at 23 ° C. under high humidity for 1 day, and then air-dried to obtain a cucumber downy mildew-infected seedling. Each of the compounds (9), (10), (13), (15), (18), (20) and (21) of the present invention was made into a flowable formulation according to Formulation Example 6, then diluted with water to give The concentration (500 ppm) was applied, and the foliage was sprayed so that it sufficiently adhered to the cucumber leaf surface. After spraying, the plants were air-dried and placed in a greenhouse at 23 ° C. for 5 days, and then the lesion area was examined. As a result, the lesion area in the plant treated with the compounds (9), (10), (13), (15), (18), (20) and (21) of the present invention is the lesion spot in the untreated plant. It was 30% or less of the area.

Test Example 7
The plastic pot was filled with soil, tomato (variety: patio) was sown and grown in a greenhouse for 20 days. Each of the compounds (7), (9), (10), (13), (18), (19), (20) and (21) of the present invention was made into a flowable preparation according to Preparation Example 6, Was diluted to a predetermined concentration (500 ppm) and sprayed on the foliage so as to adhere well to the leaf surface of the tomato seedling. After air-drying the diluted solution on the leaf surface to dryness, an aqueous suspension of Phytophthora infestans spores was spray-inoculated. After inoculation, the plant was first placed at 23 ° C. under high humidity for 1 day, followed by cultivation in an artificial weather room at 20 ° C. for 4 days, and then the lesion area was examined.
The lesion area in the plant which processed this invention compound (7), (9), (10), (13), (18), (19), (20) and (21) is the disease in an untreated plant. It was 30% or less of the spot area.

Test Example 8
Tomato (variety: patio) was sown on a plastic sponge piece and hydroponically cultivated in a plastic cup for about 20 days. Each of the compounds (9), (10), (13) and (19) of the present invention was made into a flowable formulation according to Formulation Example 6, and then 1 mg per plant in terms of weight in the above-mentioned tomato hydroponic seedling cup It was thrown into. Further, after 7 days of hydroponics, spray inoculation with an aqueous suspension of Phytophthora infestans spores. After inoculation, the plant was first placed at 23 ° C. under high humidity for 1 day, followed by cultivation in an artificial weather room at 20 ° C. for 4 days, and then the lesion area was examined.
The lesion area in the plant which processed this invention compound (9), (10), (13) and (19) was 30% or less of the lesion area in an untreated plant.

Claims (6)

Formula (1)

[Where,
R ¹ and R ² are the same or different from each other, and are hydrogen, a C1-C5 chain hydrocarbon group optionally substituted with one or more groups selected from group C, and one or more groups selected from group D. C3-C10 cycloalkyl group which may be substituted, phenyl group which may be substituted with one or more groups selected from group E, halogen, cyano group, nitro group, —O—R ⁵ group, —S— R ⁵ group, —C (═O) —R ⁵ group, —C (═O) —OR ⁵ group, —OC (═O) —R ⁵ group, —NR ⁵ R ⁶ group, —C (═O) Represents a —NR ⁵ R ⁶ group or —NR ⁵ —C (═O) —R ⁶ group,
R ⁵ and R ⁶ are the same or different from each other, and are hydrogen, a C1-C10 chain hydrocarbon group optionally substituted with one or more groups selected from group C, and one or more groups selected from group D. A C3-C10 cycloalkyl group which may be substituted or a phenyl group which may be substituted with one or more groups selected from group E.
However, ^one of R ¹ and R ² represents hydrogen, and the other represents a group other than hydrogen.
Group C is a C3-C10 cycloalkyl group which may be substituted with one or more groups selected from Group D, a halogen, a cyano group, a C1-C4 alkoxy group which may be substituted with halogen, or a halogen. An optionally substituted C1-C4 alkylthio group, an optionally substituted C1-C4 alkylsulfinyl group, an optionally substituted C1-C4 alkylsulfonyl group, and an optionally substituted halogen ( A group consisting of a (C1-C4 alkyl) carbonyl group, a (C1-C4 alkoxy) carbonyl group optionally substituted with halogen and a (C1-C4 alkyl) carbonyloxy group optionally substituted with halogen;
Group D represents a group consisting of a C1-C5 alkyl group and halogen,
Group E is halogen, cyano group, nitro group, C1-C10 chain hydrocarbon group which may be substituted with halogen, C3-C10 cycloalkyl group which may be substituted with one or more groups selected from group D C1-C4 alkoxy group optionally substituted with halogen, C1-C4 alkylthio group optionally substituted with halogen, C1-C4 alkylsulfinyl group optionally substituted with halogen, halogen-substituted May be a C1-C4 alkylsulfonyl group, a (C1-C4 alkyl) carbonyl group optionally substituted with halogen, a (C1-C4 alkoxy) carbonyl group optionally substituted with halogen, and a halogen-substituted A good (C1-C4 alkyl) carbonyloxy group is represented. ]
Or an salt thereof. ^2. The amide compound or a salt thereof according to claim 1, wherein R ¹ and R ² are the same or different from each other and are hydrogen or halogen. ^2. The amide compound or a salt thereof according to claim 1, wherein R ¹ and R ² are the same or different from each other and are hydrogen, fluorine, chlorine or bromine.   The plant disease control agent containing the amide compound or its salt of any one of Claims 1-3, and an inert support | carrier.   A method for controlling plant diseases comprising a step of applying an effective amount of the amide compound or salt thereof according to any one of claims 1 to 3 to a plant or a soil in which the plant grows.   Use of the amide compound or a salt thereof according to any one of claims 1 to 3, for controlling plant diseases.