JPWO2004011467A1 - Triazolopyrimidine derivatives and agricultural and horticultural fungicides - Google Patents

Abstract

［式中、Ｈｅｔ_Ａ〜Ｃは、ヘテロ元素を含む５員環または６員環を示し、Ｘ_Ａ〜Ｃは、ハロゲン原子、シアノ基などを示し、Ｒ_ＡおよびＲ_Ａ’は、同一または互いに異なっている、Ｃ１〜Ｃ１０アルキル基、Ｃ２〜Ｃ１０アルケニル基、Ｃ２〜Ｃ１０アルキニル基またはフェニル基を示し、Ｒ_Ｂは、窒素原子で結合している、置換されていてもよい含窒素複素環を示し、Ｒ_Ｃは、Ｃ１〜Ｃ１０アルキル基、Ｃ２〜Ｃ１０アルケニル基、Ｃ２〜Ｃ１０アルキニル基、Ｃ３〜Ｃ８シクロアルキル基、Ｃ４〜Ｃ１０シクロアルキルアルキル基またはアラルキル基を示す。］
で表される新規なトリアゾロピリミジン誘導体を含む農園芸用殺菌剤であって、高い病害防除活性を有し、薬害のない農園芸用殺菌剤。Formula (A), (B) or (C)

[ _Wherein , Het _{A to C} represent a 5-membered ring or 6-membered ring containing a hetero element, X _{A to C} represent a halogen atom, a cyano group, etc., and R _A and R _A ′ are the same or mutually R 1 represents a C1-C10 alkyl group, a C2-C10 alkenyl group, a C2-C10 alkynyl group or a phenyl group which is different, and R _B represents an optionally substituted nitrogen-containing heterocyclic ring bonded with a nitrogen atom. R _C represents a C1 to C10 alkyl group, a C2 to C10 alkenyl group, a C2 to C10 alkynyl group, a C3 to C8 cycloalkyl group, a C4 to C10 cycloalkylalkyl group or an aralkyl group. ]
An agricultural and horticultural fungicide containing a novel triazolopyrimidine derivative represented by the formula (1), having a high disease control activity and no phytotoxicity.

Description

  The present invention relates to a novel triazolopyrimidine derivative and an agricultural and horticultural fungicide containing the derivative as an active ingredient.

（式中、Ｒ_１ａは水素原子、アルキル基、アルコキシ基、アルキルチオ基、ハロアルキル基、ハロアルコキシ基、ハロアルキルチオ基、シアノ基を表し、Ｒ_２ａはアルキル基、アルコキシ基、アルキルチオ基を表し、Ｒ_{３ ａ}はアルキル基、アルコキシ基、アルキルチオ基、ハロアルキル基、ハロアルコキシ基、ハロアルキルチオ基を表す。）
（２）国際公開特許ＷＯ９９／４１２５５号公報には、下記一般式で示されるトリアゾロピリミジン誘導体が殺菌活性を有することが記載されている。

（式中、Ｒ_１ｂが置換されてもよいアルキル基、アルケニル基、アルキニル基、アルカジエニル基、アリール基、シクロアルキル基もしくはシクロアルケニル基を表し、Ｒ_２ｂが水素原子、ハロゲン原子、ヒドロキシ基、アルコキシ基などを表し、Ｒ_３ｂ、Ｒ_４ｂ、Ｒ_５ｂ、Ｒ_６ｂおよびＲ_７ｂが、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、アルコキシ基、ニトロ基もしくはシアノ基を表す。）
（３）欧州特許第２１５３８２号公報には、下記一般式で表されるトリアゾロピリミジン誘導体が殺菌活性を有することが記載されている。

（式中、Ｒ_１ｃは無置換または置換アルキル基、無置換または置換アラルキル基、無置換または置換アリール基などを表し、Ｒ_２ｃおよびＲ_３ｃは水素原子、アルキル基、アリール基を表し、Ａは窒素原子、ＣＲ_４ｃを表し、Ｒ_４ｃは水素原子、ハロゲン原子、アルキル基を表す。）
（４）国際公開特許ＷＯ００／４４７５４号公報には、下記一般式で表されるトリアゾロピリミジン誘導体が人体への脂肪蓄積を抑制する活性を有することが記載されている。

（式中、Ｒ_１ｄは水素原子、アルキル基、アルケニル基などを表し、Ｒ_{２ ｄ}およびＲ_３ｄは水素原子、ハロゲン原子、アルキル基、アルケニル基などを表し、Ｒ_４ｄは水素原子、アルキル基などを表し、Ｒ_５ｄはアルキル基、アルケニル基などを表し、Ａは窒素原子、ＣＨなどを表す。）
（５）米国特許第５５９３９９６号明細書には、下記一般式で表されるトリアゾロピリミジン誘導体が殺菌活性を有することが記載されている。

（式中、Ｒ_１ｅはアルキル基、アルケニル基、シクロアルキル基、複素環式基などを表し、Ｒ_２ｅは水素原子、アルキル基を表し、あるいは、Ｒ_{１ ｅ}およびＲ_２ｅは隣接する窒素原子と一緒になって複素環式基を表し、Ｒ_３ｅはアリール基を表し、Ｒ_４ｅは水素原子、ハロゲン原子、アルキルアミノ基を表す。）
（６）国際公開特許ＷＯ０１／９６３４１号公報には、下記一般式で表されるトリアゾロピリミジン誘導体を原料として用いたトリアゾロピリミジン−７−イリデン誘導体を製造する方法が記載されている。しかしながら、下記一般式で表されるトリアゾロピリミジン誘導体のうち、Ｒ_２ｆが複素環である誘導体は、具体例は開示されていない。

（式中、Ｒ_１ｆは水素原子、アルキル基、アルケニル基、アルキニル基、ハロアルキル基、シクロアルキル基、フェニル基、ナフチル基、複素環式基などを表し、Ｒ_２ｆはフェニル基、シクロアルキル基、複素環式基を表し、Ｒ_３ｆはハロゲン原子、アミノ基、アルコキシ基、ハロアルコキシ基、アルキルアミノ基などを表す。）
しかしながら、上記文献に記載の化合物は、後期試験例に示されるとおり、農園芸分野の病害に対し殺菌活性が不十分であり、特に治療効果はほとんどなく、また、作物に薬害を与えたりすることから、実用上満足しがたい。従って、従来の薬剤とは異なる新規な化合物を含む農園芸用殺菌剤が要望されている。Until now, several triazolopyrimidine derivatives similar in chemical structure to the present invention are known as shown below.
(1) Japanese Patent Application Laid-Open No. 05-262773 describes that a triazolopyrimidine represented by the following general formula has herbicidal activity.

(Wherein R _1a represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, a haloalkyl group, a haloalkoxy group, a haloalkylthio group or a cyano group, R _2a represents an alkyl group, an alkoxy group or an alkylthio group; _{3 a} represents an alkyl group, an alkoxy group, an alkylthio group, a haloalkyl group, a haloalkoxy group, or a haloalkylthio group.
(2) International Patent Publication No. WO99 / 41255 describes that a triazolopyrimidine derivative represented by the following general formula has bactericidal activity.

(Wherein R _1b represents an optionally substituted alkyl group, alkenyl group, alkynyl group, alkadienyl group, aryl group, cycloalkyl group or cycloalkenyl group, and R _2b represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group) And R _3b , R _4b , R _5b , R _6b and R _7b each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a nitro group or a cyano group.
(3) European Patent No. 215382 describes that a triazolopyrimidine derivative represented by the following general formula has bactericidal activity.

(Wherein R _1c represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted aryl group, etc., R _2c and R _3c represent a hydrogen atom, an alkyl group, or an aryl group, and A represents A nitrogen atom and CR _4c are represented, and R _4c represents a hydrogen atom, a halogen atom and an alkyl group.)
(4) International Patent Publication WO00 / 44754 describes that a triazolopyrimidine derivative represented by the following general formula has an activity of suppressing fat accumulation in the human body.

_{(Wherein, R 1d} is a hydrogen atom, an alkyl group, an alkenyl _{group, R 2 d,} and _{R 3d} is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl _{group, R 4d} is hydrogen, an alkyl group such as R _5d represents an alkyl group, an alkenyl group, and the like, and A represents a nitrogen atom, CH, and the like.)
(5) US Pat. No. 5,593,996 describes that a triazolopyrimidine derivative represented by the following general formula has bactericidal activity.

(Wherein R _1e represents an alkyl group, an alkenyl group, a cycloalkyl group, a heterocyclic group, etc., R _2e represents a hydrogen atom or an alkyl group, or R _{1 e} and R _2e represent an adjacent nitrogen atom and Together, they represent a heterocyclic group, R _3e represents an aryl group, and R _4e represents a hydrogen atom, a halogen atom, or an alkylamino group.)
(6) International Patent Publication WO01 / 96341 describes a method for producing a triazolopyrimidine-7-ylidene derivative using a triazolopyrimidine derivative represented by the following general formula as a raw material. However, no specific example is disclosed of a derivative in which R _2f is a heterocyclic ring among the triazolopyrimidine derivatives represented by the following general formula.

(Wherein R _1f represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, a cycloalkyl group, a phenyl group, a naphthyl group, a heterocyclic group, etc., and R _2f represents a phenyl group, a cycloalkyl group, Represents a heterocyclic group, and R _3f represents a halogen atom, an amino group, an alkoxy group, a haloalkoxy group, an alkylamino group, or the like.
However, the compounds described in the above documents have insufficient bactericidal activity against diseases in the field of agriculture and horticulture, as shown in the latter-stage test examples, have no particularly therapeutic effect, and cause phytotoxicity to crops. Therefore, it is not satisfactory in practical use. Accordingly, there is a demand for agricultural and horticultural fungicides containing novel compounds different from conventional drugs.

［式中、
Ｈｅｔ_Ａは、ヘテロ元素を含む５員環または６員環を示し、これらの環はハロゲン原子、Ｃ１〜Ｃ６アルキル基、Ｃ１〜Ｃ６アルコキシ基、Ｃ１〜Ｃ６ハロアルキル基またはＣ２〜Ｃ６アルコキシアルキル基で置換されていてもよく、
Ｘ_Ａは、ハロゲン原子、シアノ基、Ｃ１〜Ｃ６アルコキシ基、Ｃ１〜Ｃ６アルキルチオ基、Ｃ１〜Ｃ６アルキルスルフィニル基、Ｃ１〜Ｃ６アルキルスルホニル基、Ｃ１〜Ｃ６アルキルアミノ基またはＣ１〜Ｃ６アルコキシカルボニル基を示し、かつ
Ｒ_ＡおよびＲ_Ａ’は、同一または互いに異なっている、Ｃ１〜Ｃ１０アルキル基、Ｃ２〜Ｃ１０アルケニル基、Ｃ２〜Ｃ１０アルキニル基またはフェニル基（当該アルキル基、アルケニル基、アルキニル基およびフェニル基は、ハロゲン原子、Ｃ１〜Ｃ６アルキル基、Ｃ１〜Ｃ６ハロアルキル基、Ｃ１〜Ｃ６アルコキシ基、Ｃ１〜Ｃ６アルキルチオ基、Ｃ１〜Ｃ６アルコキシカルボニル基およびカルボキシル基からなる群から選ばれた１または複数の基で置換されていてもよい）を示す。］
で表されるトリアゾロピリミジン誘導体。
（２） 前記Ｈｅｔ_Ａは、以下の一般式Ｈｅｔ_１〜Ｈｅｔ_１５で表される基

（ここでＲ_１、Ｒ_２およびＲ_３は、同一または異なっている、水素原子、Ｃ１〜Ｃ６アルキル基、Ｃ１〜Ｃ６アルコキシ基、Ｃ１〜Ｃ６ハロアルキル基、またはハロゲン原子を表す）のいずれかの基を示し、
前記Ｘ_Ａは、ハロゲン原子を示し、かつ
前記Ｒ_ＡおよびＲ_Ａ’は、同一または互いに異なっている、Ｃ１〜Ｃ１０アルキル基、Ｃ２〜Ｃ１０アルケニル基またはＣ２〜Ｃ１０アルキニル基（当該アルキル基、アルケニル基およびアルキニル基は、ハロゲン原子、Ｃ１〜Ｃ６アルキル基またはＣ１〜Ｃ６ハロアルキル基で置換されていてもよい）を示す
ことを特徴とする、（１）に記載のトリアゾロピリミジン誘導体。
（３） 前記Ｈｅｔ_Ａは、前記Ｈｅｔ_１、Ｈｅｔ_６またはＨｅｔ_１２で表される基であることを特徴とする、（２）に記載のトリアゾロピリミジン誘導体。
（４） 一般式（Ｂ）

［式中、
Ｈｅｔ_Ｂは、ヘテロ元素を含む５員環または６員環を示し、これらはハロゲン原子、Ｃ１〜Ｃ６アルキル基、Ｃ１〜Ｃ６アルコキシ基、Ｃ１〜Ｃ６ハロアルキル基またはＣ２〜Ｃ６アルコキシアルキル基で置換されていてもよく、
Ｘ_Ｂは、ハロゲン原子、シアノ基、Ｃ１〜Ｃ６アルコキシ基、Ｃ１〜Ｃ６アルキルチオ基、Ｃ１〜Ｃ６アルキルスルフィニル基、Ｃ１〜Ｃ６アルキルスルホニル基、Ｃ１〜Ｃ６アルキルアミノ基またはＣ１〜Ｃ６アルコキシカルボニル基を示し、かつ
Ｒ_Ｂは、窒素原子で結合している、置換されていてもよい含窒素複素環を示す。］
で表されるトリアゾロピリミジン誘導体。
（５） 前記Ｈｅｔ_Ｂは、上記の一般式Ｈｅｔ_１〜Ｈｅｔ_１５で示される基のいずれかの基を示し、かつ
前記Ｘ_Ｂは、ハロゲン原子を示す
ことを特徴とする、（４）に記載のトリアゾロピリミジン誘導体。
（６） 前記Ｈｅｔ_Ｂは、前記Ｈｅｔ_１、Ｈｅｔ_６またはＨｅｔ_１２で表される基であることを特徴とする、（５）に記載のトリアゾロピリミジン誘導体。
（７） 一般式（Ｃ）

［式中、
Ｈｅｔ_Ｃは、ヘテロ元素を含む５員環または６員環を示し、これらの５員環または６員環はハロゲン原子、Ｃ１〜Ｃ６アルキル基、Ｃ１〜Ｃ６アルコキシ基、Ｃ１〜Ｃ６ハロアルキル基およびＣ２〜Ｃ６アルコキシアルキル基からなる群から選ばれた基によって置換されていてもよく、
Ｘ_Ｃは、ハロゲン原子、シアノ基、Ｃ１〜Ｃ６アルコキシ基またはＣ１〜Ｃ６アルキルチオ基を示し、かつ
Ｒ_Ｃは、Ｃ１〜Ｃ１０アルキル基、Ｃ２〜Ｃ１０アルケニル基、Ｃ２〜Ｃ１０アルキニル基、Ｃ３〜Ｃ８シクロアルキル基、Ｃ４〜Ｃ１０シクロアルキルアルキル基またはアラルキル基を示し、当該アラルキル基のベンゼン環はハロゲン原子、Ｃ１〜Ｃ６アルキル基、Ｃ１〜Ｃ６アルコキシ基またはＣ１〜Ｃ６アルキルチオ基により置換されていてもよい。］
で表される、トリアゾロピリミジン誘導体。
（８） 前記Ｈｅｔ_Ｃは前記一般式Ｈｅｔ_１で表される基であることを特徴とする、（７）に記載のトリアゾロピリミジン誘導体。
（９） （１）〜（８）のいずれかに記載のトリアゾロピリミジン誘導体を活性成分として含有することを特徴とする、農園芸用殺菌剤。
前記一般式（Ａ）、一般式（Ｂ）、一般式（Ｃ）または一般式Ｈｅｔ_１〜Ｈｅｔ_１５上の基であるアルキル基、またはハロアルキル基、アルコキシ基、ハロアルコキシ基、アルキルチオ基、アルコキシカルボニル基もしくはアルキルアミノ基のアルキル部分は、直鎖状であっても、分岐鎖状であってもよい。
前記一般式（Ａ）においてＨｅｔ_Ａまたは前記一般式（Ｂ）においてＨｅｔ_Ｂは、ヘテロ元素を環内に含む任意の５員環または６員環であるが、好ましくは、前記一般式Ｈｅｔ_１〜Ｈｅｔ_１５のいずれかで表される環であり、さらに好ましくは、前記Ｈｅｔ_１、Ｈｅｔ_６またはＨｅｔ_１２で表される環である。
また、前記一般式（Ｃ）においてＨｅｔ_Ｃは、ヘテロ元素を環内に含む任意の５員環または６員環であるが、好ましくは次の一般式で示されるいずれかの環であり、さらに好ましくは、前記Ｈｅｔ_１で表される環である。

Ｈｅｔ_Ａ、Ｈｅｔ_ＢもしくはＨｅｔ_Ｃ上の、またはＨｅｔ_１〜Ｈｅｔ_１５上のＲ_１、Ｒ_２もしくはＲ_３であるハロゲン原子としては、塩素原子、臭素原子、ヨウ素原子およびフッ素原子が挙げられ、Ｃ１〜Ｃ６アルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｎ−ペンチル基、イソアミル基およびｎ−ヘシキル基などが挙げられ、Ｃ１〜Ｃ６アルコキシ基としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔ−ブトキシ基、イソブトキシ基およびイソヘキシルオキシ基などが挙げられ、Ｃ１〜Ｃ６ハロアルキル基としては、トリフルオロメチル基、ジフルオロメチル基、トリクロロメチル基、ジクロロメチル基、フルオロメチル基、クロロメチル基、ヨードメチル基、ブロモメチル基、ペンタフルオロエチル基、２，２，２−トリフルオロエチル基、およびペンタクロロエチル基などが挙げられ、Ｃ２〜Ｃ６アルコキシアルキル基としては、メトキシメチル基、エトキシメチル基、ｎ−プロポキシメチル基、イソプロポキシエチル基、ｎ−ブトキシメチル基、ｓｅｃ−ブトキシメチル基、ｔ−ブトキシメチル基、イソブトキシメチル基、ｎ−ブトキシエチル基などが挙げられる。
前記一般式（Ａ）においてＲ_ＡまたはＲ_Ａ’であるＣ１〜Ｃ１０アルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、イソアミル基、ｎ−ヘシキル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基およびｎ−デシル基などが挙げられ、Ｃ２〜Ｃ１０アルケニル基としては、ビニル基、アリル基、１−ブテニル基、２−ブテニル基、１−イソブテニル基、３−メチル−２−ブテニル基、１−ペンテニル基、１−ヘキセニル基および１−オクテニル基などが挙げられ、Ｃ２〜Ｃ１０アルキニル基としては、エチニル基、２−プロピニル基、２−ブチニル基、３−ブチニル基、５−ペンチニル基、３，３−ジメチル−１−ブチニル基、４−メチル−１−ペンチニル基および７−オクチニル基などが挙げられる。また、Ｒ_ＡおよびＲ_Ａ’であるアルキル基、アルケニル基、アルキニル基またはフェニル基上の１または複数の水素と置換しているハロゲン原子としては、塩素原子、臭素原子、ヨウ素原子およびフッ素原子が挙げられ、Ｃ１〜Ｃ６アルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｎ−ペンチル基、イソアミル基およびｎ−ヘシキル基などが挙げられ、Ｃ１〜Ｃ６ハロアルキル基としては、トリフルオロメチル基、ジフルオロメチル基、トリクロロメチル基、ジクロロメチル基、フルオロメチル基、クロロメチル基、ヨードメチル基、ブロモメチル基、ペンタフルオロエチル基およびペンタクロロエチル基などが挙げられ、Ｃ１〜Ｃ６アルコキシ基としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔ−ブトキシ基、イソブトキシ基およびイソヘキシルオキシ基などが挙げられ、Ｃ１〜Ｃ６アルキルチオ基としては、メチルチオ基、エチルチオ基、ｎ−プロピルチオ基、イソプロピルチオ基、ｎ−ブチルチオ基、ｓｅｃ−ブチルチオ基、ｔ−ブチルチオ基、イソブチルチオ基およびイソヘシキルチオ基などが挙げられ、Ｃ１〜Ｃ６アルコキシカルボニル基としては、メトキシカルボニル基、エトキシカルボニル基、ｎ−プロポキシカルボニル基、イソプロポキシカルボニル基、ｎ−ブトキシカルボニル基、ｓｅｃ−ブトキシカルボニル基、ｔ−ブトキシカルボニル基、イソブトキシカルボニル基およびイソヘキシルオキシカルボニル基などが挙げられる。
前記一般式（Ｂ）においてＲ_Ｂは、トリアゾロピリミジン環と窒素原子で結合している、置換されていてもよい任意の含窒素複素環であるが、好ましくは、下記の含窒素複素環が挙げられる。

一般式（Ｃ）において、Ｒ_ＣであるＣ１〜Ｃ１０アルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、イソアミル基、ｎ−ヘシキル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基およびｎ−デシル基などが挙げられる。Ｃ２〜Ｃ１０アルケニル基としては、ビニル基、アリル基、１−ブテニル基、２−ブテニル基、１−イソブテニル基、３−メチル−２−ブテニル基、１−ペンテニル基、１−ヘキセニル基および１−オクテニル基などが挙げられる。Ｃ２〜Ｃ１０のアルキニル基としては、エチニル基、２−プロピニル基、２−ブチニル基、３−ブチニル基、５−ペンチニル基、３，３−ジメチル−１−ブチニル基、４−メチル−１−ペンチニル基および７−オクチニル基などが挙げられる。Ｃ３〜Ｃ８シクロアルキル基としては、シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプロチル基およびシクロオクチル基などが挙げられる。Ｃ４〜Ｃ１０シクロアルキルアルキル基としては、シクロプロピルメチル基、シクロプロピルエチル基、シクロブチルメチル基、シクロペンチルメチル基、シクロヘキシルメチル基およびシクロヘキシルエチル基などが挙げられる。アラルキル基としては、ベンジル基、α−フェネチル基、β−フェネチル基、３−フェニルプロピル基および４−フェニルブチル基などが挙げられる。
一般式（Ｃ）においてＲ_Ｃである、ベンゼン環にハロゲン原子の置換したアラルキル基としては、２−クロロベンジル基、３−クロロベンジル基、４−クロロベンジル基、２−クロロ−６−フルオロベンジル基、２，６−ジクロロベンジル基、２，３−ジクロロベンジル基、２，４−ジクロロベンジル基、３，４−ジクロロベンジル基、３−ブロモベンジル基、２−フルオロベンジル基、３−フルオロベンジル基、４−フルオロベンジル基、２，６−ジフルオロベンジル基、２，５−ジフルオロベンジル基、３，４−ジフルオロベンジル基、３，５−ジフルオロベンジル基、４−クロロ−α−フェネチル基および４−クロロ−β−フェネチル基などが挙げられる。ベンゼン環にＣ１〜Ｃ６アルキル基で置換したアラルキル基としては、２−メチルベンジル基、３−メチルベンジル基、４−メチルベンジル基、２，４−ジメチルベンジル基、３，４−ジメチルベンジル基、２，４，６−トリメチルベンジル基、４−エチルベンジル基、４−イソプロピルベンジル基、２，４，６−トリイソプロピルベンジル基、ｐ−ｔ−ブチルベンジル基および３，５−ジ−ｔ−ブチルベンジル基などが挙げられる。ベンゼン環にＣ１〜Ｃ６アルコキシ基で置換したアラルキル基としては、２−メトキシベンジル基、３−メトキシベンジル基、３，４−ジメトキシベンジル基、３，５−ジメトキシベンジル基、３−メトキシ−４−エトキシベンジル基、４−エトキシベンジル基、４−ｎ−プロポキシベンジル基、４−イソプロポキシベンジル基、４−ｎ−ブトキシベンジル基、４−ｓｅｃ−ブトキシベンジル基、４−イソブトキシベンジル基、４−ｔ−ブトキシベンジル基および４−イソヘキシルオキシベンジル基などが挙げられる。ベンゼン環にＣ１〜Ｃ６アルキルチオ基で置換したアラルキル基としては、２−メチルチオベンジル基、３−メチルチオベンジル基、４−メチルチオベンジル基、４−エチルチオベンジル基、４−ｎ−プロピルチオベンジル基、４−イソプロピルチオベンジル基、４−ｎ−ブチルチオベンジル基、４−ｓｅｃ−ブチルチオベンジル基、４−イソブチルチオベンジル基、４−ｔ−ブチルチオベンジル基および４−イソヘキシルチオベンジル基などが挙げられる。
一般式（Ａ）においてＸ_Ａ、一般式（Ｂ）においてＸ_Ｂまたは一般式（Ｃ）においてＸ_Ｃであるハロゲン原子としては、塩素原子、臭素原子、ヨウ素原子およびフッ素原子が挙げられる。Ｃ１〜Ｃ６アルコキシ基としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔ−ブトキシ基、イソブトキシ基、ｎ−ペンチルオキシ基およびイソヘキシルオキシ基などが挙げられる。Ｃ１〜Ｃ６アルキルチオ基としては、メチルチオ基、エチルチオ基、ｎ−プロピルチオ基、イソプロピルチオ基、ｎ−ブチルチオ基、ｓｅｃ−ブチルチオ基、ｔ−ブチルチオ基、イソブチルチオ基およびイソヘキシルチオ基などが挙げられる。
一般式（Ａ）においてＸ_Ａまたは一般式（Ｂ）においてＸ_ＢであるＣ１〜Ｃ６アルキルスルフィニル基としては、メチルスルフィニル基、エチルスルフィニル基、ｎ−プロピルスルフィニル基、イソプロピルスルフィニル基、ｎ−ブチルスルフィニル基、ｓｅｃ−ブチルスルフィニル基、ｔ−ブチルスルフィニル基、イソブチルスルフィニル基およびイソヘキシルスルフィニル基などが挙げられる。Ｃ１〜Ｃ６アルキルスルホニル基としては、メチルスルホニル基、エチルスルホニル基、ｎ−プロピルスルホニル基、イソプロピルスルホニル基、ｎ−ブチルスルホニル基、ｓｅｃ−ブチルスルホニル基、ｔ−ブチルスルホニル基、イソブチルスルホニル基およびイソヘキシルスルホニル基などが挙げられる。Ｃ１〜Ｃ６アルキルアミノ基は、モノアルキルアミノ基であっても、ジアルキルアミノ基であってもよく、アルキル部位の例としては、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、イソヘキシルなどが挙げられる。Ｃ１〜Ｃ６アルコキシカルボニル基の、アルコキシ部位としては、メトキシ、エトキシ、ｎ−プロポキシ、イソプロポキシ、ｎ−ブトキシ、ｓｅｃ−ブトキシ、ｔ−ブトキシ、イソブトキシ、ｎ−ペンチルオキシおよびイソヘキシルオキシなどが挙げられる。
一般式（Ａ）で表される本発明に係るトリアゾロピリミジン誘導体の具体例を表１〜表１０に、一般式（Ｂ）で表される本発明に係るトリアゾロピリミジン誘導体の具体例を表１１〜表２２に、一般式（Ｃ）で表される本発明に係るトリアゾロピリミジン誘導体の具体例を表２３〜表２５に示した。さらに、これらの誘導体の中間体となりうる化合物（下記するスキーム１において一般式（１）で表される化合物）の具体例を表２６に示した。
なお、表中で「Ｍｅ」はメチル基を、「Ｅｔ」はエチル基を、「ｎＰｒ」はｎ−プロピル基を、「ｉＰｒ」はイソプロピル基を、「ｎＢｕ」はｎ−ブチル基を、「ｉＢｕ」はイソブチル基を、「ｎＰｅｎ」はｎ−ペンチル基を表す。表中の化合物Ｎｏ．は、下記の実施例および試験例においても参照される。

一般式（Ａ）、一般式（Ｂ）または一般式（Ｃ）で表されるトリアゾロピリミジン誘導体は、下記のスキーム１に示される方法によって製造することができる。
スキーム１

（式中Ｈａｌｏはハロゲン原子を示し、Ｈｅｔ_Ａ、Ｈｅｔ_ＢおよびＨｅｔ_ＣならびにＲ_Ａ、Ｒ_Ａ’、Ｒ_Ｂ、Ｒ_Ｃは前記と同様であり、ＨｅｔはＨｅｔ_Ａ、Ｈｅｔ_ＢまたはＨｅｔ_Ｃのいずれかを示し、Ｗは水素原子またはナトリウム、カリウムなどのアルカリ金属原子を示し、Ｙはシアノ基、Ｃ１〜Ｃ６アルコキシ基、Ｃ１〜Ｃ６アルキルチオ基、Ｃ１〜Ｃ６アルキルスルフィニル基、Ｃ１〜Ｃ６アルキルスルホニル基、Ｃ１〜Ｃ６アルキルアミノ基またはＣ１〜Ｃ６アルコキシカルボニル基を示す）
一般式（１）の化合物と一般式（２）の化合物とを反応させる工程（Ｓｔｅｐ１）または一般式（１）の化合物と一般式（４）の化合物とを反応させる工程（Ｓｔｅｐ３）は、一般式（１）の化合物に対して好ましくは１当量の一般式（２）の化合物または一般式（４）の化合物を加え、１．０〜２．５当量の塩基の存在下、適当な有機溶媒中で行われる。反応温度は、２０〜１５０℃であり、反応時間は１〜８時間である。塩基としては、トリエチルアミン、Ｎ，Ｎ−ジエチルアニリンなどの有機塩基類、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、油性水素化ナトリウムなどの無機塩基類が使用できる。有機溶媒としては、トルエン、キシレンなどの炭化水素類、クロロホルム、クロロベンゼンなどのハロゲン化炭化水素類、ジオキサン、テトラヒドロフランなどのエーテル類、アセトニトリルなどのニトリル類、ジメチルホルムアミド、ジメチルアセトアミドなどのアミド類およびジメチルスルホキシドなどが使用できる。反応終了後は、反応液に水と、ベンゼン、トルエン、クロロホルムなどの有機溶媒を加えて抽出し、有機溶媒層を無水硫酸ナトリウム、無水硫酸マグネシウムなどにより脱水後、溶媒を留去するなどの通常処理を行う。必要ならば、クロマトグラフィーなどの操作によって精製を行う。なお、本反応の原料化合物である一般式（２）の化合物および一般式（４）の化合物は、市販品として入手可能であるか、または公知の方法により容易に製造できる公知化合物である。
このようにして得られた５−ハロゲントリアゾロピリミジン誘導体（Ａ’）または（Ｂ’）を、塩基の存在下に、一般式（３）で表される化合物であるアルコール、アルキルアミンまたはチオールなどと、あるいはアルカリ金属シアニドなどと反応させる（Ｓｔｅｐ２またはＳｔｅｐ４）ことにより一般式（Ａ’’）または（Ｂ’’）で表されるトリアゾロピリミジン誘導体を製造することができる。なお、本反応の原料化合物である一般式（３）で表される化合物は、市販品として入手可能であるか、または公知の方法により容易に製造できる公知化合物である。このような一般式（３）で表される化合物の例としては、例えばメチルアルコール、エチルアルコール、イソプロピルアルコール、メチルアミン、エチルアミン、メチルメルカプトナトリウム、シアン化ナトリウム、シアン化カリウムなどが挙げられる。
一般式（１）で表される化合物と一般式（５）で表される化合物とを反応させる工程（Ｓｔｅｐ５）は、化合物（１）に対して好ましくは１当量の化合物（５）を加え、０．０１〜１．０当量のパラジウムまたはニッケルなどの遷移金属の存在下、適当な有機溶媒中で行われる。この反応によって、一般式（Ｃ）で表わされる化合物のうち、Ｘがハロゲン原子である、５−ハロゲントリアゾロピリミジン誘導体（化合物（Ｃ’））が得られる。有機溶媒としては、トルエン、キシレンなどの炭化水素類またはジオキサン、テトラヒドロフランなどのエーテル類などが使用できる。反応温度は、２０〜１５０℃であり、好ましくは、使用される有機溶媒の沸点に近い温度であり、反応時間は１〜８時間である。
さらに、得られた一般式（Ｃ’）で表される５−ハロゲントリアゾロピリミジン誘導体を、塩基の存在下にアルコールまたはチオールを用いて、または金属シアニドなどと反応することにより、本発明の一般式（Ｃ）で表されるトリアゾロピリミジン誘導体を製造することができる。本反応で使用する塩基の例としては、例えばトリエチルアミン、Ｎ，Ｎ−ジエチルアニリンなどの有機塩基類、水酸化ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウムまたは水素化ナトリウムなどの無機塩基が挙げられ、金属シアニドの例としては、例えばシアン化ナトリウム、シアン化カリウムなどが挙げられる。
反応終了後は、反応液に水およびベンゼン、トルエンまたはクロロホルムなどの有機溶媒を加えて抽出し、分液操作をした後、有機溶媒層を無水硫酸ナトリウムまたは無水硫酸マグネシウムなどで脱水し、有機溶媒を留去するなどの通常の処理を行う。また必要ならば、クロマトグラフィー、再結晶などの操作で精製を行う。
上記した本反応の一方の原料化合物である化合物（５）は公知化合物であり、市販品を入手して用いるか、または公知の方法により製造して用いることができる。
上記スキーム１中の、一般式（１）で表されるジハロゲントリアゾロピリミジン誘導体は、以下に示すスキーム２に従って製造することができる。
スキーム２

（式中Ｈａｌｏはハロゲン原子を示し、ＲはＣ１〜Ｃ１０のアルキル基を示し、ＨｅｔはＨｅｔ_Ａ、Ｈｅｔ_ＢまたはＨｅｔ_Ｃのいずれかを示し、ここでＨｅｔ_Ａ、Ｈｅｔ_ＢおよびＨｅｔ_Ｃは前記と同様である。）
すなわち、一般式（１）で表される化合物は、一般式（７）で表されるマロン酸エステル誘導体と一般式（６）で表される３−アミノ−１，２，４−トリアゾールを縮合させて一般式（８）で表される化合物を得て、これをハロゲン化することにより製造することができる。この反応を次の縮合工程とハロゲン化工程に分けて説明する。
（縮合工程） 化合物（７）と化合物（６）とを反応させる工程は、化合物（６）に対して好ましくは１当量の化合物（７）を加え、１〜５当量の塩基の存在下、必要に応じて適当な有機溶媒中で行われる。この反応工程で用いられる塩基としては、ナトリウムメトキシドなどのアルカリ金属アルコキシド、トリエチルアミン、トリ−ｎ−プロピルアミン、トリ−ｎ−ブチルアミン、ピリジン、ジメチルアミノピリジン、Ｎ，Ｎ−ジエチルアニリンなどの有機塩基類、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウムなどの無機塩基類である。有機溶媒としては、トルエン、キシレンなどの炭化水素類、クロロベンゼンなどのハロゲン化炭化水素類、ジオキサン、テトラヒドロフランなどのエーテル類、メタノール、エタノール、ｎ−ブタノールなどのアルコール類、ジメチルホルムアミド、ジメチルアセトアミドなどのアミド類およびジメチルスルホキシドなどが使用できる。上記反応を円滑にするうえで好ましい反応温度は、２０〜１５０℃であり、好ましくは、使用される有機溶媒の沸点に近い温度であり、反応時間は、使用する原料化合物、触媒、反応温度などによって異なるが、一般的には１〜８時間である。こうして反応させれば、化合物（８）が得られる。この化合物を分取して次の反応に用いてもよいが、そのまま次の反応工程に用いることが好ましい。
（ハロゲン化工程） 上記反応で得た化合物（８）をハロゲン化して化合物（１）を得る工程は、上記工程で生成した化合物（８）を含む反応溶液に、必要に応じて脱酸剤の存在下、化合物（８）に対し１〜１０当量のハロゲン化剤を加えて反応させればよい。次に、反応液から使用した溶媒および過剰のハロゲン化剤を留去するなどの通常処理を行うか、さらに必要ならば、クロマトグラフィー、再結晶などの操作によって精製を行うことで、目的とする化合物（１）を得ることができる。ハロゲン化工程に使用できる脱酸剤としては、トリエチルアミン、トリ−ｎ−プロピルアミン、トリ−ｎ−ブチルアミン、ピリジン、ジメチルアミノピリジン、Ｎ，Ｎ−ジエチルアニリンなどの有機塩基類、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウムなどの無機塩基類があげられる。ハロゲン化工程に使用できるハロゲン化剤の例としては、オキシ塩化リン、オキシ臭化リンなどがあげられる。上記ハロゲン化剤は溶媒も兼ねるので、該反応は特に反応溶媒を必要としないが、反応に有機溶媒を使用するときは、例えばベンゼン、トルエンなどの炭化水素類、クロロベンゼン、クロロホルムなどのハロゲン化炭化水素類などが使用できる。ハロゲン化の反応温度は、５０〜１５０℃であり、反応時間は１〜１０時間である。
また、得られた一般式（１）で表されるハロゲントリアゾロピリミジン誘導体を、必要に応じて０．０５〜２．５当量の塩基の存在下、化合物（１）に対し、１〜１０当量のハロゲン化剤を加え、適当な有機溶媒中で反応させることにより、Ｈｅｔ上の水素原子をハロゲン原子に置換させることができる。反応で使用できるハロゲン化剤の例としては、塩素、塩化スルフリル、Ｎ−クロロスクシンイミド、臭素、Ｎ−ブロモスクシンイミドなどが使用できる。反応に使用できる塩基としては、トリエチルアミン、トリ−ｎ−プロピルアミン、トリ−ｎ−ブチルアミン、ピリジン、ジメチルアミノピリジン、Ｎ，Ｎ−ジエチルアニリンなどの有機塩基類、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウムなどの無機塩基類が使用できる。ハロゲン化の反応温度は、５０〜１５０℃であり、反応時間は１〜１０時間である。有機溶媒として、ベンゼン、トルエンなどの炭化水素類、クロロベンゼン、クロロホルムなどのハロゲン化炭化水素類などが使用できる。
一般式（７）で表されるマロン酸エステル誘導体は、下記するスキーム３に示す方法（Ｍｅｔｈｏｄ１〜Ｍｅｔｈｏｄ３）により製造することができる。
スキーム３

（式中、ＨｅｔおよびＲは、前記と同じ意味を表し、Ｚはハロゲン原子またはＣ１〜Ｃ１０アルコキシ基を表す。）

（式中、ＨｅｔおよびＲは、前記と同じ意味を表し、Ｌはハロゲン原子、ｐ−トルエンスルホニル基、メタンスルホニル基などの脱離基を表す。）

（式中、Ｈａｌｏ、Ｒ、Ｒ_２およびＲ_３は、前記と同じ意味を表し、ＡおよびＢは窒素原子およびＣＲ_１、あるいはＣＲ_１および窒素原子を表し、ここでＲ_１は前記と同じ意味を表す。）
以下、Ｍｅｔｈｏｄ１〜３のそれぞれについて、詳細に説明する。
（Ｍｅｔｈｏｄ１） 一般式（９）で表される化合物と一般式（１０）で表される化合物との反応は、化合物（９）に対して１〜２当量の化合物（１０）に加え、必要に応じて１〜２当量の塩基の存在下、適当な有機溶媒中で行われる。反応温度は、−７０〜１５０℃であり、反応時間は１〜８時間である。塩基としては、ナトリウムメトキシドなどのアルカリ金属アルコキシド、トリエチルアミン、Ｎ，Ｎ−ジエチルアニリンなどの有機塩基類、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、油性水素化ナトリウムなどの無機塩基類、リチウムジイソプロピルアミンなどが使用できる。有機溶媒としては、トルエン、キシレンなどの炭化水素類、クロロホルム、クロロベンゼンなどのハロゲン化炭化水素類、ジオキサン、テトラヒドロフランなどのエーテル類、ジメチルホルムアミド、ジメチルアセトアミドなどのアミド類およびジメチルスルホキシドなどが使用できる。反応終了後は、反応液に水と、ベンゼン、トルエンまたはクロロホルムなどの有機溶媒を加えて抽出し、有機溶媒層を無水硫酸ナトリウム、無水硫酸マグネシウムなどにより脱水後、溶媒を留去するなどの通常処理を行う。必要ならば、クロマトグラフィー、再結晶などの操作によって精製を行う。
なお、本反応の原料化合物である一般式（９）および一般式（１０）で表される化合物は、公知化合物であり、市販品を入手して用いるか、または公知の方法により製造して用いることができる。
（Ｍｅｔｈｏｄ２） 一般式（１１）で表される化合物と一般式（１２）で表される化合物とを反応させる工程は、化合物（１１）に対して１〜２．５当量の化合物（１２）を加え、必要に応じて１．０〜２．５当量の塩基の存在下、適当な有機溶媒中で行われる。反応温度は、２０〜１５０℃であり、反応時間は１〜８時間である。塩基としては、ナトリウムメトキシドなどのアルカリ金属アルコキシド、トリエチルアミン、Ｎ，Ｎ−ジエチルアニリンなどの有機塩基類、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、油性水素化ナトリウムなどの無機塩基類が使用できる。有機溶媒としては、トルエン、キシレンなどの炭化水素類、クロロホルム、クロロベンゼンなどのハロゲン化炭化水素類、ジオキサン、テトラヒドロフランなどのエーテル類、アセトニトリルなどのニトリル類、ジメチルホルムアミド、ジメチルアセトアミドなどのアミド類およびジメチルスルホキシドなどが使用できる。反応終了後は、反応液に水とベンゼン、トルエン、クロロホルムなどの有機溶媒を加えて抽出し、有機溶媒層を無水硫酸ナトリウム、無水硫酸マグネシウムなどにより脱水後、溶媒を留去するなどの通常処理を行う。必要ならば、クロマトグラフィーなどの操作によって精製を行う。
なお、本反応の原料化合物である一般式（１１）および一般式（１２）で表される化合物は、公知化合物であり、市販品を入手して用いるか、または公知の方法により製造して用いることができる。
（Ｍｅｔｈｏｄ３） 一般式（１３）で表される化合物と一般式（１４）で表される化合物とを反応させる工程は、化合物（１３）に対して１〜２．５当量の化合物（１４）を加え、必要に応じて１．０〜２．５当量の塩基の存在下、適当な有機溶媒中で行われる。反応温度は、２０〜１５０℃であり、好ましくは、使用される有機溶媒の沸点に近い温度、反応時間は１〜８時間である。塩基としては、ナトリウムメトキシドなどのアルカリ金属アルコキシド、トリエチルアミン、Ｎ，Ｎ−ジエチルアニリンなどの有機塩基類、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、油性水素化ナトリウムなどの無機塩基類が使用できる。有機溶媒としては、トルエン、キシレンなどの炭化水素類、クロロホルム、クロロベンゼンなどのハロゲン化炭化水素類、ジオキサン、テトラヒドロフランなどのエーテル類、アセトニトリルなどのニトリル類、ジメチルホルムアミド、ジメチルアセトアミドなどのアミド類およびジメチルスルホキシドなどが使用できる。反応終了後は、反応液に水とベンゼン、トルエン、クロロホルムなどの有機溶媒を加えて抽出し、有機溶媒層を無水硫酸ナトリウム、無水硫酸マグネシウムなどにより脱水後、溶媒を留去するなどの通常処理を行う。必要ならば、クロマトグラフィー、再結晶などの操作によって精製を行う。
なお、本反応の原料化合物である一般式（１３）および一般式（１４）の化合物は、公知化合物であり、市販品を入手して用いるか、または公知の方法により製造して用いることができる。
一般式（Ａ）、一般式（Ｂ）または一般式（Ｃ）で表される誘導体は、その塩を含む。該塩としては、塩酸塩、硫酸塩などの無機酸塩、酢酸塩、シュウ酸塩、メタンスルホン酸塩などの有機酸塩が挙げられる。
一般式（Ａ）、一般式（Ｂ）または一般式（Ｃ）で表される誘導体（以下、「本発明に係る化合物」ともいう）は、殺菌活性を示す。従って、本発明に係る化合物の一または複数を含む組成物を殺菌剤として使用することができる。特に、本発明に係る化合物の一または複数を含む組成物を、農園芸用殺菌剤として用いることができる。
本発明に係る化合物のなかで、農園芸用殺菌剤の成分として好ましい化合物は、表１〜表２５に示されるトリアゾロピリミジン誘導体であるが、さらに好ましくは、以下に記載する表２７〜３１中に示されるトリアゾロピリミジン誘導体である。表２７〜３１におけるカッコ内の化合物Ｎｏ．は表１〜２５における化合物Ｎｏ．に対応する。

本発明に係る化合物は、広範囲の種類の糸状菌に属する菌に対し、優れた殺菌力を有しうる。従って、本発明に係る化合物を有効成分とする組成物は、花弁、芝などを含む農園芸作物の種々の病害に対して、茎葉散布、水面施用、土壌施用、または種子処理などにより使用することができる。
本発明に係る化合物は、特に以下に記載する表３２〜３４中で示される病害の防除における防除効果が高い。

本発明に係る化合物を農園芸用殺菌剤の成分として用いる場合は、本発明に係る化合物を慣用の処方により製剤化して使用することができる。すなわち、本発明に係る化合物と適当な担体および補助剤、たとえほ界面活性剤、結合剤、安定剤などを配合して、農薬の製剤として一般に使用される製剤にすることができる。すなわち、本発明の一般式（１）の化合物は、例えば、粉剤、粗粉剤、ＤＬ（ドリフトレス型）粉剤、フローダスト剤、微粒剤、細粒剤、粒剤、錠剤、水和剤、水和顆粒剤、ゾル剤（フロアブル剤）、乳剤および油剤などに製剤化できる。なお、製剤化できる剤型はここに挙げたものに限られるものではない。
製剤化に際して使用できる担体としては、農園芸用殺菌剤に常用される担体であれば、固体担体または液体担体のいずれでも使用することができ、特定のものに限定されない。
このような固体担体としては、例えば、デンプン、活性炭、大豆粉、小麦粉、木粉、魚粉、粉乳などの動植物性粉末、タルク、カオリン、ベントナイト、ゼオライト、珪藻土、ホワイトカーボン、クレー、アルミナ、炭酸カルシウム、塩化カリウム、硫安などの鉱物性粉末が挙げられる。
液体担体としては、例えば、水；イソプロピルアルコール、エチレングリコールなどのアルコール類；シクロヘキサノン、メチルエチルケトンなどのケトン類；プロピレングリコールモノメチルエーテル、ジエチレングリコールモノ−ｎ−ブチルエーテルなどのエーテル類；ケロシン、軽油などの脂肪族炭化水素類；キシレン、トリメチルベンゼン、テトラメチルベンゼン、メチルナフタリン、ソルベントナフサなどの芳香族炭化水素類；Ｎ−メチル−２−ピロリドンなどのアミド類；脂肪酸のグリセリンエステルなどのエステル類；大豆油、ナタネ油などの植物油が挙げられる。
これらの担体は、単独で用いることもでき、２種以上を併用することもできる。
また、製剤化に際して使用できる界面活性剤としては、非イオン性界面活性剤、陰イオン性界面活性剤、陽イオン性界面活性剤、両性界面活性剤などがあり、具体的には次のものが使用できる。
非イオン性界面活性剤の例としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリールエーテル、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレンアルキルエステル、ポリオキシエチレンソルビタンアルキレート、ポリオキシエチレンフェニルエーテルポリマー、ポリオキシエチレンアルキレンアリールフェニルエーテル、ポリオキシエチレンアルキレングリコール、ポリオキシエチレンポリオキシプロピレンブロックポリマーなどが挙げられる。
陰イオン性界面活性剤の例としては、例えば、リグニンスルホン酸塩、アルキルアリールスルホン酸塩、ジアルキルスルホサクシネート、ポリオキシエチレンアルキルアリールエーテルサルフェート、アルキルナフタレンスルホン酸塩、ポリオキシエチレンスチリルフェニルエーテルサルフェートなどが挙げられる。
陽イオン性界面活性剤の例としては、例えば、アルキルアミン塩などが挙げられる。
両性界面活性剤の例としては、例えば、第４級アンモニウム塩アルキルベタイン、アミンオキサイドなどが挙げられる。
なお、製剤化に際して使用できる界面活性剤は、これらに限定されず、これらを単独で用いてもよく、２種以上を併用することもできる。
その他の補助剤として、粘結剤、増粘剤、固着剤、防腐剤、かび剤、溶剤、農薬活性成分の安定化剤、酸化防止剤、紫外線防止剤、結晶析出防止剤、消泡剤、物性向上剤、着色剤などが挙げられるが、これらに限定されず、これらの補助剤を、それぞれ必要に応じて添加することができる。
粘結剤、増粘剤、固着剤としては、特に限定されるものではないが、例えば、デンプン、デキストリン、セルロース、メチルセルロース、エチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、カルボキシメチルデンプン、プルラン、アルギン酸ナトリウム、アルギン酸アンモニウム、アルギン酸プロピレングリコールエステル、グアーガム、ローカストビーンガム、アラビアゴム、キサンタンガム、ゼラチン、カゼイン、ポリビニルアルコール、ポリエチレンオキサイド、ポリエチレングリコール、エチレン・プロピレンブロックポリマー、ポリアクリル酸ナトリウム、ポリビニルピロリドンなどが挙げられる。
本発明に係る化合物の添加量は、製剤の剤型および使用方法により適宜かえることができ、一般に０．１〜９０重量％の範囲で製剤中に使用するのが望ましい。
本発明に係る化合物は、単独で使用しても十分有効であるが、各種の殺菌剤や、殺虫・殺ダニ剤および共力剤から選ばれる１種または２種以上と混合して使用することもできる。本発明に係る化合物と混合して使用できる殺菌剤、殺虫剤、殺ダニ剤の代表例を以下に示す。
（殺菌剤）キャプタン、ホルペット、チウラム、ジラム、ジネブ、マンネブ、マンゼブ、プロピネブ、ポリカーバメート、クロロタロニル、キントーゼン、キャプタホル、イプロジオン、プロシミドン、フルオルイミド、メプロニル、フルトラニル、ペンシクロン、オキシカルボキシン、ホセチル、トリアジメホン、トリアジメノール、プロピコナゾール、ジクロブトラゾール、ビテルタノール、ヘキサコナゾール、ミクロブタニル、フルシラゾール、メトコナゾール、エタコナゾール、フルオトリマゾール、シプロコナゾール、エポキシコナゾール、フルトリアフェン、ベンコナゾール、ジニコナゾール、シプロコナゾール、フェナリモル、トリフルミゾール、プロクロラズ、イマザリル、ペフラゾエート、トリデモルフ、フェンプロピモルフ、トリホリン、ピリフェノックス、アニラジン、ポリオキシン、メタラキシル、オキサジキシル、フララキシル、イソプロチオラン、プロベナゾール、ピロールニトリン、ブラストサイジンＳ、カスガマイシン、バリダマイシン、硫酸ジヒドロストレプトマイシン、ベノミル、カルベンダジム、チオファネートメチル、ヒメキサゾール、塩基性塩化銅、塩基性硫酸銅、ジエトフェンカルブ、メタスルホカルブ、キノメチオネート、ビナパクリル、レシチン、重曹、ジチアノン、ジノカップ、フェナミノスルフ、ジクロメジン、ドジン、ＩＢＰ、エディフェンホス、メパニピリム、フェリムゾン、トリクラミド、フルアジナム、エトキノラック、ジメトモルフ、ピロキロン、テクロフタラム、フサライド、フェナジンオキシド、チアベンダゾール、トリシクラゾール、シモキサニル、プロパモカルブ塩酸塩、オキソリニック酸、ヒドロキシイソキサゾール、イミノクタジン三酢酸塩、テトラコナゾール、イミベンコナゾール、メチラムなど。
（殺虫・殺ダニ剤）有機リン系およびカーバメート系殺虫剤；フェンチオン、フェニトロチオン、ダイアジノン、クロルピリホス、ＥＳＰ、バミドチオン、フェントエート、ジメトエート、ホルモチオン、マラソン、トリクロルホン、チオメトン、ホスメット、ジクロルボス、アセフェート、ＥＰＢＰ、メチルパラチオン、オキシジメトンメチル、エチオン、サリチオン、シアノホス、イソキサチオン、ピリダフェンチオン、ホサロン、メチダチオン、スルプロホス、クロルフェンビンホス、テトラクロルビンホス、ジメチルビンホス、プロパホス、イソフェンホス、エチルチオメトン、プロフェノホス、ピラクロホス、モノクロトホス、アジンホスメチル、アルディカルブ、メソミル、チオジカルブ、カルボフラン、カルボスルファン、ベンフラカルブ、フラチオカルブ、プロポキスル、ＢＰＭＣ、ＭＴＭＣ、ＭＩＰＣ、カルバリル、ピリミカーブ、エチオフェンカルブ、フェノキシカルブ、ＥＤＤＰなど。
ピレスロイド系殺虫剤；ペルメトリン、シペルメトリン、デルタメスリン、フェンバレレート、フェンプロパトリン、ピレトリン、アレスリン、テトラメスリン、レスメトリン、ジメスリン、プロパスリン、フェノトリン、プロトリン、フルバリネート、シフルトリン、シハロトリン、フルシトリネート、エトフェンプロクス、シクロプロトリン、トラロメトリン、シラフルオフェン、ブロフェンプロクス、アクリナスリンなど。
ベンゾイルウレア系その他の殺虫剤；ジフルベンズロン、クロルフルアズロン、ヘキサフルムロン、トリフルムロン、テトラベンズロン、フルフェノクスロン、フルシクロクスロン、ブプロフェジン、ピリプロキシフェン、メトプレン、ベンゾエピン、ジアフェンチウロン、アセタミプリド、イミダクロプリド、ニテンピラム、フィプロニル、カルタップ、チオシクラム、ベンスルタップ、硫酸ニコチン、ロテノン、メタアルデヒド、機械油、ＢＴや昆虫ウィルスなどの微生物農薬など。
（殺線虫剤） フェナミホス、ホスチアゼートなど。
（殺ダニ剤） クロルベンジレート、フェニソブロモレート、ジコホル、アミトラズ、ＢＰＰＳ、ベンゾメート、ヘキシチアゾクス、酸化フェンブタスズ、ポリナクチン、キノメチオネート、ＣＰＣＢＳ、テトラジホン、アベルメクチン、ミルベメクチン、クロフェンテジン、シヘキサチン、ピリダベン、フェンピロキシメート、テブフェンピラド、ピリミジフェン、フェノチオカルブ、ジエノクロルなど。
一般式（Ａ）、一般式（Ｂ）または一般式（Ｃ）で表される化合物を活性成分として含有する農園芸用殺菌剤（以下、「本発明に係る農園芸用殺菌剤」ともいう）の使用方法は、一般に次のとおりである。すなわち、水和剤、液剤、乳剤、ゾル剤（フロアブル剤）、顆粒水和剤および油剤の場合は、水で５０〜１００００倍に希釈して、一般に活性成分が１〜１００００ｐｐｍの濃度の液に調整される。そしてこの希釈液を１０アール当り１０〜２０００リットル、通常は２０〜７００リットルの範囲で植物の病害発生部位の茎葉に散布される。
また、液剤、乳剤およびゾル剤（フロアブル剤）の場合は、水で希釈せずに濃厚液のまま、または水で５０倍以内に希釈して主に空中散布用の微量散布剤（ＬＶ散布、ＵＬＶ散布、Ｓ散布）として、１０アール当り５０〜５０００ｍｌの量がヘリコプターなどを使って散布される。
また、粉剤、粗粉剤、ＤＬ粉剤、フローダスト剤、微粒剤、細粒剤および粒剤の場合は、１０アール当り２〜５ｋｇ（活性成分量として５〜５００ｇ程度）が、植物の病害発生部位の茎葉、土壌表面、土壌中または水面に施用される。An object of the present invention is to provide a novel compound that meets the above-mentioned demand and an agricultural and horticultural fungicide using the same.
In order to achieve the above-mentioned object, the present inventors have synthesized many compounds and have intensively studied their usefulness. As a result, a novel triazolopyrimidine derivative having a specific structure has a broad control spectrum and high control effect as an agricultural and horticultural fungicide, and depending on the type of disease, it has both high preventive and therapeutic effects. It was found to have a controlling activity.
That is, the present invention is as follows.
(1) General formula (A)

[Where:
Het _A Represents a 5-membered or 6-membered ring containing a hetero element, and these rings are substituted with a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group or a C2-C6 alkoxyalkyl group. You may,
X _A Represents a halogen atom, a cyano group, a C1-C6 alkoxy group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 alkylamino group or a C1-C6 alkoxycarbonyl group, And
R _A And R _A 'Is the same or different from each other, and is a C1-C10 alkyl group, a C2-C10 alkenyl group, a C2-C10 alkynyl group or a phenyl group (the alkyl group, alkenyl group, alkynyl group and phenyl group are a halogen atom, C1- It may be substituted with one or more groups selected from the group consisting of C6 alkyl groups, C1-C6 haloalkyl groups, C1-C6 alkoxy groups, C1-C6 alkylthio groups, C1-C6 alkoxycarbonyl groups and carboxyl groups. ). ]
A triazolopyrimidine derivative represented by:
(2) Het _A Is the general formula Het ₁ ~ Het ₁₅ Group represented by

(Where R ₁ , R ₂ And R ₃ Are the same or different and each represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group, or a halogen atom),
X _A Represents a halogen atom, and
R _A And R _A 'Is the same or different from each other, and is a C1 to C10 alkyl group, a C2 to C10 alkenyl group or a C2 to C10 alkynyl group (the alkyl group, alkenyl group and alkynyl group are a halogen atom, a C1 to C6 alkyl group or C1 to C1). Optionally substituted with a C6 haloalkyl group)
The triazolopyrimidine derivative according to (1), characterized in that
(3) Het _A Is the Het ₁ , Het ₆ Or Het ₁₂ The triazolopyrimidine derivative according to (2), which is a group represented by the formula:
(4) General formula (B)

[Where:
Het _B Represents a 5-membered or 6-membered ring containing a hetero element, which is substituted with a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group or a C2-C6 alkoxyalkyl group. Well,
X _B Represents a halogen atom, a cyano group, a C1-C6 alkoxy group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 alkylamino group or a C1-C6 alkoxycarbonyl group, And
R _B Represents an optionally substituted nitrogen-containing heterocyclic ring bonded with a nitrogen atom. ]
A triazolopyrimidine derivative represented by:
(5) Het _B Is the above general formula Het ₁ ~ Het ₁₅ Any one of the groups represented by
X _B Represents a halogen atom
The triazolopyrimidine derivative according to (4), characterized in that
(6) Het _B Is the Het ₁ , Het ₆ Or Het ₁₂ The triazolopyrimidine derivative according to (5), which is a group represented by the formula:
(7) General formula (C)

[Where:
Het _C Represents a 5-membered or 6-membered ring containing a hetero element, and these 5-membered or 6-membered rings are a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group, and a C2-C6. Optionally substituted by a group selected from the group consisting of alkoxyalkyl groups,
X _C Represents a halogen atom, a cyano group, a C1-C6 alkoxy group or a C1-C6 alkylthio group, and
R _C Represents a C1-C10 alkyl group, a C2-C10 alkenyl group, a C2-C10 alkynyl group, a C3-C8 cycloalkyl group, a C4-C10 cycloalkylalkyl group or an aralkyl group, and the benzene ring of the aralkyl group is a halogen atom, It may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group or a C1-C6 alkylthio group. ]
A triazolopyrimidine derivative represented by:
(8) Het _C Is the general formula Het ₁ The triazolopyrimidine derivative according to (7), which is a group represented by the formula:
(9) An agricultural and horticultural fungicide containing the triazolopyrimidine derivative according to any one of (1) to (8) as an active ingredient.
Formula (A), Formula (B), Formula (C), or Formula Het ₁ ~ Het ₁₅ The alkyl group in the above group, or the alkyl part of the haloalkyl group, alkoxy group, haloalkoxy group, alkylthio group, alkoxycarbonyl group or alkylamino group may be linear or branched. .
In the general formula (A), Het _A Alternatively, in the general formula (B), Het _B Is an arbitrary 5-membered ring or 6-membered ring containing a hetero element in the ring, preferably the general formula Het ₁ ~ Het ₁₅ A ring represented by any one of the above, more preferably the Het ₁ , Het ₆ Or Het ₁₂ Is a ring represented by
In the general formula (C), Het _C Is an arbitrary 5-membered ring or 6-membered ring containing a hetero element in the ring, preferably any ring represented by the following general formula, more preferably the Het ₁ Is a ring represented by

Het _A , Het _B Or Het _C On or Het ₁ ~ Het ₁₅ R above ₁ , R ₂ Or R ₃ Examples of the halogen atom are a chlorine atom, a bromine atom, an iodine atom and a fluorine atom, and examples of the C1-C6 alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, t -Butyl group, isobutyl group, sec-butyl group, n-pentyl group, isoamyl group, n-hexyl group, and the like. Examples of C1-C6 alkoxy groups include methoxy group, ethoxy group, n-propoxy group, isopropoxy group. Group, n-butoxy group, sec-butoxy group, t-butoxy group, isobutoxy group and isohexyloxy group, etc., and C1-C6 haloalkyl group includes trifluoromethyl group, difluoromethyl group, trichloromethyl group, Dichloromethyl group, fluoromethyl group, chloromethyl group, iodomethyl group, bromomethyl Group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, pentachloroethyl group and the like, and C2-C6 alkoxyalkyl group includes methoxymethyl group, ethoxymethyl group, n-propoxymethyl group , Isopropoxyethyl group, n-butoxymethyl group, sec-butoxymethyl group, t-butoxymethyl group, isobutoxymethyl group, n-butoxyethyl group and the like.
In the general formula (A), R _A Or R _A Examples of the C1-C10 alkyl group as' include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, and an isoamyl group. , N-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like, and as C2-C10 alkenyl group, vinyl group, allyl group, 1-butenyl group, 2 -Butenyl group, 1-isobutenyl group, 3-methyl-2-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-octenyl group, and the like. Examples of the C2-C10 alkynyl group include ethynyl group, 2- Propynyl, 2-butynyl, 3-butynyl, 5-pentynyl, 3,3-dimethyl-1-butynyl, 4-methyl-1-pentynyl and 7- An octynyl group etc. are mentioned. R _A And R _A Examples of the halogen atom substituting for one or more hydrogens on the alkyl group, alkenyl group, alkynyl group or phenyl group, which include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom, include C1-C6 alkyl. Examples of the group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, an isoamyl group, and an n-hexyl group. Examples of the C1-C6 haloalkyl group include trifluoromethyl group, difluoromethyl group, trichloromethyl group, dichloromethyl group, fluoromethyl group, chloromethyl group, iodomethyl group, bromomethyl group, pentafluoroethyl group and pentachloroethyl group. Groups such as C1-C6 alkoxy groups include methoxy Group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, isobutoxy group and isohexyloxy group, and the like. As the C1-C6 alkylthio group, methylthio Group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, t-butylthio group, isobutylthio group, and isohexylthio group, and the like. As C1-C6 alkoxycarbonyl group, Carbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, isobutoxycarbonyl group and isohexyloxycarbonyl group, etc. It is below.
In the general formula (B), R _B Is an optionally substituted nitrogen-containing heterocyclic ring bonded to the triazolopyrimidine ring with a nitrogen atom, and preferably includes the following nitrogen-containing heterocyclic rings.

In general formula (C), R _C Examples of the C1-C10 alkyl group are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isoamyl group, Examples include an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group. C2-C10 alkenyl groups include vinyl, allyl, 1-butenyl, 2-butenyl, 1-isobutenyl, 3-methyl-2-butenyl, 1-pentenyl, 1-hexenyl and 1-hexenyl. An octenyl group etc. are mentioned. C2-C10 alkynyl groups include ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 5-pentynyl, 3,3-dimethyl-1-butynyl, 4-methyl-1-pentynyl Group and 7-octynyl group. Examples of the C3-C8 cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheprotyl group, and a cyclooctyl group. Examples of the C4-C10 cycloalkylalkyl group include a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group. Examples of the aralkyl group include a benzyl group, an α-phenethyl group, a β-phenethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group.
In the general formula (C), R _C As the aralkyl group having a halogen atom substituted on the benzene ring, 2-chlorobenzyl group, 3-chlorobenzyl group, 4-chlorobenzyl group, 2-chloro-6-fluorobenzyl group, 2,6-dichlorobenzyl Group, 2,3-dichlorobenzyl group, 2,4-dichlorobenzyl group, 3,4-dichlorobenzyl group, 3-bromobenzyl group, 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2,6-difluorobenzyl group, 2,5-difluorobenzyl group, 3,4-difluorobenzyl group, 3,5-difluorobenzyl group, 4-chloro-α-phenethyl group, 4-chloro-β-phenethyl group, etc. Is mentioned. Examples of the aralkyl group substituted on the benzene ring with a C1-C6 alkyl group include 2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, 2,4-dimethylbenzyl group, 3,4-dimethylbenzyl group, 2,4,6-trimethylbenzyl group, 4-ethylbenzyl group, 4-isopropylbenzyl group, 2,4,6-triisopropylbenzyl group, pt-butylbenzyl group and 3,5-di-t-butyl group A benzyl group etc. are mentioned. Aralkyl groups substituted on the benzene ring with C1-C6 alkoxy groups include 2-methoxybenzyl group, 3-methoxybenzyl group, 3,4-dimethoxybenzyl group, 3,5-dimethoxybenzyl group, 3-methoxy-4- Ethoxybenzyl group, 4-ethoxybenzyl group, 4-n-propoxybenzyl group, 4-isopropoxybenzyl group, 4-n-butoxybenzyl group, 4-sec-butoxybenzyl group, 4-isobutoxybenzyl group, 4- Examples thereof include t-butoxybenzyl group and 4-isohexyloxybenzyl group. As the aralkyl group substituted on the benzene ring with a C1-C6 alkylthio group, a 2-methylthiobenzyl group, a 3-methylthiobenzyl group, a 4-methylthiobenzyl group, a 4-ethylthiobenzyl group, a 4-n-propylthiobenzyl group, 4-isopropylthiobenzyl group, 4-n-butylthiobenzyl group, 4-sec-butylthiobenzyl group, 4-isobutylthiobenzyl group, 4-t-butylthiobenzyl group, 4-isohexylthiobenzyl group, etc. Can be mentioned.
X in the general formula (A) _A X in the general formula (B) _B Or X in the general formula (C) _C Examples of the halogen atom are chlorine atom, bromine atom, iodine atom and fluorine atom. C1-C6 alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy, isobutoxy, n-pentyloxy and isohexyloxy Groups and the like. Examples of the C1-C6 alkylthio group include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, t-butylthio group, isobutylthio group, and isohexylthio group. .
X in the general formula (A) _A Or X in the general formula (B) _B Examples of the C1-C6 alkylsulfinyl group include methylsulfinyl group, ethylsulfinyl group, n-propylsulfinyl group, isopropylsulfinyl group, n-butylsulfinyl group, sec-butylsulfinyl group, t-butylsulfinyl group, isobutylsulfinyl group. And an isohexylsulfinyl group. Examples of the C1-C6 alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an isopropylsulfonyl group, an n-butylsulfonyl group, a sec-butylsulfonyl group, a t-butylsulfonyl group, an isobutylsulfonyl group, and an isobutylsulfonyl group. And a hexylsulfonyl group. The C1-C6 alkylamino group may be a monoalkylamino group or a dialkylamino group. Examples of the alkyl moiety include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and isohexyl. Etc. Examples of the alkoxy moiety of the C1-C6 alkoxycarbonyl group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy, isobutoxy, n-pentyloxy and isohexyloxy. .
Specific examples of the triazolopyrimidine derivative according to the present invention represented by the general formula (A) are shown in Tables 1 to 10, and specific examples of the triazolopyrimidine derivative according to the present invention represented by the general formula (B) are shown. Specific examples of the triazolopyrimidine derivatives according to the present invention represented by the general formula (C) are shown in Tables 23 to 25 in Tables 11 to 22. Furthermore, specific examples of compounds that can be intermediates of these derivatives (compounds represented by general formula (1) in scheme 1 below) are shown in Table 26.
In the table, “Me” represents a methyl group, “Et” represents an ethyl group, “nPr” represents an n-propyl group, “iPr” represents an isopropyl group, “nBu” represents an n-butyl group, “ “iBu” represents an isobutyl group, and “nPen” represents an n-pentyl group. In the table, Compound No. Are also referred to in the following examples and test examples.

The triazolopyrimidine derivative represented by the general formula (A), the general formula (B), or the general formula (C) can be produced by the method shown in the following scheme 1.
Scheme 1

(In the formula, Halo represents a halogen atom, Het _A , Het _B And Het _C And R _A , R _A ', R _B , R _C Is the same as above, and Het is Het _A , Het _B Or Het _C W represents a hydrogen atom or an alkali metal atom such as sodium or potassium, Y represents a cyano group, a C1 to C6 alkoxy group, a C1 to C6 alkylthio group, a C1 to C6 alkylsulfinyl group, or a C1 to C6 alkyl. A sulfonyl group, a C1-C6 alkylamino group or a C1-C6 alkoxycarbonyl group)
The step of reacting the compound of general formula (1) with the compound of general formula (2) (Step 1) or the step of reacting the compound of general formula (1) with the compound of general formula (4) (Step 3) Preferably 1 equivalent of the compound of general formula (2) or the compound of general formula (4) is added to the compound of formula (1) and a suitable organic solvent is present in the presence of 1.0 to 2.5 equivalents of base. Done in. The reaction temperature is 20 to 150 ° C., and the reaction time is 1 to 8 hours. As the base, organic bases such as triethylamine and N, N-diethylaniline, and inorganic bases such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, and oily sodium hydride can be used. Organic solvents include hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chloroform and chlorobenzene, ethers such as dioxane and tetrahydrofuran, nitriles such as acetonitrile, amides such as dimethylformamide and dimethylacetamide, and dimethyl Sulfoxide and the like can be used. After completion of the reaction, the reaction solution is usually extracted by adding water and an organic solvent such as benzene, toluene, chloroform, etc., and the organic solvent layer is dehydrated with anhydrous sodium sulfate, anhydrous magnesium sulfate, and then the solvent is distilled off. Process. If necessary, purification is performed by an operation such as chromatography. In addition, the compound of General formula (2) and the compound of General formula (4) which are the raw material compounds of this reaction are a well-known compound which can be obtained as a commercial item, or can be easily manufactured by a well-known method.
The 5-halogen triazolopyrimidine derivative (A ′) or (B ′) thus obtained is a compound represented by the general formula (3) in the presence of a base, such as alcohol, alkylamine or thiol. Or by reacting with an alkali metal cyanide or the like (Step 2 or Step 4), a triazolopyrimidine derivative represented by the general formula (A ″) or (B ″) can be produced. In addition, the compound represented with General formula (3) which is a raw material compound of this reaction is a well-known compound which can be obtained as a commercial item, or can be easily manufactured by a well-known method. Examples of such a compound represented by the general formula (3) include methyl alcohol, ethyl alcohol, isopropyl alcohol, methylamine, ethylamine, methyl mercapto sodium, sodium cyanide, potassium cyanide and the like.
In the step of reacting the compound represented by the general formula (1) with the compound represented by the general formula (5) (Step 5), preferably 1 equivalent of the compound (5) is added to the compound (1), The reaction is carried out in a suitable organic solvent in the presence of 0.01 to 1.0 equivalent of a transition metal such as palladium or nickel. By this reaction, among the compounds represented by the general formula (C), a 5-halogen triazolopyrimidine derivative (compound (C ′)) in which X is a halogen atom is obtained. As the organic solvent, hydrocarbons such as toluene and xylene or ethers such as dioxane and tetrahydrofuran can be used. The reaction temperature is 20 to 150 ° C., preferably a temperature close to the boiling point of the organic solvent used, and the reaction time is 1 to 8 hours.
Further, by reacting the obtained 5-halogen triazolopyrimidine derivative represented by the general formula (C ′) with an alcohol or thiol in the presence of a base or with a metal cyanide or the like, A triazolopyrimidine derivative represented by the formula (C) can be produced. Examples of the base used in this reaction include organic bases such as triethylamine and N, N-diethylaniline, and inorganic bases such as sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and sodium hydride. Examples of metal cyanides include sodium cyanide and potassium cyanide.
After completion of the reaction, the reaction solution is extracted by adding water and an organic solvent such as benzene, toluene or chloroform, and after performing a liquid separation operation, the organic solvent layer is dehydrated with anhydrous sodium sulfate or anhydrous magnesium sulfate, and the organic solvent is removed. The usual processing such as distilling off is performed. If necessary, purification is carried out by operations such as chromatography and recrystallization.
Compound (5), which is one raw material compound of the above-described reaction, is a known compound and can be obtained by using a commercially available product or can be produced and used by a known method.
The dihalogen triazolopyrimidine derivative represented by the general formula (1) in the above scheme 1 can be produced according to scheme 2 shown below.
Scheme 2

(In the formula, Halo represents a halogen atom, R represents a C1-C10 alkyl group, and Het represents Het. _A , Het _B Or Het _C One of the following, where Het _A , Het _B And Het _C Is the same as described above. )
That is, the compound represented by the general formula (1) is obtained by condensing the malonic ester derivative represented by the general formula (7) and the 3-amino-1,2,4-triazole represented by the general formula (6). To obtain a compound represented by the general formula (8), which can be produced by halogenation. This reaction will be described separately in the following condensation step and halogenation step.
(Condensation step) In the step of reacting compound (7) and compound (6), preferably 1 equivalent of compound (7) is added to compound (6) and necessary in the presence of 1 to 5 equivalents of a base. In an appropriate organic solvent. Bases used in this reaction step include alkali metal alkoxides such as sodium methoxide, organic bases such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, dimethylaminopyridine, and N, N-diethylaniline. Inorganic bases such as sodium carbonate, sodium bicarbonate, potassium carbonate. Examples of organic solvents include hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorobenzene, ethers such as dioxane and tetrahydrofuran, alcohols such as methanol, ethanol and n-butanol, dimethylformamide, dimethylacetamide and the like. Amides and dimethyl sulfoxide can be used. A preferable reaction temperature for facilitating the above reaction is 20 to 150 ° C., preferably a temperature close to the boiling point of the organic solvent used, and the reaction time is a raw material compound, a catalyst, a reaction temperature, and the like. Generally, it is 1 to 8 hours although it varies depending on the situation. When reacted in this way, compound (8) is obtained. Although this compound may be fractionated and used for the next reaction, it is preferably used as it is in the next reaction step.
(Halogenation process) The process of halogenating the compound (8) obtained by the said reaction and obtaining a compound (1) is a reaction solution containing the compound (8) produced | generated at the said process. What is necessary is just to add 1-10 equivalent halogenating agent with respect to a compound (8), and to make it react in presence. Next, perform the usual treatment such as distilling off the solvent and excess halogenating agent used from the reaction solution, or if necessary, purify the product by chromatography, recrystallization, etc. Compound (1) can be obtained. Examples of deoxidizers that can be used in the halogenation step include organic bases such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, dimethylaminopyridine, N, N-diethylaniline, sodium carbonate, hydrogen carbonate Examples thereof include inorganic bases such as sodium and potassium carbonate. Examples of the halogenating agent that can be used in the halogenation step include phosphorus oxychloride and phosphorus oxybromide. Since the halogenating agent also serves as a solvent, the reaction does not particularly require a reaction solvent. However, when an organic solvent is used for the reaction, for example, hydrocarbons such as benzene and toluene, and halogenated carbonization such as chlorobenzene and chloroform. Hydrogens can be used. The reaction temperature for halogenation is 50 to 150 ° C., and the reaction time is 1 to 10 hours.
In addition, the obtained halogen triazolopyrimidine derivative represented by the general formula (1) is optionally added in an amount of 1 to 10 equivalents relative to the compound (1) in the presence of 0.05 to 2.5 equivalents of a base. By adding a halogenating agent of (2) and reacting in a suitable organic solvent, the hydrogen atom on Het can be replaced with a halogen atom. Examples of halogenating agents that can be used in the reaction include chlorine, sulfuryl chloride, N-chlorosuccinimide, bromine, and N-bromosuccinimide. Examples of the base that can be used for the reaction include organic bases such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, dimethylaminopyridine, N, N-diethylaniline, sodium carbonate, sodium hydrogen carbonate, potassium carbonate Inorganic bases such as can be used. The reaction temperature for halogenation is 50 to 150 ° C., and the reaction time is 1 to 10 hours. As the organic solvent, hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as chlorobenzene and chloroform can be used.
The malonic acid ester derivative represented by the general formula (7) can be produced by a method (Method 1 to Method 3) shown in Scheme 3 below.
Scheme 3

(In the formula, Het and R represent the same meaning as described above, and Z represents a halogen atom or a C1-C10 alkoxy group.)

(In the formula, Het and R represent the same meaning as described above, and L represents a leaving group such as a halogen atom, a p-toluenesulfonyl group, and a methanesulfonyl group.)

(Where Halo, R, R ₂ And R ₃ Represents the same meaning as described above, and A and B represent a nitrogen atom and CR ₁ Or CR ₁ And a nitrogen atom, where R ₁ Represents the same meaning as described above. )
Hereinafter, each of Methods 1 to 3 will be described in detail.
(Method 1) The reaction between the compound represented by the general formula (9) and the compound represented by the general formula (10) is added to 1-2 equivalents of the compound (10) with respect to the compound (9). Accordingly, it is carried out in a suitable organic solvent in the presence of 1 to 2 equivalents of a base. The reaction temperature is -70 to 150 ° C, and the reaction time is 1 to 8 hours. Bases include alkali metal alkoxides such as sodium methoxide, organic bases such as triethylamine and N, N-diethylaniline, inorganic bases such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, oily sodium hydride, lithium diisopropylamine Etc. can be used. As the organic solvent, hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chloroform and chlorobenzene, ethers such as dioxane and tetrahydrofuran, amides such as dimethylformamide and dimethylacetamide, and dimethyl sulfoxide can be used. After completion of the reaction, the reaction solution is usually extracted by adding water and an organic solvent such as benzene, toluene or chloroform, and the organic solvent layer is dehydrated with anhydrous sodium sulfate, anhydrous magnesium sulfate, etc. and then the solvent is distilled off. Process. If necessary, purification is performed by operations such as chromatography and recrystallization.
In addition, the compounds represented by the general formula (9) and the general formula (10) which are the raw material compounds of this reaction are known compounds, and are obtained by using commercially available products, or manufactured and used by known methods. be able to.
(Method 2) In the step of reacting the compound represented by the general formula (11) with the compound represented by the general formula (12), 1 to 2.5 equivalents of the compound (12) is added to the compound (11). In addition, the reaction is performed in a suitable organic solvent in the presence of 1.0 to 2.5 equivalents of a base as necessary. The reaction temperature is 20 to 150 ° C., and the reaction time is 1 to 8 hours. Examples of the base include alkali metal alkoxides such as sodium methoxide, organic bases such as triethylamine and N, N-diethylaniline, and inorganic bases such as sodium carbonate, sodium bicarbonate, potassium carbonate, and oily sodium hydride. Organic solvents include hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chloroform and chlorobenzene, ethers such as dioxane and tetrahydrofuran, nitriles such as acetonitrile, amides such as dimethylformamide and dimethylacetamide, and dimethyl Sulfoxide and the like can be used. After completion of the reaction, the reaction solution is extracted by adding water and an organic solvent such as benzene, toluene, chloroform, etc., and the organic solvent layer is dehydrated with anhydrous sodium sulfate, anhydrous magnesium sulfate, and the like, and the solvent is then distilled off. I do. If necessary, purification is performed by an operation such as chromatography.
In addition, the compounds represented by the general formula (11) and the general formula (12) which are the raw material compounds of this reaction are known compounds, and are obtained by using commercially available products, or manufactured and used by known methods. be able to.
(Method 3) In the step of reacting the compound represented by the general formula (13) with the compound represented by the general formula (14), 1 to 2.5 equivalents of the compound (14) is added to the compound (13). In addition, the reaction is performed in a suitable organic solvent in the presence of 1.0 to 2.5 equivalents of a base as necessary. The reaction temperature is 20 to 150 ° C., preferably a temperature close to the boiling point of the organic solvent used, and the reaction time is 1 to 8 hours. Examples of the base include alkali metal alkoxides such as sodium methoxide, organic bases such as triethylamine and N, N-diethylaniline, and inorganic bases such as sodium carbonate, sodium bicarbonate, potassium carbonate, and oily sodium hydride. Organic solvents include hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chloroform and chlorobenzene, ethers such as dioxane and tetrahydrofuran, nitriles such as acetonitrile, amides such as dimethylformamide and dimethylacetamide, and dimethyl Sulfoxide and the like can be used. After completion of the reaction, the reaction solution is extracted by adding water and an organic solvent such as benzene, toluene, chloroform, etc., and the organic solvent layer is dehydrated with anhydrous sodium sulfate, anhydrous magnesium sulfate, and the like, and the solvent is then distilled off. I do. If necessary, purification is performed by operations such as chromatography and recrystallization.
In addition, the compound of General formula (13) and General formula (14) which is a raw material compound of this reaction is a well-known compound, and it can obtain and use a commercial item or can be manufactured and used by a well-known method. .
The derivative represented by the general formula (A), the general formula (B), or the general formula (C) includes a salt thereof. Examples of the salt include inorganic acid salts such as hydrochloride and sulfate, and organic acid salts such as acetate, oxalate, and methanesulfonate.
The derivative represented by the general formula (A), the general formula (B) or the general formula (C) (hereinafter also referred to as “the compound according to the present invention”) exhibits bactericidal activity. Thus, a composition comprising one or more compounds according to the invention can be used as a fungicide. In particular, compositions comprising one or more compounds according to the invention can be used as agricultural and horticultural fungicides.
Among the compounds according to the present invention, preferable compounds as components of agricultural and horticultural fungicides are triazolopyrimidine derivatives shown in Tables 1 to 25, and more preferably in Tables 27 to 31 described below. The triazolopyrimidine derivative shown in FIG. In Tables 27-31, compound Nos. In parentheses. Are the compound Nos. In Tables 1-25. Corresponding to

The compound according to the present invention can have excellent bactericidal power against bacteria belonging to a wide variety of filamentous fungi. Therefore, the composition comprising the compound according to the present invention as an active ingredient should be used for various diseases of agricultural and horticultural crops including petals, turf, etc. by foliage application, water surface application, soil application, seed treatment, etc. Can do.
The compound according to the present invention has a particularly high control effect in controlling diseases shown in Tables 32 to 34 described below.

When the compound according to the present invention is used as a component of an agricultural and horticultural fungicide, the compound according to the present invention can be formulated into a conventional formulation and used. That is, the compound according to the present invention and an appropriate carrier and auxiliary agent, for example, a surfactant, a binder, a stabilizer and the like can be blended to obtain a preparation generally used as an agrochemical preparation. That is, the compound of the general formula (1) of the present invention includes, for example, powders, coarse powders, DL (driftless type) powders, flow dusts, fines, fines, granules, tablets, wettable powders, water It can be formulated into Japanese granules, sols (flowables), emulsions and oils. The dosage forms that can be formulated are not limited to those listed here.
As a carrier that can be used for formulation, any carrier that is commonly used for agricultural and horticultural fungicides can be used, and it is not limited to a specific carrier.
Examples of such solid carriers include animal and vegetable powders such as starch, activated carbon, soybean flour, wheat flour, wood flour, fish flour, and milk powder, talc, kaolin, bentonite, zeolite, diatomaceous earth, white carbon, clay, alumina, and calcium carbonate. , Mineral powders such as potassium chloride and ammonium sulfate.
Examples of the liquid carrier include water; alcohols such as isopropyl alcohol and ethylene glycol; ketones such as cyclohexanone and methyl ethyl ketone; ethers such as propylene glycol monomethyl ether and diethylene glycol mono-n-butyl ether; and aliphatics such as kerosene and light oil. Hydrocarbons; aromatic hydrocarbons such as xylene, trimethylbenzene, tetramethylbenzene, methylnaphthalene and solvent naphtha; amides such as N-methyl-2-pyrrolidone; esters such as glycerin esters of fatty acids; soybean oil, And vegetable oils such as rapeseed oil.
These carriers can be used alone or in combination of two or more.
Examples of surfactants that can be used for formulation include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Can be used.
Examples of nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkylate, polyoxyethylene phenyl Examples include ether polymers, polyoxyethylene alkylene aryl phenyl ethers, polyoxyethylene alkylene glycols, and polyoxyethylene polyoxypropylene block polymers.
Examples of anionic surfactants include, for example, lignin sulfonate, alkyl aryl sulfonate, dialkyl sulfo succinate, polyoxyethylene alkyl aryl ether sulfate, alkyl naphthalene sulfonate, polyoxyethylene styryl phenyl ether sulfate. Etc.
Examples of the cationic surfactant include alkylamine salts.
Examples of amphoteric surfactants include quaternary ammonium salt alkylbetaines, amine oxides, and the like.
In addition, the surfactant that can be used for formulation is not limited to these, and these may be used alone or in combination of two or more.
As other adjuvants, binders, thickeners, sticking agents, preservatives, fungicides, solvents, stabilizers for agricultural chemical active ingredients, antioxidants, UV inhibitors, crystal precipitation inhibitors, antifoaming agents, Although a physical property improver, a coloring agent, etc. are mentioned, it is not limited to these, These adjuvants can be added as needed, respectively.
The binder, thickener, and sticking agent are not particularly limited. For example, starch, dextrin, cellulose, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethyl. Starch, pullulan, sodium alginate, ammonium alginate, propylene glycol alginate, guar gum, locust bean gum, gum arabic, xanthan gum, gelatin, casein, polyvinyl alcohol, polyethylene oxide, polyethylene glycol, ethylene / propylene block polymer, sodium polyacrylate, And polyvinyl pyrrolidone.
The amount of the compound according to the present invention can be appropriately changed depending on the dosage form of the preparation and the method of use, and it is generally desirable to use it in the preparation in the range of 0.1 to 90% by weight.
The compound according to the present invention is sufficiently effective when used alone, but it is used by mixing with one or more selected from various fungicides, insecticides, acaricides and synergists. You can also. Representative examples of fungicides, insecticides and acaricides that can be used in combination with the compounds according to the present invention are shown below.
(Bactericides) captan, holpet, thiuram, diram, dineb, manneb, manzeb, propineb, polycarbamate, chlorothalonil, quintozen, captaphor, iprodione, procymidone, fluorimido, mepronil, flutolanil, pencyclon, oxycarboxyl, fosetyl, triazimephone, tri Adimenol, propiconazole, diclobutrazole, viteltanol, hexaconazole, microbutanyl, flusilazole, metconazole, etaconazole, flutrimazole, cyproconazole, epoxiconazole, flutriaphene, beconazole, diniconazole, cyproconazole, Fenarimol, triflumizole, prochloraz, imazalil, pefrazoate, tridemorph, fenpropimo , Trifolin, pyrifenox, anilazine, polyoxin, metalaxyl, oxadixyl, furaxyl, isoprothiolane, probenazole, pyrrolnitrin, blasticidin S, kasugamycin, validamycin, dihydrostreptomycin sulfate, benomyl, carbendazim, thiophanate methyl, hymexazole, basic Copper chloride, basic copper sulfate, dietofencarb, metasulfocarb, quinomethionate, binapacryl, lecithin, baking soda, dithianon, dinocup, phenaminosulf, dichromemedin, dodin, IBP, edifenphos, mepanipyrim, ferrimzone, triclamide, fludinam, ethoquinolac, dimethomol Pyroxylone, teclophthalam, fusalide, phenazine oxide, thiabenda Lumpur, tricyclazole, cymoxanil, propamocarb hydrochloride, oxolinic acid, hydroxy isoxazole, iminoctadine triacetate salt, Tetraconazole tetrazole, imibenconazole, etc. metiram.
(Insecticides and acaricides) Organophosphorus and carbamate insecticides: fenthion, fenitrothion, diazinon, chlorpyrifos, ESP, bamidione, phentoate, dimethoate, formothion, marathon, trichlorfone, thiometone, phosmet, dichlorvos, acephate, EPBP, methyl parathion, Oxydimetone methyl, ethion, salicione, cyanophos, isoxathion, pyridafenthion, hosalon, methidathione, sulfenphos, chlorfenvinphos, tetrachlorbinphos, dimethylvinphos, propaphos, isofenphos, ethylthiomethone, profenophos, pyracrophos, monocrotophos, azinephosmethyl, aldi Carb, mesomil, thiodicarb, carbofuran, carbosulfan, Furakarubu, furathiocarb, propoxur, BPMC, MTMC, MIPC, carbaryl, pirimicarb, ethiofencarb, fenoxycarb, etc. EDDP.
Pyrethroid insecticides; permethrin, cypermethrin, deltamethrin, fenvalerate, phenpropatoline, pyrethrin, allethrin, tetramethrin, resmethrin, dimeslin, proprasrin, phenothrin, protorin, fluvinate, cyfluthrin, cyhalothrin, flucitrinate, etofenprox, Cycloprotonline, tralomethrin, silafluophene, brofenprox, acrinusline and so on.
Benzoylurea and other insecticides; diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, methoprene, benzoepin, diafenthiuron, acetamiprid , Imidacloprid, nitenpyram, fipronil, cartap, thiocyclam, bensultap, nicotine sulfate, rotenone, metaldehyde, machine oil, microbial pesticides such as BT and insect virus.
(Nematicides) Phenamifos, phostiazates, etc.
(Acaricide) Chlorbenzilate, phenisobromolate, dicophor, amitraz, BPPS, benzomate, hexothiazox, fenbutazin oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentezin, cihexatin, pyridaben, fenpyroximate, tebufenpyrad , Pyrimidifen, phenothiocarb, dienochlor and the like.
Agricultural and horticultural fungicide containing the compound represented by general formula (A), general formula (B) or general formula (C) as an active ingredient (hereinafter also referred to as “agricultural and horticultural fungicide according to the present invention”). The method of using is generally as follows. That is, in the case of wettable powders, liquids, emulsions, sols (flowables), granular wettable powders, and oils, it is diluted 50 to 10,000 times with water, and the active ingredient is generally in a concentration of 1 to 10,000 ppm. Adjusted. Then, this diluted solution is sprayed on the foliage at the site of disease occurrence of the plant in the range of 10 to 2000 liters per 10 ares, usually 20 to 700 liters.
In the case of liquids, emulsions and sols (flowables), they are not diluted with water, but are concentrated liquids or diluted to 50 times with water. As an ULV spray or S spray), an amount of 50 to 5000 ml per 10 ares is sprayed using a helicopter or the like.
In addition, in the case of powder, coarse powder, DL powder, flow dust, fine granule, fine granule, and granule, 2 to 5 kg per 10 ares (about 5 to 500 g as the amount of active ingredient) is the plant disease occurrence site. Applied to the foliage, soil surface, soil or water surface.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
Examples 1 to 13 (Production Examples)
Method for producing compound represented by general formula (A) (Examples 1 to 4)

Production of 5-chloro-7-methylisobutylamino-6- (2,5-dichloro-3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine (Compound No. A-11)
In a 50 ml four-necked flask, 20 g of chloroform was added 2 g (6 mmol) of 5,7-dichloro-6- (2,5-dichloro-3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine. ) Was dissolved, and 5 ml of chloroform in which 0.8 g (8 mmol) of triethylamine and 0.5 g (6 mmol) of methylisobutylamine were dissolved was added dropwise thereto, and the mixture was stirred at room temperature for 30 minutes. After completion of the reaction, the reaction mixture was washed twice with water and then dried over anhydrous sodium sulfate. The residue obtained by evaporating the solvent under reduced pressure was purified by silica gel chromatography (developing solvent; toluene: acetone = 20: 1), and the title compound 5-chloro-7-methylisobutylamino-6- (2, 2.1 g (yield 90%) of 5-dichloro-3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine was obtained as white crystals (melting point 162-163 ° C.).
MS (M + 390): 1H-NMR (CDCl ₃ δ 8.35 (s, 1H); 6.80 (s, 1H); 3.20 (s, 3H); 3.06 (m, 1H); 82 (m, 1H); 1.92 (m, 1H); 0.81 (d, 6H))

Production of 5-chloro-7-methylisobutylamino-6- (2-methyl-5-chloro-4-pyrimidyl) -1,2,4-triazolo [1,5a] pyrimidine (Compound No. A-64)
In a 50 ml 4-necked flask, 20 ml of chloroform was added to 5,7-dichloro-6- (2-methyl-5-chloro-4-pyrimidyl) -1,2,4-triazolo [1,5a] pyrimidine 1 .9 g (6 mmol) was dissolved and added, and 5 ml of chloroform in which 0.8 g (8 mmol) of triethylamine and 0.5 g (6 mmol) of methylisobutylamine were dissolved was added dropwise thereto, followed by stirring at room temperature for 30 minutes. After completion of the reaction, the reaction mixture was washed twice with water and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (developing solvent; toluene: acetone = 20: 1) to give the title compound 5-chloro-7-methylisobutylamino-6- (2 -Methyl-5-chloro-4-pyrimidyl) -1,2,4-triazolo [1,5a] pyrimidine (1.8 g, yield 80%) was obtained as a white crystal (melting point: 153 to 154 ° C.).
1H-NMR (CDCl ₃ δ 8.78 (s, 1H); 8.38 (s, 1H); 3.46 (m, 1H) 2.95 (s, 3H); 2.84 (s, m, 4H) ); 1.93 (m, 1H); 0.85 (m, 6H))

Production of 5-chloro-7-methylisobutylamino-6- (3,5-dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine (Compound No. A-99)
In a 50 ml four-necked flask, 1.7 g of 5,7-dichloro-6- (3,5-dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine was added to 20 ml of chloroform. (6 mmol) was dissolved and added, and 5 ml of chloroform in which 0.8 g (8 mmol) of triethylamine and 0.5 g (6 mmol) of methylisobutylamine were dissolved was added dropwise thereto, followed by stirring at room temperature for 30 minutes. After completion of the reaction, the reaction mixture was washed twice with water and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel chromatography (developing solvent; toluene: acetone = 20: 1) to give 5-chloro-7-methylisobutylamino-6- (3 , 5-dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine (1.7 g, yield 84%) was obtained as white crystals (melting point: 136 to 137 ° C.).
MS (M + 1 334): 1 H-NMR (CDCl ₃ δ 8.35 (s, 1 H); 6.05 (s, 1 H); 3.39 (m, 1 H) 3.08 (m, 1 H); 2.96 (S, 3H); 2.30 (s, 3H) 2.15 (s, 3H) 1.94 (m, 1H); 0.87 (m, 6H))

Production of 5-methylthio-7-methylisobutylamino-6- (3,5-dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine (Compound No. A-102)
In a 50 ml four-necked flask, 20 ml of dimethyl sulfoxide was added to 5-chloro-7-methylisobutylamino-6- (3,5-dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a. ] 1.7 g (5 mmol) of pyrimidine was dissolved and added, and 2.3 g (5 mmol) of a 15% aqueous solution of methyl mercaptan was added dropwise, followed by stirring at room temperature for 1 hour. After completion of the reaction, 30 ml of chloroform was added to the reaction mixture, washed twice with water and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel chromatography (developing solvent; toluene: acetone = 30: 1) to give 5-methylthio-7-methylisobutylamino-6- (3 , 5-dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine (yield 85%) was obtained as white crystals (melting point 146-148 ° C.).
MS (M + 345): 1 H-NMR (CDCl ₃ δ 8.25 (s, 1 H); 6.04 (s, 1 H); 3.19 (m, 1 H) 2.94 (s, m, 4 H); 2 .53 (s, 3H); 2.31 (s, 3H) 2.12 (s, 3H) 1.91 (m, 1H); 0.82 (m, 6H))
Method for producing compound represented by general formula (B) (Examples 5 to 11)

Preparation of 5-chloro-7- (4-methyl-1-piperidyl) -6- (2,5-dichloro-3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine (Compound No. B -19)
In a 50 ml four-necked flask, 20 g of chloroform was added 2 g (6 mmol) of 5,7-dichloro-6- (2,5-dichloro-3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine. The solution was added dropwise, and 5 ml of chloroform in which 0.8 g (8 mmol) of triethylamine and 0.6 g (6 mmol) of 4-pipecoline were dissolved was added dropwise thereto and stirred at room temperature for 30 minutes. After completion of the reaction, the reaction mixture was washed twice with water and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (developing solvent; toluene: acetone = 20: 1) to give the title compound 5-chloro-7- (4-methyl-1-piperidyl). ) -6- (2,5-dichloro-3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine (2.3 g, yield: 95%) as white crystals (melting point: 176-178 ° C.) Obtained.
MS (M + 402): 1H-NMR (CDCl ₃ δ 8.35 (s, 1H); 6.85 (s, 1H); 4.10 (m, 1H); 3.54 (m, 1H); 03 (m, 1H); 2.89 (m, 1H); 1.74-1.27 (m, 5H); 0.99 (d, 3H))

Preparation of 5-chloro-7- (4-ethoxycarbonyl-1-piperidyl) -6- (2,5-dichloro-3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine (Compound No. 1) B-28)
1.7 g of 5,7-dichloro-6- (2,5-dichloro-3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine in 20 ml of chloroform in a 50 ml four-necked flask (5 mmol) was dissolved and added, and 5 ml of chloroform in which 0.65 g (6.5 mmol) of triethylamine and 0.8 g (5 mmol) of 4-ethoxycarbonylpiperidine were dissolved was added dropwise thereto and stirred at room temperature for 1 hour. After completion of the reaction, the reaction mixture was washed twice with water and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (developing solvent; toluene: acetone = 20: 1) to give the title compound 5-chloro-7- (4-ethoxycarbonylpiperidi- 1-yl) -6- (2,5-dichloro-3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine (2.0 g, yield 87%) was obtained as a white crystalline substance (melting point 156-157). ° C).
MS (M + 1 461): 1H-NMR (CDCl ₃ δ 8.37 (s, 1H); 6.86 (s, 1H); 4.16 (q, 2H); 4.02 (m, 1H); 55 (m, 1H); 3.16-3.03 (m, 2H); 2.55 (m, 1H); 2.05-1.78 (m, 4H); 1.27 (t, 3H) )

Preparation of 5-chloro-7- (3,5dimethyl-1-pyrazolyl) -6- (2,5-dichloro-3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine (Compound No. 1) B-38)
In a 50 ml four-necked flask, 0.57 g (6 mmol) of 3,5-dimethylpyrazole was dissolved in 20 ml of dimethylformamide, and 0.24 g (6 mmol) of 60% oily sodium hydride was added for 15 minutes under water cooling. And stirred at room temperature for 1 hour. Next, 2 g (6 mmol) of 5,7-dichloro-6- (2,5-dichloro-3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine was added and stirred at room temperature for 3 hours. After completion of the reaction, the reaction mixture was put into water and extracted with toluene, and the toluene layer was washed 3 times with saturated brine and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (developing solvent; toluene: acetone = 30: 1) to give the title compound 5-chloro-7- (3,5 dimethyl-1- Pyrazolyl) -6- (2,5-dichloro-3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine (1.4 g, yield 58%) was a white crystalline substance (melting point: 193 to 194 ° C.) As obtained.
MS (M + 399): 1H-NMR (CDCl ₃ δ 8.54 (s, 1H); 6.85 (s, 1H); 6.05 (s, 1H); 2.21 (s, 3H); 17 (s, 3H))

Preparation of 5-chloro-7- (4-methyl-1-piperidyl) -6- (2-methyl-5-chloro-4-pyrimidyl) -1,2,4-triazolo [1,5a] pyrimidine (Compound No. .B-68)
In a 50 ml four-necked flask, 20 ml of chloroform was added to 5,7-dichloro-6- (2-methyl-5-chloro-4-pyrimidyl) -1,2,4-triazolo [1,5a] pyrimidine 1 .9 g (6 mmol) was dissolved and added, and 5 ml of chloroform in which 0.8 g (8 mmol) of triethylamine and 0.6 g (6 mmol) of 4-pipecoline were dissolved was added dropwise thereto and stirred at room temperature for 30 minutes. After completion of the reaction, the reaction mixture was washed twice with water and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (developing solvent; toluene: acetone = 30: 1) to give the title compound 5-chloro-7- (4-methyl-1-piperidyl). ) -6- (2-Methyl-5-chloro-4-pyrimidyl) -1,2,4-triazolo [1,5a] pyrimidine (yield 88%) as white crystals (melting point 200-201 ° C.) Obtained.
MS (M + 1 378): 1H-NMR (CDCl ₃ δ 8.78 (s, 1H); 8.39 (s, 1H); 3.86 (m, 1H); 3.72 (m, 1H); 83-2.70 (m, 5H); 1.68-1.51 (m, 3H); 1.40-1.23 (m, 2H); 0.96 (d, 3H))

Preparation of 5-chloro-7- (4-methyl-1-piperidyl) -6- (3,5-dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine (Compound No. B -127)
In a 50 ml four-necked flask, 1.7 g of 5,7-dichloro-6- (3,5-dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine was added to 20 ml of chloroform. (6 mmol) was dissolved and added, and 5 ml of chloroform in which 0.8 g (8 mmol) of triethylamine and 0.6 g (6 mmol) of 4-pipecoline were dissolved was added dropwise thereto, followed by stirring at room temperature for 30 minutes. After completion of the reaction, the reaction mixture was washed twice with water and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (developing solvent; toluene: acetone = 30: 1) to give the title compound 5-chloro-7- (4-methyl-1-piperidyl). ) -6- (3,5-Dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine (1.9 g, yield 92%) as white crystals (melting point 138-140 ° C.) Obtained.
MS (M + 345): 1H-NMR (CDCl ₃ δ 8.37 (s, 1H); 6.05 (s, 1H); 4.01 (m, 1H); 3.84 (m, 1H); 92-2.74 (m, 2H); 2.31 (s, 3H); 2.13 (s, 3H); 1.71-1.55 (m, 3H); 1.40-1.26 ( m, 2H); 0.96 (d, 3H))

Preparation of 5-methoxy-7- (4-methyl-1-piperidyl) -6- (2,5-dichloro-3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine (Compound No. B -34)
In a 50 ml four-necked flask, 10 ml of tetrahydrofuran was added to 10 ml of 5-chloro-7- (4-methyl-1-piperidyl) -6- (2,5-dichloro-3-thienyl) -1,2,4- 1 g (2.5 mmol) of triazolo [1,5a] pyrimidine was dissolved and added, 0.5 g (2.5 mmol) of 28% sodium methoxide methanol solution was added dropwise, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction mixture was put into water and extracted with toluene, and the toluene layer was washed 3 times with saturated brine and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (developing solvent; toluene: acetone = 20: 1) to give the title compound 5-methoxy-7- (4-methyl-1-piperidyl). ) -6- (2,5-dichloro-3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine (0.85 g, yield 85%) as white crystals (melting point 201-203 ° C.) Obtained.
MS (M + 1 398): 1H-NMR (CDCl 3 δ8.26 (s, 1H); 6.78 (s, 1H); 4.04 (m, 4H) 3.40 (m, 1H); 3.04 (M, 1H); 2.85 (m, 1H); 1.72-1.22 (m, 5H); 0.98 (d, 3H))

Preparation of 5-methylthio-7- (4-methyl-1-piperidyl) -6- (3,5-dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine (Compound No. B -130)
In a 50 ml four-necked flask, 20 ml of dimethyl sulfoxide was added to 5-chloro-7- (4-methyl-1-piperidyl) -6- (3,5-dimethyl-1-pyrazolyl) -1,2,4. -1.2 g (3.5 mmol) of triazolo [1,5a] pyrimidine was dissolved and added, and 1.6 g (3.5 mmol) of 15% aqueous solution of methyl mercaptan was added dropwise, followed by stirring at room temperature for 1 hour. After completion of the reaction, chloroform was added to the reaction mixture, washed twice with water, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (developing solvent; toluene: acetone = 30: 1) to give the title compound 5-methylthio-7- (4-methyl-1-piperidyl). ) -6- (3,5-dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine (1.0 g, yield: 81%) as white crystals (melting point: 158 to 159 ° C.) Obtained.
MS (M + 358): 1 H-NMR (CDCl ₃ δ 8.27 (s, 1H); 6.04 (s, 1H); 3.90-3.78 (m, 2H); 2.80-2.67 (M, 2H); 2.53 (s, 3H); 2.32 (s, 3H); 2.10 (s, 3H); 1.66 to 1.26 (m, 5H); 0.95 ( d, 3H))
Production method of compounds represented by formula (C) (Examples 12 to 13)

Production of 5-chloro-7-cyclohexyl-6- (3,5-dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine (Compound No. C-1)
1.7 g of 5,7-dichloro-6- (3,5-dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine was added to 20 ml of tetrahydrofuran in a 50 ml four-necked flask. (6 mmol) dissolved and 35 mg (0.06 mmol) of bisdiphenylphosphinopropyl palladium chloride [PdCl ₂ (dppp)] were added and heated to 60 ° C. To this, 6 ml (6 mmol) of an 18% tetrahydrofuran solution of cyclohexyl magnesium bromide was added dropwise over 1 minute, and the mixture was stirred at 60 ° C. for 1 hour.
After completion of the reaction, the reaction mixture was put into water and extracted with toluene. The toluene layer was washed twice with saturated brine and then dried over anhydrous sodium sulfate. The organic solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (developing solvent; hexane: acetone = 10: 1) to give the title compound 5-chloro-7-cyclohexyl-6- (3, 0.8 g (yield 40%) of 5-dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine was obtained as white crystals (melting point mp 204-205 ° C.).
MS (M + 330)

Production of 5-chloro-7-benzyl-6- (3,5-dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine (Compound No. C-11)
In a 50 ml four-necked flask, 1.7 g of 5,7-dichloro-6- (3,5-dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine was added to 20 ml of tetrahydrofuran. (6 mmol) dissolved and 35 mg (0.06 mmol) of bisdiphenylphosphinopropyl palladium [PdCl ₂ (dppp)] were added and heated to 60 ° C. To this, 6 ml (6 mmol) of a 17% tetrahydrofuran solution of benzylmagnesium chloride was added dropwise over 3 minutes, followed by stirring at 60 ° C. for 1 hour.
After completion of the reaction, the reaction mixture was put into water and extracted with toluene. The toluene layer was washed twice with saturated brine and then dried over anhydrous sodium sulfate. The organic solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (developing solvent; hexane: acetone = 10: 1) to give the title compound 5-chloro-7-cyclohexyl-6- (3, 0.8 g (yield 40%) of 5-dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine was obtained as white crystals (melting point mp 60-61 ° C.).
MS (M + 338)
Reference production example Production method of the compound represented by the general formula (1) (reference production examples 1 to 3)
Reference production example 1
Production of 5,7-dichloro-6- (2,5-dichloro-3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine (Compound No. 3)
(1) Synthesis of 3-thienylmalonic acid diethyl ester In a 500 ml four-necked flask, 30 g (0.21 mol) of 3-thienylacetic acid and 50 g (0.42 mol) of diethyl carbonate were dissolved in 300 ml of dimethylformamide. In addition, 8.5 g (0.21 mol) of 60% oily sodium hydride was added all at once and stirred at room temperature for 4 hours. After completion of the reaction, the reaction mixture was put into water and extracted with toluene, and the toluene layer was washed 3 times with saturated brine and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (developing solvent; hexane: acetone = 20: 1) to obtain 47 g (92% yield) of 3-thienylmalonic acid diethyl ester. Obtained as a yellow oil.
MS (M + 1 243)
(2) Synthesis of 5,7-dihydroxy-6- (3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine To 50 ml of 1-butanol in a 100 ml four-necked flask 2.8 g (41 mmol) of side, 4 g (41 mmol) of 3-amino-1,2,4-triazole and 10 g (41 mmol) of 3-thienylmalonic acid diethyl ester were added, and the mixture was stirred for 6 hours with heating under reflux. After completion of the reaction, the reaction mixture was cooled to room temperature and the precipitated crystals were collected by filtration. To the crystals obtained as the sodium salt, 10% hydrochloric acid was added, and the precipitated white crystals were collected by filtration and dried to give 5,7-dihydroxy-6- (3-thienyl) -1,2,4-triazolo [1, 5a] Pyrimidine 7 g (yield 73%) was obtained.
MS (M + 234)
(3) Synthesis of 5,7-dichloro-6- (3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine (Compound No. 2) In a 50 ml four-necked flask, 7-Dihydroxy-6- (3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine (7 g, 30 mmol) and phosphorus oxychloride (30 ml) were added, and the mixture was stirred for 3 hours with heating under reflux. After completion of the reaction, phosphorus oxychloride was distilled off under reduced pressure. Toluene was added to the resulting residue for extraction, and the toluene layer was washed three times with saturated brine and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (developing solvent; toluene: acetone = 20: 1) to give 5,7-dichloro-6- (3-thienyl) -1, 6.6 g (yield 80%) of 2,4-triazolo [1,5a] pyrimidine was obtained as white crystals.
MS (M + 270): 1H-NMR (CDCl ₃ δ 8.56 (s, 1H); 7.54 (m, 2H); 7.18 (m, 1H))
(4) Synthesis of 5,7-dichloro-6- (2,5-dichloro-3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine 10 ml of chloroform in a 100 ml four-necked flask 40 ml of carbon tetrachloride, 6 g (22 mmol) of 5,7-dichloro-6- (3-thienyl) -1,2,4-triazolo [1,5a] pyrimidine, 9 g (66 mmol) of sulfuryl chloride and a catalytic amount of pyridine. In addition, the mixture was stirred for 4 hours with heating under reflux. After completion of the reaction, the reaction layer was washed once with saturated saline and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was washed with isopropyl ether to give the title compound 5,7-dichloro-6- (2,5-dichloro-3-thienyl) -1,2,4-triazolo [ 1,5a] pyrimidine (7 g, yield: 93%) was obtained as a white crystal (melting point: 165-170 ° C.).
MS (M + 1 341): 1 H-NMR (CDCl ₃ δ 8.60 (s, 1 H); 6.84 (s, 1 H))
Reference production example 2
Production of 5,7-dichloro-6- (2-methyl-5-chloro-4-pyrimidyl) -1,2,4-triazolo [1,5a] pyrimidine (Compound No. 9)
(1) Synthesis of 2-methyl-5-chloro-4-pyrimidylmalonic acid diethyl ester In a 300 ml four-necked flask, 100 ml of dimethylformamide was placed, and 3 g (69 mmol) of 60% oily sodium hydride was placed therein. added. To this, 11 g (69 mmol) of diethyl malonate was added dropwise over 10 minutes under ice-cooling. After dropwise addition, cooling was removed and the mixture was stirred at room temperature for 20 minutes. Next, 11 g (69 mmol) of 4,5-dichloro-2-methylpyrimidine was added over 30 minutes, and the mixture was stirred at room temperature for 15 hours. After completion of the reaction, the reaction mixture was put into water and extracted with toluene, and the toluene layer was washed 3 times with saturated brine and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (developing solvent; hexane: ethyl acetate = 5: 1) to give 16 g of 2-methyl-5-chloro-4-pyrimidylmalonic acid diethyl ester. (Yield 81%) was obtained as a yellow oil.
MS (M + 1 287)
(2) Synthesis of 5,7-dichloro-6- (2-methyl-5-chloro-4-pyrimidyl) -1,2,4-triazolo [1,5a] pyrimidine 50 ml capacity with Lean-Stuck tube In a four-necked flask, 6 g (20 mmol) of 2-methyl-5-chloro-4-pyrimidylmalonic acid diethyl ester, 1.8 g (20 mmol) of 3-amino-1,2,4-triazole and tri-n-propylamine 5 0.8 g (40 mmol) was added, and the mixture was stirred at 140 ° C. for 5 hours while distilling off ethanol produced during the reaction. After completion of the reaction, the temperature was lowered to room temperature, and the inside of the reaction layer was washed three times with hexane. After completion of the reaction, phosphorus oxychloride was distilled off under reduced pressure, toluene and water were added to the resulting residue, and the water bath was neutralized with sodium carbonate, followed by extraction with toluene. The toluene layer was washed twice with saturated brine and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (developing solvent; toluene: acetone = 30: 1) to give the title compound 5,7-dichloro-6- (2-methyl-5). -Chloro-4-pyrimidyl) -1,2,4-triazolo [1,5a] pyrimidine (2.5 g, yield 40%) was obtained as yellow crystals (melting point: 165 to 169 ° C.).
MS (M + 315): 1 H-NMR (CDCl ₃ δ 8.88 (s, 1H); 8.64 (s, 1H); 2.83 (s, 3H))
Reference Example 3
Production of 5,7-dichloro-6- (3,5-dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine (Compound No. 6)
(1) Synthesis of diethyl 3,5-dimethyl-1-pyrazolylmalonate 15 g (0.16 mol) of 3,5-dimethylpyrazole dissolved in 200 ml of tetrahydrofuran was added to a 500 ml four-necked flask and cooled with water. Under 60% oily sodium hydride 6.3 g (0.16 mol) was added over 15 minutes and stirred at room temperature for 1 hour. Next, 38 g (0.16 mol) of bromomalonic acid diethyl ester was added dropwise over 10 minutes and left at room temperature for 1 day. After completion of the reaction, the reaction mixture was poured into water, extracted with toluene, the toluene-tetrahydrofuran mixed organic layer was washed twice with saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (developing solvent; toluene: acetone = 20: 1) to give 23 g of diethyl 3,5-dimethyl-1-pyrazolylmalonate (yield). 58%) was obtained as a pale yellow oil.
MS (M + 254)
(2) Synthesis of 5,7-dichloro-6- (3,5-dimethyl-1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine Four 100 ml volumes equipped with Leinstadt tubes To the neck flask, 23 g (91 mmol) of 35-dimethyl-1-pyrazolylmalonic acid diethyl ester, 7.6 g (91 mmol) of 3-amino-1,2,4-triazole and 26 g (182 mmol) of tri-n-propylamine were added. The mixture was stirred at 140 ° C. for 5 hours while EtOH generated during the reaction was distilled off. After completion of the reaction, the temperature was lowered to room temperature, and the inside of the reaction layer was washed with hexane three times. To this was added 70 g (453 mmol) of phosphorus oxychloride, and the mixture was further stirred for 3 hours with heating under reflux. After completion of the reaction, phosphorus oxychloride was distilled off under reduced pressure, toluene and water were added to the resulting residue, and the water bath was neutralized with sodium carbonate, followed by extraction with toluene. The toluene layer was washed twice with saturated brine and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography (developing solvent; toluene: acetone = 20: 1) to give the title compound 5,7-dichloro-6- (3,5-dimethyl). −1-pyrazolyl) -1,2,4-triazolo [1,5a] pyrimidine (12 g, yield 45%) was obtained as yellow crystals (melting point: 156 to 160 ° C.).
MS (M + 282): 1H-NMR (CDCl ₃ δ 8.64 (s, 1H); 6.13 (s, 1H); 2.33 (s, 3H); 2.17 (s, 3H))
Examples 14 to 28 (Formulation Examples)
Formulation examples (Examples 14 to 28) in which the compound according to the present invention (compound represented by the general formula (A), (B) or (C)) is formulated as an agricultural and horticultural fungicide are described below. .
Powder (Examples 14 to 16)

Compound No. 2 parts of A-11 compound, 1 part of PAP (physical modifier) and 97 parts of clay are uniformly ground and mixed to obtain a powder containing 2% of the active ingredient.
Compound No. It can replace with A-11 and a powder can be obtained similarly using the compound of Tables 1-10.

Compound No. 2 parts of B-19 compound, 1 part of PAP (physical property improving agent) and 97 parts of clay are uniformly ground and mixed to obtain a powder containing 2% of the active ingredient.
Compound No. It can replace with B-19 and can obtain a powder similarly using the compound of Tables 11-22.

Compound No. 2 parts of C-11 compound, 1 part of PAP (physical property improving agent) and 97 parts of clay are uniformly ground and mixed to obtain a powder containing 2% of the active ingredient.
Compound No. It can replace with C-11 and a powder can be obtained similarly using the compound of Table 23-Table 25.
Wetting agent (Examples 17-19)

Compound No. 20 parts of the A-64 compound, 3 parts of potassium alkylbenzene sulfonate, 5 parts of polyoxyethylene nonylphenyl ether and 72 parts of clay are uniformly mixed and ground to obtain a wettable powder containing 20% of the active ingredient.
Compound No. Instead of A-64, a wettable powder can be similarly obtained using the compounds described in Tables 1 to 10.

Compound No. 20 parts of the compound of B-127, 3 parts of potassium alkylbenzenesulfonate, 5 parts of polyoxyethylene nonylphenyl ether and 72 parts of clay are uniformly mixed and ground to obtain a wettable powder containing 20% of the active ingredient.
Compound No. In place of B-127, wettable powders can be similarly obtained using the compounds described in Tables 11 to 22.

Compound No. 20 parts of the compound of C-1, 3 parts of potassium alkylbenzenesulfonate, 5 parts of polyoxyethylene nonylphenyl ether and 72 parts of clay are uniformly mixed and ground to obtain a wettable powder containing 20% of the active ingredient.
Compound No. In place of C-1, wettable powders can be similarly obtained using the compounds described in Table 23 to Table 25.
Emulsion (Examples 20-22)

Compound No. When 30 parts of the compound of A-11, 40 parts of methyl ethyl ketone and 30 parts of polyoxyethylene nonylphenyl ether are mixed and dissolved, an emulsion containing 30% of the active ingredient is obtained.
Compound No. An emulsion can be obtained in the same manner using the compounds shown in Tables 1 to 10 instead of A-11.

Compound No. If 30 parts of B-68 compound, 40 parts of methyl ethyl ketone and 30 parts of polyoxyethylene nonylphenyl ether are mixed and dissolved, an emulsion containing 30% of the active ingredient is obtained.
Compound No. Emulsions can be obtained in the same manner using the compounds described in Tables 11 to 22 in place of B-68.

Compound No. When 30 parts of the compound of C-1, 40 parts of methyl ethyl ketone and 30 parts of polyoxyethylene nonylphenyl ether are mixed and dissolved, an emulsion containing 30% of the active ingredient is obtained.
Compound No. Instead of C-1, emulsions can be obtained in the same manner using the compounds described in Table 23 to Table 25.
Sol agent (Examples 23 to 25)

Compound No. A part of A-99 compound, 2 parts of lauryl sulfate, 2 parts of sodium alkylnaphthalene sulfonate, 1 part of acetoxypropyl cellulose and 55 parts of water are uniformly mixed to obtain a sol containing 40% of the active ingredient.
Compound No. In place of A-99, sol agents can be similarly obtained using the compounds shown in Tables 1 to 10.

Compound No. 40 parts of B-127 compound, 2 parts of lauryl sulfate, 2 parts of sodium alkylnaphthalene sulfonate, 1 part of acetoxypropylcellulose and 55 parts of water are uniformly mixed to obtain a sol containing 40% of the active ingredient.
Compound No. In place of B-127, sol agents can be similarly obtained using the compounds described in Tables 11 to 22.

Compound No. 40 parts of C-11 compound, 2 parts of lauryl sulfate, 2 parts of sodium alkylnaphthalene sulfonate, 1 part of acetoxypropyl cellulose and 55 parts of water are uniformly mixed to obtain a sol containing 40% of the active ingredient.
Compound No. In place of C-11, sol agents can be similarly obtained using the compounds described in Table 23 to Table 25.
Granule (Examples 26 to 28)

Compound No. After adding 15 parts of water to 10 parts of A-64 compound, 1 part of lauryl sulfate, 5 parts of calcium lignin sulfonate, 30 parts of bentonite and 54 parts of clay and kneading with a kneader, the mixture is granulated with a granulator Dry with a drier to obtain granules containing 10% of the active ingredient.
Compound No. Instead of A-64, granules can be obtained in the same manner using the compounds described in Tables 1 to 10.

Compound No. After adding 15 parts of water to 10 parts of B-68 compound, 1 part of lauryl sulfate, 5 parts of calcium lignin sulfonate, 30 parts of bentonite and 54 parts of clay and kneading with a kneader, the mixture is granulated with a granulator and fluidized. Dry with a dryer to obtain granules containing 10% of the active ingredient.
Compound No. Instead of B-68, granules can be similarly obtained using the compounds described in Tables 11 to 22.

比較薬剤Ａは、下記式で表される化合物であり、米国特許第５５９３９９６号明細書記載の化合物である。

試験例２
実施例１８に準じて調製した水和剤について、試験例１と同様の方法により、防除価を算出し、該防除価を同様の基準により評価値に換算した。また、試験例１と同様の基準により水稲に対する薬害を調査した。これらの結果は、表３６のとおりである。

比較薬剤Ｂは、下記式で表される化合物であり、アメリカ特許第５５９３９９６号明細書記載の化合物である。

試験例３
実施例１９に準じて調製した水和剤について、試験例１と同様の方法により、防除価を算出し、該防除価を同様の基準により評価値に換算した。また、試験例１と同様の基準により水稲に対する薬害を調査した。これらの結果は、表３７のとおりである。

比較薬剤Ｃは、下記式で表される化合物であり、国際公開特許ＷＯ９ ９／４１２５５号公報記載の化合物である。

オオムギうどんこ病防除効果試験（試験例４〜６）
試験例４
温室内で直径６ｃｍの大きさのプラスチックポットで栽培した大麦（品種：アズマゴールデン）の１葉期苗に、実施例１７に準じて調製した水和剤の所定濃度希釈液を１ポットあたり１０ｍｌ散布した。薬剤処理翌日、あらかじめ大麦葉上で形成させたオオムギうどんこ病菌（Ｅｒｙｓｉｐｈｅ ｇｒａｍｉｎｉｓ：エリシフェ グラミニス）の分生胞子を接種し、２０℃の人工気象室内で発病管理した。接種７日後に第１葉上のオオムギうどんこ病の病斑面積歩合（％）を調査し、次式により防除価（％）を算出した。そして、試験例１と同様な方法で防除効果の評価値に換算した。
本試験は１薬液濃度区当り３ポット制で行った。また、大麦に対する薬害程度を試験例１と同じ基準で調査した。その結果は表３８のとおりである。

試験例５
実施例１８に準じて調製した水和剤について、試験例４と同様の方法により、防除価を算出し、該防除価を同様の基準により評価値に換算した。また、試験例１と同様の基準により大麦に対する薬害を調査した。これらの結果は、表３９のとおりである。

試験例６
実施例１９に準じて調製した水和剤について、試験例４と同様の方法により、防除価を算出し、該防除価を同様の基準により評価値に換算した。また、試験例１と同様の基準により大麦に対する薬害を調査した。これらの結果は、表４０のとおりである。

コムギ赤さび病防除効果試験（試験例７〜９）
試験例７
温室内で直径６ｃｍの大きさのプラスチックポットで栽培した小麦（品種：農林６１号）の１葉期苗に、実施例１７に準じて調製した水和剤の所定濃度希釈液を１ポットあたり１０ｍｌ散布した。薬剤処理翌日、あらかじめ小麦葉上で形成させたコムギ赤さび病菌（Ｐｕｃｃｉｎｉａ ｒｅｃｏｎｄｉｔａ：プクシニア レコンジタ）の夏胞子を接種し、２０℃の人工気象室内で発病管理した。接種１０日後に第１葉上の病斑数を調査し、次式により防除価（％）を算出した。そして、試験例１と同様な方法で防除効果の評価値に換算した。
本試験は１薬液濃度区当り３ポット制で行った。また、小麦に対する薬害程度を試験例１と同じ基準で調査した。その結果は表４１のとおりである。

試験例８
実施例１８に準じて調製した水和剤について、試験例７と同様の方法により、防除価を算出し、該防除価を同様の基準により評価値に換算した。また、試験例１と同様の基準により小麦に対する薬害を調査した。これらの結果は、表４２のとおりである。

試験例９
実施例１９に準じて調製した水和剤について、試験例７と同様の方法により、防除価を算出し、該防除価を同様の基準により評価値に換算した。また、試験例１と同様の基準により小麦に対する薬害を調査した。これらの結果は、表４３のとおりである。

キュウリべと病防除効果試験（試験例１０〜１２）
試験例１０
温室内で直径６ｃｍの大きさのプラスチックポットで栽培したきゅうり（品種：相模半白）の２葉期苗に、実施例１７に準じて調製した水和剤の所定濃度希釈液を１ポットあたり１０ｍｌ散布した。薬剤処理の翌日、あらかじめきゅうり葉上で形成させたキュウリべと病菌（Ｐｓｅｕｄｏｐｅｒｏｎｏｓｐｏｒａ ｃｕｂｅｎｓｉｓ：シュードヘロノスポラ クベンシス）の胞子を接種し、２０℃の人工気象室内で発病管理した。接種６日後に病斑面積歩合（％）を調査し、次式により防除価（％）を算出した。そして、試験例１と同様な方法により評価値に換算した。
本試験は１薬液濃度区当り３ポット制で行った。また、試験例１と同一の基準によりきゅうりに対する薬害程度を調査した。その結果は表４４のとおりである。

試験例１１
実施例１８に準じて調製した水和剤について、試験例１０と同様の方法により、防除価を算出し、該防除価を同様の基準により評価値に換算した。また、試験例１と同様の基準によりきゅうりに対する薬害を調査した。これらの結果は、表４５のとおりである。

試験例１２
実施例１９に準じて調製した水和剤について、試験例１０と同様の方法により、防除価を算出し、該防除価を同様の基準により評価値に換算した。また、試験例１と同様の基準によりきゅうりに対する薬害を調査した。これらの結果は、表４６のとおりである。

キュウリ灰色かび病防除効果試験（試験例１３〜１５）
試験例１３
温室内で直径６ｃｍの大きさのプラスチックポットで栽培したきゅうり（品種：相模半白）の１．５葉期苗に、実施例１７に準じて調製した水和剤の所定濃度希釈液を１ポットあたり１０ｍｌ散布した。薬剤処理の翌日、あらかじめジャガイモ煎汁培地上で培養したキュウリ灰色かび病菌（Ｂｏｔｒｙｔｉｓ ｃｉｎｅｒｅａ：ボトリチス シネレア）の含菌寒天片を接種し、２０℃の湿室内に入れた。接種４日後に病斑直径（ｃｍ）を測定し、次式により防除価（％）を算出した。そして、試験例１と同様な方法で評価値に換算した。
本試験は１薬液濃度区当り３ポット制で行った。また、試験例１と同一の基準によりきゅうりに対する薬害程度を調査した。その結果は表４７のとおりである。

試験例１４
実施例１８に準じて調製した水和剤について、試験例１３と同様の方法により、防除価を算出し、該防除価を同様の基準により評価値に換算した。また、試験例１と同様の基準によりきゅうりに対する薬害を調査した。これらの結果は、表４８のとおりである。

試験例１５
実施例１９に準じて調製した水和剤について、試験例１３と同様の方法により、防除価を算出し、該防除価を同様の基準により評価値に換算した。また、試験例１と同様の基準によりきゅうりに対する薬害を調査した。これらの結果は、表４９のとおりである。

キュウリ灰色かび病防除効果試験（治療効果）（試験例１６〜１７）
試験例１６
温室内で直径６ｃｍの大きさのプラスチックポットで栽培したきゅうり（品種：相模半白）の１．５葉期苗の第１葉上に、あらかじめジャガイモ煎汁培地上で培養したキュウリ灰色かび病菌（Ｂｏｔｒｙｔｉｓ ｃｉｎｅｒｅａ：ボトリチス シネレア）の含菌寒天片を接種し、２０℃の湿室内に１日間保持した。接種１日後、実施例１７に準じて調製した水和剤の所定濃度希釈液を１ポットあたり１０ｍｌ散布した。散布後は、再び２０℃の湿室内に入れた。散布４日後に、病斑直径（ｃｍ）を測定し、次式により防除価（％）を算出した。
本試験は１薬液濃度区当り３ポット制で行った。その結果は表５０のとおりである。

試験例１７
実施例１８に準じて調製した水和剤について、試験例１６と同様の方法により、防除価を算出した。これらの結果は、表５１のとおりである。

Compound No. 15 parts of water was added to 10 parts of the compound of C-1, 1 part of lauryl sulfate, 5 parts of calcium lignin sulfonate, 30 parts of bentonite and 54 parts of clay and kneaded with a kneader, and then granulated with a granulator and fluidized. Dry with a drier to obtain granules containing 10% of the active ingredient.
Compound No. Instead of C-1, granules can be obtained in the same manner using the compounds described in Table 23 to Table 25.
Test Examples Specific examples of the usefulness of the compounds according to the present invention as active ingredients of agricultural and horticultural fungicides and the usefulness of the agricultural and horticultural fungicides according to the present invention are shown in Test Examples 1 to 17.
Rice Blast Control Effect Test (Test Examples 1 to 3)
Test example 1
10 ml per one pot of a predetermined concentration of wettable powder prepared according to Example 17 was sprayed on the three-leaf seedlings of paddy rice (variety: Asahi) grown in a plastic pot with a diameter of 6 cm in a greenhouse. . The day after the drug treatment, conidia of rice blast fungus (Pyricularia oryzae) previously formed on oatmeal agar medium were inoculated and the disease was controlled in an artificial climate room at 24 ° C. Five days after the inoculation of the disease, the number of rice blast spots on the third leaf was examined, and the control value (%) was calculated by the following formula. And the control value (%) was converted into an evaluation value according to the following criteria.
This test was conducted in a three-pot system per chemical solution concentration group. In addition, the degree of chemical damage to paddy rice was investigated according to the following criteria. The results are shown in Table 35.
The evaluation value of the control effect and the investigation index of the degree of chemical damage are the same in the following Test Examples 2 to 15.

Comparative drug A is a compound represented by the following formula, and is a compound described in US Pat. No. 5,593,996.

Test example 2
About the wettable powder prepared according to Example 18, the control value was computed by the method similar to Test Example 1, and this control value was converted into the evaluation value by the same reference | standard. In addition, phytotoxicity to paddy rice was investigated according to the same criteria as in Test Example 1. These results are shown in Table 36.

Comparative drug B is a compound represented by the following formula, and is a compound described in US Pat. No. 5,593,996.

Test example 3
About the wettable powder prepared according to Example 19, the control value was computed by the method similar to Test Example 1, and this control value was converted into the evaluation value by the same reference | standard. In addition, phytotoxicity to paddy rice was investigated according to the same criteria as in Test Example 1. These results are shown in Table 37.

Comparative drug C is a compound represented by the following formula, and is a compound described in International Publication No. WO9 / 41255.

Barley powdery mildew control effect test (Test Examples 4-6)
Test example 4
10 ml per pot of a predetermined concentration of a wettable powder prepared according to Example 17 is applied to a 1-leaf seedling of barley (variety: Azuma Golden) cultivated in a plastic pot with a diameter of 6 cm in a greenhouse. did. The day after drug treatment, conidia of barley powdery mildew (Erysiphe graminis) previously formed on barley leaves were inoculated, and the disease was controlled in an artificial climate room at 20 ° C. Seven days after the inoculation, the lesion area ratio (%) of barley powdery mildew on the first leaf was investigated, and the control value (%) was calculated by the following formula. And it converted into the evaluation value of the control effect by the method similar to Test Example 1.
This test was conducted in a three-pot system per chemical solution concentration group. Further, the degree of phytotoxicity to barley was investigated according to the same criteria as in Test Example 1. The results are shown in Table 38.

Test Example 5
About the wettable powder prepared according to Example 18, the control value was computed by the method similar to Test Example 4, and this control value was converted into the evaluation value by the same reference | standard. Moreover, the phytotoxicity to barley was investigated according to the same criteria as in Test Example 1. These results are shown in Table 39.

Test Example 6
About the wettable powder prepared according to Example 19, the control value was computed by the method similar to Test Example 4, and this control value was converted into the evaluation value by the same reference | standard. Moreover, the phytotoxicity to barley was investigated according to the same criteria as in Test Example 1. These results are shown in Table 40.

Wheat red rust control effect test (Test Examples 7 to 9)
Test Example 7
10 ml per pot of a predetermined concentration dilution of wettable powder prepared according to Example 17 is applied to a single leaf seedling of wheat (variety: Norin 61) grown in a plastic pot with a diameter of 6 cm in a greenhouse. Scattered. The day after the drug treatment, summer spores of wheat red rust fungus (Puccinia recondita) previously formed on wheat leaves were inoculated, and the disease was controlled in an artificial climate room at 20 ° C. Ten days after the inoculation, the number of lesions on the first leaf was examined, and the control value (%) was calculated by the following formula. And it converted into the evaluation value of the control effect by the method similar to Test Example 1.
This test was conducted in a three-pot system per chemical solution concentration group. Further, the degree of phytotoxicity to wheat was investigated according to the same criteria as in Test Example 1. The results are shown in Table 41.

Test Example 8
About the wettable powder prepared according to Example 18, the control value was computed by the method similar to Test Example 7, and this control value was converted into the evaluation value by the same reference | standard. Moreover, the phytotoxicity with respect to wheat was investigated by the same standard as Test Example 1. These results are shown in Table 42.

Test Example 9
About the wettable powder prepared according to Example 19, the control value was computed by the method similar to Test Example 7, and this control value was converted into the evaluation value by the same reference | standard. Moreover, the phytotoxicity with respect to wheat was investigated by the same standard as Test Example 1. These results are shown in Table 43.

Cucumber downy mildew control effect test (Test Examples 10 to 12)
Test Example 10
10 ml per pot of a predetermined concentration diluting solution of wettable powder prepared according to Example 17 was applied to a 2-leaf stage seedling of cucumber (variety: Sagamihanjiro) grown in a plastic pot with a diameter of 6 cm in a greenhouse. Scattered. The day after the drug treatment, spore of Pseudoperonospora cubis (Pseudoperonospora cubensis) previously formed on cucumber leaves was inoculated, and the disease was controlled in an artificial climate room at 20 ° C. The lesion area ratio (%) was investigated 6 days after the inoculation, and the control value (%) was calculated by the following formula. And it converted into the evaluation value by the method similar to Test Example 1.
This test was conducted in a three-pot system per chemical solution concentration group. In addition, the degree of chemical damage to cucumbers was investigated according to the same criteria as in Test Example 1. The results are shown in Table 44.

Test Example 11
About the wettable powder prepared according to Example 18, the control value was computed by the method similar to Test Example 10, and this control value was converted into the evaluation value by the same reference | standard. Further, phytotoxicity against cucumbers was investigated according to the same criteria as in Test Example 1. These results are shown in Table 45.

Test Example 12
About the wettable powder prepared according to Example 19, the control value was computed by the method similar to Test Example 10, and this control value was converted into the evaluation value by the same reference | standard. Further, phytotoxicity against cucumbers was investigated according to the same criteria as in Test Example 1. These results are shown in Table 46.

Cucumber gray mold control effect test (Test Examples 13 to 15)
Test Example 13
One pot of dilute solution of wettability prepared according to Example 17 was added to 1.5 leaf seedlings of cucumber (variety: Sagamihanjiro) cultivated in a plastic pot with a diameter of 6 cm in a greenhouse. 10 ml per unit was sprayed. The day after the drug treatment, inoculated with agar-containing agar pieces of cucumber gray mold fungus (Botrytis cinerea) previously cultured on a potato broth medium, and placed in a 20 ° C. humid chamber. The lesion diameter (cm) was measured 4 days after the inoculation, and the control value (%) was calculated by the following formula. And it converted into an evaluation value by the method similar to Test Example 1.
This test was conducted in a three-pot system per chemical solution concentration group. In addition, the degree of chemical damage to cucumbers was investigated according to the same criteria as in Test Example 1. The results are shown in Table 47.

Test Example 14
About the wettable powder prepared according to Example 18, the control value was computed by the method similar to Test Example 13, and this control value was converted into the evaluation value by the same reference | standard. Further, phytotoxicity against cucumbers was investigated according to the same criteria as in Test Example 1. These results are shown in Table 48.

Test Example 15
About the wettable powder prepared according to Example 19, the control value was computed by the method similar to Test Example 13, and this control value was converted into the evaluation value by the same reference | standard. Further, phytotoxicity against cucumbers was investigated according to the same criteria as in Test Example 1. These results are shown in Table 49.

Cucumber gray mold control effect test (therapeutic effect) (Test Examples 16 to 17)
Test Example 16
A cucumber gray mold fungus previously cultured on a potato broth medium on the first leaf of a 1.5 leaf seedling of a cucumber (variety: Sagamihanjiro) grown in a plastic pot with a diameter of 6 cm in a greenhouse. Botrytis cinerea: Botrytis cinerea) was inoculated with agar-containing agar pieces and kept in a humid chamber at 20 ° C. for 1 day. One day after inoculation, 10 ml of a predetermined concentration diluted solution of wettable powder prepared according to Example 17 was sprayed per pot. After spraying, it was again placed in a humid chamber at 20 ° C. Four days after spraying, the lesion diameter (cm) was measured, and the control value (%) was calculated by the following formula.
This test was conducted in a three-pot system per chemical solution concentration group. The results are shown in Table 50.

Test Example 17
For the wettable powder prepared according to Example 18, the control value was calculated in the same manner as in Test Example 16. These results are shown in Table 51.

Industrial applicability

  The composition comprising the compound according to the present invention is effective for various diseases such as rice blast, barley powdery mildew, wheat red rust, cucumber downy mildew, and cucumber gray mold disease as described above. Can be controlled. Therefore, the compound according to the present invention is useful as an active ingredient of agricultural and horticultural fungicides.

Claims (9)

Formula (A)

[Where:
Het _A represents a 5-membered or 6-membered ring containing a hetero element, and these rings are a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group or a C2-C6 alkoxyalkyl group. May be replaced,
X _A represents a halogen atom, a cyano group, a C1-C6 alkoxy group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 alkylamino group or a C1-C6 alkoxycarbonyl group. R _A and R _A ′ are the same or different from each other, and are a C1-C10 alkyl group, a C2-C10 alkenyl group, a C2-C10 alkynyl group or a phenyl group (the alkyl group, alkenyl group, alkynyl group and phenyl group). The group is one or more selected from the group consisting of a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 alkylthio group, a C1-C6 alkoxycarbonyl group, and a carboxyl group. Optionally substituted with a group). ]
A triazolopyrimidine derivative represented by: The Het _A is a group represented by the following general formulas Het _{1 to} Het ₁₅

(Wherein R ₁ , R ₂ and R ₃ are the same or different and each represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group, or a halogen atom) Group,
X _A represents a halogen atom, and R _A and R _A ′ are the same or different from each other, and are a C1-C10 alkyl group, a C2-C10 alkenyl group, or a C2-C10 alkynyl group (the alkyl group, alkenyl group). 2. The triazolopyrimidine derivative according to claim 1, wherein the group and the alkynyl group are each optionally substituted with a halogen atom, a C1-C6 alkyl group or a C1-C6 haloalkyl group. The triazolopyrimidine derivative according to claim 2, wherein the Het _A is a group represented by the Het ₁ , Het ₆ or Het ₁₂ . General formula (B)

[Where:
Het _B represents a 5- or 6-membered ring containing a hetero element, which is substituted with a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group or a C2-C6 alkoxyalkyl group. You may,
X _B is halogen atom, cyano group, C1 -C6 alkoxy, C1 -C6 alkylthio, C1 -C6 alkylsulfinyl groups, C1 -C6 alkylsulfonyl group, a C1 -C6 alkylamino group or C1 -C6 alkoxycarbonyl group shows, and R _B is attached at the nitrogen atom, a nitrogen-containing heterocyclic ring which may be substituted. ]
A triazolopyrimidine derivative represented by: The Het _B is a _group represented by the following general formulas Het _{1 to} Het ₁₅

(Wherein R ₁ , R ₂ and R ₃ may be the same or different and each represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group or a halogen atom) It indicates the group, and wherein X _B is characterized by a halogen atom, triazolopyrimidine derivative of claim 4. The triazolopyrimidine derivative according to claim 5, wherein the Het _B is a group represented by the Het ₁ , Het ₆ or Het ₁₂ . General formula (C)

[Where:
Het _C represents a 5-membered or 6-membered ring containing a hetero element, and these 5-membered or 6-membered rings are a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group and a C2 May be substituted by a group selected from the group consisting of -C6 alkoxyalkyl groups,
X _C represents a halogen atom, a cyano group, a C1-C6 alkoxy group or a C1-C6 alkylthio group, and R _C represents a C1-C10 alkyl group, a C2-C10 alkenyl group, a C2-C10 alkynyl group, a C3-C8 A cycloalkyl group, a C4-C10 cycloalkylalkyl group or an aralkyl group, wherein the benzene ring of the aralkyl group may be substituted by a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group or a C1-C6 alkylthio group; Good. ]
A triazolopyrimidine derivative represented by: The Het _C is represented by the following general formula Het ₁

[Wherein R ₁ , R ₂ and R ₃ are the same or different and each represents a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group or a C1-C6 haloalkyl group]. The triazolopyrimidine derivative according to claim 7, which is a group. An agricultural and horticultural fungicide comprising the triazolopyrimidine derivative according to any one of claims 1 to 8 as an active ingredient.