JP2013227242A - Herbicidal composition - Google Patents

Abstract

（式中、Ｒ¹はアルキル基等、Ｒ²はアルコキシ基等、Ｇはヒドロキシ基等、Ｚはアルキル基等、ｎは１〜５の整数を表す。）
【選択図】なしA herbicidal composition is provided.
A herbicidal composition comprising a pyridazinone compound represented by formula (I) and at least one compound selected from group A below. Group A: A group consisting of diflufenican, picolinaphene, norflurazon, fluridone, flurochloridone, flurtamone, and beflubutamide.

(In the formula, R ¹ represents an alkyl group, R ² represents an alkoxy group, G represents a hydroxy group, Z represents an alkyl group, and n represents an integer of 1 to 5.)
[Selection figure] None

Description

  The present invention relates to a herbicide composition and the like.

  A large number of herbicides are currently sold and used. (For example, see Non-Patent Document 1)

The Pesticide Manual (Fightenent Edition) (2009), British Crop Production Council (ISBN: 978-1-901396-18-8)

  An object of the present invention is to provide a herbicidal composition having an excellent weed control effect.

〔式中、Ｒ¹はハロゲン、Ｃ_1-6アルキル基またはＣ_1-6アルコキシ基より選ばれる１種以上の置換基を有していてもよいフェニルＣ_1-6アルキル基、水素、Ｃ_1-6アルキル基、Ｃ_1-6ハロアルキル基、Ｃ_3-8シクロアルキル基、Ｃ_3-8ハロシクロアルキル基、（Ｃ_1-6アルキル）Ｃ_3-8シクロアルキル基、（Ｃ_3-8シクロアルキル）Ｃ_1-6アルキル基、（Ｃ_3-8シクロアルキル）Ｃ_3-8シクロアルキル基、（Ｃ_3-8ハロシクロアルキル）Ｃ_1-6アルキル基、｛（Ｃ_1-6アルキル）Ｃ_3-8シクロアルキル｝Ｃ_1-6アルキル基、（Ｃ_1-6アルコキシ）Ｃ_1-6アルキル基、（Ｃ_3-8シクロアルコキシ）Ｃ_1-6アルキル基、｛（Ｃ_1-6アルコキシ）Ｃ_1-6アルコキシ｝Ｃ_1-6アルキル基、（Ｃ_1-6アルキルチオ）Ｃ_1-6アルキル基、（Ｃ_1-6アルキルスルフィニル）Ｃ_1-6アルキル基、（Ｃ_1-6アルキルスルホニル）Ｃ_1-6アルキル基、Ｃ_3-6アルケニル基、Ｃ_3-6アルキニル基又はテトラヒドロピラニル基を表し、
Ｒ²はハロゲン、シアノ基、ニトロ基、Ｃ_1-6アルコキシ基、Ｃ_1-6ハロアルコキシ基、Ｃ_1-6アルキルチオ基、Ｃ_1-6アルキルスルフィニル基、Ｃ_1-6アルキルスルホニル基、Ｃ_1-6ハロアルキルチオ基、Ｃ_1-6ハロアルキルスルフィニル基、Ｃ_1-6ハロアルキルスルホニル基、Ｃ_3-8シクロアルコキシ基、（Ｃ_3-8シクロアルキル）Ｃ_1-6アルコキシ基、（Ｃ_1-6アルキルチオ）Ｃ_1-6アルコキシ基、（Ｃ_1-6アルコキシ）Ｃ_1-6アルコキシ基、Ｃ_3-6アルケニルオキシ基、Ｃ_3-6アルキニルオキシ基、シアノＣ_1-6アルコキシ基、（Ｃ_1-6アルコキシカルボニル）Ｃ_1-6アルコキシ基、カルバモイルＣ_1-6アルコキシ基、｛（Ｃ_1-6アルキル）アミノカルボニル｝Ｃ_1-6アルコキシ基、｛ジ（Ｃ_1-6アルキル）アミノカルボニル｝Ｃ_1-6アルコキシ基、アミノ基、Ｃ_1-6アルキルアミノ基、ジ（Ｃ_1-6アルキル）アミノ基、ホルミルアミノ基、（Ｃ_1-6アルキル）カルボニルアミノ基、ヒドロキシＣ_1-6アルキル基、（Ｃ_1-6アルコキシ）Ｃ_1-6アルキル基、（Ｃ_1-6ハロアルコキシ）Ｃ_1-6アルキル基、（Ｃ_3-8シクロアルコキシ）Ｃ_1-6アルキル基、｛（Ｃ_3-8シクロアルキル）Ｃ_1-6アルコキシ｝Ｃ_1-6アルキル基、（Ｃ_1-6アルキルチオ）Ｃ_1-6アルキル基、（Ｃ_1-6ハロアルキルチオ）Ｃ_1-6アルキル基、シアノＣ_1-6アルキル基、ヒドロキシイミノＣ_1-6アルキル基、（Ｃ_1-6アルコキシイミノ）Ｃ_1-6アルキル基、ホルミル基又は（Ｃ_1-6アルキル）カルボニル基を表し、
Ｇは水素又は下記式

｛式中、Ｌは酸素又はイオウを表し、
Ｒ³はＣ_1-6アルキル基、Ｃ_3-8シクロアルキル基、Ｃ_2-6アルケニル基、Ｃ_2-6アルキニル基、Ｃ_6-10アリール基、（Ｃ_6-10アリール）Ｃ_1-6アルキル基、Ｃ_1-6アルコキシ基、Ｃ_3-8シクロアルコキシ基、Ｃ_3-6アルケニルオキシ基、Ｃ_3-6アルキニルオキシ基、Ｃ_6-10アリールオキシ基、（Ｃ_6-10アリール）Ｃ_1-6アルコキシ基、ジ（Ｃ_1-6アルキル）アミノ基、ジ（Ｃ_3-6アルケニル）アミノ基、（Ｃ_1-6アルキル）（Ｃ_6-10アリール）アミノ基又は５〜６員のヘテロアリール基を表し、
Ｒ⁴はＣ_1-6アルキル基、Ｃ_6-10アリール基又はジ（Ｃ_1-6アルキル）アミノ基を表し、
Ｒ⁵及びＲ⁶は同一又は異なっていてもよく、Ｃ_1-6アルキル基、Ｃ_3-8シクロアルキル基、Ｃ_6-10アリール基、Ｃ_1-6アルコキシ基、Ｃ_3-8シクロアルコキシ基、Ｃ_6-10アリールオキシ基、（Ｃ_6-10アリール）Ｃ_1-6アルコキシ基、Ｃ_1-6アルキルチオ基又はジ（Ｃ_1-6アルキル）アミノ基を表し、
Ｒ⁷は水素又はＣ_1-6アルキル基を表し、
Ｗはハロゲン、Ｃ_1-6アルキル基またはＣ_1-6アルコキシ基より選ばれる１種以上の置換基を有していてもよいフェニル基、Ｃ_1-6アルコキシ基、Ｃ_1-6アルキルチオ基、Ｃ_1-6アルキルスルフィニル基又はＣ_1-6アルキルスルホニル基を表す（但し、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＷの各々で表されるいずれの基もハロゲンを有していてもよく、Ｃ_3-8シクロアルキル基、Ｃ_6-10アリール基、（Ｃ_6-10アリール）Ｃ_1-6アルキル基のアリール部分、Ｃ_3-8シクロアルコキシ基、Ｃ_6-10アリールオキシ基、（Ｃ_6-10アリール）Ｃ_1-6アルコキシ基のアリール部分、（Ｃ_1-6アルキル）（Ｃ_6-10アリール）アミノ基のアリール部分及び５〜６員のヘテロアリール基はいずれもＣ_1-6アルキル基により置換されていてもよい。）。｝
で表されるいずれかの基を表し、
Ｚはハロゲン、シアノ基、ニトロ基、Ｃ_1-6アルキル基、Ｃ_2-6アルケニル基、Ｃ_2-6アルキニル基、Ｃ_1-6アルコキシ基、Ｃ_1-6アルキルチオ基又はＣ_3-8シクロアルキル基を表し（但し、Ｚで表されるＣ_1-6アルキル基、Ｃ_2-6アルケニル基、Ｃ_2-6アルキニル基、Ｃ_1-6アルコキシ基及びＣ_1-6アルキルチオ基はハロゲンを有していてもよく、Ｃ_3-8シクロアルキル基はハロゲン及びＣ_1-6アルキル基からなる群より選ばれる少なくとも一種の基により置換されていてもよい）、
ｎは１〜５の整数を表す（但し、ｎが２以上である場合、各々のＺは同一又は異なっていてもよい。）〕で示されるピリダジノン化合物と、下記Ａ群から選ばれる少なくとも１種の化合物とを含有することを特徴とする除草用組成物。
Ａ群：
ジフルフェニカン、ピコリナフェン、ノルフルラゾン、フルリドン、フルロクロリドン、フルルタモン、およびベフルブタミドからなる群。
［２］ Ｒ¹がメチル基を表し、
Ｒ²がジメチルアミノ基、メチルチオ基、メチルスルフィニル基、メトキシ基、エトキシ基、ノルマルプロピルオキシ基、メトキシメチル基、シアノ基、シアノメチル基、２，２−ジフルオロエトキシ基、ジメチルアミノカルボニルメトキシ基、塩素原子、臭素原子又はフッ素原子を表し、
Ｇが水素、メトキシメチル基、エトキシメチル基、アセチル基、プロピオニル基、ピバロイル基、メトキシカルボニル基、エトキシカルボニル基、アリルオキシカルボニル基、フェノキシカルボニル基又はメチルスルホニル基を表し、
Ｚがメチル基、エチル基又はビニル基を表し
ｎが３を表す（但し、各々のＺは同一又は異なっていてもよい。）［１］に記載の除草用組成物。
［３］ Ｂ群から選ばれる少なくとも１種の化合物をさらに含有することを特徴とする［１］または［２］に記載の除草用組成物。
Ｂ群
ベノキサコール、クロキントセットメキシル、シオメトリニル、ジクロルミッド、フェンクロラゾールエチル、フェンクロリム、フルラゾール、フリラゾール、メフェンピルジエチル、オキサベトリニル、イソキサジフェンエチル、シプロスルファミド、フルクソフェニム、１，８−ナフタル酸無水物、および、ＡＤ−６７からなる群。
［４］ Ｂ群から選ばれる少なくとも１種の化合物が、クロキントセットメキシル又はメフェンピルジエチルである［３］に記載の除草用組成物。
［５］ Ａ群から選ばれる少なくとも１種の化合物が、ジフルフェニカン、またはピコリナフェンである［１］〜［４］いずれか一に記載の除草用組成物。
［６］ Ａ群から選ばれる少なくとも１種の化合物が、ノルフルラゾンである［１］〜［４］いずれか一に記載の除草用組成物。
［７］ Ａ群から選ばれる少なくとも１種の化合物が、フルリドンである［１］〜［４］いずれか一に記載の除草用組成物。
［８］ Ａ群から選ばれる少なくとも１種の化合物が、フルロクロリドンである［１］〜［４］いずれか一に記載の除草用組成物。
［９］ Ａ群から選ばれる少なくとも１種の化合物が、フルルタモンである［１］〜［４］いずれか一に記載の除草用組成物。
［１０］ Ａ群から選ばれる少なくとも１種の化合物が、ベフルブタミドである［１］〜［４］いずれか一に記載の除草用組成物。
［１１］ 式（Ｉ）

〔式中、Ｒ¹はメチル基を表し、
Ｒ²はジメチルアミノ基、メチルチオ基、メチルスルフィニル基、メトキシ基、エトキシ基、ノルマルプロピルオキシ基、メトキシメチル基、シアノ基、シアノメチル基、２，２−ジフルオロエトキシ基、ジメチルアミノカルボニルメトキシ基、塩素原子、臭素原子又はフッ素原子を表し、
Ｇは水素、メトキシメチル基、エトキシメチル基、アセチル基、プロピオニル基、ピバロイル基、メトキシカルボニル基、エトキシカルボニル基、アリルオキシカルボニル基、フェノキシカルボニル基又はメチルスルホニル基を表し、
Ｚはメチル基、エチル基又はビニル基を表し
ｎは３を表す（但し、各々のＺは同一又は異なっていてもよい。）〕で示されるピリダジノン化合物と、
ジフルフェニカン、ピコリナフェン、またはベフルフタミドとを含有することを特徴とする除草用組成物。
［１２］ 式（Ｉ）

〔式中、Ｒ¹はハロゲン、Ｃ_1-6アルキル基またはＣ_1-6アルコキシ基より選ばれる１種以上の置換基を有していてもよいフェニルＣ_1-6アルキル基、水素、Ｃ_1-6アルキル基、Ｃ_1-6ハロアルキル基、Ｃ_3-8シクロアルキル基、Ｃ_3-8ハロシクロアルキル基、（Ｃ_1-6アルキル）Ｃ_3-8シクロアルキル基、（Ｃ_3-8シクロアルキル）Ｃ_1-6アルキル基、（Ｃ_3-8シクロアルキル）Ｃ_3-8シクロアルキル基、（Ｃ_3-8ハロシクロアルキル）Ｃ_1-6アルキル基、｛（Ｃ_1-6アルキル）Ｃ_3-8シクロアルキル｝Ｃ_1-6アルキル基、（Ｃ_1-6アルコキシ）Ｃ_1-6アルキル基、（Ｃ_3-8シクロアルコキシ）Ｃ_1-6アルキル基、｛（Ｃ_1-6アルコキシ）Ｃ_1-6アルコキシ｝Ｃ_1-6アルキル基、（Ｃ_1-6アルキルチオ）Ｃ_1-6アルキル基、（Ｃ_1-6アルキルスルフィニル）Ｃ_1-6アルキル基、（Ｃ_1-6アルキルスルホニル）Ｃ_1-6アルキル基、Ｃ_3-6アルケニル基、Ｃ_3-6アルキニル基又はテトラヒドロピラニル基を表し、
Ｒ²はハロゲン、シアノ基、ニトロ基、Ｃ_1-6アルコキシ基、Ｃ_1-6ハロアルコキシ基、Ｃ_1-6アルキルチオ基、Ｃ_1-6アルキルスルフィニル基、Ｃ_1-6アルキルスルホニル基、Ｃ_1-6ハロアルキルチオ基、Ｃ_1-6ハロアルキルスルフィニル基、Ｃ_1-6ハロアルキルスルホニル基、Ｃ_3-8シクロアルコキシ基、（Ｃ_3-8シクロアルキル）Ｃ_1-6アルコキシ基、（Ｃ_1-6アルキルチオ）Ｃ_1-6アルコキシ基、（Ｃ_1-6アルコキシ）Ｃ_1-6アルコキシ基、Ｃ_3-6アルケニルオキシ基、Ｃ_3-6アルキニルオキシ基、シアノＣ_1-6アルコキシ基、（Ｃ_1-6アルコキシカルボニル）Ｃ_1-6アルコキシ基、カルバモイルＣ_1-6アルコキシ基、｛（Ｃ_1-6アルキル）アミノカルボニル｝Ｃ_1-6アルコキシ基、｛ジ（Ｃ_1-6アルキル）アミノカルボニル｝Ｃ_1-6アルコキシ基、アミノ基、Ｃ_1-6アルキルアミノ基、ジ（Ｃ_1-6アルキル）アミノ基、ホルミルアミノ基、（Ｃ_1-6アルキル）カルボニルアミノ基、ヒドロキシＣ_1-6アルキル基、（Ｃ_1-6アルコキシ）Ｃ_1-6アルキル基、（Ｃ_1-6ハロアルコキシ）Ｃ_1-6アルキル基、（Ｃ_3-8シクロアルコキシ）Ｃ_1-6アルキル基、｛（Ｃ_3-8シクロアルキル）Ｃ_1-6アルコキシ｝Ｃ_1-6アルキル基、（Ｃ_1-6アルキルチオ）Ｃ_1-6アルキル基、（Ｃ_1-6ハロアルキルチオ）Ｃ_1-6アルキル基、シアノＣ_1-6アルキル基、ヒドロキシイミノＣ_1-6アルキル基、（Ｃ_1-6アルコキシイミノ）Ｃ_1-6アルキル基、ホルミル基又は（Ｃ_1-6アルキル）カルボニル基を表し、
Ｇは水素又は下記式

｛式中、Ｌは酸素又はイオウを表し、
Ｒ³はＣ_1-6アルキル基、Ｃ_3-8シクロアルキル基、Ｃ_2-6アルケニル基、Ｃ_2-6アルキニル基、Ｃ_6-10アリール基、（Ｃ_6-10アリール）Ｃ_1-6アルキル基、Ｃ_1-6アルコキシ基、Ｃ_3-8シクロアルコキシ基、Ｃ_3-6アルケニルオキシ基、Ｃ_3-6アルキニルオキシ基、Ｃ_6-10アリールオキシ基、（Ｃ_6-10アリール）Ｃ_1-6アルコキシ基、ジ（Ｃ_1-6アルキル）アミノ基、ジ（Ｃ_3-6アルケニル）アミノ基、（Ｃ_1-6アルキル）（Ｃ_6-10アリール）アミノ基又は５〜６員のヘテロアリール基を表し、
Ｒ⁴はＣ_1-6アルキル基、Ｃ_6-10アリール基又はジ（Ｃ_1-6アルキル）アミノ基を表し、
Ｒ⁵及びＲ⁶は同一又は異なっていてもよく、Ｃ_1-6アルキル基、Ｃ_3-8シクロアルキル基、Ｃ_6-10アリール基、Ｃ_1-6アルコキシ基、Ｃ_3-8シクロアルコキシ基、Ｃ_6-10アリールオキシ基、（Ｃ_6-10アリール）Ｃ_1-6アルコキシ基、Ｃ_1-6アルキルチオ基又はジ（Ｃ_1-6アルキル）アミノ基を表し、
Ｒ⁷は水素又はＣ_1-6アルキル基を表し、
Ｗはハロゲン、Ｃ_1-6アルキル基またはＣ_1-6アルコキシ基より選ばれる１種以上の置換基を有していてもよいフェニル基、Ｃ_1-6アルコキシ基、Ｃ_1-6アルキルチオ基、Ｃ_1-6アルキルスルフィニル基又はＣ_1-6アルキルスルホニル基を表す（但し、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＷの各々で表されるいずれの基もハロゲンを有していてもよく、Ｃ_3-8シクロアルキル基、Ｃ_6-10アリール基、（Ｃ_6-10アリール）Ｃ_1-6アルキル基のアリール部分、Ｃ_3-8シクロアルコキシ基、Ｃ_6-10アリールオキシ基、（Ｃ_6-10アリール）Ｃ_1-6アルコキシ基のアリール部分、（Ｃ_1-6アルキル）（Ｃ_6-10アリール）アミノ基のアリール部分及び５〜６員のヘテロアリール基はいずれもＣ_1-6アルキル基により置換されていてもよい。）。｝
で表されるいずれかの基を表し、
Ｚはハロゲン、シアノ基、ニトロ基、Ｃ_1-6アルキル基、Ｃ_2-6アルケニル基、Ｃ_2-6アルキニル基、Ｃ_1-6アルコキシ基、Ｃ_1-6アルキルチオ基又はＣ_3-8シクロアルキル基を表し（但し、Ｚで表されるＣ_1-6アルキル基、Ｃ_2-6アルケニル基、Ｃ_2-6アルキニル基、Ｃ_1-6アルコキシ基及びＣ_1-6アルキルチオ基はハロゲンを有していてもよく、Ｃ_3-8シクロアルキル基はハロゲン及びＣ_1-6アルキル基からなる群より選ばれる少なくとも一種の基により置換されていてもよい）、
ｎは１〜５の整数を表す（但し、ｎが２以上である場合、各々のＺは同一又は異なっていてもよい。）〕で示されるピリダジノン化合物と下記Ａ群から選ばれる少なくとも１種の化合物との有効量を雑草または雑草の生育する土壌に施用する雑草の防除方法。
Ａ群
ジフルフェニカン、ピコリナフェン、ノルフルラゾン、フルリドン、フルロクロリドン、フルルタモン、およびベフルブタミドからなる群。
［１３］
Ｂ群から選ばれる少なくとも１種の化合物をさらに含有することを特徴とする［１２］記載の雑草の防除方法。
Ｂ群
ベノキサコール、クロキントセットメキシル、シオメトリニル、ジクロルミッド、フェンクロラゾールエチル、フェンクロリム、フルラゾール、フリラゾール、メフェンピルジエチル、オキサベトリニル、イソキサジフェンエチル、シプロスルファミド、フルクソフェニム、１，８−ナフタル酸無水物、および、ＡＤ−６７からなる群。
［１４］
雑草を防除するための［１］〜［１１］いずれか一に記載の組成物の使用。 As a result of intensive studies to find a herbicidal composition having an excellent weed control effect, the present inventors have found a herbicidal composition containing a pyridazinone compound represented by the following formula (I) and a specific herbicide. The present inventors have found that they have an excellent weed control effect, and have reached the present invention.
That is, the present invention is as follows.
[1] Formula (I)

[Wherein, R ¹ is halogen, C _1-6 alkyl group or a C _1-6 1 or more which may have a substituent phenyl C _1-6 alkyl group selected from alkoxy groups, hydrogen, C _{1 -6} alkyl group, C _1-6 haloalkyl group, C _3-8 cycloalkyl group, C _3-8 halocycloalkyl group, (C _1-6 alkyl) C _3-8 cycloalkyl group, (C _3-8 cyclo Alkyl) C _1-6 alkyl group, (C _3-8 cycloalkyl) C _3-8 cycloalkyl group, (C _3-8 halocycloalkyl) C _1-6 alkyl group, {(C _1-6 alkyl) C _3-8 cycloalkyl} C _1-6 alkyl group, (C _1-6 alkoxy) C _1-6 alkyl group, (C _3-8 cycloalkoxy) C _1-6 alkyl group, {(C _1-6 alkoxy) C _1-6 alkoxy} C _1-6 alkyl group, (C _1-6 alkylthio) C _1-6 alkyl group, (C _1-6 alkylsulfinyl) C _1-6 alkyl group, (C _{1- 6} alkylsulfonyl) represents a C _1-6 alkyl group, a C _3-6 alkenyl group, a C _3-6 alkynyl group or a tetrahydropyranyl group,
R ² is halogen, cyano group, nitro group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C _{1-6 1-6} haloalkylthio group, C _1-6 haloalkylsulfinyl group, C _1-6 haloalkylsulfonyl group, C _3-8 cycloalkoxy group, (C _3-8 cycloalkyl) C _1-6 alkoxy group, (C _{1- 6} alkylthio) C _1-6 alkoxy group, (C _1-6 alkoxy) C _1-6 alkoxy group, C _3-6 alkenyloxy group, C _3-6 alkynyloxy group, cyano C _1-6 alkoxy group, (C _1-6 alkoxycarbonyl) C _1-6 alkoxy group, carbamoyl C _1-6 alkoxy group, {(C _1-6 alkyl) aminocarbonyl} C _1-6 alkoxy group, {di (C _1-6 alkyl) aminocarbonyl } C _1-6 alkoxy group, amino group, C _1-6 al Killamino group, di (C _1-6 alkyl) amino group, formylamino group, (C _1-6 alkyl) carbonylamino group, hydroxy C _1-6 alkyl group, (C _1-6 alkoxy) C _1-6 alkyl group , (C _1-6 haloalkoxy) C _1-6 alkyl group, (C _3-8 cycloalkoxy) C _1-6 alkyl group, {(C _3-8 cycloalkyl) C _1-6 alkoxy} C _1-6 Alkyl group, (C _1-6 alkylthio) C _1-6 alkyl group, (C _1-6 haloalkylthio) C _1-6 alkyl group, cyano C _1-6 alkyl group, hydroxyimino C _1-6 alkyl group, ( C _1-6 alkoxyimino) represents a C _1-6 alkyl group, a formyl group or a (C _1-6 alkyl) carbonyl group,
G is hydrogen or the following formula

{Wherein L represents oxygen or sulfur;
R ³ is a C _1-6 alkyl group, C _3-8 cycloalkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _6-10 aryl group, (C _6-10 aryl) C _1-6 Alkyl group, C _1-6 alkoxy group, C _3-8 cycloalkoxy group, C _3-6 alkenyloxy group, C _3-6 alkynyloxy group, C _6-10 aryloxy group, (C _6-10 aryl) C _1-6 alkoxy group, di (C _1-6 alkyl) amino group, di (C _3-6 alkenyl) amino group, (C _1-6 alkyl) (C _6-10 aryl) amino group or 5-6 membered Represents a heteroaryl group,
R ⁴ represents a C _1-6 alkyl group, a C _6-10 aryl group or a di (C _1-6 alkyl) amino group,
R ⁵ and R ⁶ may be the same or different and are a C _1-6 alkyl group, a C _3-8 cycloalkyl group, a C _6-10 aryl group, a C _1-6 alkoxy group, a C _3-8 cycloalkoxy group. , A C _6-10 aryloxy group, a (C _6-10 aryl) C _1-6 alkoxy group, a C _1-6 alkylthio group or a di (C _1-6 alkyl) amino group,
R ⁷ represents hydrogen or a C _1-6 alkyl group,
W is a phenyl group optionally having one or more substituents selected from halogen, a C _1-6 alkyl group or a C _1-6 alkoxy group, a C _1-6 alkoxy group, a C _1-6 alkylthio group, C _1-6 alkyl sulfinyl group or a C _1-6 alkylsulfonyl group (provided ^{that, R 3, R 4, R} 5, any of the groups represented by each of R ⁶ and W have a halogen Well, a C _3-8 cycloalkyl group, a C _6-10 aryl group, an aryl part of a (C _6-10 aryl) C _1-6 alkyl group, a C _3-8 cycloalkoxy group, a C _6-10 aryloxy group, The aryl moiety of (C _6-10 aryl) C _1-6 alkoxy group, the (C _1-6 alkyl) (C _6-10 aryl) amino moiety and the 5-6 membered heteroaryl group are all C _{1. -6} may be substituted by an alkyl group). }
Any one of the groups represented by
Z is halogen, cyano group, nitro group, C _1-6 alkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _1-6 alkoxy group, C _1-6 alkylthio group or C _3-8 cyclo Represents an alkyl group (provided that a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _1-6 alkoxy group and a C _1-6 alkylthio group represented by Z have halogen). And the C _3-8 cycloalkyl group may be substituted with at least one group selected from the group consisting of halogen and C _1-6 alkyl groups),
n represents an integer of 1 to 5 (provided that when n is 2 or more, each Z may be the same or different)], and at least one selected from the following group A: And a herbicidal composition comprising:
Group A:
A group consisting of diflufenican, picolinafen, norflurazon, fluridone, flurochloridone, flurtamone, and beflubutamide.
[2] R ¹ represents a methyl group,
R ² is dimethylamino group, methylthio group, methylsulfinyl group, methoxy group, ethoxy group, normal propyloxy group, methoxymethyl group, cyano group, cyanomethyl group, 2,2-difluoroethoxy group, dimethylaminocarbonylmethoxy group, chlorine Represents an atom, bromine atom or fluorine atom,
G represents hydrogen, methoxymethyl group, ethoxymethyl group, acetyl group, propionyl group, pivaloyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, phenoxycarbonyl group or methylsulfonyl group;
The herbicidal composition according to [1], wherein Z represents a methyl group, an ethyl group, or a vinyl group, and n represents 3 (however, each Z may be the same or different).
[3] The herbicidal composition according to [1] or [2], further comprising at least one compound selected from Group B.
Group B Benoxacol, Croquintoset Mexil, Ciomethrinyl, Dichlormid, Fenchlorazole Ethyl, Fenchlorim, Flurazole, Furirazole, Mefenpyr Diethyl, Oxabetrinyl, Isoxadiphenethyl, Cyprosulfamide, Flxophenim, 1,8-Naphthal The group consisting of acid anhydride and AD-67.
[4] The herbicidal composition according to [3], wherein at least one compound selected from Group B is croquint set mexil or mefenpyr diethyl.
[5] The herbicidal composition according to any one of [1] to [4], wherein at least one compound selected from Group A is diflufenican or picolinaphene.
[6] The herbicidal composition according to any one of [1] to [4], wherein at least one compound selected from Group A is norflurazon.
[7] The herbicidal composition according to any one of [1] to [4], wherein at least one compound selected from Group A is fluridone.
[8] The herbicidal composition according to any one of [1] to [4], wherein at least one compound selected from Group A is flurochloridone.
[9] The herbicidal composition according to any one of [1] to [4], wherein at least one compound selected from Group A is flurtamone.
[10] The herbicidal composition according to any one of [1] to [4], wherein at least one compound selected from Group A is beflubutamide.
[11] Formula (I)

[Wherein R ¹ represents a methyl group,
R ² is dimethylamino group, methylthio group, methylsulfinyl group, methoxy group, ethoxy group, normal propyloxy group, methoxymethyl group, cyano group, cyanomethyl group, 2,2-difluoroethoxy group, dimethylaminocarbonylmethoxy group, chlorine Represents an atom, bromine atom or fluorine atom,
G represents hydrogen, methoxymethyl group, ethoxymethyl group, acetyl group, propionyl group, pivaloyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, phenoxycarbonyl group or methylsulfonyl group,
Z represents a methyl group, an ethyl group or a vinyl group, n represents 3 (wherein each Z may be the same or different)], and a pyridazinone compound represented by
A herbicidal composition comprising diflufenican, picolinaphene, or befluftamide.
[12] Formula (I)

[Wherein, R ¹ is halogen, C _1-6 alkyl group or a C _1-6 1 or more which may have a substituent phenyl C _1-6 alkyl group selected from alkoxy groups, hydrogen, C _{1 -6} alkyl group, C _1-6 haloalkyl group, C _3-8 cycloalkyl group, C _3-8 halocycloalkyl group, (C _1-6 alkyl) C _3-8 cycloalkyl group, (C _3-8 cyclo Alkyl) C _1-6 alkyl group, (C _3-8 cycloalkyl) C _3-8 cycloalkyl group, (C _3-8 halocycloalkyl) C _1-6 alkyl group, {(C _1-6 alkyl) C _3-8 cycloalkyl} C _1-6 alkyl group, (C _1-6 alkoxy) C _1-6 alkyl group, (C _3-8 cycloalkoxy) C _1-6 alkyl group, {(C _1-6 alkoxy) C _1-6 alkoxy} C _1-6 alkyl group, (C _1-6 alkylthio) C _1-6 alkyl group, (C _1-6 alkylsulfinyl) C _1-6 alkyl group, (C _{1- 6} alkylsulfonyl) represents a C _1-6 alkyl group, a C _3-6 alkenyl group, a C _3-6 alkynyl group or a tetrahydropyranyl group,
R ² is halogen, cyano group, nitro group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C _{1-6 1-6} haloalkylthio group, C _1-6 haloalkylsulfinyl group, C _1-6 haloalkylsulfonyl group, C _3-8 cycloalkoxy group, (C _3-8 cycloalkyl) C _1-6 alkoxy group, (C _{1- 6} alkylthio) C _1-6 alkoxy group, (C _1-6 alkoxy) C _1-6 alkoxy group, C _3-6 alkenyloxy group, C _3-6 alkynyloxy group, cyano C _1-6 alkoxy group, (C _1-6 alkoxycarbonyl) C _1-6 alkoxy group, carbamoyl C _1-6 alkoxy group, {(C _1-6 alkyl) aminocarbonyl} C _1-6 alkoxy group, {di (C _1-6 alkyl) aminocarbonyl } C _1-6 alkoxy group, amino group, C _1-6 al Killamino group, di (C _1-6 alkyl) amino group, formylamino group, (C _1-6 alkyl) carbonylamino group, hydroxy C _1-6 alkyl group, (C _1-6 alkoxy) C _1-6 alkyl group , (C _1-6 haloalkoxy) C _1-6 alkyl group, (C _3-8 cycloalkoxy) C _1-6 alkyl group, {(C _3-8 cycloalkyl) C _1-6 alkoxy} C _1-6 Alkyl group, (C _1-6 alkylthio) C _1-6 alkyl group, (C _1-6 haloalkylthio) C _1-6 alkyl group, cyano C _1-6 alkyl group, hydroxyimino C _1-6 alkyl group, ( C _1-6 alkoxyimino) represents a C _1-6 alkyl group, a formyl group or a (C _1-6 alkyl) carbonyl group,
G is hydrogen or the following formula

{Wherein L represents oxygen or sulfur;
R ³ is a C _1-6 alkyl group, C _3-8 cycloalkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _6-10 aryl group, (C _6-10 aryl) C _1-6 Alkyl group, C _1-6 alkoxy group, C _3-8 cycloalkoxy group, C _3-6 alkenyloxy group, C _3-6 alkynyloxy group, C _6-10 aryloxy group, (C _6-10 aryl) C _1-6 alkoxy group, di (C _1-6 alkyl) amino group, di (C _3-6 alkenyl) amino group, (C _1-6 alkyl) (C _6-10 aryl) amino group or 5-6 membered Represents a heteroaryl group,
R ⁴ represents a C _1-6 alkyl group, a C _6-10 aryl group or a di (C _1-6 alkyl) amino group,
R ⁵ and R ⁶ may be the same or different and are a C _1-6 alkyl group, a C _3-8 cycloalkyl group, a C _6-10 aryl group, a C _1-6 alkoxy group, a C _3-8 cycloalkoxy group. , A C _6-10 aryloxy group, a (C _6-10 aryl) C _1-6 alkoxy group, a C _1-6 alkylthio group or a di (C _1-6 alkyl) amino group,
R ⁷ represents hydrogen or a C _1-6 alkyl group,
W is a phenyl group optionally having one or more substituents selected from halogen, a C _1-6 alkyl group or a C _1-6 alkoxy group, a C _1-6 alkoxy group, a C _1-6 alkylthio group, C _1-6 alkyl sulfinyl group or a C _1-6 alkylsulfonyl group (provided ^{that, R 3, R 4, R} 5, any of the groups represented by each of R ⁶ and W have a halogen Well, a C _3-8 cycloalkyl group, a C _6-10 aryl group, an aryl part of a (C _6-10 aryl) C _1-6 alkyl group, a C _3-8 cycloalkoxy group, a C _6-10 aryloxy group, The aryl moiety of (C _6-10 aryl) C _1-6 alkoxy group, the (C _1-6 alkyl) (C _6-10 aryl) amino moiety and the 5-6 membered heteroaryl group are all C _{1. -6} may be substituted by an alkyl group). }
Any one of the groups represented by
Z is halogen, cyano group, nitro group, C _1-6 alkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _1-6 alkoxy group, C _1-6 alkylthio group or C _3-8 cyclo Represents an alkyl group (provided that a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _1-6 alkoxy group and a C _1-6 alkylthio group represented by Z have halogen). And the C _3-8 cycloalkyl group may be substituted with at least one group selected from the group consisting of halogen and C _1-6 alkyl groups),
n represents an integer of 1 to 5 (provided that, when n is 2 or more, each Z may be the same or different)] and at least one selected from the following group A: A method for controlling weeds, wherein an effective amount of the compound is applied to weeds or soil where weeds grow.
Group A A group consisting of diflufenican, picolinaphene, norflurazon, fluridone, flurochloridone, flurtamone, and beflubutamide.
[13]
The method for controlling weeds according to [12], further comprising at least one compound selected from Group B.
Group B Benoxacol, Croquintoset Mexil, Ciomethrinyl, Dichlormid, Fenchlorazole Ethyl, Fenchlorim, Flurazole, Furirazole, Mefenpyr Diethyl, Oxabetrinyl, Isoxadiphenethyl, Cyprosulfamide, Flxophenim, 1,8-Naphthal The group consisting of acid anhydride and AD-67.
[14]
Use of the composition according to any one of [1] to [11] for controlling weeds.

  According to the present invention, a herbicidal composition having an excellent weed control effect can be provided.

〔式中、Ｒ¹はハロゲン、Ｃ_1-6アルキル基またはＣ_1-6アルコキシ基より選ばれる１種以上の置換基を有していてもよいフェニルＣ_1-6アルキル基、水素、Ｃ_1-6アルキル基、Ｃ_1-6ハロアルキル基、Ｃ_3-8シクロアルキル基、Ｃ_3-8ハロシクロアルキル基、（Ｃ_1-6アルキル）Ｃ_3-8シクロアルキル基、（Ｃ_3-8シクロアルキル）Ｃ_1-6アルキル基、（Ｃ_3-8シクロアルキル）Ｃ_3-8シクロアルキル基、（Ｃ_3-8ハロシクロアルキル）Ｃ_1-6アルキル基、｛（Ｃ_1-6アルキル）Ｃ_3-8シクロアルキル｝Ｃ_1-6アルキル基、（Ｃ_1-6アルコキシ）Ｃ_1-6アルキル基、（Ｃ_3-8シクロアルコキシ）Ｃ_1-6アルキル基、｛（Ｃ_1-6アルコキシ）Ｃ_1-6アルコキシ｝Ｃ_1-6アルキル基、（Ｃ_1-6アルキルチオ）Ｃ_1-6アルキル基、（Ｃ_1-6アルキルスルフィニル）Ｃ_1-6アルキル基、（Ｃ_1-6アルキルスルホニル）Ｃ_1-6アルキル基、Ｃ_3-6アルケニル基、Ｃ_3-6アルキニル基又はテトラヒドロピラニル基を表し、
Ｒ²はハロゲン、シアノ基、ニトロ基、Ｃ_1-6アルコキシ基、Ｃ_1-6ハロアルコキシ基、Ｃ_1-6アルキルチオ基、Ｃ_1-6アルキルスルフィニル基、Ｃ_1-6アルキルスルホニル基、Ｃ_1-6ハロアルキルチオ基、Ｃ_1-6ハロアルキルスルフィニル基、Ｃ_1-6ハロアルキルスルホニル基、Ｃ_3-8シクロアルコキシ基、（Ｃ_3-8シクロアルキル）Ｃ_1-6アルコキシ基、（Ｃ_1-6アルキルチオ）Ｃ_1-6アルコキシ基、（Ｃ_1-6アルコキシ）Ｃ_1-6アルコキシ基、Ｃ_3-6アルケニルオキシ基、Ｃ_3-6アルキニルオキシ基、シアノＣ_1-6アルコキシ基、（Ｃ_1-6アルコキシカルボニル）Ｃ_1-6アルコキシ基、カルバモイルＣ_1-6アルコキシ基、｛（Ｃ_1-6アルキル）アミノカルボニル｝Ｃ_1-6アルコキシ基、｛ジ（Ｃ_1-6アルキル）アミノカルボニル｝Ｃ_1-6アルコキシ基、アミノ基、Ｃ_1-6アルキルアミノ基、ジ（Ｃ_1-6アルキル）アミノ基、ホルミルアミノ基、（Ｃ_1-6アルキル）カルボニルアミノ基、ヒドロキシＣ_1-6アルキル基、（Ｃ_1-6アルコキシ）Ｃ_1-6アルキル基、（Ｃ_1-6ハロアルコキシ）Ｃ_1-6アルキル基、（Ｃ_3-8シクロアルコキシ）Ｃ_1-6アルキル基、｛（Ｃ_3-8シクロアルキル）Ｃ_1-6アルコキシ｝Ｃ_1-6アルキル基、（Ｃ_1-6アルキルチオ）Ｃ_1-6アルキル基、（Ｃ_1-6ハロアルキルチオ）Ｃ_1-6アルキル基、シアノＣ_1-6アルキル基、ヒドロキシイミノＣ_1-6アルキル基、（Ｃ_1-6アルコキシイミノ）Ｃ_1-6アルキル基、ホルミル基又は（Ｃ_1-6アルキル）カルボニル基を表し、
Ｇは水素又は下記式

｛式中、Ｌは酸素又はイオウを表し、
Ｒ³はＣ_1-6アルキル基、Ｃ_3-8シクロアルキル基、Ｃ_2-6アルケニル基、Ｃ_2-6アルキニル基、Ｃ_6-10アリール基、（Ｃ_6-10アリール）Ｃ_1-6アルキル基、Ｃ_1-6アルコキシ基、Ｃ_3-8シクロアルコキシ基、Ｃ_3-6アルケニルオキシ基、Ｃ_3-6アルキニルオキシ基、Ｃ_6-10アリールオキシ基、（Ｃ_6-10アリール）Ｃ_1-6アルコキシ基、ジ（Ｃ_1-6アルキル）アミノ基、ジ（Ｃ_3-6アルケニル）アミノ基、（Ｃ_1-6アルキル）（Ｃ_6-10アリール）アミノ基又は５〜６員のヘテロアリール基を表し、
Ｒ⁴はＣ_1-6アルキル基、Ｃ_6-10アリール基又はジ（Ｃ_1-6アルキル）アミノ基を表し、
Ｒ⁵及びＲ⁶は同一又は異なっていてもよく、Ｃ_1-6アルキル基、Ｃ_3-8シクロアルキル基、Ｃ_6-10アリール基、Ｃ_1-6アルコキシ基、Ｃ_3-8シクロアルコキシ基、Ｃ_6-10アリールオキシ基、（Ｃ_6-10アリール）Ｃ_1-6アルコキシ基、Ｃ_1-6アルキルチオ基又はジ（Ｃ_1-6アルキル）アミノ基を表し、
Ｒ⁷は水素又はＣ_1-6アルキル基を表し、
Ｗはハロゲン、Ｃ_1-6アルキル基またはＣ_1-6アルコキシ基より選ばれる１種以上の置換基を有していてもよいフェニル基、Ｃ_1-6アルコキシ基、Ｃ_1-6アルキルチオ基、Ｃ_1-6アルキルスルフィニル基又はＣ_1-6アルキルスルホニル基を表す（但し、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＷの各々で表されるいずれの基もハロゲンを有していてもよく、Ｃ_3-8シクロアルキル基、Ｃ_6-10アリール基、（Ｃ_6-10アリール）Ｃ_1-6アルキル基のアリール部分、Ｃ_3-8シクロアルコキシ基、Ｃ_6-10アリールオキシ基、（Ｃ_6-10アリール）Ｃ_1-6アルコキシ基のアリール部分、（Ｃ_1-6アルキル）（Ｃ_6-10アリール）アミノ基のアリール部分及び５〜６員のヘテロアリール基はいずれもＣ_1-6アルキル基により置換されていてもよい。）。｝
で表されるいずれかの基を表し、
Ｚはハロゲン、シアノ基、ニトロ基、Ｃ_1-6アルキル基、Ｃ_2-6アルケニル基、Ｃ_2-6アルキニル基、Ｃ_1-6アルコキシ基、Ｃ_1-6アルキルチオ基又はＣ_3-8シクロアルキル基を表し（但し、Ｚで表されるＣ_1-6アルキル基、Ｃ_2-6アルケニル基、Ｃ_2-6アルキニル基、Ｃ_1-6アルコキシ基及びＣ_1-6アルキルチオ基はハロゲンを有していてもよく、Ｃ_3-8シクロアルキル基はハロゲン及びＣ_1-6アルキル基からなる群より選ばれる少なくとも一種の基により置換されていてもよい）、
ｎは１〜５の整数を表す（但し、ｎが２以上である場合、各々のＺは同一又は異なっていてもよい。）〕で示されるピリダジノン化合物（以下、本化合物と記す。）と、下記Ａ群から選ばれる少なくとも１種の化合物（以下、本化合物Ａと記す。）とを含有する。
Ａ群：
ジフルフェニカン、ピコリナフェン、ノルフルラゾン、フルリドン、フルロクロリドン、フルルタモン、およびベフルブタミドからなる群。
また、下記Ｂ群から選ばれる少なくとも１種の化合物（以下、本化合物Ｂと記す。）を含有してもよい。
Ｂ群
ベノキサコール、クロキントセットメキシル、シオメトリニル、ジクロルミッド、フェンクロラゾールエチル、フェンクロリム、フルラゾール、フリラゾール、メフェンピルジエチル、オキサベトリニル、イソキサジフェンエチル、シプロスルファミド、フルクソフェニム、１，８−ナフタル酸無水物、および、ＡＤ−６７からなる群。 The herbicidal composition of the present invention (hereinafter referred to as the present herbicidal composition) has the formula (I)

[Wherein, R ¹ is halogen, C _1-6 alkyl group or a C _1-6 1 or more which may have a substituent phenyl C _1-6 alkyl group selected from alkoxy groups, hydrogen, C _{1 -6} alkyl group, C _1-6 haloalkyl group, C _3-8 cycloalkyl group, C _3-8 halocycloalkyl group, (C _1-6 alkyl) C _3-8 cycloalkyl group, (C _3-8 cyclo Alkyl) C _1-6 alkyl group, (C _3-8 cycloalkyl) C _3-8 cycloalkyl group, (C _3-8 halocycloalkyl) C _1-6 alkyl group, {(C _1-6 alkyl) C _3-8 cycloalkyl} C _1-6 alkyl group, (C _1-6 alkoxy) C _1-6 alkyl group, (C _3-8 cycloalkoxy) C _1-6 alkyl group, {(C _1-6 alkoxy) C _1-6 alkoxy} C _1-6 alkyl group, (C _1-6 alkylthio) C _1-6 alkyl group, (C _1-6 alkylsulfinyl) C _1-6 alkyl group, (C _{1- 6} alkylsulfonyl) represents a C _1-6 alkyl group, a C _3-6 alkenyl group, a C _3-6 alkynyl group or a tetrahydropyranyl group,
R ² is halogen, cyano group, nitro group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C _{1-6 1-6} haloalkylthio group, C _1-6 haloalkylsulfinyl group, C _1-6 haloalkylsulfonyl group, C _3-8 cycloalkoxy group, (C _3-8 cycloalkyl) C _1-6 alkoxy group, (C _{1- 6} alkylthio) C _1-6 alkoxy group, (C _1-6 alkoxy) C _1-6 alkoxy group, C _3-6 alkenyloxy group, C _3-6 alkynyloxy group, cyano C _1-6 alkoxy group, (C _1-6 alkoxycarbonyl) C _1-6 alkoxy group, carbamoyl C _1-6 alkoxy group, {(C _1-6 alkyl) aminocarbonyl} C _1-6 alkoxy group, {di (C _1-6 alkyl) aminocarbonyl } C _1-6 alkoxy group, amino group, C _1-6 al Killamino group, di (C _1-6 alkyl) amino group, formylamino group, (C _1-6 alkyl) carbonylamino group, hydroxy C _1-6 alkyl group, (C _1-6 alkoxy) C _1-6 alkyl group , (C _1-6 haloalkoxy) C _1-6 alkyl group, (C _3-8 cycloalkoxy) C _1-6 alkyl group, {(C _3-8 cycloalkyl) C _1-6 alkoxy} C _1-6 Alkyl group, (C _1-6 alkylthio) C _1-6 alkyl group, (C _1-6 haloalkylthio) C _1-6 alkyl group, cyano C _1-6 alkyl group, hydroxyimino C _1-6 alkyl group, ( C _1-6 alkoxyimino) represents a C _1-6 alkyl group, a formyl group or a (C _1-6 alkyl) carbonyl group,
G is hydrogen or the following formula

{Wherein L represents oxygen or sulfur;
R ³ is a C _1-6 alkyl group, C _3-8 cycloalkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _6-10 aryl group, (C _6-10 aryl) C _1-6 Alkyl group, C _1-6 alkoxy group, C _3-8 cycloalkoxy group, C _3-6 alkenyloxy group, C _3-6 alkynyloxy group, C _6-10 aryloxy group, (C _6-10 aryl) C _1-6 alkoxy group, di (C _1-6 alkyl) amino group, di (C _3-6 alkenyl) amino group, (C _1-6 alkyl) (C _6-10 aryl) amino group or 5-6 membered Represents a heteroaryl group,
R ⁴ represents a C _1-6 alkyl group, a C _6-10 aryl group or a di (C _1-6 alkyl) amino group,
R ⁵ and R ⁶ may be the same or different and are a C _1-6 alkyl group, a C _3-8 cycloalkyl group, a C _6-10 aryl group, a C _1-6 alkoxy group, a C _3-8 cycloalkoxy group. , A C _6-10 aryloxy group, a (C _6-10 aryl) C _1-6 alkoxy group, a C _1-6 alkylthio group or a di (C _1-6 alkyl) amino group,
R ⁷ represents hydrogen or a C _1-6 alkyl group,
W is a phenyl group optionally having one or more substituents selected from halogen, a C _1-6 alkyl group or a C _1-6 alkoxy group, a C _1-6 alkoxy group, a C _1-6 alkylthio group, C _1-6 alkyl sulfinyl group or a C _1-6 alkylsulfonyl group (provided ^{that, R 3, R 4, R} 5, any of the groups represented by each of R ⁶ and W have a halogen Well, a C _3-8 cycloalkyl group, a C _6-10 aryl group, an aryl part of a (C _6-10 aryl) C _1-6 alkyl group, a C _3-8 cycloalkoxy group, a C _6-10 aryloxy group, The aryl moiety of (C _6-10 aryl) C _1-6 alkoxy group, the (C _1-6 alkyl) (C _6-10 aryl) amino moiety and the 5-6 membered heteroaryl group are all C _{1. -6} may be substituted by an alkyl group). }
Any one of the groups represented by
Z is halogen, cyano group, nitro group, C _1-6 alkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _1-6 alkoxy group, C _1-6 alkylthio group or C _3-8 cyclo Represents an alkyl group (provided that a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _1-6 alkoxy group and a C _1-6 alkylthio group represented by Z have halogen). And the C _3-8 cycloalkyl group may be substituted with at least one group selected from the group consisting of halogen and C _1-6 alkyl groups),
n represents an integer of 1 to 5 (provided that each Z may be the same or different when n is 2 or more)], and a pyridazinone compound (hereinafter referred to as the present compound). At least one compound selected from the following group A (hereinafter referred to as the present compound A).
Group A:
A group consisting of diflufenican, picolinafen, norflurazon, fluridone, flurochloridone, flurtamone, and beflubutamide.
Moreover, you may contain the at least 1 sort (s) of compound (henceforth this compound B) chosen from the following B group.
Group B Benoxacol, Croquintoset Mexil, Ciomethrinyl, Dichlormid, Fenchlorazole Ethyl, Fenchlorim, Flurazole, Furirazole, Mefenpyr Diethyl, Oxabetrinyl, Isoxadiphenethyl, Cyprosulfamide, Flxophenim, 1,8-Naphthal The group consisting of acid anhydride and AD-67.

The substituent of the pyridazinone compound represented by the formula (I) which is an active ingredient of the herbicidal composition of the present invention will be described.
The C _1-6 alkyl group means an alkyl group having 1 to 6 carbon atoms. For example, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a sec-butyl group, a tert- Examples include a butyl group, a normal pentyl group, a sec-pentyl group, an isopentyl group, a neopentyl group, a normal hexyl group, and an isohexyl group.
The C _2-6 alkenyl group means an alkenyl group having 2 to 6 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 1-buten-3-yl group, and a 3-buten-1-yl group.
The C _2-6 alkynyl group means an alkynyl group having 2 to 6 carbon atoms, and examples thereof include an ethynyl group, a propargyl group, and a 2-butynyl group.
The C _1-6 haloalkyl group means a C _1-6 alkyl group having a halogen such as fluorine, chlorine, bromine, iodine, etc., for example, a trifluoromethyl group, a chloromethyl group, a 2,2-difluoroethyl group, Examples include 2,2,2-trichloroethyl group, 2,2,2-trifluoroethyl group, and 2,2,2-trifluoro-1,1-dichloroethyl group.
The C _3-8 cycloalkyl group means a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.
The C _3-8 halocycloalkyl group means a cycloalkyl group having 3 to 8 carbon atoms having a halogen such as fluorine, chlorine, bromine, iodine, etc., for example, 2-chlorocyclopropyl group and 4,4-difluoro A cyclohexyl group is mentioned.
(C _1-6 alkyl) C _3-8 cycloalkyl group means a C _3-8 cycloalkyl group having a C _1-6 alkyl group, for example, ethylcyclopropyl group, isobutylcyclopropyl Group, 3-methylcyclopentyl group and 4-methylcyclohexyl group.

(C _3-8 cycloalkyl) C _1-6 alkyl group means a C _1-6 alkyl group substituted with a C _3-8 cycloalkyl group, such as a cyclopropylmethyl group and a cyclopentyl group. A methyl group is mentioned.
(C _3-8 cycloalkyl) The C _3-8 cycloalkyl group means a C _3-8 cycloalkyl group having a C _3-8 cycloalkyl group, such as a 2-cyclopropylcyclopropyl group. And 3-cyclopropylcyclopentyl group.
(C _3-8 halocycloalkyl) C _1-6 alkyl group means an alkyl group having 1 to 6 carbon atoms having a cycloalkyl group having 3 to 8 carbon atoms having halogen such as fluorine, chlorine, bromine or iodine. Meaning, for example, 2-chlorocyclopropylmethyl group and 3-chlorocyclopentylethyl group.
{(C _1-6 alkyl) C _3-8 cycloalkyl} C _1-6 alkyl group is a C _1-6 alkyl group having (a C _3-8 cycloalkyl group having a C _1-6 alkyl). 6 means an alkyl group, and examples thereof include 2-methylcyclopropylmethyl group and 3-methylcyclopentylmethyl group.
The hydroxy C _1-6 alkyl group means a hydroxyl group and an alkyl group having 1 to 6 carbon atoms, and examples thereof include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, and a 3-hydroxypropyl group. It is done.
(C _1-6 haloalkoxy) C _1-6 alkyl group means a C _1-6 alkyl group having (a C _1-6 alkoxy group having a halogen such as fluorine, chlorine, bromine, iodine). Meaning, for example, 2,2-difluoroethoxymethyl group, 2,2,2-trifluoroethoxymethyl group, 2,2-difluoroethoxyethyl group and 2,2,2-trifluoroethoxyethyl group.
{(C _3-8 cycloalkyl) C _1-6 alkoxy} C _1-6 alkyl group means carbon having 1 to 6 carbon atoms having (cycloalkyl group having 3 to 8 carbon atoms). This means an alkyl group of 1 to 6, and examples thereof include a cyclopropylmethoxymethyl group.
(C _1-6 haloalkylthio) C _1-6 alkyl group means an alkyl group having 1 to 6 carbon atoms having (an alkylthio group having 1 to 6 carbon atoms having a halogen such as fluorine, chlorine, bromine or iodine). Meaning, for example, a trifluoromethylthiomethyl group, a 2,2-difluoroethylthiomethyl group, and a 2,2,2-trifluoroethylthiomethyl group.
The cyano C _1-6 alkyl group means a C _1-6 alkyl group having a cyano group, and examples thereof include a cyanomethyl group, a 1-cyanoethyl group, a 2-cyanoethyl group, and a 3-cyanoethyl group.
The hydroxyimino C _1-6 alkyl group means a C _1-6 alkyl group having a hydroxyimino group, and examples thereof include a hydroxyiminomethyl group.
(C _1-6 alkoxyimino) C _1-6 alkyl group means a C _1-6 alkyl group having (C _1-6 alkoxyimino group), for example, methoxyiminomethyl group and ethoxy An iminomethyl group may be mentioned.

(C _1-6 alkoxy) C _1-6 alkyl group means a C _1-6 alkyl group having a C _1-6 alkoxy group, such as a methoxymethyl group, 1-methoxyethyl group, An ethoxymethyl group, a butoxymethyl group, and a 2-ethoxyethyl group are mentioned.
(C _3-8 cycloalkoxy) C _1-6 alkyl group means a C _1-6 alkyl group having a C _3-8 cycloalkoxy group, for example, a cyclopropyloxymethyl group and cyclopentyloxy A methyl group is mentioned.
{(C _1-6 alkoxy) C _1-6 alkoxy} C _1-6 alkyl group is a C _{1-6 having a} (C _1-6 alkoxy group having a C _1-6 alkoxy group). And includes, for example, a methoxymethoxymethyl group and a (1-ethoxyethoxy) methyl group.

(C _1-6 alkylthio) C _1-6 alkyl group means a C _1-6 alkyl group having a C _1-6 alkylthio group, for example, methylthiomethyl group, 1- (methylthio) ethyl Group, ethylthiomethyl group, butylthiomethyl group and 2- (ethylthio) ethyl group.
(C _1-6 alkylsulfinyl) C _1-6 alkyl group means an alkyl group having 1 to 6 carbon atoms having an alkylsulfinyl group having 1 to 6 carbon atoms, such as a methylsulfinylmethyl group, 1- ( Examples include methylsulfinyl) ethyl group, ethylsulfinylmethyl group, butylsulfinylmethyl group and 2- (ethylsulfinyl) ethyl group.
(C _1-6 alkylsulfonyl) The C _1-6 alkyl group means a C _1-6 alkyl group having a C _1-6 alkylsulfonyl group, for example, a methylsulfonylmethyl group, 1- ( A methylsulfonyl) ethyl group, an ethylsulfonylmethyl group, a butylsulfonylmethyl group and a 2- (ethylsulfonyl) ethyl group.
Halogen, a C _1-6 alkyl group or a C _1-6 substituted phenyl C _1-6 alkyl group optionally having one or more substituents selected from alkoxy groups, halogen, C _1-6 alkyl group or C _1-6 alkyl group having a phenyl group which may have one or more substituents selected from C _1-6 alkoxy groups means, for example, benzyl group, 2-fluorobenzyl group, 3 -Fluorobenzyl group, 4-fluorobenzyl group, 2-chlorobenzyl group, 3-chlorobenzyl group, 4-chlorobenzyl group, 2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, 2-methoxy Examples include benzyl group, 3-methoxybenzyl group, 4-methoxybenzyl group, phenethyl group, 4-phenylbutyl group and 6-phenylhexyl group.

C _1-6 alkoxy group means an alkoxy group having 1 to 6 carbon atoms, such as methoxy group, ethoxy group, normal propyloxy group, isopropyloxy group, normal butoxy group, isobutoxy group, sec-butoxy group, Examples thereof include a tert-butoxy group, a normal pentoxy group, a sec-pentoxy group, an isopentoxy group, a neopentoxy group, a normal hexyloxy group, and an isohexyloxy group.
The C _1-6 haloalkoxy group means a C _1-6 alkoxy group having a halogen such as fluorine, chlorine, bromine, iodine, etc., for example, trifluoromethoxy group, 2,2-difluoroethoxy group, 2 2,2-trichloroethoxy group, 3,3-difluoropropyloxy group, and 2,2,2-trifluoroethoxy group.
(C _3-8 cycloalkyl) C _1-6 alkoxy group means a C _1-6 alkoxy group having a C _3-8 cycloalkyl group, such as a cyclopropylmethoxy group, 1-cyclo Examples include propylethoxy group and cyclopentylmethoxy group.
(C _1-6 alkylthio) C _1-6 alkoxy group means a C _1-6 alkoxy group having (C _1-6 alkylthio group), for example, methylthiomethoxy group, methylthioethoxy group, Examples thereof include a methylthiopropoxy group, an ethylthiomethoxy group, and an ethylthioethoxy group.
(C _1-6 alkoxy) C _1-6 alkoxy group means a C _1-6 alkoxy group having (C _1-6 alkoxy group), for example, methoxymethoxy group, ethoxymethoxy group, Examples thereof include normal propyloxymethoxy group, isopropyloxymethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group and 3-methoxypropyloxy group.
The cyano C _1-6 alkoxy group means a C _1-6 alkoxy group having a cyano group, such as a cyanomethoxy group, a 1-cyanomethoxy group, a 2-cyanoethoxy group, and a 3-cyanopropyloxy group. Is mentioned.
(C _1-6 alkoxycarbonyl) C _1-6 alkoxy group means a C _1-6 alkoxy group having (a carbonyl group having a C _1-6 alkoxy group), for example, methoxycarbonylmethoxy Groups and ethoxycarbonylmethoxy groups.
The carbamoyl C _1-6 alkoxy group means a C _1-6 alkoxy group having a carbamoyl group, and examples thereof include a carbamoylmethoxy group.
{(C _1-6 alkyl) aminocarbonyl} C _1-6 alkoxy group means a C _1-6 alkoxy group having (a carbonyl group having an amino group having a C _1-6 alkyl group). Examples thereof include a methylaminocarbonylmethoxy group.
{Di (C _1-6 alkyl) aminocarbonyl} C _1-6 alkoxy group means carbon having {(a carbonyl group having two identical or different alkyl groups having 1 to 6 carbon atoms)}. This means an alkoxy group of 1 to 6, and examples thereof include a dimethylaminocarbonylmethoxy group.

The C _1-6 alkylthio group means an alkylthio group having 1 to 6 carbon atoms, and examples thereof include a methylthio group, an ethylthio group, and an isopropylthio group.
The C _1-6 alkylsulfinyl group means an alkylsulfinyl group having 1 to 6 carbon atoms, and examples thereof include a methylsulfinyl group, an ethylsulfinyl group, and an isopropylsulfinyl group.
The C _1-6 alkylsulfonyl group means an alkylsulfonyl group having 1 to 6 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, and an isopropylsulfonyl group.

The C _1-6 haloalkylthio group means an alkylthio group having 1 to 6 carbon atoms having a halogen such as fluorine, chlorine, bromine or iodine, and examples thereof include a trichloromethylthio group, a trifluoromethylthio group, and 2,2-difluoro. Examples thereof include an ethylthio group, a 2,2,2-trifluoroethylthio group, a 2,2,2-trichloroethylthio group, and a 3-chloropropylthio group.
The C _1-6 haloalkylsulfinyl group means a C _1-6 alkylsulfinyl group having a halogen such as fluorine, chlorine, bromine, iodine, etc., for example, a trichloromethylsulfinyl group, a trifluoromethylsulfinyl group, 2, Examples include 2-difluoroethylsulfinyl group, 2,2,2-trifluoroethylsulfinyl group, 2,2,2-trichloroethylsulfinyl group and 3-chloropropylsulfinyl group.
The C _1-6 haloalkylsulfonyl group means a C _1-6 alkylsulfonyl group having a halogen such as fluorine, chlorine, bromine, iodine, etc., and examples thereof include a trichloromethylsulfonyl group, a trifluoromethylsulfonyl group, 2, Examples include 2-difluoroethylsulfonyl group, 2,2,2-trifluoroethylsulfonyl group, 2,2,2-trichloroethylsulfonyl group and 3-chloropropylsulfonyl group.
The C _3-8 cycloalkoxy group means a C _3-8 cycloalkoxy group, and examples thereof include a cyclopropyloxy group, a cyclopentyloxy group, and cyclohexyloxy.

The C _1-6 alkylamino group means an alkylamino group having 1 to 6 carbon atoms, and examples thereof include a methylamino group, an ethylamino group, and an isopropylamino group.
The di (C _1-6 alkyl) amino group means an amino group having two identical or different alkyl groups having 1 to 6 carbon atoms, and examples thereof include a dimethylamino group, a diethylamino group, and an ethylmethylamino group. It is done.
The (C _1-6 alkyl) carbonylamino group means an amino group having a carbonyl group having an alkyl group having 1 to 6 carbon atoms, and examples thereof include an acetamido group and a propionylamino group.
The (C _1-6 alkyl) carbonyl group means a carbonyl group having an alkyl group having 1 to 6 carbon atoms, and examples thereof include an acetyl group, a propionyl group, a butyryl group, and a pivaloyl group.
The C _6-10 aryl group means an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
(C _6-10 aryl) C _1-6 alkyl group means an alkyl group having 1 to 6 carbon atoms having an aryl group having 6 to 10 carbon atoms, and examples thereof include a benzyl group and a phenethyl group.

The C _3-6 alkenyloxy group means an alkenyloxy group having 3 to 6 carbon atoms, and examples thereof include an allyloxy group and a 2-butenyloxy group.
The C _3-6 alkynyloxy group means an alkynyloxy group having 3 to 6 carbon atoms, and examples thereof include a propargyloxy group and a 2-butynyloxy group.
The C _6-10 aryloxy group means an aryloxy group having 6 to 10 carbon atoms, and examples thereof include a phenoxy group and a naphthyloxy group.
The (C _6-10 aryl) C _1-6 alkoxy group means a C _1-6 alkoxy group having a C _6-10 aryl group, and examples thereof include a benzyloxy group and a phenethyloxy group. It is done.
The di (C _3-6 alkenyl) amino group means an amino group having two identical or different alkenyl groups having 3 to 6 carbon atoms, such as diallylamino group and di (3-butenyl) amino group. Can be mentioned.
(C _1-6 alkyl) (C _6-10 aryl) amino group means an amino group having a C 1-6 alkyl group and a C _6-10 aryl group, for example, methylphenylamino group and ethyl group A phenylamino group is mentioned.

The 5- to 6-membered heteroaryl group means an aromatic 5- or 6-membered heterocyclic group containing 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur, such as a 3-pyridyl group, Examples include a 3-thienyl group and a 1-pyrazolyl group.
The C _1-3 alkyl group means an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, a normal propyl group, and an isopropyl group.
The C _1-3 alkoxy group means an alkoxy group having 1 to 3 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a normal propyloxy group, and an isopropyloxy group.
The C _1-3 alkylthio group means an alkylthio group having 1 to 3 carbon atoms, and examples thereof include a methylthio group, an ethylthio group, and a propylthio group.
The C _1-3 alkylsulfinyl group means an alkylsulfinyl group having 1 to 3 carbon atoms, and examples thereof include a methylsulfinyl group, an ethylsulfinyl group, and a propylsulfinyl group.
The C _1-3 alkylsulfonyl group means an alkylsulfonyl group having 1 to 3 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, and a propylsulfonyl group.
The di (C _1-3 alkyl) amino group means an amino group having two identical or different alkyl groups having 1 to 3 carbon atoms, and examples thereof include a dimethylamino group, a diethylamino group, and an ethylmethylamino group. It is done.
C _1-3 haloalkyl group means a C _1-6 alkyl group having a halogen such as fluorine, chlorine, bromine, iodine, etc., for example, trifluoromethyl group, chloromethyl group, 2,2-difluoroethyl group, Examples include 2,2,2-trichloroethyl group, 2,2,2-trifluoroethyl group, and 2,2,2-trifluoro-1,1-dichloroethyl group.
The (C _3-6 cycloalkyl) methyl group means a methyl group having a cycloalkyl group having 3 to 6 carbon atoms, and examples thereof include a cyclopropylmethyl group and a cyclopentylmethyl group.
The C _3-6 alkenyl group means an alkenyl group having 3 to 6 carbon atoms, and examples thereof include an allyl group, a 1-buten-3-yl group, and a 3-buten-1-yl group.
The C _3-6 alkynyl group means an alkynyl group having 3 to 6 carbon atoms, and examples thereof include a propargyl group and a 2-butynyl group.
The C _1-3 haloalkoxy group means a C _1-3 alkoxy group having a halogen such as fluorine, chlorine, bromine, iodine, etc., and examples thereof include a trifluoromethoxy group, a 2,2-difluoroethoxy group, 2 2,2-trichloroethoxy group, 3,3-difluoropropyloxy group, and 2,2,2-trifluoroethoxy group.
The cyclopropyl C _1-3 alkoxy group means a C _1-3 alkoxy group having a cyclopropyl group, and examples thereof include a cyclopropylmethoxy group, a 1-cyclopropylethoxy group, and a 2-cyclopropylethoxy group. It is done.
The (C _1-3 alkylthio) C _1-3 alkoxy group means a C _1-3 alkoxy group having a C _1-3 alkylthio group, such as a methylthiomethoxy group, a methylthioethoxy group, a methylthiopropoxy group. Group, ethylthiomethoxy group and ethylthioethoxy group.
(C _1-3 alkoxy) A C _1-3 alkoxy group means a C _1-3 alkoxy group having a C _1-3 alkoxy group, such as a methoxymethoxy group, an ethoxymethoxy group, n- Examples thereof include a propyloxymethoxy group, an isopropyloxymethoxy group, a 2-methoxyethoxy group, a 2-ethoxyethoxy group, and a 3-methoxypropyloxy group.
The cyano C _1-3 alkoxy group means a C _1-3 alkoxy group having a cyano group, such as a cyanomethoxy group, a 1-cyanomethoxy group, a 2-cyanoethoxy group, and a 3-cyanopropyloxy group. Is mentioned.
(C _1-3 alkyl) carbonylamino group means an amino group having a carbonyl group having an alkyl group having 1 to 3 carbon atoms, and examples thereof include an acetamido group and a propionylamino group.
The hydroxy C _1-3 alkyl group means an alkyl group having 1 to 3 carbon atoms as a hydroxyl group, and examples thereof include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, and a 3-hydroxypropyl group. It is done.
(C _1-3 alkoxy) C _1-3 alkyl group means a C _1-3 alkyl group having a C _1-3 alkoxy group, such as a methoxymethyl group, 1-methoxyethyl group, An ethoxymethyl group and 2-ethoxyethyl group are mentioned.
The cyano C _1-3 alkyl group means a C _1-3 alkyl group having a cyano group, and examples thereof include a cyanomethyl group, a 1-cyanoethyl group, a 2-cyanoethyl group, and a 3-cyanoethyl group.
Examples of the halogen include fluorine, chlorine, bromine and iodine.

  The present compound and the present compound A, which are active ingredients of the herbicidal composition of the present invention, may take the form of an agriculturally acceptable salt with an inorganic base or an organic base, etc. Are also included. Examples of such salts include inorganic bases (eg, alkali metal (lithium, sodium, potassium, etc.) hydroxides, carbonates, hydrogen carbonates, acetates, hydrides, alkaline earth metals (magnesium, calcium, Hydroxide), hydride, etc., ammonia), organic bases (eg, dimethylamine, triethylamine, piperazine, pyrrolidine, piperidine, 2-phenylethylamine, benzylamine, ethanolamine, diethanolamine, pyridine, collidine, etc.), Examples thereof include salts formed by mixing with metal alkoxides (for example, sodium methoxide, potassium tert-butoxide, magnesium methoxide and the like).

When the present compound that is an active ingredient of the herbicidal composition of the present invention has one or more asymmetric centers, the compound has two or more stereoisomers (for example, enantiomers, diastereomers, etc.). This compound includes all of these stereoisomers and a mixture of any two or more thereof.
When the compound has geometric isomerism based on a double bond or the like, the compound contains two or more geometric isomers (for example, E / Z or trans / cis isomers, S-trans / S-cis). Each isomer) and the like. The compound includes all of these geometric isomers and mixtures of any two or more thereof.

Examples of the pyridazinone compound represented by the formula (I) that is an active ingredient of the herbicidal composition of the present invention include the compounds shown below.
[Aspect 1] formula (I), R ¹ is halogen, C _1-6 alkyl group or a C _1-6 1 or more which may have a substituent phenyl C _1-6 alkyl selected from alkoxy groups Group, hydrogen, C _1-6 alkyl group, C _1-6 haloalkyl group, C _3-8 cycloalkyl group, (C _3-8 cycloalkyl) C _1-6 alkyl group, (C _1-6 alkoxy) C _{1 A} compound which is a _-6 alkyl group or a C _3-6 alkenyl group, a C _3-6 alkynyl group,
[Aspect 2] In [Aspect 1], R ¹ is hydrogen, C _1-3 alkyl group, C _1-3 haloalkyl group, cyclopropyl group, cyclopropylmethyl group, C _3-6 alkenyl group or C _1-3 alkoxy. A compound that is a methyl group,
[Aspect 3] In [Aspect 2], R ¹ is hydrogen or a C _1-3 alkyl group,
[Aspect 4] In [Aspect 3], R ¹ is a methyl group,
[Aspect 5] In [Aspect 3], a compound wherein R ¹ is hydrogen,
[Aspect 6] In the formula (I) or [Aspect 1] to [Aspect 5], R ² is halogen, cyano group, nitro group, C _1-3 alkoxy group, C _1-3 haloalkoxy group, C _1-3. alkylthio group, C _1-3 alkylsulfinyl group, C _1-3 alkylsulfonyl group, C _1-3 haloalkylthio group, C _1-3 haloalkylsulfinyl group, C _1-3 haloalkylsulfonyl group, C _3-6 cycloalkoxy group , (C _3-6 cycloalkyl) C _1-3 alkoxy group, amino group, C _1-3 alkylamino group, di (C _1-3 alkyl) amino group, (C _1-6 alkylthio) C _1-6 alkoxy Group, (C _1-6 alkoxy) C _1-6 alkoxy group, C _3-6 alkenyloxy group, C _3-6 alkynyloxy group, cyano C _1-6 alkoxy group, (C _1-6 alkoxycarbonyl) C _{1 -6} alkoxy, carbamoyl C _1-6 alkoxy group, {(C _1-6 alkyl) A Roh carbonyl} C _1-6 alkoxy group, {di (C _1-6 alkyl) amino carbonyl} C _1-6 alkoxy group, formylamino group, (C _1-6 alkyl) carbonylamino group, a hydroxy C _1-6 alkyl Group, (C _1-6 alkoxy) C _1-6 alkyl group, (C _1-6 haloalkoxy) C _1-6 alkyl group, (C _3-8 cycloalkoxy) C _1-6 alkyl group, {(C _{3 -8} cycloalkyl) C _1-6 alkoxy} C _1-6 alkyl group, (C _1-6 alkylthio) C _1-6 alkyl group, (C _1-6 haloalkylthio) C _1-6 alkyl group, cyano C _{1 A} compound which is a _-6 alkyl group, a hydroxyimino C _1-6 alkyl group, a (C _1-6 alkoxyimino) C _1-6 alkyl group, a formyl group or a (C _1-6 alkyl) carbonyl group,
[Aspect 7] In [Aspect 6], R ² is halogen, C _1-3 alkoxy group, C _1-3 alkylthio group, C _1-3 alkylsulfinyl group, C _1-3 alkylsulfonyl group, di (C _{1- 3} alkyl) amino group, (C _1-6 alkylthio) C _1-6 alkoxy group, (C _1-6 alkoxy) C _1-6 alkoxy group, C _3-6 alkenyloxy group, C _3-6 alkynyloxy group, Cyano C _1-6 alkoxy group, hydroxy C _1-6 alkyl group, (C _1-6 alkoxy) C _1-6 alkyl group, (C _3-8 cycloalkoxy) C _1-6 alkyl group, cyano C _1-6 A compound which is an alkyl group, a hydroxyimino C _1-6 alkyl group or a formyl group,
[Aspect 8] In [Aspect 7], a compound wherein R ² is a C _1-3 alkoxy group,

[Aspect 9] In [Aspect 8], a compound in which R ² is a methoxy group,
[Aspect 10] In [Aspect 8], R ² is an ethoxy group,
[Aspect 11] In [Aspect 7], R ² is a C _1-3 alkylthio group,
[Aspect 12] In [Aspect 11], R ² is a methylthio group,
[Aspect 13] In [Aspect 11], R ² is an ethylthio group,
[Aspect 14] In [Aspect 7], a compound wherein R ² is a C _1-3 alkylsulfinyl group,
[Aspect 15] In [Aspect 14], a compound in which R ² is a methylsulfinyl group,
[Aspect 16] In [Aspect 14], a compound wherein R ² is an ethylsulfinyl group,

｛式中、Ｒ^3aはＣ_1-6アルキル基、Ｃ_6-10アリール基、Ｃ_1-6アルコキシ基、Ｃ_3-6アルケニルオキシ基、Ｃ_3-6アルキニルオキシ基又はＣ_6-10アリールオキシ基を表し、
Ｗ^aがハロゲン、Ｃ_1-6アルキル基またはＣ_1-6アルコキシ基より選ばれる１種以上の置換基を有していてもよいフェニル基又はＣ_1-3アルコキシ基を表す。｝
で表されるいずれかの基を表す化合物、
[態様６７] [態様６６]において、Ｇが水素又は下記式

｛式中、Ｒ^3aはＣ_1-3アルキル基、フェニル基、Ｃ_1-3アルコキシ基、アリルオキシ基、プロパルギルオキシ基又はフェノキシ基を表し、
Ｗ^aがハロゲン、Ｃ_1-6アルキル基またはＣ_1-6アルコキシ基より選ばれる１種以上の置換基を有していてもよいフェニル基又はＣ_1-2アルコキシ基を表す。｝
で表されるいずれかの基である化合物、
[態様６８] [態様６７]において、Ｇが水素である化合物、 [Aspect 17] In [Aspect 7], a compound wherein R ² is a C _1-3 alkylsulfonyl group,
[Aspect 18] In [Aspect 17], a compound wherein R ² is a methylsulfonyl group,
[Aspect 19] In [Aspect 17], a compound in which R ² is an ethylsulfonyl group,
[Aspect 20] In [Aspect 7], a compound wherein R ^{2 is a} di (C _1-3 alkyl) amino group,
[Aspect 21] In [Aspect 20], a compound wherein R ² is a dimethylamino group,
[Aspect 22] In [Aspect 7], a compound wherein R ² is halogen,
[Aspect 23] In [Aspect 22], a compound in which R ² is fluorine,
[Aspect 24] In [Aspect 22], a compound wherein R ² is chlorine,
[Aspect 25] In [Aspect 22], a compound wherein R ² is bromine,
[Aspect 26] In [Aspect 7], a compound wherein R ² is a (C _1-6 alkylthio) C _1-6 alkoxy group,
[Aspect 27] In [Aspect 26], a compound wherein R ² is a methylthiomethoxy group,
[Aspect 28] In [Aspect 26], a compound wherein R ² is a methylthioethoxy group,
[Aspect 29] In [Aspect 7], a compound wherein R ² is a (C _1-6 alkoxy) C _1-6 alkoxy group,
[Aspect 30] In [Aspect 29], a compound wherein R ² is a methoxymethoxy group,
[Aspect 31] In [Aspect 29], a compound wherein R ² is an ethoxymethoxy group,
[Aspect 32] In [Aspect 7], a compound wherein R ² is a C _3-6 alkenyloxy group,
[Aspect 33] In [Aspect 32], a compound wherein R ² is an allyloxy group,
[Aspect 34] In [Aspect 7], a compound wherein R ² is a C _3-6 alkynyloxy group,
[Aspect 35] In [Aspect 34], a compound wherein R ² is a propargyloxy group,
[Aspect 36] In [Aspect 7], a compound wherein R ² is a cyano C _1-6 alkoxy group,
[Aspect 37] In [Aspect 36], a compound wherein R ² is a cyanomethoxy group,
[Aspect 38] In [Aspect 7], a compound wherein R ² is a hydroxy C _1-6 alkyl group,
[Aspect 39] In [Aspect 38], a compound wherein R ² is a hydroxymethyl group,
[Aspect 40] In [Aspect 7], a compound wherein R ² is a (C _1-6 alkoxy) C _1-6 alkyl group,
[Aspect 41] In [Aspect 40], a compound wherein R ² is a methoxymethyl group,
[Aspect 43] In [Aspect 7], a compound wherein R ² is a (C _3-8 cycloalkoxy) C _1-6 alkyl group,
[Aspect 44] In [Aspect 43], a compound wherein R ² is a (cyclopropyloxy) methyl group,
[Aspect 45] In [Aspect 7], a compound wherein R ² is a cyano C _1-6 alkyl group,
[Aspect 46] In [Aspect 45], a compound wherein R ² is a cyanomethyl group,
[Aspect 47] In [Aspect 7], a compound wherein R ² is a hydroxyimino C _1-6 alkyl group,
[Aspect 48] In [Aspect 47], the compound wherein R ² is a hydroxyiminomethyl group,
[Aspect 49] In [Aspect 7], a compound wherein R ² is a formyl group,
[Aspect 50] In [Aspect 6], a compound wherein R ² is a (C _1-6 alkoxycarbonyl) C _1-6 alkoxy group,
[Aspect 51] In [Aspect 50], a compound wherein R ² is a (methoxycarbonyl) methoxy group,
[Aspect 52] In [Aspect 50], a compound wherein R ² is an (ethoxycarbonyl) methoxy group,
[Aspect 53] In [Aspect 6], a compound wherein R ² is a carbamoyl C _1-6 alkoxy group,
[Aspect 54] In [53], the compound wherein R ² is a carbamoylmethoxy group,
[Aspect 55] In [Aspect 6], a compound wherein R ² is a {di (C _1-6 alkyl) aminocarbonyl} C _1-6 alkoxy group,
[Aspect 56] In [Aspect 55], a compound wherein R ² is a (dimethylaminocarbonyl) methoxy group,
[Aspect 57] In [Aspect 6], a compound wherein R ² is a (C _1-6 alkyl) carbonylamino group,
[Aspect 58] In [Aspect 57], a compound wherein R ² is an acetamide group,
[Aspect 59] In [Aspect 6], a compound wherein R ² is a (C _1-6 alkylthio) C _1-6 alkyl group,
[Aspect 60] In [Aspect 59], a compound wherein R ² is a methylthiomethyl group,
[Aspect 61] In [Aspect 6], a compound wherein R ² is a (C _1-6 alkoxyimino) C _1-6 alkyl group,
[Aspect 62] In [Aspect 61], a compound wherein R ² is a (methoxyimino) methyl group,
[Aspect 63] In [Aspect 6], a compound wherein R ² is a cyano group,
[Aspect 64] In [Aspect 6], a compound wherein R ² is a nitro group,
[Aspect 65] In [Aspect 6], a compound wherein R ² is an amino group,
[Aspect 66] In Formula (I) or [Aspect 1] to [Aspect 65], G is hydrogen or the following formula:

{Wherein R ^3a represents a C _1-6 alkyl group, a C _6-10 aryl group, a C _1-6 alkoxy group, a C _3-6 alkenyloxy group, a C _3-6 alkynyloxy group or a C _6-10 aryloxy group. Represents a group,
W ^a represents a phenyl group or a C _1-3 alkoxy group which may have one or more substituents selected from halogen, a C _1-6 alkyl group or a C _1-6 alkoxy group. }
A compound representing any group represented by:
[Aspect 67] In [Aspect 66], G is hydrogen or the following formula:

{Wherein R ^3a represents a C _1-3 alkyl group, a phenyl group, a C _1-3 alkoxy group, an allyloxy group, a propargyloxy group, or a phenoxy group,
W ^a represents a phenyl group or a C _1-2 alkoxy group which may have one or more substituents selected from halogen, a C _1-6 alkyl group or a C _1-6 alkoxy group. }
A compound which is any group represented by:
[Aspect 68] In [Aspect 67], a compound wherein G is hydrogen,

[Aspect 69] In [Aspect 67], a compound wherein G is a (C _1-3 alkyl) carbonyl group,
[Aspect 70] In [Aspect 69], a compound wherein G is an acetyl group,
[Aspect 71] In [Aspect 69], a compound wherein G is a propionyl group,
[Aspect 72] In [Aspect 67], a compound wherein G is a benzoyl group,
[Aspect 73] In [Aspect 67], a compound wherein G is a C _1-3 alkoxycarbonyl group,
[Aspect 74] In [Aspect 73], a compound wherein G is a methoxycarbonyl group,
[Aspect 75] In [Aspect 73], a compound wherein G is an ethoxycarbonyl group,
[Aspect 76] In [Aspect 67], a compound wherein G is an allyloxycarbonyl group,

[Aspect 77] In [Aspect 67], a compound wherein G is a propargyloxycarbonyl group,
[Aspect 78] In [Aspect 67], a compound wherein G is a phenoxycarbonyl group,
[Aspect 79] In [Aspect 67], a compound wherein G is a C _1-2 alkoxymethyl group,
[Aspect 80] In [Aspect 79], a compound wherein G is a methoxymethyl group,
[Aspect 81] In [Aspect 79], a compound wherein G is an ethoxymethyl group,
[Aspect 82] In [Aspect 67], G is a phenyl group,
[Aspect 83] In [Aspect 67], G is a 4-methoxyphenyl group,
[Aspect 84] In the formula (I) or [Aspect 1] to [Aspect 83], Z is a halogen, a cyano group, a nitro group, a _C1-3 alkyl group, a _C2-3 alkenyl group, a _C2-3 alkynyl group. C _1-3 alkoxy group, C _1-3 alkylthio group or cyclopropyl group, wherein C _1-3 alkyl group, C _2-3 alkenyl group, C _2-3 alkynyl group represented by Z, C _{The 1-3} alkoxy group and the C _1-3 alkylthio group may have a halogen, the cyclopropyl group may have at least one selected from the group consisting of a halogen and a methyl group, and n is 1 to 1 A compound that represents an integer of 3 and when n is 2 or more, each Z may be the same or different
[Aspect 85] In [Aspect 84], Z is halogen, cyano group, nitro group, methyl group, ethyl group, vinyl group, allyl group, ethynyl group, propargyl group, methoxy group, ethoxy group, methylthio group, ethylthio group or A methyl group, an ethyl group, a vinyl group, an allyl group, an ethynyl group, a propargyl group, a methoxy group, an ethoxy group, a methylthio group, and an ethylthio group represented by Z may have a halogen. The cyclopropyl group may have at least one selected from the group consisting of halogen and methyl group, n represents an integer of 1 to 3, and when n is 2 or more, each Z is the same or Compounds that may be different,
[Aspect 86] In [Aspect 85], Z is halogen, cyano group, nitro group, methyl group, trifluoromethyl group, ethyl group, 2,2,2-trifluoroethyl group, vinyl group, allyl group, ethynyl group. , Propargyl group, methoxy group, trifluoromethoxy group, ethoxy group, methylthio group, trifluoromethylthio group, ethylthio group or cyclopropyl group, n represents an integer of 1 to 3, and n is 2 or more, Each Z may be the same or different,

[Aspect 87] In [Aspect 86], Z is fluorine, chlorine, bromine, cyano group, methyl group, trifluoromethyl group, ethyl group, vinyl group, allyl group, ethynyl group, methoxy group, ethoxy group, or methylthio group. Yes, n represents an integer of 1 to 3, and when n is 2 or more, each Z may be the same or different compound,
[Aspect 88] In [Aspect 87], when Z is a _C1-3 alkyl group, n represents an integer of 1 to 3, and n is 2 or more, each Z may be the same or different. Compound,
[Aspect 89] In [Aspect 88], when Z is a methyl group or an ethyl group, n represents an integer of 1 to 3, and when n is 2 or more, each Z may be the same or different ,
[Aspect 90] In [Aspect 89], (Z) _n is a 2,4,6-trimethyl group,
[Aspect 91] In [Aspect 89], (Z) _n is a 2,4-dimethyl-6-ethyl group,
[Aspect 92] In [Aspect 89], (Z) _n is a 2,6-diethyl-4-methyl group,
[Aspect 93] In [Aspect 89], (Z) _n is a 2,4,6-triethyl group,
[Aspect 94] In [Aspect 89], (Z) a compound wherein _n is a 2-ethyl-4,6-dimethyl group,
[Aspect 95] In [Aspect 86], Z is a methyl group, an ethyl group, a vinyl group, an ethynyl group, a trifluoromethyl group, a trifluoromethoxy group, or a halogen, n represents an integer of 1 to 3, and n is When two or more, each Z may be the same or different,
[Aspect 96] In [Aspect 95], (Z) _n is a 2-vinyl-4,6-dimethyl group,
[Aspect 97] In [Aspect 95], (Z) a compound wherein _n is a 2-ethynyl-4,6-dimethyl group,
[Aspect 98] In [Aspect 95], (Z) a compound wherein _n is a 2-trifluoromethoxy group,
[Aspect 99] In [Aspect 95], (Z) a compound wherein _n is a 2-trifluoromethyl-4-chloro group,

〔式中、Ｒ¹はＣ_1-6アルコキシ基を有していてもよいフェニルＣ_1-6アルキル基、Ｃ_1-6アルキル基、Ｃ_3-6アルケニル基又は（Ｃ_3-8シクロアルキル）Ｃ_1-6アルキル基を表し、Ｒ²はハロゲン、シアノ基、ニトロ基、Ｃ_1-6アルコキシ基、Ｃ_1-6ハロアルコキシ基、Ｃ_1-6アルキルチオ基、Ｃ_1-6アルキルスルフィニル基、Ｃ_1-6アルキルスルホニル基、（Ｃ_3-8シクロアルキル）Ｃ_1-6アルコキシ基、（Ｃ_1-6アルキルチオ）Ｃ_1-6アルコキシ基、（Ｃ_1-6アルコキシ）Ｃ_1-6アルコキシ基、Ｃ_3-6アルケニルオキシ基、Ｃ_3-6アルキニルオキシ基、シアノＣ_1-6アルコキシ基、（Ｃ_1-6アルコキシカルボニル）Ｃ_1-6アルコキシ基、カルバモイルＣ_1-6アルコキシ基、｛ジ（Ｃ_1-6アルキル）アミノカルボニル｝Ｃ_1-6アルコキシ基、アミノ基、ジ（Ｃ_1-6アルキル）アミノ基、（Ｃ_1-6アルキル）カルボニルアミノ基、ヒドロキシＣ_1-6アルキル基、（Ｃ_1-6アルコキシ）Ｃ_1-6アルキル基、シアノＣ_1-6アルキル基、ヒドロキシイミノＣ_1-6アルキル基、又はホルミル基を表し、Ｇは水素又は下記式

｛式中、Ｌは酸素を表し、Ｒ³はＣ_1-6アルキル基、Ｃ_6-10アリール基、Ｃ_1-6アルコキシ基、Ｃ_3-6アルケニルオキシ基を表し、Ｒ⁴はＣ_1-6アルキル基を表し、Ｒ⁷は水素を表し、ＷはＣ_1-6アルコキシ基を有していてもよいフェニル基又はＣ_1-6アルコキシ基を表す（但し、Ｒ³、Ｒ⁴及びＷの各々で表されるいずれの基もハロゲンを有していてもよく、Ｃ_6-10アリール基はＣ_1-6アルキル基により置換されていてもよい。）。｝で表されるいずれかの基を表し、Ｚはハロゲン、Ｃ_1-6アルキル基、Ｃ_2-6アルケニル基、Ｃ_2-6アルキニル基又はＣ_1-6アルコキシ基を表し（但し、Ｚで表されるＣ_1-6アルキル基、Ｃ_2-6アルケニル基、Ｃ_2-6アルキニル基及びＣ_1-6アルコキシ基はハロゲンを有していてもよい）、ｎは１〜３の整数を表す（但し、ｎが２以上である場合、各々のＺは同一又は異なっていてもよい。）〕で示されるピリダジノン化合物。
［態様１０１］ 式（Ｉ−ＩＩ）

〔式中、Ｒ²¹は水素、Ｃ_1-6アルキル基、Ｃ_1-6ハロアルキル基、Ｃ_3-8シクロアルキル基、Ｃ_3-8ハロシクロアルキル基、（Ｃ_1-6アルキル）Ｃ_3-8シクロアルキル基、（Ｃ_3-8シクロアルキル）Ｃ_1-6アルキル基、（Ｃ_3-8シクロアルキル）Ｃ_3-8シクロアルキル基、（Ｃ_3-8ハロシクロアルキル）Ｃ_1-6アルキル基、｛（Ｃ_1-6アルキル）Ｃ_3-8シクロアルキル｝Ｃ_1-6アルキル基、（Ｃ_1-6アルコキシ）Ｃ_1-6アルキル基、（Ｃ_3-8シクロアルコキシ）Ｃ_1-6アルキル基、｛（Ｃ_1-6アルコキシ）Ｃ_1-6アルコキシ｝Ｃ_1-6アルキル基、（Ｃ_1-6アルキルチオ）Ｃ_1-6アルキル基、（Ｃ_1-6アルキルスルフィニル）Ｃ_1-6アルキル基、（Ｃ_1-6アルキルスルホニル）Ｃ_1-6アルキル基又はテトラヒドロピラニル基を表し、Ｒ²²はハロゲン、シアノ基、ニトロ基、Ｃ_1-6アルコキシ基、Ｃ_1-6ハロアルコキシ基、Ｃ_1-6アルキルチオ基、Ｃ_1-6アルキルスルフィニル基、Ｃ_1-6アルキルスルホニル基、Ｃ_1-6ハロアルキルチオ基、Ｃ_1-6ハロアルキルスルフィニル基、Ｃ_1-6ハロアルキルスルホニル基、Ｃ_3-8シクロアルコキシ基、（Ｃ_3-8シクロアルキル）Ｃ_1-6アルコキシ基、アミノ基、Ｃ_1-6アルキルアミノ基又はジ（Ｃ_1-6アルキル）アミノ基を表し、Ｇ²¹は水素又は下記式

｛式中、Ｌ²¹は酸素又はイオウを表し、Ｒ³¹はＣ_1-6アルキル基、Ｃ_3-8シクロアルキル基、Ｃ_2-6アルケニル基、Ｃ_2-6アルキニル基、Ｃ_6-10アリール基、（Ｃ_6-10アリール）Ｃ_1-6アルキル基、Ｃ_1-6アルコキシ基、Ｃ_3-8シクロアルコキシ基、Ｃ_3-6アルケニルオキシ基、Ｃ_3-6アルキニルオキシ基、Ｃ_6-10アリールオキシ基、（Ｃ_6-10アリール）Ｃ_1-6アルコキシ基、ジ（Ｃ_1-6アルキル）アミノ基、ジ（Ｃ_3-6アルケニル）アミノ基、（Ｃ_1-6アルキル）（Ｃ_6-10アリール）アミノ基又は５〜６員のヘテロアリール基を表し、Ｒ⁴¹はＣ_1-6アルキル基、Ｃ_6-10アリール基又はジ（Ｃ_1-6アルキル）アミノ基を表し、Ｒ⁵¹及びＲ⁶¹は同一又は異なっていてもよく、Ｃ_1-6アルキル基、Ｃ_3-8シクロアルキル基、Ｃ_6-10アリール基、Ｃ_1-6アルコキシ基、Ｃ_3-8シクロアルコキシ基、Ｃ_6-10アリールオキシ基、（Ｃ_6-10アリール）Ｃ_1-6アルコキシ基、Ｃ_1-6アルキルチオ基又はジ（Ｃ_1-6アルキル）アミノ基を表し、Ｒ⁷¹は水素又はＣ_1-6アルキル基を表し、Ｗ²¹はＣ_1-6アルコキシ基、Ｃ_1-6アルキルチオ基、Ｃ_1-6アルキルスルフィニル基、Ｃ_1-6アルキルスルホニル基を表す（但し、Ｒ³¹、Ｒ⁴¹、Ｒ⁵¹、Ｒ⁶¹及びＷ²¹の各々で表されるいずれの基もハロゲンを有していてもよく、Ｃ_3-8シクロアルキル基、Ｃ_6-10アリール基、（Ｃ_6-10アリール）Ｃ_1-6アルキル基のアリール部分、Ｃ_3-8シクロアルコキシ基、Ｃ_6-10アリールオキシ基、（Ｃ_6-10アリール）Ｃ_1-6アルコキシ基のアリール部分、（Ｃ_1-6アルキル）（Ｃ_6-10アリール）アミノ基のアリール部分及び５〜６員のヘテロアリール基はいずれもＣ_1-6アルキル基により置換されていてもよい。）。｝で表されるいずれかの基を表し、Ｚ²¹はハロゲン、シアノ基、ニトロ基、Ｃ_1-6アルキル基、Ｃ_2-6アルケニル基、Ｃ_2-6アルキニル基、Ｃ_1-6アルコキシ基、Ｃ_1-6アルキルチオ基又はＣ_3-8シクロアルキル基を表し（但し、Ｚ²¹で表されるＣ_1-6アルキル基、Ｃ_2-6アルケニル基、Ｃ_2-6アルキニル基、Ｃ_1-6アルコキシ基及びＣ_1-6アルキルチオ基はハロゲンを有していてもよく、Ｃ_3-8シクロアルキル基はハロゲン及びＣ_1-6アルキル基からなる群より選ばれる少なくとも一種の基により置換されていてもよい）、ｒは１〜５の整数を表す（但し、ｒが２以上である場合、各々のＺ²¹は同一又は異なっていてもよい。）。〕
で示されるピリダジノン化合物。
［態様１０２］ Ｒ²¹が水素又はＣ_1-3アルキル基であり、Ｒ²²がＣ_1-3アルコキシ基、Ｃ_1-3アルキルチオ基、Ｃ_1-3アルキルスルフィニル基、Ｃ_1-3アルキルスルホニル基又はジ（Ｃ_1-3アルキル）アミノ基であり、Ｇ²¹が水素又は下記式

｛式中、Ｒ^31aはＣ_1-6アルキル基、Ｃ_6-10アリール基、Ｃ_1-6アルコキシ基、Ｃ_3-6アルケニルオキシ基、Ｃ_3-6アルキニルオキシ基又はＣ_6-10アリールオキシ基を表し、
Ｗ^21aがＣ_1-3アルコキシ基を表す。｝で表されるいずれかの基であり、Ｚ²¹がＣ_1-3アルキル基であり、ｒが１〜３の整数である（但し、ｒが２以上である場合、各々のＺ²¹は同一又は異なっていてもよい。）、［態様１０１］記載のピリダジノン化合物。
［態様１０３］ Ｒ²¹がメチル基であり、Ｒ²²がメトキシ基、エトキシ基、メチルチオ基、メチルスルフィニル基、メチルスルホニル基又はジメチルアミノ基であり、Ｇ²¹が水素、アセチル基、プロピオニル基、ベンゾイル基、メトキシカルボニル基、エトキシカルボニル基、アリルオキシカルボニル基、フェノキシカルボニル基、メトキシメチル基又はエトキシメチル基であり、Ｚ²¹がメチル基又はエチル基である、［態様１０２］記載のピリダジノン化合物。
［態様１０４］ Ｇ²¹が水素である［態様１０１］〜［態様１０３］のいずれか一項記載のピリダジノン化合物。 [Aspect 100] Formula (I)

[Wherein, R ¹ is a phenyl C _1-6 alkyl group, a C _1-6 alkyl group, a C _3-6 alkenyl group or (C _3-8 cycloalkyl) optionally having a C _1-6 alkoxy group. C _1-6 alkyl group, R ² is halogen, cyano group, nitro group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, (C _3-8 cycloalkyl) C _1-6 alkoxy group, (C _1-6 alkylthio) C _1-6 alkoxy group, (C _1-6 alkoxy) C _1-6 alkoxy group C _3-6 alkenyloxy group, C _3-6 alkynyloxy group, cyano C _1-6 alkoxy group, (C _1-6 alkoxycarbonyl) C _1-6 alkoxy group, carbamoyl C _1-6 alkoxy group, {di (C _1-6 alkyl) amino carbonyl} C _1-6 alkoxy group, an amino group, di (C _1-6 alkyl) A Amino group, (C _1-6 alkyl) carbonylamino group, a hydroxy C _1-6 alkyl group, (C _1-6 alkoxy) C _1-6 alkyl, cyano C _1-6 alkyl group, hydroxyimino C _1-6 Represents an alkyl group or a formyl group, G is hydrogen or the following formula

{Wherein L represents oxygen, R ³ represents a C _1-6 alkyl group, a C _6-10 aryl group, a C _1-6 alkoxy group, a C _3-6 alkenyloxy group, and R ⁴ represents a C _1- represents an _alkyl group, R ⁷ represents hydrogen, W represents a C _1-6 alkoxy group which may have a phenyl group or a C _1-6 alkoxy group (wherein, R ^3, R ⁴ and W Any group represented by each may have a halogen, and the C _6-10 aryl group may be substituted with a C _1-6 alkyl group. }, Z represents a halogen, a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group or a C _1-6 alkoxy group (provided that Z is A C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group and a C _1-6 alkoxy group represented by this group may have a halogen), and n represents an integer of 1 to 3. (However, when n is 2 or more, each Z may be the same or different.)].
[Aspect 101] Formula (I-II)

[Wherein R ²¹ is hydrogen, C _1-6 alkyl group, C _1-6 haloalkyl group, C _3-8 cycloalkyl group, C _3-8 halocycloalkyl group, (C _1-6 alkyl) C _{3-3 8} cycloalkyl group, (C _3-8 cycloalkyl) C _1-6 alkyl group, (C _3-8 cycloalkyl) C _3-8 cycloalkyl group, (C _3-8 halocycloalkyl) C _1-6 alkyl Group, {(C _1-6 alkyl) C _3-8 cycloalkyl} C _1-6 alkyl group, (C _1-6 alkoxy) C _1-6 alkyl group, (C _3-8 cycloalkoxy) C _1-6 Alkyl group, {(C _1-6 alkoxy) C _1-6 alkoxy} C _1-6 alkyl group, (C _1-6 alkylthio) C _1-6 alkyl group, (C _1-6 alkylsulfinyl) C _1-6 alkyl group, a (C _1-6 alkylsulfonyl) C _1-6 alkyl group or a tetrahydropyranyl group, R ²² is halogen, cyano group, nitro group, C _1-6 alkoxy Shi group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C _1-6 haloalkylthio group, C _1-6 haloalkylsulfinyl group, C _1-6 haloalkylsulfonyl group, C _3-8 cycloalkoxy group, (C _3-8 cycloalkyl) C _1-6 alkoxy group, amino group, C _1-6 alkylamino group or di (C _1-6 alkyl) Represents an amino group, G ²¹ represents hydrogen or the following formula

{Wherein L ²¹ represents oxygen or sulfur, and R ³¹ represents a C _1-6 alkyl group, a C _3-8 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _6-10 aryl Group, (C _6-10 aryl) C _1-6 alkyl group, C _1-6 alkoxy group, C _3-8 cycloalkoxy group, C _3-6 alkenyloxy group, C _3-6 alkynyloxy group, C _{6- 10} aryloxy group, (C _6-10 aryl) C _1-6 alkoxy group, di (C _1-6 alkyl) amino group, di (C _3-6 alkenyl) amino group, (C _1-6 alkyl) (C _6-10 aryl) represents an amino group or a 5-6 membered heteroaryl group, R ⁴¹ represents a C _1-6 alkyl group, a C _6-10 aryl group or a di (C _1-6 alkyl) amino group, R ⁵¹ and R ⁶¹ may be the same or different, C _1-6 alkyl group, C _3-8 cycloalkyl group, C _6-10 aryl group, C _1-6 alkoxy, C _3-8 cycloalkyl Represents alkoxy group, C _6-10 aryloxy group, a (C _6-10 aryl) C _1-6 alkoxy group, C _1-6 alkylthio group or a di (C _1-6 alkyl) amino group, R ⁷¹ is hydrogen or Represents a C _1-6 alkyl group, and W ²¹ represents a C _1-6 alkoxy group, a C _1-6 alkylthio group, a C _1-6 alkylsulfinyl group, or a C _1-6 alkylsulfonyl group (provided that R ³¹ , R Any group represented by each of ⁴¹ , R ⁵¹ , R ^61, and W ²¹ may have a halogen, such as a C _3-8 cycloalkyl group, a C _6-10 aryl group, or (C _6-10 aryl). ) Aryl moiety of C _1-6 alkyl group, C _3-8 cycloalkoxy group, C _6-10 aryloxy group, (C _6-10 aryl) aryl moiety of C _1-6 alkoxy group, (C _1-6 alkyl) ) (both C _6-10 aryl) heteroaryl group aryl moiety and 5-6 membered amino groups are C _1-6 alkyl groups Ri may be substituted.). }, Z ²¹ is halogen, cyano group, nitro group, C _1-6 alkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _1-6 alkoxy group Represents a C _1-6 alkylthio group or a C _3-8 cycloalkyl group (provided that a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group represented by Z ²¹ , C _{1- The 6} alkoxy group and the C _1-6 alkylthio group may have a halogen, and the C _3-8 cycloalkyl group is substituted with at least one group selected from the group consisting of a halogen and a C _1-6 alkyl group. And r represents an integer of 1 to 5 (provided that when r is 2 or more, each Z ²¹ may be the same or different). ]
A pyridazinone compound represented by:
[Aspect 102] R ²¹ is hydrogen or a C _1-3 alkyl group, and R ²² is a C _1-3 alkoxy group, a C _1-3 alkylthio group, a C _1-3 alkylsulfinyl group, or a C _1-3 alkylsulfonyl group. Or a di (C _1-3 alkyl) amino group, and G ²¹ is hydrogen or the following formula

{Wherein R ^31a represents a C _1-6 alkyl group, a C _6-10 aryl group, a C _1-6 alkoxy group, a C _3-6 alkenyloxy group, a C _3-6 alkynyloxy group, or a C _6-10 aryloxy group. Represents a group,
W ^21a represents a C _1-3 alkoxy group. }, Z ²¹ is a C _1-3 alkyl group, and r is an integer of 1 to 3 (provided that when r is 2 or more, each Z ²¹ is the same) Or may be different.), A pyridazinone compound according to [Aspect 101].
Aspect 103] R ²¹ is a methyl group, R ²² is a methoxy group, an ethoxy group, a methylthio group, methylsulfinyl group, a methylsulfonyl group or dimethylamino group, G ²¹ is hydrogen, an acetyl group, a propionyl group, a benzoyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an allyloxycarbonyl group, a phenoxycarbonyl group, a methoxymethyl group or an ethoxymethyl group, Z ²¹ is a methyl group or an ethyl group, [embodiment 102] pyridazinone compound according.
[Aspect 104] The pyridazinone compound according to any one of [Aspect 101] to [Aspect 103], wherein G ²¹ is hydrogen.

[態様１０５] 式（Ｉ−ＩＩ）において、Ｒ²¹が水素、Ｃ_1-6アルキル基、Ｃ_1-6ハロアルキル基、Ｃ_3-8シクロアルキル基、（Ｃ_3-8シクロアルキル）Ｃ_1-6アルキル基又は（Ｃ_1-6アルコキシ）Ｃ_1-6アルキル基である化合物、
[態様１０６] [態様１０５］において、Ｒ²¹が水素、Ｃ_1-3アルキル基、Ｃ_1-3ハロアルキル基、シクロプロピル基、シクロプロピルメチル基又はＣ_1-3アルコキシメチル基である化合物、
[態様１０７] [態様１０６]において、Ｒ²¹が水素又はＣ_1-3アルキル基である化合物、
[態様１０８] [態様１０７］において、Ｒ²¹がメチル基である化合物、
[態様１０９] [態様１１０７]において、Ｒ²¹が水素である化合物、
[態様１１０] 式（Ｉ−ＩＩ）または[態様１０５]〜[態様１０９]において、Ｒ²²がハロゲン、シアノ基、ニトロ基、Ｃ_1-3アルコキシ基、Ｃ_1-3ハロアルコキシ基、Ｃ_1-3アルキルチオ基、Ｃ_1-3アルキルスルフィニル基、Ｃ_1-3アルキルスルホニル基、Ｃ_1-3ハロアルキルチオ基、Ｃ_1-3ハロアルキルスルフィニル基、Ｃ_1-3ハロアルキルスルホニル基、Ｃ_3-6シクロアルコキシ基、（Ｃ_3-6シクロアルキル）Ｃ_1-3アルコキシ基、アミノ基、Ｃ_1-3アルキルアミノ基又はジ（Ｃ_1-3アルキル）アミノ基である化合物、
[態様１１１] [態様１１０]において、Ｒ²²がＣ_1-3アルコキシ基、Ｃ_1-3アルキルチオ基、Ｃ_1-3アルキルスルフィニル基、Ｃ_1-3アルキルスルホニル基又はジ（Ｃ_1-3アルキル）アミノ基である化合物、
[態様１１２] [態様１１１]において、Ｒ²²がＣ_1-3アルコキシ基である化合物、 Among the pyridazinone compounds represented by the formula (I) which are active ingredients of the herbicidal composition of the present invention, examples of the compound represented by the formula (I-II) include the compounds shown below.

[Aspect 105] In formula (I-II), R ²¹ represents hydrogen, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _3-8 cycloalkyl group, (C _3-8 cycloalkyl) C _{1- A} compound which is a ₆ alkyl group or a (C _1-6 alkoxy) C _1-6 alkyl group,
[Aspect 106] In [Aspect 105], a compound wherein R ²¹ is hydrogen, a C _1-3 alkyl group, a C _1-3 haloalkyl group, a cyclopropyl group, a cyclopropylmethyl group, or a C _1-3 alkoxymethyl group,
[Aspect 107] In [Aspect 106], a compound wherein R ²¹ is hydrogen or a C _1-3 alkyl group,
[Aspect 108] In [Aspect 107], a compound wherein R ²¹ is a methyl group,
[Aspect 109] In [Aspect 1107], a compound wherein R ²¹ is hydrogen,
[Aspect 110] In Formula (I-II) or [Aspect 105] to [Aspect 109], R ²² is halogen, cyano group, nitro group, C _1-3 alkoxy group, C _1-3 haloalkoxy group, C _{1. -3} alkylthio group, C _1-3 alkylsulfinyl group, C _1-3 alkylsulfonyl group, C _1-3 haloalkylthio group, C _1-3 haloalkylsulfinyl group, C _1-3 haloalkylsulfonyl group, C _3-6 cycloalkyl A compound which is an alkoxy group, a (C _3-6 cycloalkyl) C _1-3 alkoxy group, an amino group, a C _1-3 alkylamino group or a di (C _1-3 alkyl) amino group,
[Aspect 111] In [Aspect 110], R ²² is a C _1-3 alkoxy group, a C _1-3 alkylthio group, a C _1-3 alkylsulfinyl group, a C _1-3 alkylsulfonyl group, or di (C _1-3 alkyl). ) A compound that is an amino group,
[Aspect 112] In [Aspect 111], a compound wherein R ²² is a C _1-3 alkoxy group,

[Aspect 113] In [Aspect 112], a compound wherein R ²² is a methoxy group,
[Aspect 114] In [Aspect 112], a compound wherein R ²² is an ethoxy group,
[Aspect 115] In [Aspect 111], a compound wherein R ²² is a C _1-3 alkylthio group,
[Aspect 116] In [Aspect 115], a compound wherein R ²² is a methylthio group,
[Aspect 117] In [Aspect 115], a compound wherein R ²² is an ethylthio group,
[Aspect 118] In [Aspect 111], a compound wherein R ²² is a C _1-3 alkylsulfinyl group,
[Aspect 119] In [Aspect 118], a compound wherein R ²² is a methylsulfinyl group,
[Aspect 120] In [Aspect 118], a compound wherein R ²² is an ethylsulfinyl group,

｛式中、Ｒ^3aはＣ_1-6アルキル基、Ｃ_6-10アリール基、Ｃ_1-6アルコキシ基、Ｃ_3-6アルケニルオキシ基、Ｃ_3-6アルキニルオキシ基又はＣ_6-10アリールオキシ基を表し、
Ｗ²¹がＣ_1-3アルコキシ基を表す。｝
で表されるいずれかの基を表す化合物、
[態様１２７] [態様１２６]において、Ｇ²¹が水素又は下記式

｛式中、Ｒ^32aはＣ_1-3アルキル基、フェニル基、Ｃ_1-3アルコキシ基、アリルオキシ基、プロパルギルオキシ基又はフェノキシ基を表し、
Ｗ^22aがＣ_1-2アルコキシ基を表す。｝
で表されるいずれかの基である化合物、
[態様１２８] [態様１２７]において、Ｇ²¹が水素である化合物、 [Aspect 121] In [Aspect 111], a compound wherein R ²² is a C _1-3 alkylsulfonyl group,
[Aspect 122] In [Aspect 121], a compound wherein R ²² is a methylsulfonyl group,
[Aspect 123] In [Aspect 121], a compound wherein R ²² is an ethylsulfonyl group,
[Aspect 124] In [Aspect 111], a compound wherein R ^{22 is a} di (C _1-3 alkyl) amino group,
[Aspect 125] In [Aspect 124], a compound wherein R ²² is a dimethylamino group,
Aspect 126] Formula (I-II) or aspect 105] In ~ [Embodiment 125], G ²¹ is hydrogen or the following formula

{Wherein R ^3a represents a C _1-6 alkyl group, a C _6-10 aryl group, a C _1-6 alkoxy group, a C _3-6 alkenyloxy group, a C _3-6 alkynyloxy group or a C _6-10 aryloxy group. Represents a group,
W ²¹ represents a C _1-3 alkoxy group. }
A compound representing any group represented by:
Aspect 127] In Aspect 126], G ²¹ is hydrogen or the following formula

{Wherein R ^32a represents a C _1-3 alkyl group, a phenyl group, a C _1-3 alkoxy group, an allyloxy group, a propargyloxy group, or a phenoxy group;
W ^22a represents a C _1-2 alkoxy group. }
A compound which is any group represented by:
[Aspect 128] In [Aspect 127], a compound wherein G ²¹ is hydrogen,

[Aspect 129] In [Aspect 127], a compound wherein G ²¹ is a (C _1-3 alkyl) carbonyl group,
[Aspect 130] In [Aspect 129], a compound wherein G ²¹ is an acetyl group,
[Aspect 131] In [Aspect 129], G ²¹ is a propionyl group,
[Aspect 132] In [Aspect 127], a compound wherein G ²¹ is a benzoyl group,
[Aspect 133] In [Aspect 127], a compound wherein G ²¹ is a C _1-3 alkoxycarbonyl group,
[Aspect 134] In [Aspect 133], a compound wherein G ²¹ is a methoxycarbonyl group,
[Aspect 135] In [Aspect 133], a compound wherein G ²¹ is an ethoxycarbonyl group,
[Aspect 136] In [Aspect 127], a compound wherein G ²¹ is an allyloxycarbonyl group,

[Aspect 137] In [Aspect 127], a compound wherein G ²¹ is a propargyloxycarbonyl group,
[Aspect 138] In [Aspect 127], a compound wherein G ²¹ is a phenoxycarbonyl group,
[Aspect 139] In [Aspect 127], a compound wherein G ²¹ is a C _1-2 alkoxymethyl group,
[Aspect 140] In [Aspect 139], a compound wherein G ²¹ is a methoxymethyl group,
[Aspect 141] In [Aspect 139], a compound wherein G ²¹ is an ethoxymethyl group,
In Aspect 142] Formula (I-II) or aspect 105] ~ [Embodiment 141], Z ²¹ is a halogen, cyano group, nitro group, C _1-3 alkyl, C _2-3 alkenyl group, C _{2- 3} alkynyl group, C _1-3 alkoxy group, C _1-3 alkylthio group or cyclopropyl group, wherein C _1-3 alkyl group represented by Z ²¹ , C _2-3 alkenyl group, C _2-3 The alkynyl group, C _1-3 alkoxy group and C _1-3 alkylthio group may have a halogen, and the cyclopropyl group may have at least one selected from the group consisting of a halogen and a methyl group, r represents an integer of 1 to 3, and when r is 2 or more, each Z ²¹ may be the same or different
[Aspect 143] In [Aspect 142], Z ²¹ is halogen, cyano group, nitro group, methyl group, ethyl group, vinyl group, allyl group, ethynyl group, propargyl group, methoxy group, ethoxy group, methylthio group, ethylthio group Or a methyl group, an ethyl group, a vinyl group, an allyl group, an ethynyl group, a propargyl group, a methoxy group, an ethoxy group, a methylthio group, or an ethylthio group represented by Z ²¹ has a halogen. The cyclopropyl group may have at least one selected from the group consisting of a halogen and a methyl group, r represents an integer of 1 to 3, and when r is 2 or more, each Z ²¹ Are the same or different compounds,
In Aspect 144] [Embodiment 143], halogen Z ^21, a cyano group, a nitro group, a methyl group, a trifluoromethyl group, an ethyl group, a 2,2,2-trifluoroethyl group, a vinyl group, an allyl group, ethynyl A group, a propargyl group, a methoxy group, a trifluoromethoxy group, an ethoxy group, a methylthio group, a trifluoromethylthio group, an ethylthio group or a cyclopropyl group, r represents an integer of 1 to 3, and r is 2 or more Each Z ²¹ may be the same or different,

[Aspect 145] In [Aspect 144], Z ²¹ is fluorine, chlorine, bromine, cyano group, methyl group, trifluoromethyl group, ethyl group, vinyl group, allyl group, ethynyl group, methoxy group, ethoxy group, or methylthio group And r represents an integer of 1 to 3, and when r is 2 or more, each Z ²¹ may be the same or different,
[Aspect 146] In [Aspect 142], when Z ²¹ is a C _1-3 alkyl group, r represents an integer of 1 to 3, and r is 2 or more, each Z ²¹ is the same or different. A good compound,
[Aspect 147] In [Aspect 146], when Z ²¹ is a methyl group or an ethyl group, r represents an integer of 1 to 3, and r is 2 or more, each Z ²¹ may be the same or different. Good compound,
[Aspect 148] In [Aspect 147], (Z ²¹ ) _r is a 2,4,6-trimethyl group,
[Aspect 149] In [Aspect 147], (Z ²¹ ) _r is a 2,4-dimethyl-6-ethyl group,
[Aspect 150] In [Aspect 147], (Z ²¹ ) _r is a 2,6-diethyl-4-methyl group,
[Aspect 151] The compound according to [Aspect 147], wherein (Z ²¹ ) _r is a 2,4,6-triethyl group.

Examples of the herbicidal composition of the present invention include the following compositions.
[Aspect 152] In the formula (I), R ¹ is a methyl group, R ² is a methoxy group or an ethoxy group, G is hydrogen, n is 3, and Z is a methyl group or an ethyl group. A herbicidal composition comprising a compound and diflufenican.
[Aspect 153] In Formula (I), R ¹ is a methyl group, R ² is a methoxy group or an ethoxy group, G is hydrogen, n is 3, and Z is a methyl group or an ethyl group A herbicidal composition comprising a compound, diflufenican, and cloquintoset mexil.
[Aspect 154] In the formula (I), a compound in which R ¹ is a methyl group, R ² is a methoxy group, G is hydrogen, and (Z) _n is a 2,6-diethyl-4-methyl group And a herbicidal composition containing diflufenican.
[Aspect 155] In the formula (I), R ¹ is a methyl group, R ² is a methoxy group, G is hydrogen, and (Z) _n is a 2,6-diethyl-4-methyl group And a herbicidal composition containing diflufenican and cloquintoset mexil.
[Aspect 156] Compound represented by formula (I), wherein R ¹ is a methyl group, R ² is an ethoxy group, G is hydrogen, and (Z) _n is a 2-ethyl-4,6-dimethyl group. And a herbicidal composition containing diflufenican.
[Aspect 157] Compound represented by formula (I), wherein R ¹ is a methyl group, R ² is an ethoxy group, G is hydrogen, and (Z) _n is a 2-ethyl-4,6-dimethyl group. And a herbicidal composition containing diflufenican and cloquintoset mexil.

  The present compound A which is an active ingredient of the herbicidal composition of the present invention is known as a phytoene desaturase inhibitor (PDS inhibitor), and is a compound that inhibits phytoene desaturase involved in carotenoid biosynthesis. That is.

The present compound A, which is an active ingredient of the herbicidal composition of the present invention, is classified into a pyridinecarboxamide herbicide and a pyridazinone herbicide, respectively. These compounds were identified in the Pesticide Manual, Fifteenth Edition (2009), British Crop Production Council (ISBN: 978-1-901396-18-8), or identified by a CAS number. A compound.

化合物Ａは公知の化合物であり，例えば、ペスティサイドマニュアル（Ｔｈｅ Ｐｅｓｔｉｃｉｄｅ Ｍａｎｕａｌ）Ｆｉｆｔｅｅｎｔｈ Ｅｄｉｔｉｏｎ（２００９）、Ｂｒｉｔｉｓｈ Ｃｒｏｐ Ｐｒｏｄｕｃｔｉｏｎ Ｃｏｕｎｃｉｌ（ＩＳＢＮ：９７８−１−９０１３９６−１８−８）に記載された文献等により製造することができる。

Compound A is a known compound, for example, according to the literature described in The Pesticide Manual, Fifteenth Edition (2009), British Crop Production Council (ISBN: 978-1901396-18-8), etc. Can be manufactured.

The present compound B, which is an active ingredient of the herbicidal composition of the present invention, is known as a drug relieving agent, and the Pesticide Manual, Fifteenth Edition (2009), British Crop Production Council (ISBN: 978-1). -901396-18-8) or a compound specified by a CAS number.

Cyprosulfamide is a known compound and can be produced, for example, by the method described in US Pat. No. 6,251,827.
Benoxacol, croquintoset mexil, ciomethrinyl, dichlormid, fenchlorazole ethyl, fenchlorim, flurazole, flirazole, mefenpyrdiethyl, oxabetrinyl, isoxadifenethyl, floxophenim, 1,8-naphthalic anhydride, and AD -67 is a known compound and is commercially available. Moreover, it can manufacture by the literature etc. which were described in the pestiside manual (The Pesticide Manual) Fifteenth Edition (2009), British Crop Production Council (ISBN: 978-1-901396-18-8).

  The herbicidal composition of the present invention has herbicidal activity against a wide range of weeds, and is effectively effective in a wide range of crop fields, vegetable fields, orchards, or non-agricultural lands where normal plowing and non-plowing cultivation is performed. Can control weeds.

Examples of the control target of the herbicidal composition of the present invention include the following.
Crabgrass (Digitaria ciliaris), goosegrass (Eleusine indica), green foxtail (Setaria viridis), giant foxtail (Setaria faberi), Kin green foxtail (Setaria glauca), barnyardgrass (Echinochloa crus-galli), creeping bentgrass (Agrostis alba), fall panicum (Panicum dichotomiflorum) , Texas panicum, Panchumia pterphylla, Alexander glass, Brachiaria decumbens, Sorban sorghum um halepense), shutter Kane (Andropogon sorghum), bermudagrass (Cynodon dactylon), oats (Avena fatua), darnel (Lolium multiflorum), black grass (Alopecurus myosuroides), downy brome (Bromus tectorum), Arechinochahiki (Bromus sterilis), Himekanari Phallis minor, Apera spica-venti, Sparrow annua, Agropyron repens, Cyperus iria, Cyprus, Cyprus, Cysus Cyperus esculentus, Portulaca oleraceu, Amaranthus retroflex, Amaranthus hydrus, Amaranthus hydranthus, Amaranthus hydrus American deer (Sida spinosa), buckwheat (Fallopia convolvulus), Sanaeta (Polygonum scabulum), American Saneda (Persicaria pennsylvanica), Harutade (Persicaria vulgaris) Rumex crispus), broadleaf dock (Rumex obtusifolius), Japanese knotweed (Fallopia japonica), common lambsquarters (Chenopodium album), kochia (Kochia scoparia), knotweed (Polygonum longisetum), black nightshade (Solanum nigrum), white Bana Datura (Datura stramonium), Ipomoea purpurea (Ipomoea purpurea), American morning glory (Ipomoea hederacea), Malba American morning glory (Ipomoea hederacea var. integriuscula), beans morning glory (Ipomoea lacunosa), field bindweed (Convolvulus arvensis), Lamium purpureum (Lamium purpureum), henbit (Lamium amplexicaule), cocklebur (Xanthium pensylvanicum), wild sunflower (Helianthus annuus), Inukamitsure (Matricaria perforata or inodora), Chamomile (Matricaria chamomilla), corn marigold (Chrysanthemum segetum), orrasia (Matricaria matricariaides), ragweed (Ambrosia artemisiifo) ia), Ambrosia trifida (Ambrosia trifida), Erigeron canadensis (Erigeron canadensis), mugwort (Artemisia princeps), goldenrod (Solidago altissima), Erigeron bonariensis (Conyza bonariensis), the United States horn Aeschynomene indica (Sesbania exaltata), sicklepod (Cassia obtusifolia), Florida Bega Weed (Desmodium tortusum), White clover (Trifolium repens), Kudzu (Pueraria lobata), Caladium pea (Vicia angustifolia), Clover (Commelina communis) lina benghalensis), cleavers (Galium aparine), chickweed (Stellaria media), wild radish (Raphanus raphanistrum), Noharagarashi (Sinapis arvensis), shepherd's purse (Capsella bursa-pastoris), persian speedwell (Veronica persica), Veronica Hederifolia (Veronica hederifolia), field Pansy (Viola arvensis), Wild pansy (Viola tricolor), Papaver rhoeas, Forget-me-nots (Myosotis scorpioides), Otoweed (Asclepias syriaca) phorbia helioscopia), Euphorbia nutans (Chamaesyce nutans), the United States Fuuro (Geranium carolinianum), Netherlands Fuuro (Erodium cicutarium), horsetail (Equisetum arvense), Ashikaki (Leersia japonica), barnyardgrass (Echinochloa oryzicola), barnyardgrass (Echinochloa crus-galli var. formosensis), leptochloa chinensis (Leptochloa chinensis), smallflower umbrellaplant (Cyperus difformis), fimbristylis miliacea (Fimbristylis miliacea), Eleocharis acicularis (Eleocharis acicularis), Scirpus (Scirpus juncoides), Taiwan Yamai (Scirpus wallichii), Cyperus (Cyperus serotinus), water chestnut (Eleocharis kuroguwai ), Bobchochoenus koshevnikikovii, Shizunofectus nipponicus, Konogi (Mononochoria vaginalis), Azena (Lindernia procucu) bens), Abunome (Dopatrium junceum), Rotala indica (Rotala indica), Ammannia multiflora Roxb (Ammannia multiflora), Elatine triandra Schk (Elatine triandra), Choujitade (Ludwigia epilobioides), arrowhead (Sagittaria pygmaea), alisma canaliculatum (Alisma canaliculatum), Alismataceae (Sagittaria trifolia) , Potamogeton distinctus, Seri (Oenanthe javanica), Mizuhakobe (Callirichiche palustris), Azeto pepper (Lindernia mitrantha), American azena (Linder) ubia), Eclipta prostrata (Eclipta prostrata), Ibokusa (Murdannia keisak), Paspalum distichum (Paspalum distichum), Ezonosayanukagusa (Leersia oryzoides) weeds such as. Naganetera phyloxeroides, Frogsbit (Limnobium spongia), Waterfern (Salvinia spp.), Duckweed (Pistia stratiotes), Water pennywort (genus Hydrocotyle spp.) demersum), duckweed (genus Lemna), cabbage caroliniana, blackberry (Hydrilla verticillata), Southern naad (Najas guadalupensis), pondweet (Potamogeton) n illinoensis, etc. Potamogeton Pectinatus) Water meal (Wolffia genus), water mills foil such (Myriophyllum spicatum, Myriophyllum heterophyllum etc.), water hyacinth (Eichhornia crassipes) or the like aquatic plants. Mosses, moss, hornworts. Cyanobacteria. Ferns. Suckers of perennial crops (fruits, stones, berries, nuts, citrus, hops, grapes, etc.).

The herbicidal composition of the present invention is used as a herbicide in agricultural land such as fields, paddy fields, lawns, orchards, or non-agricultural land. The herbicidal composition of the present invention can control weeds in the cultivated land in the cultivated land and the like where the “plants” listed below are cultivated.
"plant";
Agricultural crops: corn, rice, wheat, barley, rye, sorghum, cotton, soybean, peanut, buckwheat, sugar beet, rapeseed, sunflower, sugarcane, tobacco, hop, etc.
Vegetables: Solanum vegetables (eggplants, tomatoes, peppers, peppers, potatoes, etc.), cucurbits (cucumbers, pumpkins, zucchini, watermelons, melons, cucumbers, etc.), cruciferous vegetables (radish, turnip, horseradish, kohlrabi, Chinese cabbage) , Cabbage, mustard, broccoli, cauliflower, etc.), asteraceae vegetables (burdock, garlic, artichoke, lettuce, etc.), liliaceae vegetables (leek, onion, garlic, asparagus, etc.), celery family vegetables (carrot, parsley, celery, American Bow Fu etc.), Rubiaceae vegetables (spinach, chard, etc.), Lamiaceae vegetables (silla, mint, basil etc.), legumes (peas, kidney beans, azuki bean, broad beans, chickpea etc.), strawberries, sweet potatoes, yam, taro , Konjac, ginger, ok Etc..
Fruit trees: fruits (apples, pears, pears, quince, quince, etc.), nuclear fruits (peaches, plums, nectarines, umes, sweet cherry, apricots, prunes, etc.), citrus (citrus mandarin orange, lemon, lime, grapefruit) ), Nuts (chestnut, walnut, hazel, almond, pistachio, cashew nut, macadamia nut, etc.), berries (blueberry, cranberry, blackberry, raspberry, etc.), grape, oyster, olive, loquat, banana, coffee, Date palm, coconut palm, oil palm etc.
Trees other than fruit trees: tea, mulberry, flowering trees (Satsuki, camellia, hydrangea, sasanqua, shikimi, sakura, yurinoki, crape myrtle, snapdragon, etc.), roadside trees (ash, birch, dogwood, eucalyptus, ginkgo, lilac, maple, oak) , Poplar, redwood, fu, sycamore, zelkova, blackfish, Japanese amberjack, moths, pine, pine, spruce, yew, elm, Japanese cypress, etc.), coral jug, dogwood, cedar, cypress, croton, masaki, kanamochi, etc.
Other: Flowers (Rose, Carnation, Chrysanthemum, Eustoma, Gypsophila, Gerbera, Marigold, Salvia, Petunia, Verbena, Tulip, Aster, Gentian, Lily, Pansy, Cyclamen, Orchid, Lily of the valley, Lavender, Stock, Habutton, Primula, Poinsettia, gladiolus, cattleya, daisy, symbidium, begonia, etc.), biofuel plants (Jatropha, safflower, Amanas, switchgrass, miscanthus, danchiku, kenaf, cassava, willow, etc.), houseplants, etc.

  The “plant” includes genetically modified crops.

  The herbicidal composition of the present invention contains the present compound and the present compound A. Further, it optionally contains one compound selected from Group B. The herbicidal composition of the present invention is usually further supplemented with formulation carriers such as an inert carrier and a surfactant, a sticking agent, a dispersing agent, a stabilizer, and the like. Formulated into dry flowables, emulsions, aqueous solutions, oils, aerosols, microcapsules and the like. In this herbicidal composition, the total weight of the present compound and the present compound A, and optionally one compound selected from the group B, is usually 0.1 to 80%.

Inert carriers include solid carriers and liquid carriers.
Examples of the solid carrier include clays (for example, kaolin, diatomaceous earth, synthetic hydrous silicon oxide, fusami clay, bentonite, acidic clay), talc, and other inorganic minerals (for example, sericite, quartz powder, sulfur powder, activated carbon, Examples of the liquid carrier include water, alcohols (for example, methanol, ethanol), ketones (for example, acetone, methyl ethyl ketone), aromatic carbonization, and the like. Hydrogens (eg, benzene, toluene, xylene, ethylbenzene, methylnaphthalene), aliphatic hydrocarbons (eg, n-hexane, cyclohexane, kerosene), esters (eg, ethyl acetate, butyl acetate), nitriles (eg, , Acetonitrile, isobutylnitrile), ethers (eg Dioxane, diisopropyl ether), acid amides (e.g., N, N- dimethylformamide, dimethylacetamide), halogenated hydrocarbons (e.g., dichloroethane, trichlorethylene, and carbon tetrachloride), and the like.

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

  Other formulation adjuvants include, for example, fixing agents and dispersants, specifically casein, gelatin, polysaccharides (eg starch, arabic gum, cellulose derivatives, alginic acid), lignin derivatives, bentonite, saccharides, synthetic water-soluble high Molecules (for example, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids), PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (2-tert-butyl-4) -Mixtures of methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, fatty acids or esters thereof.

When a solution obtained by diluting the preparation of the herbicidal composition of the present invention with water or the like is sprayed, an adjuvant may be added to the sprayed solution. Examples of auxiliary agents that can be added include surfactants (nonionic surfactants such as fatty acid alkyl esters and alkylpolyoxyethylene ethers, ionic surfactants such as alkylbenzene sulfonates and dialkyldimethylammonium salts), crop, and the like. oil, vegetative oil, crop oil concentrate, methylated seed oil, organosilicon spreader, liquid fertilizer (ammonium sulfate, urea ammonia nitrate, etc.), and the like. These adjuvants may be used alone or in combination of two or more.

The method for controlling weeds with the herbicidal composition of the present invention comprises applying an effective amount of the present compound and an effective amount of the present compound A, and optionally an effective amount of at least one compound selected from the group B to the soil where weeds or weeds grow. It is a method to do. Examples of the method of applying the herbicidal composition of the present invention include a method of treating the weeding composition of the present invention with foliage on weeds, a method of treating the herbicidal composition on the soil surface where weeds grow, and the present herbicidal process And a method of admixing the composition for use in soil where weeds grow. In the weed control method of the present invention, the total amount of the present compound per 10,000 m ^{2 of} area to control weeds and the present compound A, and optionally one compound selected from the group B, is usually 1 to 5000 g, preferably 1 to 3000 g.

When the present compound A is diflufenican in the herbicidal composition of the present invention, the mixing ratio of the present compound and diflufenican is 1: 0.001 to 1: 100, preferably 1: 0.004 to 1:50 by weight. Range.
When the present compound A is picolinafene in the herbicidal composition of the present invention, the mixing ratio of the present compound and picolinafene is 1: 0.01 to 1:50, preferably 1: 0.1 to 1:10 by weight. Range.
When the present compound A is norflurazon in the herbicidal composition of the present invention, the mixing ratio of the present compound and norflurazon is in the range of 1: 0.1 to 1: 500, preferably 1: 1 to 1: 200 in terms of weight ratio. It is.
When the present compound A is fluridone in the herbicidal composition of the present invention, the mixing ratio of the present compound and fluridone is from 1: 0.01 to 1: 100, preferably from 1: 0.5 to 1:50 by weight. Range.
When the present compound A is flurochloridone in the herbicidal composition of the present invention, the mixing ratio of the present compound and flurochloridone is from 1: 0.01 to 1: 100, preferably 1: 0.5 by weight. It is in the range of ˜1: 70.
When the present compound A is flurtamone in the herbicidal composition of the present invention, the mixing ratio of the present compound and flurtamone is 1: 0.01 to 1: 100, preferably 1: 0.5 to 1:40, by weight. Range.
When the present compound A is beflubutamide in the herbicidal composition of the present invention, the mixing ratio of the present compound and beflubutamide is 1: 0.01 to 1: 100, preferably 1: 0.3 to 1:30, by weight. Range.
When the present compound B is benoxacol in the herbicidal composition of the present invention, the mixing ratio of the present compound and benoxacol is 1: 0.01 to 1:10, preferably 1: 0.03 to 1: 5 by weight. Range.
In the herbicidal composition of the present invention, when the present compound B is cloquintoset mexil, the mixing ratio of the present compound and croquintoset mexil is 1: 0.01 to 1:10, preferably 1 in weight ratio. : The range of 0.03 to 1: 5.
In the herbicidal composition of the present invention, when the present compound B is ciomethrinyl, the mixing ratio of the present compound and ciomethrinyl is 1: 0.01 to 1:10, preferably 1: 0.03 to 1: 5 by weight. Range.
When the present compound B is dichlormid in the herbicidal composition of the present invention, the mixing ratio of the present compound and dichlormid is 1: 0.01 to 1:10, preferably 1: 0.03 to 1: 5 in weight ratio. Range.
When the present compound B is fenchlorazole ethyl in the herbicidal composition of the present invention, the mixing ratio of the present compound and fenchlorazole ethyl is 1: 0.01 to 1:10, preferably 1: 0 in weight ratio. 0.03 to 1: 5.
When the present compound B is fencrolim in the herbicidal composition of the present invention, the mixing ratio of the present compound and fencrolim is 1: 0.01 to 1:10, preferably 1: 0.03 to 1: 5, by weight. Range.
When the present compound B is flurazole in the herbicidal composition of the present invention, the mixing ratio of the present compound and flurazole is in a weight ratio of 1: 0.01 to 1:10, preferably 1: 0.03 to 1: 5. Range.
When the present compound B is flirazole in the herbicidal composition of the present invention, the mixing ratio of the present compound and flirazole is 1: 0.01 to 1:10, preferably 1: 0.03 to 1: 5, by weight. Range.
When the present compound B is mefenpyrdiethyl in the herbicidal composition of the present invention, the mixing ratio of the present compound and mefenpyrdiethyl is 1: 0.01 to 1:10, preferably 1: 0 by weight. 0.03 to 1: 5.
In the herbicidal composition of the present invention, when the present compound B is oxabetrinyl, the mixing ratio of the present compound and oxavetrinyl is 1: 0.01 to 1:10, preferably 1: 0.03 to 1: 5 by weight. Range.
When the present compound B is isoxadifen in the herbicidal composition of the present invention, the mixing ratio of the present compound and isoxadifen is 1: 0.01 to 1:10, preferably 1: 0. It is in the range of ˜1: 5.
When the present compound B is cyprosulfamide in the herbicidal composition of the present invention, the mixing ratio of the present compound and cyprosulfamide is 1: 0.01 to 1:10, preferably 1: 0, in weight ratio. 0.03 to 1: 5.
In the herbicidal composition of the present invention, when the present compound B is flxophenim, the mixing ratio of the present compound and flxophenim is 1: 0.01 to 1:10, preferably 1: 0.03 to 1: 5 in weight ratio. Range.
When the present compound B is 1,8-naphthalic anhydride in the herbicidal composition of the present invention, the mixing ratio of the present compound and 1,8-naphthalic anhydride is 1: 0.01 to 1 by weight. : 10, preferably in the range of 1: 0.03 to 1: 5.
When the present compound B is AD-67 in the herbicidal composition of the present invention, the mixing ratio of the present compound and AD-67 is 1: 0.01 to 1:10, preferably 1: 0.03, by weight. It is in the range of ˜1: 5.

  The herbicidal composition of the present invention can also be prepared by formulating each active ingredient and then mixing them.

  The herbicidal composition of the present invention can be mixed or used in combination with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners and the like.

Below, the manufacture example of the pyridazinone compound shown by Formula (I) is shown. In Production Examples and Reference Examples, room temperature usually indicates 10 to 30 ° C. ¹ H NMR represents a proton nuclear magnetic resonance spectrum, tetramethylsilane was used as an internal standard, and chemical shift (δ) was expressed in ppm.
The symbols used in the production examples and reference examples have the following meanings.
CDCl ₃ : deuterated chloroform, s: singlet, d: doublet, t: triplet, q: quartet, brs: wide singlet, m: multiplet, J: coupling constant, Me: methyl group, Et: ethyl group, Pr: Propyl group, i-Pr: i-propyl group, c-Pr: cyclopropyl group, t-Bu: t-butyl group, Ph: phenyl group, OMe: methoxy group, OEt: ethoxy group, OPr: propoxy group, OBu : Butoxy group, Ac: acetyl group, Bn: benzyl group, Boc: t-butoxycarbonyl group, TMS: trimethylsilyl group, PMB: p-methoxybenzyl group, MOM: methoxymethyl group.

４−（２，６−ジエチル−４−メチルフェニル）−６−ジメチルアミノ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−１−２））の合成
ｔ−ブトキシカリウム３８０ｍｇ（３．３８ｍｍｏｌ）を無水テトラヒドロフラン１０ｍｌに溶解した溶液に、２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−メチルヒドラゾノ］−２−ジメチルアミノ酢酸エチル（化合物（ＩＩ−２））２８０ｍｇ（０．８４０ｍｍｏｌ）を無水テトラヒドロフラン３ｍｌに溶解した溶液をゆっくり滴下した。この混合物を室温で１５分撹拌した。この反応液に水を加え、酢酸エチルで２回抽出した。合わせた有機層を、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧濃縮した。得られた固体をヘキサンで洗浄し、ろ過し、固体を乾燥して化合物（Ｉ−１−２）２３０ｍｇを得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０８（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２５〜２．４５（４Ｈ，ｍ），２．３６（３Ｈ，ｓ），２．８４（６Ｈ，ｓ），３．７１（３Ｈ，ｓ），７．０２（２Ｈ，ｓ）。 Production Example 1

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-dimethylamino-5-hydroxy-2-methyl-3 (2H) -pyridazinone (compound (I-1-2)) t-butoxypotassium To a solution of 380 mg (3.38 mmol) dissolved in 10 ml of anhydrous tetrahydrofuran, ethyl 2- [2- (2,6-diethyl-4-methylphenyl) acetyl-2-methylhydrazono] -2-dimethylaminoacetate (compound) (II-2)) A solution prepared by dissolving 280 mg (0.840 mmol) in 3 ml of anhydrous tetrahydrofuran was slowly added dropwise. The mixture was stirred at room temperature for 15 minutes. Water was added to the reaction solution, and the mixture was extracted twice with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained solid was washed with hexane, filtered, and the solid was dried to obtain 230 mg of compound (I-1-2).
¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (6H, t, J = 7.6 Hz), 2.25 to 2.45 (4H, m), 2.36 (3H, s), 2.84 (6H, s), 3.71 (3H, s), 7.02 (2H, s).

This compound produced according to Production Example 1 is shown in Table 7 together with compound (I-1-2).

1) ¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (6H, t, J = 7.6 Hz), 2.25 to 2.43 (4H, m), 2.36 (3H, s), 2 .51 (3H, s), 3.81 (3H, s), 5.75 (1H, brs), 7.03 (2H, s).
2) ¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (6H, t, J = 7.6 Hz), 1.27 (3H, t, J = 7.6 Hz), 2.27 to 2.45 ( 4H, m), 2.51 (3H, s), 2.66 (2H, q, J = 7.6 Hz), 3.81 (3H, s), 5.69 (1H, brs), 7.05 (2H, s).
3) ¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (3H, t, J = 7.5 Hz), 2.06 (3H, s), 2.27-2.43 (2H, m), 2 .34 (3H, s), 2.51 (3H, s), 3.80 (3H, s), 5.42 (1H, brs), 7.00 (1H, s), 7.02 (1H, s).

４−（２，６−ジエチル−４−メチルフェニル）−５−ヒドロキシ−２−メチル−６−メチルスルフィニル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−２−１））の合成
化合物（Ｉ−１−５）０．１５ｇ（０．４６８ｍｍｏｌ）をクロロホルム５ｍｌに溶解した溶液に、氷冷下ｍ−クロロ過安息香酸０．０８１ｇ（０．４６８ｍｍｏｌ）を加えた。アイスバスをはずし、室温で５．５時間攪拌した。反応混合物に酢酸エチルを加え、亜硫酸水素ナトリウム水溶液、飽和食塩水で順次洗浄し、無水硫酸マグネシウムで乾燥し、減圧濃縮した。残さをシリカゲルカラムクロマトグラフィー（酢酸エチル）で精製し、化合物（Ｉ−２−１）０．１０ｇを固体として得た（収率６３％）。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０７〜１．１６（６Ｈ，ｍ），２．３０〜２．４５（４Ｈ，ｍ），２．３５（３Ｈ，ｓ），３．１１（３Ｈ，ｓ），３．８０（３Ｈ，ｓ），７．００（２Ｈ，ｓ）。 Production Example 2

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -5-hydroxy-2-methyl-6-methylsulfinyl-3 (2H) -pyridazinone (Compound (I-2-1)) Compound (I- 1-5) 0.081 g (0.468 mmol) of m-chloroperbenzoic acid was added to a solution of 0.15 g (0.468 mmol) dissolved in 5 ml of chloroform under ice cooling. The ice bath was removed and the mixture was stirred at room temperature for 5.5 hours. Ethyl acetate was added to the reaction mixture, washed successively with aqueous sodium hydrogen sulfite solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate) to obtain 0.10 g of compound (I-2-1) as a solid (yield 63%).
¹ H NMR (CDCl ₃ ) δ ppm: 1.07-1.16 (6H, m), 2.30-2.45 (4H, m), 2.35 (3H, s), 3.11 (3H , S), 3.80 (3H, s), 7.00 (2H, s).

This compound produced according to Production Example 2 is shown in Table 8 together with compound (I-2-1).

1) ¹ H NMR: described in the above production example.
2) ¹ H NMR (CDCl ₃ ) δ ppm: 1.08 to 1.15 (6H, m), 1.26 (3H, t, J = 7.6 Hz), 2.32 to 2.46 (4H, m), 2.65 (2H, q, J = 7.6 Hz), 3.11 (3H, s), 3.81 (3H, s), 7.01 (2H, s).
3) ¹ H NMR (CDCl ₃ ) δ ppm: 1.07-1.16 (3H, m), 2.09 (1.5 H, s), 2.10 (1.5 H, s), 2.29 -2.47 (2H, m), 2.32 (3H, s), 3.11 (3H, s), 3.80 (3H, s), 6.96 (1H, s). 6.98 (1H, s), 10.37 (1H, brs).

４−（２，６−ジエチル−４−メチルフェニル）−５−ヒドロキシ−２−メチル−６−メチルスルホニル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−３−１））の合成
化合物（Ｉ−１−５）９．６４ｇ（３０．３ｍｍｏｌ）をクロロホルム３００ｍｌに溶解した溶液に、氷冷下ｍ−クロロ過安息香酸２１．２８ｇ（１２３ｍｍｏｌ）をゆっくり添加した。アイスバスをはずし、室温で４時間攪拌した。反応混合物に酢酸エチルを加え、亜硫酸水素ナトリウム水溶液、飽和食塩水で順次洗浄し、無水硫酸マグネシウムで乾燥し、減圧濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１：１→酢酸エチル）で精製し、化合物（Ｉ−３−１）５．７２ｇを固体として得た（収率５４％）。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１０（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２６〜２．４１（４Ｈ，ｍ），２．３６（３Ｈ，ｓ），３．８６（３Ｈ，ｓ），３．９０（３Ｈ，ｓ），７．０２（２Ｈ，ｓ）。 Production Example 3

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -5-hydroxy-2-methyl-6-methylsulfonyl-3 (2H) -pyridazinone (compound (I-3-1)) Compound (I- 1-5) 21.28 g (123 mmol) of m-chloroperbenzoic acid was slowly added to a solution of 9.64 g (30.3 mmol) dissolved in 300 ml of chloroform under ice cooling. The ice bath was removed and the mixture was stirred at room temperature for 4 hours. Ethyl acetate was added to the reaction mixture, washed successively with aqueous sodium hydrogen sulfite solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1 → ethyl acetate) to obtain 5.72 g of compound (I-3-1) as a solid (yield 54%).
¹ H NMR (CDCl ₃ ) δ ppm: 1.10 (6H, t, J = 7.6 Hz), 2.26 to 2.41 (4H, m), 2.36 (3H, s), 3.86 (3H, s), 3.90 (3H, s), 7.02 (2H, s).

This compound produced according to Production Example 3 is shown in Table 9 together with compound (I-3-1).

1) ¹ H NMR: described in the above production example.
2) ¹ H NMR (CDCl ₃ ) δ ppm: 1.10 (6H, t, J = 7.7 Hz), 1.27 (3H, t, J = 7.6 Hz), 2.24 to 2.43 ( 4H, m), 2.66 (2H, q, J = 7.7 Hz), 3.36 (3H, s), 3.90 (3H, s), 7.03 (2H, s).
3) ¹ H NMR (CDCl ₃ ) δ ppm: 1.10 (3H, t, J = 7.6 Hz), 2.07 (3H, s), 2.26-2.43 (2H, m), 2 .33 (3H, s), 3.36 (3H, s), 3.90 (3H, s), 6.98 (1H, s), 7.00 (1H, s), 8.37 (1H, brs).
4) ¹ H NMR (CDCl ₃ ) δ ppm: 1.14 (6H, t, J = 7.6 Hz), 2.30-2.48 (7H, m), 3.20 (3H, s), 3 .88 (3H, s), 4.58 (2H, s), 7.03 (2H, s), 7.05-7.09 (2H, m), 7.25-7.30 (3H, m ).

４−（２，６−ジエチル−４−メチルフェニル）−５−ヒドロキシ−６−メトキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−４−１））の合成
化合物（Ｉ−３−１）５．３４ｇ（１５．２ｍｍｏｌ）を無水ＤＭＦ１３０ｍｌに溶解した溶液にナトリウムメトキシド９．７１ｇ（１８０ｍｍｏｌ）を加え、１０５℃で２０分間攪拌した。反応混合物を室温まで冷却した後、１Ｎ塩酸３００ｍｌを加え、酢酸エチルで２回抽出した。合わせた有機層を２回水洗し、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１：１→１：２→酢酸エチル）で精製し、化合物（Ｉ−４−１）４．３０ｇを得た（収率９３％）。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２７〜２．４６（４Ｈ，ｍ），２．３５（３Ｈ，ｓ），３．７０（３Ｈ，ｓ），３．９９（３Ｈ，ｓ），５．６２（１Ｈ，ｂｒｓ），７．００（２Ｈ，ｓ）。 Production Example 4

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -5-hydroxy-6-methoxy-2-methyl-3 (2H) -pyridazinone (Compound (I-4-1)) Compound (I-3) -1) To a solution of 5.34 g (15.2 mmol) dissolved in 130 ml of anhydrous DMF was added 9.71 g (180 mmol) of sodium methoxide, and the mixture was stirred at 105 ° C. for 20 minutes. The reaction mixture was cooled to room temperature, 300 ml of 1N hydrochloric acid was added, and the mixture was extracted twice with ethyl acetate. The combined organic layers were washed twice with water, washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1 → 1: 2 → ethyl acetate) to obtain 4.30 g of compound (I-4-1) (yield 93%).
¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.6 Hz), 2.27 to 2.46 (4H, m), 2.35 (3H, s), 3.70 (3H, s), 3.99 (3H, s), 5.62 (1H, brs), 7.00 (2H, s).

This compound produced according to Production Example 4 is shown in Table 10 together with compound (I-4-1).

1) ¹ H NMR: described in the above production example.
2) ¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.6 Hz), 1.26 (3H, t, J = 7.6 Hz), 2.28 to 2.47 ( 4H, m), 2.66 (2H, q, J = 7.6 Hz), 3.70 (3H, s), 3.99 (3H, s), 5.62 (1H, brs), 7.02 (2H, s).
3) ¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.6 Hz), 1.48 (3H, t, J = 7.1 Hz), 2.27 to 2.46 ( 4H, m), 2.35 (3H, s), 3.68 (3H, s), 4.36 (2H, q, J = 7.1 Hz), 5.67 (1H, brs), 7.00 (2H, s).
4) ¹ H NMR (CDCl ₃ ) δ ppm: 1.10 (6H, t, J = 7.5 Hz), 1.27 (3H, t, J = 7.6 Hz), 1.48 (3H, t, J = 7.0 Hz), 2.28 to 2.47 (4H, m), 2.66 (2H, q, J = 7.6 Hz), 3.68 (3H, s), 4.36 (2H, q, J = 7.0 Hz), 5.67 (1H, brs), 7.02 (2H, s).
5) ¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (3H, t, J = 7.5 Hz), 2.07 (3H, s), 2.29-2.47 (2H, m), 2 .33 (3H, s), 3.69 (3H, s), 3.99 (3H, s), 5.61 (1H, s), 6.97 (1H, s). 6.99 (1H, s).
6) ¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (3H, t, J = 7.7 Hz), 1.47 (3H, t, J = 7.1 Hz), 2.28-2.48 ( 2H, m), 2.07 (3H, s), 2.33 (3H, s), 3.68 (3H, s), 4.36 (2H, q, J = 7.1 Hz), 5.66. (1H, s), 6.96 (1H, s). 6.98 (1H, s).

４−（２，６−ジエチル−４−メチルフェニル）−５−エトキシカルボニルオキシ−６−メトキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−５−５））の合成
化合物（Ｉ−４−１）０．２０１ｇ（０．６６ｍｍｏｌ）およびトリエチルアミン０．１０６ｇ（１．０５ｍｍｏｌ）をＴＨＦ１．５ｍｌに溶解した溶液に、氷冷下クロロ炭酸エチル０．１４７ｇ（１．３５ｍｍｏｌ）をＴＨＦ１ｍｌに溶解した溶液を滴下した。アイスバスをはずし、室温で１６時間攪拌した。この反応混合物に水５ｍｌを加え、酢酸エチルで３回抽出した。合わせた有機層を、無水硫酸マグネシウムで乾燥し、減圧濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝３：２）で精製し、化合物（Ｉ−５−５）０．１９３ｇを固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１０（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．２４（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），２．２５〜２．４４（４Ｈ，ｍ），２．３４（３Ｈ，ｓ），３．７２（３Ｈ，ｓ），３．９２（３Ｈ，ｓ），４．１７（２Ｈ，ｑ，Ｊ＝７．１Ｈｚ），６．９６（２Ｈ，ｓ）。 Production Example 5

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -5-ethoxycarbonyloxy-6-methoxy-2-methyl-3 (2H) -pyridazinone (Compound (I-5-5)) Compound (I -4-1) In a solution of 0.201 g (0.66 mmol) and 0.106 g (1.05 mmol) of triethylamine in 1.5 ml of THF, 0.147 g (1.35 mmol) of ethyl chlorocarbonate in 1 ml of THF under ice cooling. The dissolved solution was added dropwise. The ice bath was removed and the mixture was stirred at room temperature for 16 hours. 5 ml of water was added to the reaction mixture, and the mixture was extracted 3 times with ethyl acetate. The combined organic layers were dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 2) to obtain 0.193 g of compound (I-5-5) as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.10 (6H, t, J = 7.6 Hz), 1.24 (3H, t, J = 7.1 Hz), 2.25 to 2.44 (4H, m), 2.34 (3H, s), 3.72 (3H, s), 3.92 (3H, s), 4.17 (2H, q, J = 7.1 Hz), 6.96 (2H) , S).

This compound produced according to Production Example 5 is shown in Table 11 together with compound (I-5-5).

1) ¹ H NMR (CDCl ₃ ) δ ppm: 1.10 (6H, t, J = 7.6 Hz), 2.03 (3H, s), 2.24 to 2.43 (4H, m), 2 .34 (3H, s), 3.72 (3H, s), 3.90 (3H, s), 6.95 (2H, s).
2) ¹ H NMR (CDCl ₃ ) δ ppm: 0.95 (3H, t, J = 7.6 Hz), 1.09 (6H, t, J = 7.6 Hz), 2.23 to 2.43 ( 6H, m), 2.33 (3H, s), 3.72 (3H, s), 3.89 (3H, s), 6.94 (2H, s).
3) ¹ H NMR (CDCl ₃ ) δ ppm: 0.90 (9H, s), 1.09 (6H, t, J = 7.6 Hz), 2.21 to 2.46 (4H, m), 2 .29 (3H, s), 3.69 (3H, s), 3.97 (3H, s), 6.92 (2H, s).
4) ¹ H NMR (CDCl ₃ ) δ ppm: 1.10 (6H, t, J = 7.6 Hz), 2.24 to 2.44 (4H, m), 2.34 (3H, s), 3 .73 (3H, s), 3.76 (3H, s), 3.92 (3H, s), 6.96 (2H, s).
5) ¹ H NMR: described in the above production example.
6) ¹ H NMR (CDCl ₃ ) δ ppm: 1.10 (6H, t, J = 7.6 Hz), 2.24 to 2.43 (4H, m), 2.34 (3H, s), 3 .73 (3H, s), 3.91 (3H, s), 4.57 to 4.60 (2H, m), 5.17 to 5.30 (2H, m), 5.75 to 5.87 (1H, m), 6.95 (2H, s).
7) ¹ H NMR (CDCl ₃ ) δ ppm: 1.11 (6H, t, J = 7.5 Hz), 2.28 to 2.46 (4H, m), 2.37 (3H, s), 3 .74 (3H, s), 3.97 (3H, s), 6.96 to 7.05 (2H, m), 7.00 (2H, s), 7.21 to 7.29 (1H, m ), 7.31-7.39 (2H, m).
8) ¹ H NMR (CDCl ₃ ) δ ppm: 1.15 (6H, t, J = 7.6 Hz), 2.34 (3H, s), 2.39 (4H, q, J = 7.6 Hz) , 2.54 (3H, s), 3.74 (3H, s), 3.98 (3H, s), 7.00 (2H, s).
9) ¹ H NMR (CDCl ₃ ) δ ppm: 2.12 (3H, s), 2.31 (3H, s), 3.74 (3H, s), 3.80 (3H, s), 3. 93 (3H, s), 7.01 (1H, s), 7.30 (1H, s).

４−（２，６−ジエチル−４−メチルフェニル）−６−メトキシ−５−メトキシメトキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−６−１））の合成
６０％水素化ナトリウム０．０７０ｇ（１．６０ｍｍｏｌ）および無水ＤＭＦ０．５ｍｌの混合物に、氷冷下化合物（Ｉ−４−１）０．２０１ｇ（０．６６ｍｍｏｌ）をＤＭＦ２ｍｌに溶解した溶液を滴下した。この混合物を氷冷下６分間攪拌した後、そこにクロロメチル メチル エーテル０．１２２ｇ（１．５２ｍｍｏｌ）をＤＭＦ０．５ｍｌに溶解した溶液を滴下した。この反応液を室温で２時間攪拌した。反応混合物に水を加え、酢酸エチルで３回抽出した。合わせた有機層を、水、飽和食塩水で順次洗浄し、無水硫酸マグネシウムで乾燥し、減圧濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２：１）で精製し、化合物（Ｉ−６−１）０．１６８ｇを固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１３（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２８〜２．５０（４Ｈ，ｍ），２．３４（３Ｈ，ｓ），３．０３（３Ｈ，ｓ），３．６９（３Ｈ，ｓ），３．９２（３Ｈ，ｓ），４．８４（２Ｈ，ｓ），６．９５（２Ｈ，ｓ）。 Production Example 6

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-methoxy-5-methoxymethoxy-2-methyl-3 (2H) -pyridazinone (compound (I-6-1)) 60% hydrogenation To a mixture of 0.070 g (1.60 mmol) of sodium and 0.5 ml of anhydrous DMF, a solution of 0.201 g (0.66 mmol) of compound (I-4-1) dissolved in 2 ml of DMF was added dropwise under ice cooling. The mixture was stirred for 6 minutes under ice cooling, and then a solution of 0.122 g (1.52 mmol) of chloromethyl methyl ether dissolved in 0.5 ml of DMF was added dropwise thereto. The reaction was stirred at room temperature for 2 hours. Water was added to the reaction mixture, and the mixture was extracted 3 times with ethyl acetate. The combined organic layers were washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to obtain 0.168 g of compound (I-6-1) as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.13 (6H, t, J = 7.6 Hz), 2.28 to 2.50 (4H, m), 2.34 (3H, s), 3.03 (3H, s), 3.69 (3H, s), 3.92 (3H, s), 4.84 (2H, s), 6.95 (2H, s).

This compound produced according to Production Example 6 is shown in Table 12 together with compound (I-6-1).

1) ¹ H NMR: described in the above production example.
2) ¹ H NMR (CDCl ₃ ) δ ppm: 1.00 (3H, t, J = 7.1 Hz), 1.13 (6H, t, J = 7.6 Hz), 2.29 to 2.47 ( 4H, m), 2.34 (3H, s), 3.26 (2H, q, J = 7.1 Hz), 3.69 (3H, s), 3.91 (3H, s), 4.86 (2H, s), 6.95 (2H, s).

４−（２，６−ジエチル−４−メチルフェニル）−６−メトキシメトキシ−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−７−１））の合成
窒素雰囲気下で４−（２，６−ジエチル−４−メチルフェニル）−６−ヒドロキシ−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン１２０ｍｇ（０．３１７ｍｍｏｌ）を無水ＤＭＦ２ｍｌに溶解した溶液に、５℃で６０％水素化ナトリウム２０ｍｇ（０．５０ｍｍｏｌ）を加えた。この混合物を５分間撹拌した後、８０％クロロメチルメチルエーテル０．０４ｍｌ（０．４７ｍｍｏｌ）を加えた。アイスバスをはずし、室温でさらに３０分撹拌した。この反応液に水を加え、酢酸エチルで２回抽出した。合わせた有機層を２回水洗し、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮して、化合物（Ｉ−７−１）１１５ｍｇをオイルとして得た（収率８５％）。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１０（６Ｈ，ｔ，Ｊ＝７．５Ｈｚ），２．２２−２．４８（７Ｈ，ｍ），３．５７（３Ｈ，ｓ），３．６８（３Ｈ，ｓ），４．７８（２Ｈ，ｓ），５．４６（２Ｈ，ｓ），６．９７（２Ｈ，ｓ），６．９９−７．０４（２Ｈ，ｍ），７．２０−７．２５（３Ｈ，ｍ）． Production Example 7

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-methoxymethoxy-5-benzyloxy-2-methyl-3 (2H) -pyridazinone (compound (I-7-1)) under nitrogen atmosphere In a solution of 4- (2,6-diethyl-4-methylphenyl) -6-hydroxy-5-benzyloxy-2-methyl-3 (2H) -pyridazinone 120 mg (0.317 mmol) in 2 ml of anhydrous DMF, 60% sodium hydride 20 mg (0.50 mmol) was added at 5 ° C. After stirring this mixture for 5 minutes, 0.04 ml (0.47 mmol) of 80% chloromethyl methyl ether was added. The ice bath was removed and the mixture was further stirred at room temperature for 30 minutes. Water was added to the reaction solution, and the mixture was extracted twice with ethyl acetate. The combined organic layer was washed twice with water, washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 115 mg of compound (I-7-1) as an oil (yield 85%). .
¹ H NMR (CDCl ₃ ) δ ppm: 1.10 (6H, t, J = 7.5 Hz), 2.22-2.48 (7H, m), 3.57 (3H, s), 3.68 (3H, s), 4.78 (2H, s), 5.46 (2H, s), 6.97 (2H, s), 6.99-7.04 (2H, m), 7.20- 7.25 (3H, m).

This compound produced according to Production Example 7 is shown in Table 13 together with compound (I-7-1).

1) ¹ H NMR: described in the above production example.
2) ¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.6 Hz), 2.21-2.32 (2H, m), 2.34-2.46 (5H, m), 3.67 (3H, s), 3.77 (3H, s), 4.72 (2H, s), 4.76 (2H, d, J = 5.6 Hz), 5.32 (1H) , D, J = 10.4 Hz), 5.45 (1H, d, J = 17.1 Hz), 6.04-6.18 (1H, m), 6.74 (2H, d, J = 8. 5 Hz), 6.92 (2H, d, J = 8.5 Hz), 6.97 (2H, s).
3) ¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.6 Hz), 2.19-2.31 (2H, m), 2.33-2.44 (5H, m), 2.56 (1H, t, J = 2.4 Hz), 3.68 (3H, s), 3.77 (3H, s), 4.73 (2H, s), 4.90 (2H) , D, J = 2.4 Hz), 6.75 (2H, d, J = 8.5 Hz), 6.95 (2H, d, J = 8.5 Hz), 6.97 (2H, s).
4) ¹ H NMR (CDCl ₃ ) δ ppm: 1.12 (6H, t, J = 7.5 Hz), 2.24-2.47 (7H, m), 3.70 (3H, s), 3 .77 (3H, s), 4.60 (2H, s), 4.92 (2H, s), 6.78 (2H, d, J = 8.5 Hz), 6.94 (2H, d, J = 8.7 Hz), 6.99 (2H, s).

４−（２，６−ジエチル−４−メチルフェニル）−６−メトキシ−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−８−１））の合成
４−（２，６−ジエチル−４−メチルフェニル）−６−ヒドロキシ−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン５００ｍｇ（２．３５ｍｍｏｌ）をアセトン１０ｍｌに溶解した溶液に、ヨードプロパン４４３ｍｇ（２．５９ｍｍｏｌ）および炭酸セシウム９２０ｍｇ（２．５９ｍｍｏｌ）を加え、加熱還流下２．５時間撹拌した。この反応混合物をろ過し、ろ液を減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２：１）で精製し、化合物（Ｉ−８−１）６４３ｍｇ（収率７０％）を得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０６（３Ｈ，ｔ，Ｊ＝７．２Ｈｚ），１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．８０−１．９０（２Ｈ，ｍ），２．２２−２．３３（２Ｈ，ｍ），２．３４−２．４５（５Ｈ，ｍ），３．６８（３Ｈ，ｓ），４．２０（２Ｈ，ｔ，Ｊ＝６．６Ｈｚ），４．８０（２Ｈ，ｓ），６．９６（２Ｈ，ｓ），６．９８−７．０１（２Ｈ，ｍ），７．１９−７．２４（３Ｈ，ｍ）． Production Example 8

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-methoxy-5-benzyloxy-2-methyl-3 (2H) -pyridazinone (compound (I-8-1)) 4- (2 , 6-Diethyl-4-methylphenyl) -6-hydroxy-5-benzyloxy-2-methyl-3 (2H) -pyridazinone 500 mg (2.35 mmol) in 10 ml of acetone, 443 mg of iodopropane (2 .59 mmol) and 920 mg (2.59 mmol) of cesium carbonate were added, and the mixture was stirred for 2.5 hours with heating under reflux. The reaction mixture was filtered and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to obtain 643 mg (yield 70%) of compound (I-8-1).
¹ H NMR (CDCl ₃ ) δ ppm: 1.06 (3H, t, J = 7.2 Hz), 1.09 (6H, t, J = 7.6 Hz), 1.80-1.90 (2H, m), 2.22-2.33 (2H, m), 2.34-2.45 (5H, m), 3.68 (3H, s), 4.20 (2H, t, J = 6. 6 Hz), 4.80 (2H, s), 6.96 (2H, s), 6.98-7.01 (2H, m), 7.19-7.24 (3H, m).

This compound produced according to Production Example 8 is shown in Table 14 together with compound (I-8-1).

１）¹Ｈ ＮＭＲ：上記製造例に記載。
２）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．９９（３Ｈ，ｔ，Ｊ＝７．５Ｈｚ），１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．４４−１．５５（２Ｈ，ｍ），１．７５−１．８４（２Ｈ，ｍ），２．２２−２．３２（２Ｈ，ｍ），２．３４−２．４５（５Ｈ，ｍ），３．６８（３Ｈ，ｓ），４．２３（２Ｈ，ｔ，Ｊ＝６．６Ｈｚ），４．７９（２Ｈ，ｓ），６．９６（２Ｈ，ｓ），６．９７−７．０１（２Ｈ，ｍ），７．１９−７．２４（３Ｈ，ｍ）．
３）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０９（６Ｈ，ｔ，Ｊ＝７．５Ｈｚ），１．４１（６Ｈ，ｄ，Ｊ＝６．１Ｈｚ），２．２２−２．３２（２Ｈ，ｍ），２．３４−２．４５（２Ｈ，ｍ），２．３７（３Ｈ，ｓ），３．６７（３Ｈ，ｓ），４．７９（２Ｈ，ｓ），５．０７−５．１４（１Ｈ，ｍ），６．９６（２Ｈ，ｓ），６．９７−７．０１（２Ｈ，ｍ），７．１９−７．２３（３Ｈ，ｍ）．
４）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．３７−０．４２（２Ｈ，ｍ），０．６３−０．６９（２Ｈ，ｍ），１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．２９−１．３６（１Ｈ，ｍ），２．２２−２．３２（２Ｈ，ｍ），２．３４−２．４５（２Ｈ，ｍ），２．３７ （３Ｈ，ｓ），３．６６（３Ｈ，ｓ），４．０８（２Ｈ，ｄ，Ｊ＝７．１Ｈｚ），４．８４（２Ｈ，ｓ），６．９６（２Ｈ，ｓ），７．０２−７．０６（２Ｈ，ｍ），７．２０−７．２５（３Ｈ，ｍ）．
５）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１０（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２２−２．３３（２Ｈ，ｍ），２．３４−２．４４（２Ｈ，ｍ），２．３８（３Ｈ，ｓ），３．６８（３Ｈ，ｓ），４．４５（２Ｈ，ｔｄ，Ｊ＝１３．３，４．２Ｈｚ），４．７５（２Ｈ，ｓ），６．１４（１Ｈ，ｔｔ，Ｊ＝５５．２，４．２Ｈｚ），６．９７（２Ｈ，ｓ），６．９８−７．０２（２Ｈ，ｍ），７．２１−７．２５（３Ｈ，ｍ）．
６）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２１−２．４４（７Ｈ，ｍ），３．６８（３Ｈ，ｓ），４．６５（２Ｈ，ｑ，Ｊ＝８．３Ｈｚ），４．７６（２Ｈ，ｓ），６．９６−７．０２（４Ｈ，ｍ），７．２０−７．２５（３Ｈ，ｍ）．
７）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０８（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．１９−２．３１（２Ｈ，ｍ），２．３２−２．４３（２Ｈ，ｍ），２．３７（３Ｈ，ｓ），３．６３（３Ｈ，ｓ），３．８４（３Ｈ，ｓ），４．８６（４Ｈ，ｓ），６．９６（２Ｈ，ｓ），７．００−７．０５（２Ｈ，ｍ），７．２０−７．２４（３Ｈ，ｍ）．
８）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０９（６Ｈ，ｔ，Ｊ＝７．５Ｈｚ），２．２２−２．４５（１０Ｈ，ｍ），３．６９（３Ｈ，ｓ），４．７７（２Ｈ，ｓ），５．３９（２Ｈ，ｓ），６．９６（２Ｈ，ｓ），６．９９−７．０３（２Ｈ，ｍ），７．２０−７．２４（３Ｈ，ｍ）．
９）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１０（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．１９（３Ｈ，ｓ），２．２３−２．３３（２Ｈ，ｍ），２．３５−２．４６（５Ｈ，ｍ），２．９０（２Ｈ，ｔ，Ｊ＝６．７Ｈｚ），３．６７（３Ｈ，ｓ），４．４２（２Ｈ，ｔ，Ｊ＝６．７Ｈｚ），４．７８（２Ｈ，ｓ），６．９６（２Ｈ，ｓ），６．９９−７．０２（２Ｈ，ｍ），７．２０−７．２４（３Ｈ，ｍ）.

1) ¹ H NMR: described in the above production example.
2) ¹ H NMR (CDCl ₃ ) δ ppm: 0.99 (3H, t, J = 7.5 Hz), 1.09 (6H, t, J = 7.6 Hz), 1.44 to 1.55 ( 2H, m), 1.75-1.84 (2H, m), 2.22-2.32 (2H, m), 2.34-2.45 (5H, m), 3.68 (3H, s), 4.23 (2H, t, J = 6.6 Hz), 4.79 (2H, s), 6.96 (2H, s), 6.97-7.01 (2H, m), 7 19-7.24 (3H, m).
3) ¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.5 Hz), 1.41 (6H, d, J = 6.1 Hz), 2.22-2.32 ( 2H, m), 2.34-2.45 (2H, m), 2.37 (3H, s), 3.67 (3H, s), 4.79 (2H, s), 5.07-5. .14 (1H, m), 6.96 (2H, s), 6.97-7.01 (2H, m), 7.19-7.23 (3H, m).
4) ¹ H NMR (CDCl ₃ ) δ ppm: 0.37-0.42 (2H, m), 0.63-0.69 (2H, m), 1.09 (6H, t, J = 7. 6Hz), 1.29-1.36 (1H, m), 2.22-2.32 (2H, m), 2.34-2.45 (2H, m), 2.37 (3H, s) 3.66 (3H, s), 4.08 (2H, d, J = 7.1 Hz), 4.84 (2H, s), 6.96 (2H, s), 7.02-7.06 (2H, m), 7.20-7.25 (3H, m).
5) ¹ H NMR (CDCl ₃ ) δ ppm: 1.10 (6H, t, J = 7.6 Hz), 2.22-2.33 (2H, m), 2.34-2.44 (2H, m), 2.38 (3H, s), 3.68 (3H, s), 4.45 (2H, td, J = 13.3, 4.2 Hz), 4.75 (2H, s), 6 .14 (1H, tt, J = 55.2, 4.2 Hz), 6.97 (2H, s), 6.98-7.02 (2H, m), 7.21-7.25 (3H, m).
6) ¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.6 Hz), 2.21-2.44 (7H, m), 3.68 (3H, s), 4 .65 (2H, q, J = 8.3 Hz), 4.76 (2H, s), 6.96-7.02 (4H, m), 7.20-7.25 (3H, m).
7) ¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (6H, t, J = 7.6 Hz), 2.19-2.31 (2H, m), 2.32-2.43 (2H, m), 2.37 (3H, s), 3.63 (3H, s), 3.84 (3H, s), 4.86 (4H, s), 6.96 (2H, s), 7. 00-7.05 (2H, m), 7.20-7.24 (3H, m).
8) ¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.5 Hz), 2.22-2.45 (10H, m), 3.69 (3H, s), 4 .77 (2H, s), 5.39 (2H, s), 6.96 (2H, s), 6.99-7.03 (2H, m), 7.20-7.24 (3H, m ).
9) ¹ H NMR (CDCl ₃ ) δ ppm: 1.10 (6H, t, J = 7.6 Hz), 2.19 (3H, s), 2.23-2.33 (2H, m), 2 .35-2.46 (5H, m), 2.90 (2H, t, J = 6.7 Hz), 3.67 (3H, s), 4.42 (2H, t, J = 6.7 Hz) , 4.78 (2H, s), 6.96 (2H, s), 6.99-7.02 (2H, m), 7.20-7.24 (3H, m).

４−（２，６−ジエチル−４−メチルフェニル）−６−メトキシメトキシ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−９−１））の合成
化合物（Ｉ−７−１）１１０ｍｇ（０．２６ｍｍｏｌ）、１０％パラジウム−炭素２０ｍｇおよび酢酸エチル１５ｍｌの混合物を常圧の水素雰囲気下３０℃で１時間撹拌した。この反応混合物をセライトろ過し、ろ液を減圧下濃縮し、化合物（Ｉ−９−１）７０ｍｇ（収率８０％）を得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０８ （６Ｈ，ｔ，Ｊ＝７．６ Ｈｚ），２．２５−２．４５（７Ｈ，ｍ），３．５９（３Ｈ，ｓ），３．６８（３Ｈ，ｓ），５．４８（２Ｈ，ｓ），５．９１（１Ｈ，ｂｒｓ）， ７．００（２Ｈ，ｓ）． Production Example 9

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-methoxymethoxy-5-hydroxy-2-methyl-3 (2H) -pyridazinone (Compound (I-9-1)) Compound (I- 7-1) A mixture of 110 mg (0.26 mmol), 10% palladium-carbon 20 mg and ethyl acetate 15 ml was stirred at 30 ° C. for 1 hour under a hydrogen atmosphere under normal pressure. The reaction mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure to obtain 70 mg (yield 80%) of compound (I-9-1).
¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (6H, t, J = 7.6 Hz), 2.25 to 2.45 (7H, m), 3.59 (3H, s), 3. 68 (3H, s), 5.48 (2H, s), 5.91 (1H, brs), 7.00 (2H, s).

This compound produced according to Production Example 9 is shown in Table 15 together with compound (I-9-1).

１）¹Ｈ ＮＭＲ：上記製造例に記載。
２）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０５（３Ｈ，ｔ，Ｊ＝７．０Ｈｚ），１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．８２−１．９３（２Ｈ，ｍ），２．２７−２．４６（７Ｈ，ｍ），３．６７（３Ｈ，ｓ），４．２５（２Ｈ，ｔ，Ｊ＝７．０Ｈｚ），５．６６（１Ｈ，ｂｒｓ），７．００（２Ｈ，ｓ）．
３）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．００（３Ｈ，ｔ，Ｊ＝７．５Ｈｚ），１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．４４−１．５５（２Ｈ，ｍ），１．７８−１．８７（２Ｈ，ｍ），２．２７−２．４６（７Ｈ，ｍ），３．６７（３Ｈ，ｓ），４．２９（２Ｈ，ｔ，Ｊ＝６．８Ｈｚ），５．６７（１Ｈ，ｂｒｓ），６．９９（２Ｈ，ｓ）．
４）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．４３（６Ｈ，ｄ，Ｊ＝６．１Ｈｚ），２．２７−２．４５（７Ｈ，ｍ），３．６７（３Ｈ，ｓ），５．１１−５．２２（１Ｈ，ｍ），５．７１（１Ｈ，ｂｒｓ），６．９９（２Ｈ，ｓ）．
５）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．３７−０．４３（２Ｈ，ｍ），０．６４−０．７２（２Ｈ，ｍ），１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．２７−１．３８（１Ｈ，ｍ），２．２８−２．４６（７Ｈ，ｍ），３．６６（３Ｈ，ｓ），４．１１（２Ｈ，ｄ，Ｊ＝７．３Ｈｚ），５．７７（１Ｈ，ｂｒｓ），７．００（２Ｈ，ｓ）．
６）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２６−２．４５（７Ｈ，ｍ），３．６８（３Ｈ，ｓ），４．５０（２Ｈ，ｔｄ，Ｊ＝１３．２，４．２Ｈｚ），６．１９（１Ｈ，ｔｔ，Ｊ＝５４．９，４．２Ｈｚ），７．０２（２Ｈ，ｓ）．
７）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ）， ２．２６−２．４５（７Ｈ，ｍ），３．６８（３Ｈ，ｓ），４．６８（２Ｈ，ｑ，Ｊ＝８．３Ｈｚ），５．７１（１Ｈ，ｂｒｓ），７．０２（２Ｈ，ｓ）．
８）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２７−２．４６（７Ｈ，ｍ），３．６５（３Ｈ，ｓ），３．８５ （３Ｈ，ｓ），４．８７（２Ｈ，ｓ），７．００（２Ｈ，ｓ）．
９）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０８（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２６−２．４２（７Ｈ，ｍ），３．６７（３Ｈ，ｓ），４．７６（２Ｈ，ｓ），５．４３（２Ｈ，ｂｒｓ），６．５２（１Ｈ，ｂｒｓ），７．０２（２Ｈ，ｓ）．
１０）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０７（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２６−２．４４（７Ｈ，ｍ），３．０１（３Ｈ，ｓ），３．０５（３Ｈ，ｓ），３．６５（３Ｈ，ｓ），４．８７（２Ｈ，ｓ），６．９５（２Ｈ，ｓ）．

1) ¹ H NMR: described in the above production example.
2) ¹ H NMR (CDCl ₃ ) δ ppm: 1.05 (3H, t, J = 7.0 Hz), 1.09 (6H, t, J = 7.6 Hz), 1.82-1.93 ( 2H, m), 2.27-2.46 (7H, m), 3.67 (3H, s), 4.25 (2H, t, J = 7.0 Hz), 5.66 (1H, brs) , 7.00 (2H, s).
3) ¹ H NMR (CDCl ₃ ) δ ppm: 1.00 (3H, t, J = 7.5 Hz), 1.09 (6H, t, J = 7.6 Hz), 1.44 to 1.55 ( 2H, m), 1.78-1.87 (2H, m), 2.27-2.46 (7H, m), 3.67 (3H, s), 4.29 (2H, t, J = 6.8 Hz), 5.67 (1H, brs), 6.99 (2H, s).
4) ¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.6 Hz), 1.43 (6H, d, J = 6.1 Hz), 2.27-2.45 ( 7H, m), 3.67 (3H, s), 5.11-5.22 (1H, m), 5.71 (1H, brs), 6.99 (2H, s).
5) ¹ H NMR (CDCl ₃ ) δ ppm: 0.37-0.43 (2H, m), 0.64-0.72 (2H, m), 1.09 (6H, t, J = 7. 6Hz), 1.27-1.38 (1H, m), 2.28-2.46 (7H, m), 3.66 (3H, s), 4.11 (2H, d, J = 7. 3 Hz), 5.77 (1H, brs), 7.00 (2H, s).
6) ¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.6 Hz), 2.26-2.45 (7H, m), 3.68 (3H, s), 4 .50 (2H, td, J = 13.2, 4.2 Hz), 6.19 (1H, tt, J = 54.9, 4.2 Hz), 7.02 (2H, s).
7) ¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.6 Hz), 2.26-2.45 (7H, m), 3.68 (3H, s), 4 .68 (2H, q, J = 8.3 Hz), 5.71 (1H, brs), 7.02 (2H, s).
8) ¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.6 Hz), 2.27-2.46 (7H, m), 3.65 (3H, s), 3 .85 (3H, s), 4.87 (2H, s), 7.00 (2H, s).
9) ¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (6H, t, J = 7.6 Hz), 2.26-2.42 (7H, m), 3.67 (3H, s), 4 .76 (2H, s), 5.43 (2H, brs), 6.52 (1H, brs), 7.02 (2H, s).
10) ¹ H NMR (CDCl ₃ ) δ ppm: 1.07 (6H, t, J = 7.6 Hz), 2.26-2.44 (7H, m), 3.01 (3H, s), 3 .05 (3H, s), 3.65 (3H, s), 4.87 (2H, s), 6.95 (2H, s).

４−（２，６−ジエチル−４−メチルフェニル）−６−アリルオキシ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−１０−１））の合成
化合物（Ｉ−７−２）２４０ｍｇ（０．５３ｍｍｏｌ）をアセトニトリル：水＝４：１の混合溶媒６ｍｌに溶解した溶液に、氷冷下硝酸アンモニウムセリウム（ＩＶ）７４０ｍｇ（１．２８ｍｍｏｌ）を加えた。アイスバスをはずし、一晩撹拌した。この反応液に水を加え、酢酸エチルで２回抽出し、合わせた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝３：１）で精製し、化合物（Ｉ−１０−１）１０７ｍｇ（収率６１％）を黄色固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０９（６Ｈ，ｔ，Ｊ＝７．５Ｈｚ），２．２６−２．４６（７Ｈ，ｍ），３．６８（３Ｈ，ｓ），４．８０（２Ｈ，ｄ，Ｊ＝６．０Ｈｚ），５．３６（１Ｈ，ｄ，Ｊ＝１０．４Ｈｚ），５．４６（１Ｈ，ｄ，Ｊ＝１７．１Ｈｚ），５．８４（１Ｈ，ｂｒｓ），６．０６−６．１８（１Ｈ，ｍ），７．００（２Ｈ，ｓ）． Production Example 10

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-allyloxy-5-hydroxy-2-methyl-3 (2H) -pyridazinone (compound (I-10-1)) (I-7 -2) To a solution of 240 mg (0.53 mmol) dissolved in 6 ml of a mixed solvent of acetonitrile: water = 4: 1, 740 mg (1.28 mmol) of ammonium cerium (IV) nitrate was added under ice cooling. The ice bath was removed and stirred overnight. Water was added to the reaction mixture, and the mixture was extracted twice with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1) to obtain 107 mg (yield 61%) of compound (I-10-1) as a yellow solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.5 Hz), 2.26-2.46 (7H, m), 3.68 (3H, s), 4.80 (2H, d, J = 6.0 Hz), 5.36 (1H, d, J = 10.4 Hz), 5.46 (1H, d, J = 17.1 Hz), 5.84 (1H, brs) , 6.06-6.18 (1H, m), 7.00 (2H, s).

This compound produced according to Production Example 10 is shown in Table 16 together with compound (I-10-1).

１）¹Ｈ ＮＭＲ：上記製造例に記載。
２）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０８（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２６−２．４５（７Ｈ，ｍ），２．５９（１Ｈ，ｔ，Ｊ＝２．４Ｈｚ），３．６９（３Ｈ，ｓ），４．９３（２Ｈ，ｄ，Ｊ＝２．４Ｈｚ），５．９８（１Ｈ，ｂｒｓ），７．００（２Ｈ，ｓ）．
３）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δｐｐｍ：１．０８（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２３−２．４４（７Ｈ，ｍ），３．７０（３Ｈ，ｓ），４．９４（２Ｈ，ｓ），６．０７（１Ｈ，ｂｒｓ），７．０２（２Ｈ，ｓ）．

1) ¹ H NMR: described in the above production example.
2) ¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (6H, t, J = 7.6 Hz), 2.26-2.45 (7H, m), 2.59 (1H, t, J = 2.4 Hz), 3.69 (3 H, s), 4.93 (2 H, d, J = 2.4 Hz), 5.98 (1 H, brs), 7.00 (2 H, s).
3) ¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (6H, t, J = 7.6 Hz), 2.23-2.44 (7H, m), 3.70 (3H, s), 4. 94 (2H, s), 6.07 (1H, brs), 7.02 (2H, s).

４−（２，６−ジエチル−４−メチルフェニル）−５、６−ビス（メトキシメトキシ）−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−１１））の合成
窒素雰囲気下で４−（２，６−ジエチル−４−メチルフェニル）−５、６−ジヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン２７０ｍｇ（０．９３ｍｍｏｌ）を無水ＤＭＦ３ｍｌに溶解した溶液に、５℃で６０％水素化ナトリウム１１０ｍｇ（２．８０ｍｍｏｌ）を加えた。この混合物を５分間撹拌した後、８０％クロロメチル メチル エーテル０．２７ｍｌ（２．８ｍｍｏｌ）を加えた。アイスバスをはずし、室温で３０分撹拌した。この反応液に水を加え、酢酸エチルで２回抽出した。合わせた有機層を２回水洗し、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２：１）で精製し、無色固体の化合物（Ｉ−１１）２０ｍｇ（収率５％）および化合物（Ｉ−９−１）１２８ｍｇ（収率４１％）を得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１３（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．３４（７Ｈ，ｓ），３．０４（３Ｈ，ｓ），３．５８（３Ｈ，ｓ），３．６８（３Ｈ，ｓ），４．８８（２Ｈ，ｓ），５．４５ ２Ｈ，ｓ），６．９６（２Ｈ，ｓ）． Production Example 11

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -5,6-bis (methoxymethoxy) -2-methyl-3 (2H) -pyridazinone (compound (I-11)) 4 under a nitrogen atmosphere To a solution of 270 mg (0.93 mmol) of-(2,6-diethyl-4-methylphenyl) -5,6-dihydroxy-2-methyl-3 (2H) -pyridazinone in 3 ml of anhydrous DMF, 60% at 5 ° C. Sodium hydride 110 mg (2.80 mmol) was added. After stirring the mixture for 5 minutes, 0.27 ml (2.8 mmol) of 80% chloromethyl methyl ether was added. The ice bath was removed and the mixture was stirred at room temperature for 30 minutes. Water was added to the reaction solution, and the mixture was extracted twice with ethyl acetate. The combined organic layers were washed twice with water, washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to give 20 mg (yield 5%) of colorless solid compound (I-11) and 128 mg (yield 41) of compound (I-9-1). %).
¹ H NMR (CDCl ₃ ) δ ppm: 1.13 (6H, t, J = 7.6 Hz), 2.34 (7H, s), 3.04 (3H, s), 3.58 (3H, s ), 3.68 (3H, s), 4.88 (2H, s), 5.45 2H, s), 6.96 (2H, s).

４−（２，６−ジエチル−４−メチルフェニル）−６−エトキシ−５−ヒドロキシ−２−ベンジル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−１２−１））の合成
ｔ−ブトキシカリウム１２．４ｇ（１１０ｍｍｏｌ）を無水テトラヒドロフラン８０ｍｌに加えた溶液に、２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−ベンジルヒドラゾノ］−２−（ドデシルチオ）酢酸エチル１６．４ｇ（２７．６ｍｍｏｌ）を無水テトラヒドロフラン２０ｍｌに溶解した溶液を室温で２０分かけて滴下した。この反応液を室温で１０分撹拌した後、１Ｎ塩酸２００ｍｌを加え、ｔｅｒｔ−ブチルメチルエーテルで２回抽出した。合わせた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２：１）で精製し、化合物（Ｉ−１２−１）１．４８ｇ（収率１３％、固体）および４−（２，６−ジエチル−４−メチルフェニル）−６−ドデシルチオ−５−ヒドロキシ−２−ベンジル−３（２Ｈ）−ピリダジノン２．７１ｇ化合物（Ｉ−１２−１−Ｂ）（収率１７％、オイル）を得た。
化合物（Ｉ−１２−１）の¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０５（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．４３（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），２．２４−２．４３（７Ｈ，ｍ），４．３２（２Ｈ，ｑ，Ｊ＝７．１Ｈｚ），５．２２（２Ｈ，ｓ），６．９８（２Ｈ，ｓ），７．２３−７．３４（３Ｈ，ｍ），７．３８−７．４３（２Ｈ，ｍ）．

化合物（Ｉ−１２−１−Ｂ）の¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８８（３Ｈ，ｔ，Ｊ＝６．８Ｈｚ），１．０３（６Ｈ，ｔ，Ｊ＝７．５Ｈｚ），１．２３−１．３４（１６Ｈ，ｍ），１．３７−１．４７（２Ｈ，ｍ），１．６２−１．７３（２Ｈ，ｍ），２．２２−２．３９（７Ｈ，ｍ），３．０１（２Ｈ，ｔ，Ｊ＝７．５Ｈｚ），５．３２（２Ｈ，ｓ），６．９０（１Ｈ，ｓ），７．００（２Ｈ，ｓ），７．２４−７．３４（３Ｈ，ｍ），７．３７−７．４２（２Ｈ，ｍ）． Production Example 12

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-ethoxy-5-hydroxy-2-benzyl-3 (2H) -pyridazinone (compound (I-12-1)) t-butoxypotassium 12 To a solution of 4 g (110 mmol) in 80 ml of anhydrous tetrahydrofuran, ethyl 2- [2- (2,6-diethyl-4-methylphenyl) acetyl-2-benzylhydrazono] -2- (dodecylthio) acetate 16. A solution of 4 g (27.6 mmol) dissolved in 20 ml of anhydrous tetrahydrofuran was added dropwise at room temperature over 20 minutes. The reaction mixture was stirred at room temperature for 10 minutes, 200 ml of 1N hydrochloric acid was added, and the mixture was extracted twice with tert-butyl methyl ether. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1), and 1.48 g of compound (I-12-1) (13% yield, solid) and 4- (2,6-diethyl-4) -Methylphenyl) -6-dodecylthio-5-hydroxy-2-benzyl-3 (2H) -pyridazinone 2.71 g compound (I-12-1-B) (yield 17%, oil) was obtained.
¹ H NMR (CDCl ₃ ) δ ppm of compound (I-12-1): 1.05 (6H, t, J = 7.6 Hz), 1.43 (3H, t, J = 7.1 Hz), 2 .24-2.43 (7H, m), 4.32 (2H, q, J = 7.1 Hz), 5.22 (2H, s), 6.98 (2H, s), 7.23-7 .34 (3H, m), 7.38-7.43 (2H, m).

¹ H NMR (CDCl ₃ ) δ ppm of compound (I-12-1-B): 0.88 (3H, t, J = 6.8 Hz), 1.03 (6H, t, J = 7.5 Hz) , 1.23-1.34 (16H, m), 1.37-1.47 (2H, m), 1.62-1.73 (2H, m), 2.22-2.39 (7H, m), 3.01 (2H, t, J = 7.5 Hz), 5.32 (2H, s), 6.90 (1H, s), 7.00 (2H, s), 7.24-7 .34 (3H, m), 7.37-7.42 (2H, m).

This compound produced according to Production Example 12 is shown in Table 17 together with compound (I-12-1).

１）¹Ｈ ＮＭＲ：上記製造例に記載。
２）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．４７（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），２．１４（３Ｈ，ｓ），２．３２（３Ｈ，ｓ），３．６８（３Ｈ，ｓ），４．３７（２Ｈ，ｑ，Ｊ＝７．１Ｈｚ），７．０５（１Ｈ，ｓ），７．３４（１Ｈ，ｓ）．
３）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．３６−０．４４（２Ｈ，ｍ），０．４６−０．５３ （２Ｈ，ｍ），１．０９（６Ｈ，ｔ，Ｊ＝７．５Ｈｚ），１．２６−１．３５（１Ｈ，ｍ），１．４８（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），２．２８−２．４７（７Ｈ，ｍ），３．９３（２Ｈ，ｄ，Ｊ＝７．０Ｈｚ），４．３８（２Ｈ，ｑ，Ｊ＝７．１Ｈｚ），５．６６（１Ｈ，ｂｒｓ），６．９９（２Ｈ，ｓ）．
４）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．４６（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），２．２７−２．４６（７Ｈ，ｍ），４．３６（２Ｈ，ｑ，Ｊ＝７．１Ｈｚ），４．６３−４．６８（２Ｈ，ｍ），５．１５−５．２４（２Ｈ，ｍ），５．７２（１Ｈ，ｓ），５．９３−６．０５（１Ｈ，ｍ），６．９９（２Ｈ，ｓ）．
５）¹Ｈ ＮＭＲ：上記製造例に記載。
６）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８８（３Ｈ，ｔ，Ｊ＝６．８Ｈｚ），１．２２−１．３８（１８Ｈ，ｍ），１．３８−１．７７（２Ｈ，ｍ），２．１３（３Ｈ，ｓ），２．３３（３Ｈ，ｓ），３．０４（２Ｈ，ｔ，Ｊ＝７．３Ｈｚ），３．８１（３Ｈ，ｓ），５．９６（１Ｈ，ｂｒｓ）， ７．０８（１Ｈ，ｓ），７．３７（１Ｈ，ｓ）．
７）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．３８−０．４６（２Ｈ，ｍ），０．４８−０．５５（２Ｈ，ｍ），０．８８（３Ｈ，ｔ，Ｊ＝６．９Ｈｚ），１．０８（６Ｈ，ｔ，Ｊ＝７．５Ｈｚ），１．１６−１．３８（１７Ｈ，ｍ），１．４１−１．５１（２Ｈ，ｍ），１．７０−１．８１（２Ｈ，ｍ），２．２６−２．４４（７Ｈ，ｍ），３．０７（２Ｈ，ｔ，Ｊ＝７．４Ｈｚ），４．０４（２Ｈ，ｄ，Ｊ＝７．２Ｈｚ），５．５１（１Ｈ，ｂｒｓ），７．０２（２Ｈ，ｓ）．

1) ¹ H NMR: described in the above production example.
2) ¹ H NMR (CDCl ₃ ) δ ppm: 1.47 (3H, t, J = 7.1 Hz), 2.14 (3H, s), 2.32 (3H, s), 3.68 (3H , S), 4.37 (2H, q, J = 7.1 Hz), 7.05 (1H, s), 7.34 (1H, s).
3) ¹ H NMR (CDCl ₃ ) δ ppm: 0.36-0.44 (2H, m), 0.46-0.53 (2H, m), 1.09 (6H, t, J = 7. 5Hz), 1.26-1.35 (1H, m), 1.48 (3H, t, J = 7.1 Hz), 2.28-2.47 (7H, m), 3.93 (2H, d, J = 7.0 Hz), 4.38 (2H, q, J = 7.1 Hz), 5.66 (1H, brs), 6.99 (2H, s).
4) ¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.6 Hz), 1.46 (3H, t, J = 7.1 Hz), 2.27-2.46 ( 7H, m), 4.36 (2H, q, J = 7.1 Hz), 4.63-4.68 (2H, m), 5.15-5.24 (2H, m), 5.72 ( 1H, s), 5.93-6.05 (1H, m), 6.99 (2H, s).
5) ¹ H NMR: described in the above production example.
6) ¹ H NMR (CDCl ₃ ) δ ppm: 0.88 (3H, t, J = 6.8 Hz), 1.22-1.38 (18H, m), 1.38-1.77 (2H, m), 2.13 (3H, s), 2.33 (3H, s), 3.04 (2H, t, J = 7.3 Hz), 3.81 (3H, s), 5.96 (1H) , Brs), 7.08 (1H, s), 7.37 (1H, s).
7) ¹ H NMR (CDCl ₃ ) δ ppm: 0.38-0.46 (2H, m), 0.48-0.55 (2H, m), 0.88 (3H, t, J = 6. 9 Hz), 1.08 (6H, t, J = 7.5 Hz), 1.16-1.38 (17H, m), 1.41-1.51 (2H, m), 1.70-1. 81 (2H, m), 2.26-2.44 (7H, m), 3.07 (2H, t, J = 7.4 Hz), 4.04 (2H, d, J = 7.2 Hz), 5.51 (1H, brs), 7.02 (2H, s).

Production Example 13
4- (2,6-Diethyl-4-methylphenyl) -6-dodecylsulfonyl-5-hydroxy-2-methyl-3 (2H) -pyridazinone was used as a raw material in the same manner as in Production Example 4, and 4- (2 , 6-Diethyl-4-methylphenyl) -6-methoxy-5-hydroxy-2-benzyl-3 (2H) -pyridazinone (compound (I-13-1)).

This compound produced according to Production Example 13 is shown in Table 18.

１）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：：１．０５（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２３−２．４２（７Ｈ，ｍ），３．９４（３Ｈ，ｓ），５．２４（２Ｈ，ｓ），６．９９（２Ｈ，ｓ），７．２４−７．３４（３Ｈ，ｍ），７．３８−７．４３（２Ｈ，ｍ）．
２）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：２．１４（３Ｈ，ｓ），２．３２（３Ｈ，ｓ），３．７０（３Ｈ，ｓ），３．９９（３Ｈ，ｓ），７．０５（１Ｈ，ｓ），７．３４（１Ｈ，ｓ）．
３）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．３９−０．４５（２Ｈ，ｍ），０．４６−０．５３（２Ｈ，ｍ）， １．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．２６−１．３７（１Ｈ，ｍ），２．２８−２．４７（７Ｈ，ｍ），３．９５（２Ｈ，ｄ，Ｊ＝７．２Ｈｚ），４．００（３Ｈ，ｓ），５．６５（１Ｈ，ｂｒｓ），７．００（２Ｈ，ｓ）．
４）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：２．０８（６Ｈ，ｓ），２．３０（３ Ｈ，ｓ），３．７０（３Ｈ，ｓ），３．９９（３Ｈ，ｓ），６．９６（２Ｈ，ｓ）．
５）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：３．６７（３Ｈ，ｓ），３．９９（３Ｈ，ｓ），６．０３（１Ｈ，ｂｒｓ），７．２１（１Ｈ，ｄ，Ｊ＝８．４Ｈｚ），７．５９（１Ｈ，ｄ，Ｊ＝８．４Ｈｚ），７．７６（１Ｈ，ｓ）．
６）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：３．６８（３Ｈ，ｓ），３．９９（３Ｈ，ｓ），６．１１（１Ｈ，ｂｒｓ），７．３３−７．４７（４Ｈ，ｍ）．

1) ¹ H NMR (CDCl ₃ ) δ ppm :: 1.05 (6H, t, J = 7.6 Hz), 2.23-2.42 (7H, m), 3.94 (3H, s), 5.24 (2H, s), 6.99 (2H, s), 7.24-7.34 (3H, m), 7.38-7.43 (2H, m).
2) ¹ H NMR (CDCl ₃ ) δ ppm: 2.14 (3H, s), 2.32 (3H, s), 3.70 (3H, s), 3.99 (3H, s), 7. 05 (1H, s), 7.34 (1H, s).
3) ¹ H NMR (CDCl ₃ ) δ ppm: 0.39-0.45 (2H, m), 0.46-0.53 (2H, m), 1.09 (6H, t, J = 7. 6 Hz), 1.26-1.37 (1 H, m), 2.28-2.47 (7 H, m), 3.95 (2 H, d, J = 7.2 Hz), 4.00 (3 H, s), 5.65 (1H, brs), 7.00 (2H, s).
4) ¹ H NMR (CDCl ₃ ) δ ppm: 2.08 (6H, s), 2.30 (3 H, s), 3.70 (3H, s), 3.99 (3H, s), 6 .96 (2H, s).
5) ¹ H NMR (CDCl ₃ ) δ ppm: 3.67 (3H, s), 3.99 (3H, s), 6.03 (1H, brs), 7.21 (1H, d, J = 8) .4 Hz), 7.59 (1 H, d, J = 8.4 Hz), 7.76 (1 H, s).
6) ¹ H NMR (CDCl ₃ ) δ ppm: 3.68 (3H, s), 3.99 (3H, s), 6.11 (1H, brs), 7.33-7.47 (4H, m ).

４−（２−ビニル−４，６−ジメチルフェニル）−６−メトキシ−５−メトキシカルボニルオキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−１４））の合成
窒素雰囲気下化合物（Ｉ−５−９）０．６７０ｇ（１．６９ｍｍｏｌ）及びトリブチル（ビニル）すず０．６５６ｇ（２．０１ ｍｍｏｌ）をトルエン２５ｍｌに溶解した溶液に、テトラキス（トリフェニルホスフィン）パラジウム（０）０．１１７ｇ（０．１０１ｍｍｏｌ）を加え、９５℃で５．５時間撹拌した。室温まで冷却後、反応液をセライトでろ過した。ろ液を減圧濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２：１）で精製し、化合物（Ｉ−１４）０．５７０ｇ（収率９８％）を得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：２．０７（３Ｈ，ｓ），２．３４（３Ｈ，ｓ），３．７３（３Ｈ，ｓ），３．７５（３Ｈ，ｓ），３．９２（３Ｈ，ｓ），５．１４（１Ｈ，ｄｄ，Ｊ＝１．２，１１．０Ｈｚ），５．６４（１Ｈ，ｄｄ，Ｊ＝１．２，１７．２Ｈｚ），６．４２（１Ｈ，ｄｄ，Ｊ＝１１．０，１７．２Ｈｚ），７．００（１Ｈ，ｓ），７．２７（１Ｈ，ｓ）． Production Example 14

Synthesis of 4- (2-vinyl-4,6-dimethylphenyl) -6-methoxy-5-methoxycarbonyloxy-2-methyl-3 (2H) -pyridazinone (compound (I-14)) Compound under nitrogen atmosphere ( I-5-9) 0.670 g (1.69 mmol) and 0.656 g (2.01 mmol) of tributyl (vinyl) tin were dissolved in 25 ml of toluene. Tetrakis (triphenylphosphine) palladium (0) 117 g (0.101 mmol) was added, and the mixture was stirred at 95 ° C. for 5.5 hours. After cooling to room temperature, the reaction solution was filtered through celite. The filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to obtain 0.570 g (yield 98%) of compound (I-14).
¹ H NMR (CDCl ₃ ) δ ppm: 2.07 (3H, s), 2.34 (3H, s), 3.73 (3H, s), 3.75 (3H, s), 3.92 ( 3H, s), 5.14 (1H, dd, J = 1.2, 11.0 Hz), 5.64 (1H, dd, J = 1.2, 17.2 Hz), 6.42 (1H, dd) , J = 11.0, 17.2 Hz), 7.00 (1H, s), 7.27 (1H, s).

４−（２−ビニル−４，６−ジメチルフェニル）−６−メトキシ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−１５））の合成
化合物（Ｉ−１４）０．５９４ｇ（１．６９ｍｍｏｌ）をエタノール１２ｍｌに溶解した溶液に、１Ｎ水酸化ナトリウム水溶液６ｍｌを加え、室温で５時間攪拌した。反応液に水１５ｍｌを加えｔ−ブチルメチルエーテルで洗浄した。水層に濃塩酸１ｍｌを加えて酸性にし、クロロホルムで２回抽出した。合わせた有機層を無水硫酸マグネシウムで乾燥し、減圧濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝３０：７０）で精製し、化合物（Ｉ−１５）０．３８９ｇ（収率７１％）を無色固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：２．０９（３Ｈ，ｓ），２．３５（３Ｈ，ｓ），３．７０（３Ｈ，ｓ），３．９８（３Ｈ，ｓ），５．１５（１Ｈ，ｄｄ，Ｊ＝１．２，１１．０Ｈｚ），５．６７（１Ｈ，ｄｄ，Ｊ＝１．２，１７．５Ｈｚ），５．７１（１Ｈ，ｂｒｓ），６．４５（１Ｈ，ｄｄ，Ｊ＝１１．０，１７．５Ｈｚ），７．０５（１Ｈ，ｓ），７．３２（１Ｈ，ｓ）． Production Example 15

Synthesis of 4- (2-vinyl-4,6-dimethylphenyl) -6-methoxy-5-hydroxy-2-methyl-3 (2H) -pyridazinone (Compound (I-15)) Compound (I-14) 0 . A solution of 594 g (1.69 mmol) in 12 ml of ethanol was added with 6 ml of 1N aqueous sodium hydroxide solution and stirred at room temperature for 5 hours. 15 ml of water was added to the reaction solution and washed with t-butyl methyl ether. The aqueous layer was acidified with 1 ml of concentrated hydrochloric acid, and extracted twice with chloroform. The combined organic layers were dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 30: 70) to obtain 0.389 g (yield 71%) of compound (I-15) as a colorless solid.
¹ H NMR (CDCl ₃ ) δ ppm: 2.09 (3H, s), 2.35 (3H, s), 3.70 (3H, s), 3.98 (3H, s), 5.15 ( 1H, dd, J = 1.2, 11.0 Hz), 5.67 (1H, dd, J = 1.2, 17.5 Hz), 5.71 (1H, brs), 6.45 (1H, dd) , J = 11.0, 17.5 Hz), 7.05 (1H, s), 7.32 (1H, s).

原料として４−（２−トリメチルシリルエチニル−４，６−ジメチルフェニル）−６−メトキシ−５−メトキシカルボニルオキシ−２−メチル−３（２Ｈ）−ピリダジノンを用い、製造例１５と同様にして４−（２−エチニル−４，６−ジメチルフェニル）−６−メトキシ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−１６））を得た（収率６８％）。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：２．１３（３Ｈ，ｓ），２．３２（３Ｈ，ｓ），２．９４（１Ｈ，ｓ），３．７０（３Ｈ，ｓ），３．９９（３Ｈ，ｓ），５．８８（１Ｈ，ｂｒｓ），７．１２（１Ｈ，ｓ），７．２９（１Ｈ，ｓ）． Production Example 16

4- (2-Trimethylsilylethynyl-4,6-dimethylphenyl) -6-methoxy-5-methoxycarbonyloxy-2-methyl-3 (2H) -pyridazinone was used as a raw material in the same manner as in Production Example 15, and 4- (2-Ethynyl-4,6-dimethylphenyl) -6-methoxy-5-hydroxy-2-methyl-3 (2H) -pyridazinone (compound (I-16)) was obtained (yield 68%).
¹ H NMR (CDCl ₃ ) δ ppm: 2.13 (3H, s), 2.32 (3H, s), 2.94 (1H, s), 3.70 (3H, s), 3.99 ( 3H, s), 5.88 (1H, brs), 7.12 (1H, s), 7.29 (1H, s).

４−（２，６−ジエチル−４−メチルフェニル）−６−アミノ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−１７））の合成
４−（２，６−ジエチル−４−メチルフェニル）−６−ビス（４−メトキシベンジル）アミノ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン１０ｇ（１８．９ｍｍｏｌ）をメタノール２５０ｍｌに溶解した溶液に、１０％パラジウム−炭素８２４ｍｇおよび濃塩酸０．６ｍｌを加え、常圧の水素雰囲気下３５℃で４時間撹拌した。この反応混合物をセライトろ過し、ろ液を減圧下濃縮した。得られた固体をアセトン１００ｍｌでよく洗浄し、ろ過して、化合物（Ｉ−１７）の塩酸塩４．２９ｇ（収率７０％）を得た。ろ液を濃縮し、残さをシリカゲルカラムクロマトグラフィーで精製し、化合物（Ｉ−１７）１．５４ｇ（収率２８％）を得た。
¹Ｈ ＮＭＲ（ＤＭＳＯ−ｄ₆）δ ｐｐｍ：０．９６（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２３（４Ｈ，ｑ，Ｊ＝７．６Ｈｚ），２．２８（３Ｈ，ｓ），３．３６（３Ｈ，ｓ），５．３１（１Ｈ，ｂｒｓ），６．８６（２Ｈ，ｓ）． Production Example 17

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-amino-5-hydroxy-2-methyl-3 (2H) -pyridazinone (Compound (I-17)) 4- (2,6- To a solution of 10 g (18.9 mmol) of diethyl-4-methylphenyl) -6-bis (4-methoxybenzyl) amino-5-hydroxy-2-methyl-3 (2H) -pyridazinone in 250 ml of methanol, 10% Palladium-carbon (824 mg) and concentrated hydrochloric acid (0.6 ml) were added, and the mixture was stirred at 35 ° C. for 4 hours under an atmospheric pressure of hydrogen. The reaction mixture was filtered through celite, and the filtrate was concentrated under reduced pressure. The obtained solid was thoroughly washed with 100 ml of acetone and filtered to obtain 4.29 g (yield 70%) of hydrochloride of compound (I-17). The filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain 1.54 g (yield 28%) of compound (I-17).
¹ H NMR (DMSO-d ₆ ) δ ppm: 0.96 (6H, t, J = 7.6 Hz), 2.23 (4H, q, J = 7.6 Hz), 2.28 (3H, s) , 3.36 (3H, s), 5.31 (1H, brs), 6.86 (2H, s).

４−（２，６−ジエチル−４−メチルフェニル）−６−クロロ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−１８））の合成
化合物（Ｉ−１７）５００ｍｇ（１．７４ｍｍｏｌ）をアセトニトリル３ｍｌに溶解し、これに濃塩酸２ｍｌを加え、氷冷した。この溶液に亜硝酸ナトリウム３２３ｍｇ（４．６８ｍｍｏｌ）を少しずつ加えた。添加終了後、３０分撹拌した。この反応液に水を加え、酢酸エチルで２回抽出した。合わせた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝３：１）で精製し、化合物（Ｉ−１８）２５１ｍｇ（収率４７％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２４−２．４３（７Ｈ，ｍ），３．７９（３Ｈ，ｓ），５．７２（１Ｈ，ｓ），７．０４（２Ｈ，ｓ）． Production Example 18

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-chloro-5-hydroxy-2-methyl-3 (2H) -pyridazinone (Compound (I-18)) Compound (I-17) 500 mg (1.74 mmol) was dissolved in 3 ml of acetonitrile, 2 ml of concentrated hydrochloric acid was added thereto, and the mixture was ice-cooled. To this solution, 323 mg (4.68 mmol) of sodium nitrite was added little by little. After completion of the addition, the mixture was stirred for 30 minutes. Water was added to the reaction solution, and the mixture was extracted twice with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1) to obtain 251 mg (yield 47%) of compound (I-18) as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.6 Hz), 2.24-2.43 (7H, m), 3.79 (3H, s), 5.72 (1H, s), 7.04 (2H, s).

原料として濃塩酸の代わりに４８％臭化水素酸を用い、製造例１８と同様にして４−（２，６−ジエチル−４−メチルフェニル）−６−ブロモ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−１９））を得た（収率４１％）。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０８（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２４−２．４２（７Ｈ，ｍ），３．８０（３Ｈ，ｓ），５．６４（１Ｈ，ｓ），７．０４（２Ｈ，ｓ）． Production Example 19

4- (2,6-diethyl-4-methylphenyl) -6-bromo-5-hydroxy-2-methyl- was used in the same manner as in Production Example 18 except that 48% hydrobromic acid was used as a raw material instead of concentrated hydrochloric acid. 3 (2H) -pyridazinone (compound (I-19)) was obtained (yield 41%).
¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (6H, t, J = 7.6 Hz), 2.24-2.42 (7H, m), 3.80 (3H, s), 5.64 (1H, s), 7.04 (2H, s).

４−（２，６−ジエチル−４−メチルフェニル）−６−フルオロ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−２０））の合成
化合物（Ｉ−１７）５００ｍｇ（１．７４ｍｍｏｌ）を７０％フッ化水素−ピリジン３．５ｍｌに溶解し、−１０℃に冷却した。この溶液に亜硝酸ナトリウム１８０ｍｇ（２．６０ｍｍｏｌ）を少しずつ加えた。添加終了後、１０分撹拌した。この反応液に水を加え、ｔｅｒｔ−ブチルメチルエーテルで３回抽出した。合わせた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２：１）で精製し、化合物（Ｉ−２０）３８７ｍｇ（収率７６％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２５−２．４４（７Ｈ，ｍ），３．７０（３Ｈ，ｓ），５．６８（１Ｈ，ｓ），７．０４（２Ｈ，ｓ）． Production Example 20

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-fluoro-5-hydroxy-2-methyl-3 (2H) -pyridazinone (Compound (I-20)) Compound (I-17) 500 mg (1.74 mmol) was dissolved in 3.5 ml of 70% hydrogen fluoride-pyridine and cooled to -10 ° C. To this solution, sodium nitrite 180 mg (2.60 mmol) was added little by little. After completion of the addition, the mixture was stirred for 10 minutes. Water was added to the reaction mixture, and the mixture was extracted 3 times with tert-butyl methyl ether. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to obtain 387 mg (yield 76%) of compound (I-20) as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.6 Hz), 2.25-2.44 (7H, m), 3.70 (3H, s), 5.68 (1H, s), 7.04 (2H, s).

４−（２，６−ジエチル−４−メチルフェニル）−６−ブロモ−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−２１−１））の合成
化合物（Ｉ−１９）９５３ｍｇ（２．７１ｍｍｏｌ）をアセトン２０ｍｌに溶解した溶液に、ベンジルブロミド５１０ｍｇ（２．９８ｍｍｏｌ）および炭酸カリウム４５０ｍｇ（３．２５ｍｍｏｌ）を加え、加熱還流下２時間撹拌した。反応混合物を室温まで冷却した後、ろ過し、ろ液を減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝４：１）で精製し、化合物（Ｉ−２１）９８０ｍｇ（収率８１％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１３（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２８−２．４８（７Ｈ，ｍ），３．７９（３Ｈ，ｓ），４．５２（２Ｈ，ｓ），７．００（２Ｈ，ｓ），７．０５−７．１０（２Ｈ，ｍ），７．２５−７．３１（３Ｈ，ｍ）． Production Example 21

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-bromo-5-benzyloxy-2-methyl-3 (2H) -pyridazinone (Compound (I-21-1)) Compound (I- 19) To a solution of 953 mg (2.71 mmol) dissolved in 20 ml of acetone, 510 mg (2.98 mmol) of benzyl bromide and 450 mg (3.25 mmol) of potassium carbonate were added, and the mixture was stirred for 2 hours with heating under reflux. The reaction mixture was cooled to room temperature and then filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 4: 1) to obtain 980 mg (yield 81%) of compound (I-21) as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.13 (6H, t, J = 7.6 Hz), 2.28-2.48 (7H, m), 3.79 (3H, s), 4.52 (2H, s), 7.00 (2H, s), 7.05-7.10 (2H, m), 7.25-7.31 (3H, m).

This compound produced according to Production Example 21 is shown in Table 19 together with compound (I-21-1).

１）¹Ｈ ＮＭＲ：上記製造例に記載。
２）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０９（６Ｈ，ｔ，Ｊ＝７．５Ｈｚ），２．２２−２．４７（７Ｈ，ｍ），３．６９（３Ｈ，ｓ），３．９３（３Ｈ，ｓ），４．７５（２Ｈ，ｓ），６．９５−７．０２（４Ｈ，ｍ），７．２０−７．２５（３Ｈ，ｍ）．
３）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０９（６Ｈ，ｔ，Ｊ ＝７．６Ｈｚ），１．４４（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），２．２２−２．３３（２Ｈ，ｍ），２．３４−２．４５（５Ｈ，ｍ），３．６７（３Ｈ，ｓ），４．３０（２Ｈ，ｑ，Ｊ＝７．１Ｈｚ），４．７９（２Ｈ，ｓ），６．９６（２Ｈ，ｓ），６．９８−７．０２（２Ｈ，ｍ），７．２０−７．２４（３Ｈ，ｍ）．
４）¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１３（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ）， ２．２７−２．５３（１０Ｈ，ｍ），３．７８（３Ｈ，ｓ），４．４７（２Ｈ，ｓ），６．９８（２Ｈ，ｓ），７．０７−７．１３（２Ｈ，ｍ），７．２４−７．３１（３Ｈ，ｍ）．

1) ¹ H NMR: described in the above production example.
2) ¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.5 Hz), 2.22-2.47 (7H, m), 3.69 (3H, s), 3 .93 (3H, s), 4.75 (2H, s), 6.95-7.02 (4H, m), 7.20-7.25 (3H, m).
3) ¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.6 Hz), 1.44 (3H, t, J = 7.1 Hz), 2.22-2.33 ( 2H, m), 2.34-2.45 (5H, m), 3.67 (3H, s), 4.30 (2H, q, J = 7.1 Hz), 4.79 (2H, s) 6.96 (2H, s), 6.98-7.02 (2H, m), 7.20-7.24 (3H, m).
4) ¹ H NMR (CDCl ₃ ) δ ppm: 1.13 (6H, t, J = 7.6 Hz), 2.27-2.53 (10H, m), 3.78 (3H, s), 4 .47 (2H, s), 6.98 (2H, s), 7.07-7.13 (2H, m), 7.24-7.31 (3H, m).

４−（２，６−ジエチル−４−メチルフェニル）−６−アセトアミド−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−２２））の合成
化合物（Ｉ−１７）７５０ｍｇ（２．６１ｍｍｏｌ）およびアセトニトリル１０ｍｌの混合物にトリエチルアミン１．７ｍｌ（１２．２ｍｍｏｌ）を加え、氷冷した。この混合物に塩化アセチル０．６ｍｌ（６．９２ｍｍｏｌ）をゆっくり滴下した。アイスバスをはずし、室温で３０分撹拌した。反応混合物に２Ｎ水酸化ナトリウム水溶液１０ｍｌを加え、室温でさらに１５分撹拌した。この反応液に２Ｎ塩酸１５ｍｌを加え、酢酸エチルで２回抽出した。合わせた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。得られた固体をｔｅｒｔ−ブチルメチルエーテルで洗浄し、化合物（Ｉ−２２）５９０ｍｇ（収率６８％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２０（３Ｈ，ｓ），２．２８−２．４４（７Ｈ，ｍ），３．７２（３Ｈ，ｓ），６．９８（２Ｈ，ｓ），８．２４（１Ｈ，ｓ），１１．５３（１Ｈ，ｓ）． Production Example 22

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-acetamido-5-hydroxy-2-methyl-3 (2H) -pyridazinone (Compound (I-22)) 750 mg of Compound (I-17) To a mixture of 2.61 mmol) and 10 ml of acetonitrile, 1.7 ml (12.2 mmol) of triethylamine was added and ice-cooled. To this mixture, 0.6 ml (6.92 mmol) of acetyl chloride was slowly added dropwise. The ice bath was removed and the mixture was stirred at room temperature for 30 minutes. To the reaction mixture was added 10 ml of 2N aqueous sodium hydroxide solution, and the mixture was further stirred at room temperature for 15 minutes. To this reaction solution was added 15 ml of 2N hydrochloric acid, and the mixture was extracted twice with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained solid was washed with tert-butyl methyl ether to obtain 590 mg (yield 68%) of compound (I-22) as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.6 Hz), 2.20 (3H, s), 2.28-2.44 (7H, m), 3.72 (3H, s), 6.98 (2H, s), 8.24 (1H, s), 11.53 (1H, s).

４−（２，６−ジエチル−４−メチルフェニル）−６−ニトロ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−２３））の合成
化合物（Ｉ−１７）５００ｍｇ（１．７４ｍｍｏｌ）をメタノール１５ｍｌに溶解した溶液にタングステン酸ナトリウム２水和物５７ｍｇ（０．１７ｍｍｏｌ）および３０％過酸化水素水１．２ｍｌを加え、加熱還流下３時間撹拌した。室温まで冷却後、反応液に飽和食塩水を加え、酢酸エチルで２回抽出し、合わせた有機層を無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２：１）で精製し、化合物（Ｉ−２３）２１５ｍｇ（収率３９％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１０（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２６−２．４２（７Ｈ，ｍ），３．９６（３Ｈ，ｓ），７．０３（２Ｈ，ｓ），９．５０（１Ｈ，ｂｒｓ）． Production Example 23

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-nitro-5-hydroxy-2-methyl-3 (2H) -pyridazinone (Compound (I-23)) Compound (I-17) 500 mg To a solution obtained by dissolving (1.74 mmol) in 15 ml of methanol, 57 mg (0.17 mmol) of sodium tungstate dihydrate and 1.2 ml of 30% aqueous hydrogen peroxide were added, and the mixture was stirred for 3 hours with heating under reflux. After cooling to room temperature, saturated brine was added to the reaction mixture, and the mixture was extracted twice with ethyl acetate. The combined organic layers were dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to obtain 215 mg (yield 39%) of compound (I-23) as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.10 (6H, t, J = 7.6 Hz), 2.26-2.42 (7H, m), 3.96 (3H, s), 7.03 (2H, s), 9.50 (1H, brs).

４−（２，６−ジエチル−４−メチルフェニル）−６−ヒドロキシメチル−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−２４−１））の合成
４−（２，６−ジエチル−４−メチルフェニル）−６−ヒドロキシメチル−５−（４−メチルフェニルスルホニル）−２−メチル−３（２Ｈ）−ピリダジノン２．５８ｇ（５．８５ｍｍｏｌ）を１，３−ジメチルイミダゾリジノン３０ｍｌに溶解した溶液に２Ｎ水酸化ナトリウム水溶液１５ｍｌを加え、７０℃で１２時間撹拌した。この反応液を室温まで冷却後、２Ｎ塩酸２５ｍｌを加え、酢酸エチルで２回抽出し、合わせた有機層を２回水洗し、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１：１→１：２）で精製し、化合物（Ｉ−２４−１）８４２ｍｇ（収率４７％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０７（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２３−２．４３（７Ｈ，ｍ），３．７９（３Ｈ，ｓ），４．６８（２Ｈ，ｓ），７．０２（２Ｈ，ｓ）． Production Example 24

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-hydroxymethyl-5-hydroxy-2-methyl-3 (2H) -pyridazinone (compound (I-24-1)) 4- (2 , 6-Diethyl-4-methylphenyl) -6-hydroxymethyl-5- (4-methylphenylsulfonyl) -2-methyl-3 (2H) -pyridazinone 2.58 g (5.85 mmol) To a solution dissolved in 30 ml of imidazolidinone, 15 ml of 2N aqueous sodium hydroxide solution was added and stirred at 70 ° C. for 12 hours. The reaction mixture was cooled to room temperature, 25 ml of 2N hydrochloric acid was added, and the mixture was extracted twice with ethyl acetate. The combined organic layer was washed twice with water, washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. did. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1 → 1: 2) to obtain 842 mg (yield 47%) of compound (I-24-1) as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.07 (6H, t, J = 7.6 Hz), 2.23-2.43 (7H, m), 3.79 (3H, s), 4.68 (2H, s), 7.02 (2H, s).

製造例２４に準じて４−（２，４，６−トリエチルフェニル）−６−ヒドロキシメチル−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−２４−２））を製造した。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０８（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．２７（３Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２５−２．４８（４Ｈ，ｍ），２．６６（２Ｈ，ｑ，Ｊ＝７．６Ｈｚ），３．８１（３Ｈ，ｓ），４．７２（２Ｈ，ｄ，Ｊ＝３．４Ｈｚ），７．０５（２Ｈ，ｓ）．

4- (2,4,6-triethylphenyl) -6-hydroxymethyl-5-hydroxy-2-methyl-3 (2H) -pyridazinone (compound (I-24-2)) is produced according to Production Example 24. did.
¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (6H, t, J = 7.6 Hz), 1.27 (3H, t, J = 7.6 Hz), 2.25-2.48 (4H, m), 2.66 (2H, q, J = 7.6 Hz), 3.81 (3H, s), 4.72 (2H, d, J = 3.4 Hz), 7.05 (2H, s) .

４−（２，６−ジエチル−４−メチルフェニル）−６−ホルミル−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−２５−１））の合成
化合物（Ｉ−２４−１）６８１ｍｇ（２．２５ｍｍｏｌ）をクロロホルム１０ｍｌに溶解した溶液に２，２，６，６−テトラメチルピペリジン １−オキシル３５ｍｇ（０．２２４ｍｍｏｌ）およびヨードベンゼン＝ジアセタート７９８ｍｇ（２．４７ｍｍｏｌ）を加え、室温で５分撹拌した。この反応液に１Ｎ塩酸１０ｍｌを加え、酢酸エチルで２回抽出し、合わせた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝７０：３０）で精製し、化合物（Ｉ−２５−１）４２２ｍｇ（収率６２％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０８（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２６−２．４３（７Ｈ，ｍ），３．９５（３Ｈ，ｓ），６．９９（２Ｈ，ｓ），９．８２（１Ｈ，ｓ），１０．０３（１Ｈ，ｓ）． Production Example 25

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-formyl-5-hydroxy-2-methyl-3 (2H) -pyridazinone (Compound (I-25-1)) Compound (I-24) -1) To a solution of 681 mg (2.25 mmol) dissolved in 10 ml of chloroform, 35 mg (0.224 mmol) of 1,2,6,6-tetramethylpiperidine 1-oxyl and 798 mg (2.47 mmol) of iodobenzene diacetate were added. And stirred at room temperature for 5 minutes. To this reaction solution was added 10 ml of 1N hydrochloric acid, and the mixture was extracted twice with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 70: 30) to obtain 422 mg (yield 62%) of compound (I-25-1) as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (6H, t, J = 7.6 Hz), 2.26-2.43 (7H, m), 3.95 (3H, s), 6.99 (2H, s), 9.82 (1H, s), 10.03 (1H, s).

¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．２６（３Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２７−２．４４（４Ｈ，ｍ），２．６６（２Ｈ，ｑ，Ｊ＝７．６Ｈｚ），３．９５（３Ｈ，ｓ），７．０１（２Ｈ， ｓ），９．８２（１Ｈ，ｓ），１０．０４（１Ｈ，ｓ）． 4- (2,4,6-triethylphenyl) -6-formyl-5-hydroxy-2-methyl-3 (2H) -pyridazinone (compound (I-25-2)) was produced according to Production Example 25. .

¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.6 Hz), 1.26 (3H, t, J = 7.6 Hz), 2.27-2.44 (4H, m), 2.66 (2H, q, J = 7.6 Hz), 3.95 (3H, s), 7.01 (2H, s), 9.82 (1H, s), 10.04 (1H , S).

４−（２，６−ジエチル−４−メチルフェニル）−６−ヒドロキシイミノメチル−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−２６−１））の合成
化合物（Ｉ−２５−１）４３８ｍｇ（１．４５ｍｍｏｌ）をＴＨＦ１６ｍｌに溶解した溶液にヒドロキシルアミン塩酸塩１５２ｍｇ（２．１８ｍｍｏｌ）、ギ酸ナトリウム２４６ｍｇ（３．６２ｍｍｏｌ）および水１０ｍｌを加え、室温で３０分撹拌した。この反応液に１Ｎ塩酸１０ｍｌを加え、酢酸エチルで２回抽出し、合わせた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮し、化合物（Ｉ−２６−１）４６０ｍｇ（収率１００％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０８（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２６−２．４３（７Ｈ，ｍ），３．８４（３Ｈ，ｓ），６．９８（２Ｈ，ｓ），８．１６（１Ｈ，ｓ），８．２０（１Ｈ，ｓ），９．９１（１Ｈ，ｓ）． Production Example 26

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-hydroxyiminomethyl-5-hydroxy-2-methyl-3 (2H) -pyridazinone (Compound (I-26-1)) Compound (I -25-1) To a solution of 438 mg (1.45 mmol) dissolved in 16 ml of THF, 152 mg (2.18 mmol) of hydroxylamine hydrochloride, 246 mg (3.62 mmol) of sodium formate and 10 ml of water were added and stirred at room temperature for 30 minutes. To this reaction solution was added 10 ml of 1N hydrochloric acid, and the mixture was extracted twice with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and compound (I-26-1) 460 mg (yield 100%) was obtained as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (6H, t, J = 7.6 Hz), 2.26-2.43 (7H, m), 3.84 (3H, s), 6.98 (2H, s), 8.16 (1H, s), 8.20 (1H, s), 9.91 (1H, s).

¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０７（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ，Ｅｔ），１．２５（３Ｈ，ｔ，Ｊ＝７．６Ｈｚ，Ｅｔ），２．１８−２．４８（４Ｈ，ｍ，Ｅｔ），２．６３（２Ｈ，ｑ，Ｊ＝７．６Ｈｚ，Ｅｔ），３．８３（３Ｈ，ｓ， Ｎ−Ｍｅ），６．９９（２Ｈ，ｓ，Ｐｈ），８．１３（１Ｈ，ｓ），８．５１（１Ｈ，ｂｒｓ，ＯＨ），１０．００（１Ｈ，ｂｒｓ，ＯＨ）． 4- (2,4,6-triethylphenyl) -6-hydroxyiminomethyl-5-hydroxy-2-methyl-3 (2H) -pyridazinone (compound (I-26-2)) was prepared according to Preparation Example 26. Manufactured.

¹ H NMR (CDCl ₃ ) δ ppm: 1.07 (6H, t, J = 7.6 Hz, Et), 1.25 (3H, t, J = 7.6 Hz, Et), 2.18-2. 48 (4H, m, Et), 2.63 (2H, q, J = 7.6 Hz, Et), 3.83 (3H, s, N-Me), 6.99 (2H, s, Ph), 8.13 (1H, s), 8.51 (1H, brs, OH), 10.00 (1H, brs, OH).

４−（２，６−ジエチル−４−メチルフェニル）−６−シアノ−５−アセトキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−２７−１））の合成
化合物（Ｉ−２６−１）４３３ｍｇ（１．３７ｍｍｏｌ）を無水酢酸３ｍｌに加え、１３０℃で１４時間撹拌した。この反応液を減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝４：１）で精製し、化合物（Ｉ−２７−１）３７４ｍｇ（収率７５％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１０（６Ｈ，ｔ，Ｊ＝７．５Ｈｚ），２．０７（３Ｈ，ｓ），２．２９（４Ｈ，ｑ，Ｊ＝７．５Ｈｚ），２．３５（３Ｈ，ｓ），３．９１（３Ｈ，ｓ），６．９７（２Ｈ，ｓ）． Production Example 27

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-cyano-5-acetoxy-2-methyl-3 (2H) -pyridazinone (Compound (I-27-1)) Compound (I-26 -1) 433 mg (1.37 mmol) was added to 3 ml of acetic anhydride and stirred at 130 ° C. for 14 hours. The reaction solution was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 4: 1) to obtain 374 mg (yield 75%) of compound (I-27-1) as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.10 (6H, t, J = 7.5 Hz), 2.07 (3H, s), 2.29 (4H, q, J = 7.5 Hz), 2 .35 (3H, s), 3.91 (3H, s), 6.97 (2H, s).

¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１０（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．２６（３Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．０７（３Ｈ，ｓ），２．３１（４Ｈ，ｑ，Ｊ＝７．６Ｈｚ），２．６５（２Ｈ，ｑ，Ｊ＝７．６Ｈｚ），３．９１（３Ｈ，ｓ），６．９９（２Ｈ，ｓ）． 4- (2,4,6-triethylphenyl) -6-cyano-5-acetoxy-2-methyl-3 (2H) -pyridazinone (compound (I-27-2)) was produced according to Production Example 27. .

¹ H NMR (CDCl ₃ ) δ ppm: 1.10 (6H, t, J = 7.6 Hz), 1.26 (3H, t, J = 7.6 Hz), 2.07 (3H, s), 2 .31 (4H, q, J = 7.6 Hz), 2.65 (2H, q, J = 7.6 Hz), 3.91 (3H, s), 6.99 (2H, s).

４−（２，６−ジエチル−４−メチルフェニル）−６−シアノ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−２８−１））の合成
化合物（Ｉ−２７−１）３０２ｍｇ（０．８８９ｍｍｏｌ）をエタノール４ｍｌに溶解した溶液に２Ｎ水酸化ナトリウム水溶液１．３ｍｌを加え、室温で一晩撹拌した。この反応液に２Ｎ塩酸４ｍｌを加え、酢酸エチルで２回抽出し、合わせた有機層を２回水洗し、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをヘキサン：ｔｅｒｔ−ブチルメチルエーテル＝２：１の混合溶媒で洗浄し、化合物（Ｉ−２８−１）１９０ｍｇ（収率７１％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０７（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２３−２．４３（７Ｈ，ｍ），３．７９（３Ｈ，ｓ），４．６８（１Ｈ，ｓ），７．０２（２Ｈ，ｓ）． Production Example 28

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-cyano-5-hydroxy-2-methyl-3 (2H) -pyridazinone (Compound (I-28-1)) Compound (I-27 -1) To a solution of 302 mg (0.889 mmol) dissolved in 4 ml of ethanol was added 1.3 ml of 2N aqueous sodium hydroxide solution, and the mixture was stirred overnight at room temperature. To this reaction solution was added 4 ml of 2N hydrochloric acid, and the mixture was extracted twice with ethyl acetate. The combined organic layer was washed twice with water, washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was washed with a mixed solvent of hexane: tert-butyl methyl ether = 2: 1 to obtain 190 mg (yield 71%) of compound (I-28-1) as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.07 (6H, t, J = 7.6 Hz), 2.23-2.43 (7H, m), 3.79 (3H, s), 4.68 (1H, s), 7.02 (2H, s).

製造例２８に準じて４−（２，４，６−トリエチルフェニル）−６−シアノ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−２８−２））を製造した。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δｐｐｍ：１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．２７（３Ｈ，ｔ，Ｊ＝７．７Ｈｚ），２．２５−２．４２（４Ｈ，ｍ），２．６７（２Ｈ，ｑ，Ｊ＝７．７Ｈｚ），３．８８（３Ｈ，ｓ），６．１３（１Ｈ，ｂｒｓ），７．０８（２Ｈ，ｓ）．

4- (2,4,6-triethylphenyl) -6-cyano-5-hydroxy-2-methyl-3 (2H) -pyridazinone (compound (I-28-2)) was produced according to Production Example 28. .
¹ H NMR (CDCl ₃ ) δ ppm: 1.09 (6H, t, J = 7.6 Hz), 1.27 (3H, t, J = 7.7 Hz), 2.25-2.42 (4H, m ), 2.67 (2H, q, J = 7.7 Hz), 3.88 (3H, s), 6.13 (1H, brs), 7.08 (2H, s).

４−（２，６−ジエチル−４−メチルフェニル）−６−ヒドロキシメチル−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−２９））の合成
４−（２，６−ジエチル−４−メチルフェニル）−６−メトキシメトキシメチル−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン２．３ｇ（４．９１ｍｍｏｌ）をメタノール１５ｍｌに溶解した溶液に、濃塩酸２ｍｌおよび水１ｍｌを加え、６５℃で７５分撹拌した。この反応液を室温まで冷却後、２Ｎ水酸化ナトリウム水溶液で中和し、酢酸エチルで２回抽出し、合わせた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１：１）で精製し、化合物（Ｉ−２９）１．６４ｇ（収率８５％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１５（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．３２−２．５３（７Ｈ，ｍ），２．７４（１Ｈ， ｔ，Ｊ＝５．９Ｈｚ），３．７９（３Ｈ，ｓ），４．４３（２Ｈ，ｓ），４．６１（２Ｈ，ｄ，Ｊ＝５．９Ｈｚ），６．９９（２Ｈ，ｓ），７．０３−７．０８（２Ｈ，ｍ），７．２８−７．３２（３Ｈ，ｍ）． Production Example 29

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-hydroxymethyl-5-benzyloxy-2-methyl-3 (2H) -pyridazinone (Compound (I-29)) 4- (2, To a solution of 2.3 g (4.91 mmol) of 6-diethyl-4-methylphenyl) -6-methoxymethoxymethyl-5-benzyloxy-2-methyl-3 (2H) -pyridazinone in 15 ml of methanol, concentrated hydrochloric acid was added. 2 ml and 1 ml of water were added and stirred at 65 ° C. for 75 minutes. The reaction mixture was cooled to room temperature, neutralized with 2N aqueous sodium hydroxide solution and extracted twice with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. . The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1) to obtain 1.64 g (yield 85%) of compound (I-29) as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.15 (6H, t, J = 7.6 Hz), 2.32-2.53 (7H, m), 2.74 (1H, t, J = 5. 9 Hz), 3.79 (3H, s), 4.43 (2H, s), 4.61 (2H, d, J = 5.9 Hz), 6.99 (2H, s), 7.03-7 .08 (2H, m), 7.28-7.32 (3H, m).

４−（２，６−ジエチル−４−メチルフェニル）−６−シアノメチル−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−３０））の合成
４−（２，６−ジエチル−４−メチルフェニル）−６−ブロモメチル−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン６７５ｍｇ（１．４８ｍｍｏｌ）をＤＭＳＯ４ｍｌに溶解した溶液に、シアン化ナトリウム８０ｍｇ（１．６３ｍｍｏｌ）を加え、室温で３０分撹拌した。この反応液に水を加え、酢酸エチルで２回抽出し、合わせた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２：１）で精製し、化合物（Ｉ−３０）４０５ｍｇ（収率６６％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１６（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．３２−２．５１（７Ｈ，ｍ），３．６５（２Ｈ，ｓ），３．７８（３Ｈ，ｓ），４．４７（２Ｈ，ｓ），７．００（２Ｈ，ｓ），７．０７−７．１２（２Ｈ，ｍ），７．２９−７．３４（３Ｈ，ｍ）． Production Example 30

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-cyanomethyl-5-benzyloxy-2-methyl-3 (2H) -pyridazinone (Compound (I-30)) 4- (2,6 -Diethyl-4-methylphenyl) -6-bromomethyl-5-benzyloxy-2-methyl-3 (2H) -pyridazinone 675 mg (1.48 mmol) in DMSO 4 ml was dissolved in 80 mg (1.63 mmol) sodium cyanide. ) And stirred at room temperature for 30 minutes. Water was added to the reaction mixture, and the mixture was extracted twice with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to obtain 405 mg (yield 66%) of compound (I-30) as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.16 (6H, t, J = 7.6 Hz), 2.32-2.51 (7H, m), 3.65 (2H, s), 3.78 (3H, s), 4.47 (2H, s), 7.00 (2H, s), 7.07-7.12 (2H, m), 7.29-7.34 (3H, m).

４−（２，６−ジエチル−４−メチルフェニル）−６−シアノメチル−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−３１））の合成
化合物（Ｉ−３０）４００ｍｇ（０．９９６ｍｍｏｌ）、酢酸エチル１０ｍｌおよび１０％パラジウム−炭素３０ｍｇの混合物を、常圧の水素雰囲気下１時間撹拌した。得られた反応液をセライトでろ過し、ろ液を減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（酢酸エチル）で精製し、化合物（Ｉ−３１）２９１ｍｇ（収率９３％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０７（６Ｈ，ｔ，Ｊ＝７．７Ｈｚ），２．２２−２．４２（７Ｈ，ｍ），３．７８（２Ｈ，ｓ），３．８１（３Ｈ，ｓ），５．８３（１Ｈ，ｂｒｓ），７．０４（２Ｈ，ｓ）． Production Example 31

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-cyanomethyl-5-hydroxy-2-methyl-3 (2H) -pyridazinone (Compound (I-31)) Compound (I-30) 400 mg (0.996 mmol), 10 ml of ethyl acetate and 30 mg of 10% palladium-carbon were stirred for 1 hour under a hydrogen atmosphere at normal pressure. The resulting reaction solution was filtered through celite, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate) to obtain 291 mg (yield 93%) of compound (I-31) as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.07 (6H, t, J = 7.7 Hz), 2.22-2.42 (7H, m), 3.78 (2H, s), 3.81 (3H, s), 5.83 (1H, brs), 7.04 (2H, s).

４−（２，６−ジエチル−４−メチルフェニル）−６−メトキシメチル−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−３２））の合成
化合物（Ｉ−２９）５００ｍｇ（１．２７ｍｍｏｌ）を無水テトラヒドロフラン８ｍｌに溶解した溶液に、５℃でヨウ化メチル０．１６ｍｌおよび６０％水素化ナトリウム５６ｍｇ（１．４ｍｍｏｌ）を加えた。アイスバスをはずし、室温で３０分撹拌した。この反応液に水を加え、酢酸エチルで２回抽出し、合わせた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２：１）で精製し、化合物（Ｉ−３２）５０６ｍｇ（収率９７％）をオイルとして得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１３（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．３１−２．５２（７Ｈ，ｍ），３．４１（３Ｈ，ｓ），３．８０（３Ｈ，ｓ），４．４０（２Ｈ，ｓ），４．４５（２Ｈ，ｓ），６．９９（２Ｈ，ｓ），７．０４−７．０８（２Ｈ，ｍ），７．２６−７．３１（３Ｈ，ｍ）． Production Example 32

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-methoxymethyl-5-benzyloxy-2-methyl-3 (2H) -pyridazinone (Compound (I-32)) Compound (I-29) ) To a solution of 500 mg (1.27 mmol) in 8 ml of anhydrous tetrahydrofuran, 0.16 ml of methyl iodide and 56 mg (1.4 mmol) of 60% sodium hydride were added at 5 ° C. The ice bath was removed and the mixture was stirred at room temperature for 30 minutes. Water was added to the reaction mixture, and the mixture was extracted twice with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to obtain 506 mg (yield 97%) of compound (I-32) as an oil.
¹ H NMR (CDCl ₃ ) δ ppm: 1.13 (6H, t, J = 7.6 Hz), 2.31-2.52 (7H, m), 3.41 (3H, s), 3.80 (3H, s), 4.40 (2H, s), 4.45 (2H, s), 6.99 (2H, s), 7.04-7.08 (2H, m), 7.26- 7.31 (3H, m).

４−（２，６−ジエチル−４−メチルフェニル）−６−メトキシメチル−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−３３−１））の合成
化合物（Ｉ−３２）５００ｍｇ（１．２３ｍｍｏｌ）を氷酢酸４ｍｌに溶解した溶液に、４８％臭化水素酸０．５ｍｌを加え、７０℃で１時間撹拌した。この反応液を室温まで冷却後、水を加え、酢酸エチルで２回抽出し、合わせた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２：１）で精製し、化合物（Ｉ−３３−１）２９２ｍｇ（収率７４％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０８（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２６−２．４４（７Ｈ，ｍ），３．５０（３Ｈ，ｓ），３．７９（３Ｈ，ｓ），４．５９（２Ｈ，ｓ），６．８１（１Ｈ，ｓ），７．０１（２Ｈ，ｓ）． Production Example 33

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-methoxymethyl-5-hydroxy-2-methyl-3 (2H) -pyridazinone (compound (I-33-1)) (I- 32) To a solution of 500 mg (1.23 mmol) in 4 ml of glacial acetic acid, 0.5 ml of 48% hydrobromic acid was added and stirred at 70 ° C. for 1 hour. The reaction mixture was cooled to room temperature, water was added, and the mixture was extracted twice with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to obtain 292 mg (yield 74%) of compound (I-33-1) as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (6H, t, J = 7.6 Hz), 2.26-2.44 (7H, m), 3.50 (3H, s), 3.79 (3H, s), 4.59 (2H, s), 6.81 (1H, s), 7.01 (2H, s).

化合物（Ｉ−４−３）の合成
原料として２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−メチルヒドラゾノ］−２−（ドデシルチオ）酢酸エチル（幾何異性体約２：１の混合物）を用い、製造例１２と同様にして化合物（Ｉ−４−３）（収率２０％）および４−（２，６−ジエチル−４−メチルフェニル）−６−ドデシルチオ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（収率３１％）を得た。

４−（２，６−ジエチル−４−メチルフェニル）−６−ドデシルチオ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノンの¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８８（３Ｈ，ｔ，Ｊ＝６．８Ｈｚ），１．０８（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．１９−１．３８（１６Ｈ，ｍ），１．４１−１．５１（２Ｈ，ｍ），１．６９−１．７９（２Ｈ，ｍ），２．２５−２．４４（７Ｈ，ｍ），３．０６（２Ｈ，ｔ，Ｊ＝７．４Ｈｚ），３．７９（３Ｈ，ｓ），５．５５（１Ｈ，ｂｒｓ），７．０２（２Ｈ，ｓ）． Production Example 34

Synthesis of Compound (I-4-3) Ethyl 2- [2- (2,6-diethyl-4-methylphenyl) acetyl-2-methylhydrazono] -2- (dodecylthio) acetate (geometric isomer Compound (I-4-3) (yield 20%) and 4- (2,6-diethyl-4-methylphenyl) -6-dodecylthio- 5-hydroxy-2-methyl-3 (2H) -pyridazinone (yield 31%) was obtained.

¹ H NMR (CDCl ₃ ) δ ppm of 4- (2,6-diethyl-4-methylphenyl) -6-dodecylthio-5-hydroxy-2-methyl-3 (2H) -pyridazinone: 0.88 (3H, t, J = 6.8 Hz), 1.08 (6H, t, J = 7.6 Hz), 1.19-1.38 (16H, m), 1.41-1.51 (2H, m), 1.69-1.79 (2H, m), 2.25-2.44 (7H, m), 3.06 (2H, t, J = 7.4 Hz), 3.79 (3H, s), 5.55 (1H, brs), 7.02 (2H, s).

４−（２，６−ジエチル−４−メチルフェニル）−６−カルバモイルメトキシ−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−３５−１））の合成
（４−（２，６−ジエチル−４−メチルフェニル）−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン−６−イル）オキシ酢酸５３０ｍｇ（１．５３ｍｍｏｌ）、塩化チオニル２９０ｍｇ（２．４３ｍｍｏｌ）およびＤＭＦ１０ｍｇをトルエン１５ｍｌに加え、５０℃で４５分撹拌した。この反応液を室温まで冷却した後、減圧下濃縮した。残さをＴＨＦ５ｍｌに溶解し、これを氷冷下アンモニア水２ｍｌにゆっくり加えた。この反応液を室温で３０分撹拌した後、反応液に水を加え、酢酸エチルで抽出した。有機層を飽和食塩水で洗浄した後、減圧下濃縮し、化合物（Ｉ−３５−１）５００ｍｇ（収率９４％）を得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１５（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．３０−２．５１（７Ｈ，ｍ），３．６７（３Ｈ，ｓ），４．６２（２Ｈ，ｓ），４．７０（２Ｈ，ｓ），５．３３（１Ｈ，ｂｒｓ），６．１１（１Ｈ，ｂｒｓ），７．００（２Ｈ，ｓ），７．０６−７．１０（２Ｈ，ｍ），７．２７−７．３１（３Ｈ，ｍ）． Production Example 35

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-carbamoylmethoxy-5-benzyloxy-2-methyl-3 (2H) -pyridazinone (compound (I-35-1)) (2,6-diethyl-4-methylphenyl) -5-benzyloxy-2-methyl-3 (2H) -pyridazinon-6-yl) oxyacetic acid 530 mg (1.53 mmol), thionyl chloride 290 mg (2.43 mmol) 10 mg of DMF was added to 15 ml of toluene, and the mixture was stirred at 50 ° C. for 45 minutes. The reaction solution was cooled to room temperature and then concentrated under reduced pressure. The residue was dissolved in 5 ml of THF, and this was slowly added to 2 ml of aqueous ammonia under ice cooling. After stirring this reaction liquid at room temperature for 30 minutes, water was added to the reaction liquid and extracted with ethyl acetate. The organic layer was washed with saturated brine, and then concentrated under reduced pressure to obtain 500 mg (yield 94%) of compound (I-35-1).
¹ H NMR (CDCl ₃ ) δ ppm: 1.15 (6H, t, J = 7.6 Hz), 2.30-2.51 (7H, m), 3.67 (3H, s), 4.62 (2H, s), 4.70 (2H, s), 5.33 (1H, brs), 6.11 (1H, brs), 7.00 (2H, s), 7.06-7.10 ( 2H, m), 7.27-7.31 (3H, m).

¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０８（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２０−２．３０（２Ｈ，ｍ），２．３２−２．４３（２Ｈ，ｍ），２．３６（３Ｈ，ｓ），３．０４（３Ｈ，ｓ），３．０７（３Ｈ，ｓ），３．６４（３Ｈ，ｓ），４．９６（２Ｈ，ｓ），４．９６（２Ｈ，ｓ），６．９５（２Ｈ，ｓ），７．００−７．０４（２Ｈ，ｍ），７．１８−７．２２（３Ｈ，ｍ）． In the same manner as in Production Example 35, 4- (2,6-diethyl-4-methylphenyl) -6-dimethylaminocarbonylmethoxy-5-benzyloxy-2-methyl-3 (2H) -pyridazinone (compound (I-35 -2)) (yield 73%).

¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (6H, t, J = 7.6 Hz), 2.20-2.30 (2H, m), 2.32-2.43 (2H, m) , 2.36 (3H, s), 3.04 (3H, s), 3.07 (3H, s), 3.64 (3H, s), 4.96 (2H, s), 4.96 ( 2H, s), 6.95 (2H, s), 7.00-7.04 (2H, m), 7.18-7.22 (3H, m).

４−（２，６−ジエチル−４−メチルフェニル）−６−ホルミル−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−３６））の合成
製造例２５と同様にして、化合物（Ｉ−３６）を得た（収率５４％）。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１２（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２９−２．４７（７Ｈ，ｍ），３．９３（３Ｈ，ｓ），４．６０（２Ｈ，ｓ），７．０１（２Ｈ，ｓ），７．０３−７．０８（２Ｈ，ｍ），７．２４−７．３０（３Ｈ，ｍ），９．９２（１Ｈ，ｓ）. Production Example 36

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-formyl-5-benzyloxy-2-methyl-3 (2H) -pyridazinone (Compound (I-36)) In the same manner as in Production Example 25 Compound (I-36) was obtained (yield 54%).
¹ H NMR (CDCl ₃ ) δ ppm: 1.12 (6H, t, J = 7.6 Hz), 2.29-2.47 (7H, m), 3.93 (3H, s), 4.60 (2H, s), 7.01 (2H, s), 7.03-7.08 (2H, m), 7.24-7.30 (3H, m), 9.92 (1H, s).

２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−メチルヒドラゾノ］−２−ジメチルアミノ酢酸エチル（化合物（ＩＩ−２））の合成
参考例１−１

Ｅ−２−（２−メチルヒドラゾノ）酢酸エチル（化合物（ＸＶＩ−１））
４７％グリオキシル酸エチルのトルエン溶液（ポリマー型）４６７．８４ｇ（２．１５ｍｏｌ）にＴＨＦ６２０ｍｌを加え、氷冷した。これにメチルヒドラジン１０３ｇ（１．０２ｅｑ）をゆっくり滴下した。滴下終了後０℃で３０分撹拌し、次にアイスバスをはずして室温で１６時間撹拌した。この反応液を減圧下濃縮し、残さにトルエン４００ｍｌを加えて、減圧下濃縮した。得られた固体にｔｅｒｔ−ブチルメチルエーテル２００ｍｌを加えて洗浄した後、０℃で３０分静置した。次にこれをろ過し、冷たいｔｅｒｔ−ブチルメチルエーテル１００ｍｌで洗浄し、化合物（ＸＶＩ−１）２２３．９１ｇ（収率７８．８％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．３４（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），２．９７（３Ｈ，ｄ，Ｊ＝４．４Ｈｚ），４．２９（２Ｈ，ｑ，Ｊ＝７．１Ｈｚ），６．５７（１Ｈ、ｂｒｓ）、６．６９（１Ｈ，ｓ）。 Next, Reference Example 1 and Reference Example 2 show production examples of the compound represented by the formula (II).
Reference example 1

Synthesis Reference Example 1-1 of Ethyl 2- [2- (2,6-diethyl-4-methylphenyl) acetyl-2-methylhydrazono] -2-dimethylaminoacetate (Compound (II-2))

E-2- (2-Methylhydrazono) ethyl acetate (compound (XVI-1))
620 ml of THF was added to 467.84 g (2.15 mol) of a 47% ethyl glyoxylate toluene solution (polymer type), and the mixture was ice-cooled. To this, 103 g (1.02 eq) of methyl hydrazine was slowly added dropwise. After completion of dropping, the mixture was stirred at 0 ° C. for 30 minutes, then the ice bath was removed and the mixture was stirred at room temperature for 16 hours. The reaction mixture was concentrated under reduced pressure, 400 ml of toluene was added to the residue, and the mixture was concentrated under reduced pressure. The obtained solid was washed by adding 200 ml of tert-butyl methyl ether, and then allowed to stand at 0 ° C. for 30 minutes. Next, this was filtered and washed with 100 ml of cold tert-butyl methyl ether to obtain 223.91 g (yield 78.8%) of compound (XVI-1) as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.34 (3H, t, J = 7.1 Hz), 2.97 (3H, d, J = 4.4 Hz), 4.29 (2H, q, J = 7.1 Hz), 6.57 (1H, brs), 6.69 (1H, s).

Ｚ−２−クロロ−２−（２−メチルヒドラゾノ）酢酸エチル（化合物（ＸＶＩＩ−１））
化合物（ＸＶＩ−１）２４．０１ｇ（１８４ｍｍｏｌ）をＤＭＦ１００ｍｌに溶かし、５０℃に加熱した。これにＮ−クロロスクシンイミド２７．１５ｇ（２０３ｍｍｏｌ）を、内温が５０〜６０℃になるようにゆっくり加えた。添加終了後、３０分撹拌した。反応液に水３００ｍｌを加え、ｔｅｒｔ−ブチルメチルエーテルで２回抽出し、合わせた有機層を水で洗浄し、飽和食塩水で洗浄し、硫酸ナトリウムで乾燥し、濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝３：１）で精製し、化合物（ＸＶＩＩ−１）２２．９７ｇ（収率７５．６％）を固体で得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．３６（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），３．２９（３Ｈ，ｄ，Ｊ＝３．９Ｈｚ，），４．３５（２Ｈ，ｑ，Ｊ＝７．１Ｈｚ），６．４４（１Ｈ，ｂｒｓ）。 Reference Example 1-2

Z-2-Chloro-2- (2-methylhydrazono) ethyl acetate (compound (XVII-1))
Compound (XVI-1) 24.01 g (184 mmol) was dissolved in DMF 100 ml and heated to 50 ° C. To this, 27.15 g (203 mmol) of N-chlorosuccinimide was slowly added so that the internal temperature became 50 to 60 ° C. After completion of the addition, the mixture was stirred for 30 minutes. 300 ml of water was added to the reaction solution, followed by extraction twice with tert-butyl methyl ether, and the combined organic layer was washed with water, washed with saturated brine, dried over sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1) to obtain 22.97 g (yield: 75.6%) of compound (XVII-1) as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.36 (3H, t, J = 7.1 Hz), 3.29 (3H, d, J = 3.9 Hz), 4.35 (2H, q, J = 7.1 Hz), 6.44 (1H, brs).

Ｚ−２−ジメチルアミノ−２−（２−メチルヒドラゾノ）酢酸エチル（化合物（ＶＩ−１））
化合物（ＸＶＩＩ−１）１．３３ｇ（８．０９ｍｍｏｌ）をＴＨＦ３０ｍｌに溶解した溶液に、室温下５０％ジメチルアミン水溶液１５ｍｌ（１６６ｍｍｏｌ）を加えた。この混合物を加熱還流下９時間攪拌した。反応混合物を室温まで冷却した後、そこに水３０ｍｌを加え、酢酸エチルで２回抽出した。合わせた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧濃縮し、化合物（ＶＩ−１）１．３４ｇ（収率９５％）をオイルとして得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．３４（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），２．５８（６Ｈ，ｓ），３．１５（３Ｈ，ｄ，Ｊ＝４．４Ｈｚ），４．２７（２Ｈ，ｑ，Ｊ＝７．１Ｈｚ），６．２８（１Ｈ，ｂｒｓ）。 Reference Example 1-3

Z-2-dimethylamino-2- (2-methylhydrazono) ethyl acetate (compound (VI-1))
To a solution of 1.33 g (8.09 mmol) of compound (XVII-1) in 30 ml of THF, 15 ml (166 mmol) of 50% aqueous dimethylamine solution was added at room temperature. The mixture was stirred for 9 hours under heating to reflux. The reaction mixture was cooled to room temperature, 30 ml of water was added thereto, and the mixture was extracted twice with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 1.34 g (yield 95%) of compound (VI-1) as an oil.
¹ H NMR (CDCl ₃ ) δ ppm: 1.34 (3H, t, J = 7.1 Hz), 2.58 (6H, s), 3.15 (3H, d, J = 4.4 Hz), 4 .27 (2H, q, J = 7.1 Hz), 6.28 (1H, brs).

２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−メチルヒドラゾノ］−２−ジメチルアミノ酢酸エチル（化合物（ＩＩ−２））
化合物（ＶＩ−１）３６５ｍｇ（２．１０ｍｍｏｌ）をＴＨＦ８ｍｌに溶解した溶液にピリジン１９５ｍｇ（２．４６ｍｍｏｌ）を加え、氷冷した。この溶液に２−（２，６−ジエチル−４−メチルフェニル）アセチルクロリド（化合物（Ｖ−１））４７４ｍｇ（２．１１ｍｍｏｌ）をＴＨＦ３ｍｌに溶解した溶液をゆっくり滴下した。この反応液を室温で２時間攪拌した。反応液に水を加え、酢酸エチルで２回抽出した。合わせた有機層を飽和炭酸水素ナトリウム水溶液、飽和食塩水で順次洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮して、化合物（ＩＩ−２）７５０ｍｇ（２．０７ｍｍｏｌ）をオイルとして得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１４〜１．２１（６Ｈ，ｍ），１．３４〜１．４０（３Ｈ，ｍ），２．２８（３Ｈ，ｓ），２．４７〜２．５８（４Ｈ，ｍ），３．０１（６Ｈ，ｓ），３．０８（３Ｈ，ｓ），３．６６（２Ｈ，ｓ），４．３０〜４．３４（２Ｈ，ｍ），６．８８（２Ｈ，ｓ）。 Reference Example 1-4

2- [2- (2,6-Diethyl-4-methylphenyl) acetyl-2-methylhydrazono] -2-dimethylaminoacetic acid ethyl (compound (II-2))
To a solution of 365 mg (2.10 mmol) of compound (VI-1) in 8 ml of THF, 195 mg (2.46 mmol) of pyridine was added and ice-cooled. A solution prepared by dissolving 474 mg (2.11 mmol) of 2- (2,6-diethyl-4-methylphenyl) acetyl chloride (compound (V-1)) in 3 ml of THF was slowly added dropwise to this solution. The reaction was stirred at room temperature for 2 hours. Water was added to the reaction mixture, and the mixture was extracted twice with ethyl acetate. The combined organic layers were washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 750 mg (2.07 mmol) of compound (II-2) as an oil.
¹ H NMR (CDCl ₃ ) δ ppm: 1.14 to 1.21 (6H, m), 1.34 to 1.40 (3H, m), 2.28 (3H, s), 2.47 to 2 .58 (4H, m), 3.01 (6H, s), 3.08 (3H, s), 3.66 (2H, s), 4.30-4.34 (2H, m), 6. 88 (2H, s).

The following compounds were obtained in the same manner as in Reference Example 1.
2-Dimethylamino-2- [2-methyl-2- (2,4,6-trimethylphenyl) acetylhydrazono] ethyl acetate (compound (II-1))
¹ H NMR (CDCl ₃ ) δ ppm: 1.37 (3H, t, J = 7.1 Hz), 2.21 (6H, s), 2.23 (3H, s), 3.01 (6H, s ), 3.08 (3H, s), 3.62 (2H, s), 4.36 (2H, q, J = 7.1 Hz), 6.82 (2H, s).
2-Dimethylamino-2- [2-methyl-2- (2,4,6-triethylphenyl) acetylhydrazono] ethyl acetate (compound (II-3))
¹ H NMR (CDCl ₃ ) δ ppm: 1.12 to 1.28 (9H, m), 1.33 to 1.42 (3H, m), 2.51 to 2.68 (6H, m), 3 .01 (6H, s), 3.08 (3H, s), 3.67 (2H, s), 4.32 to 4.41 (2H, m), 6.87 (2H, s).

２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−メチルヒドラゾノ］−２−（メチルチオ）酢酸エチル（化合物（ＩＩ−５））の合成
参考例２−１

Ｅ−２−［２−（ｔ−ブトキシカルボニル）ヒドラゾノ］酢酸エチル（化合物（Ｘ−１））
ｔ−ブチル＝カーバゼート２５．５ｇ（１９３ｍｍｏｌ）をＴＨＦ６０ｍｌに溶解させた溶液に、４７％グリオキシル酸エチルのトルエン溶液（ポリマー型）４６．１ｇ（２１２ｍｍｏｌ）を加え、６０℃で３０分間攪拌した。反応液を室温まで冷却し、減圧濃縮した。得られた固体をヘキサン：酢酸エチル＝５：１で洗浄し、化合物（Ｘ−１）３３．９ｇ（収率８０％）を無色固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．３４（３Ｈ，ｔ，Ｊ＝７．２Ｈｚ），１．５３（９Ｈ，ｓ），４．３１（２Ｈ，ｑ，Ｊ＝７．２Ｈｚ），７．５４（１Ｈ，ｂｒｓ），８．２５（１Ｈ，ｓ）． Reference example 2

Synthesis Reference Example 2-1 of Ethyl 2- [2- (2,6-diethyl-4-methylphenyl) acetyl-2-methylhydrazono] -2- (methylthio) acetate (Compound (II-5))

E-2- [2- (t-Butoxycarbonyl) hydrazono] ethyl acetate (compound (X-1))
To a solution of 25.5 g (193 mmol) of t-butyl = carbazate dissolved in 60 ml of THF, 46.1 g (212 mmol) of a toluene solution (polymer type) of 47% ethyl glyoxylate was added and stirred at 60 ° C. for 30 minutes. The reaction solution was cooled to room temperature and concentrated under reduced pressure. The obtained solid was washed with hexane: ethyl acetate = 5: 1 to obtain 33.9 g (yield 80%) of compound (X-1) as a colorless solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.34 (3H, t, J = 7.2 Hz), 1.53 (9H, s), 4.31 (2H, q, J = 7.2 Hz), 7 .54 (1H, brs), 8.25 (1H, s).

Ｅ−２−（２−ｔ−ブトキシカルボニル−２−メチルヒドラゾノ）酢酸エチル（化合物（ＸＩＩ−１））
５５％水素化ナトリウム６．９８ｇ（１６０ｍｍｏｌ）およびＤＭＦ１８０ｍｌの混合物に、氷冷下化合物（Ｘ−１）３１．２２ｇ（１４４ｍｍｏｌ）を１３分かけて添加した。得られた混合物にヨードメタン３０．７３ｇ（２１７ｍｍｏｌ）を１４分かけて滴下した。この混合物を室温で３．５時間攪拌した。反応混合物に水を加え、酢酸エチルで３回抽出した。合わせた有機層を水洗し、無水硫酸マグネシウムで乾燥し、減圧濃縮し、化合物（ＸＩＩ−１）３１．３５ｇの粗精製物をオイルとして得た。これを精製せずに次の反応に使用した。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δｐｐｍ：１．３６（３Ｈ，ｔ，Ｊ＝７．２Ｈｚ），１．５７（９Ｈ，ｓ），３．２８（３Ｈ，ｓ），４．３３（２Ｈ，ｑ，Ｊ＝７．２Ｈｚ），６．９７（１Ｈ，ｓ）。 Reference Example 2-2

E-2- (2-t-butoxycarbonyl-2-methylhydrazono) ethyl acetate (compound (XII-1))
To a mixture of 5.98 g (160 mmol) of 55% sodium hydride and 180 ml of DMF, 31.22 g (144 mmol) of compound (X-1) was added over 13 minutes under ice cooling. To the resulting mixture, 30.73 g (217 mmol) of iodomethane was added dropwise over 14 minutes. The mixture was stirred at room temperature for 3.5 hours. Water was added to the reaction mixture, and the mixture was extracted 3 times with ethyl acetate. The combined organic layers were washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 31.35 g of a crude purified product of compound (XII-1) as an oil. This was used in the next reaction without purification.
¹ H NMR (CDCl ₃ ) δ ppm: 1.36 (3H, t, J = 7.2 Hz), 1.57 (9H, s), 3.28 (3H, s), 4.33 (2H, q, J = 7.2 Hz), 6.97 (1H, s).

Ｚ−２−（２−ｔ−ブトキシカルボニル−２−メチルヒドラゾノ）−２−クロロ酢酸エチル（化合物（ＸＩＩＩ−１））
化合物（ＸＩＩ−１）１．１ｇ（４．７７ｍｍｏｌ）を酢酸エチル１０ｍｌ溶解した溶液に、Ｎ−クロロスクシンイミド２．４５ｇ（１８．３ｍｍｏｌ）を加え、５０℃で９時間攪拌した。反応混合物を室温まで冷却した後、減圧濃縮した。残さをヘキサン：酢酸エチル＝３：１の混合溶媒で洗浄し、ろ過した。そのろ液を濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝３：１）で精製し、化合物（ＸＩＩＩ−１）１．０ｇ（収率７９％）を（性状微黄色油状物）得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．３８（３Ｈ，ｔ，Ｊ＝７．２Ｈｚ），１．５４（９Ｈ，ｓ），３．５５（３Ｈ，ｓ），４．３７（２Ｈ，ｑ，Ｊ＝７．２Ｈｚ）。 Reference Example 2-3

Z-2- (2-t-butoxycarbonyl-2-methylhydrazono) -2-chloroacetic acid ethyl (compound (XIII-1))
2.45 g (18.3 mmol) of N-chlorosuccinimide was added to a solution of 1.1 g (4.77 mmol) of compound (XII-1) in 10 ml of ethyl acetate, and the mixture was stirred at 50 ° C. for 9 hours. The reaction mixture was cooled to room temperature and then concentrated under reduced pressure. The residue was washed with a mixed solvent of hexane: ethyl acetate = 3: 1 and filtered. The filtrate was concentrated. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1) to obtain 1.0 g (yield 79%) of compound (XIII-1) (property slightly yellow oil).
¹ H NMR (CDCl ₃ ) δ ppm: 1.38 (3H, t, J = 7.2 Hz), 1.54 (9H, s), 3.55 (3H, s), 4.37 (2H, q , J = 7.2 Hz).

Ｚ−２−［２−（ｔ−ブトキシカルボニル）−２−メチルヒドラゾノ］−２−（メチルチオ）酢酸エチル（化合物（ＸＶ−１））
１５％メチルメルカプタン水溶液１．９４ｇ（４．１５ｍｍｏｌ）をＴＨＦ１０ｍｌに溶解させた溶液に、氷冷下化合物（ＸＩＩＩ−１）１．０ｇ（３．７７ｍｍｏｌ）をＴＨＦ５ｍｌに溶解した溶液を滴下した。混合物を室温で１時間攪拌した後、反応液に水を加え、酢酸エチルで２回抽出した。合わせた有機層を、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２：１）で精製し、化合物（ＸＶ−１）９００ｍｇ（収率８６％）を得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．３９（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），１．４９（９Ｈ，ｓ），２．３９（３Ｈ，ｓ），３．２０（３Ｈ，ｓ），４．３８（２Ｈ，ｑ，Ｊ＝７．２Ｈｚ）。 Reference Example 2-4

Z-2- [2- (t-butoxycarbonyl) -2-methylhydrazono] -2- (methylthio) acetic acid ethyl (compound (XV-1))
To a solution of 1.94 g (4.15 mmol) of 15% methyl mercaptan aqueous solution dissolved in 10 ml of THF, a solution of 1.0 g (3.77 mmol) of compound (XIII-1) dissolved in 5 ml of THF was added dropwise under ice cooling. The mixture was stirred at room temperature for 1 hour, water was added to the reaction mixture, and the mixture was extracted twice with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to obtain 900 mg (yield 86%) of compound (XV-1).
¹ H NMR (CDCl ₃ ) δ ppm: 1.39 (3H, t, J = 7.1 Hz), 1.49 (9H, s), 2.39 (3H, s), 3.20 (3H, s ), 4.38 (2H, q, J = 7.2 Hz).

２−（２−メチルヒドラゾノ）−２−（メチルチオ）酢酸エチル（化合物（ＶＩ−２））
化合物（ＸＶ−１）４．４７ｇ（１６．１ｍｍｏｌ）をジオキサン１３ｍｌに溶解させた溶液に４．０Ｍ塩化水素ジオキサン溶液２３ｍｌ（９２ｍｍｏｌ）を加えた。この混合物を室温で２時間攪拌した。この反応液に飽和炭酸水素ナトリウム水溶液を加えてアルカリ性にし、酢酸エチルで２回抽出した。合わせた有機層を、飽和食塩水で洗浄した後、無水硫酸マグネシウムで乾燥し減圧濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝３：１）で精製し、化合物（ＶＩ−２）のＥ体１．９５ｇ（収率６８％）（淡黄色固体）および化合物（ＶＩ−２）のＺ体０．６３ｇ（収率２２％）を得た。

Ｅ−２−（２−メチルヒドラゾノ）−２−（メチルチオ）酢酸エチル
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．３５（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），２．２９（３Ｈ，ｓ），３．２１（３Ｈ，ｄ，Ｊ＝３．９Ｈｚ），４．２６（２Ｈ，ｑ，Ｊ＝７．１Ｈｚ），９．９６（１Ｈ，ｂｒｓ）。

Ｚ−２−（２−メチルヒドラゾノ）−２−（メチルチオ）酢酸エチル
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．３６（３Ｈ，ｔ，Ｊ＝７．２Ｈｚ），２．２８（３Ｈ，ｓ），３．３３（３Ｈ，ｄ，Ｊ＝４．１Ｈｚ），４．３３（２Ｈ，ｑ，Ｊ＝７．２Ｈｚ），７．３２（１Ｈ，ｂｒｓ）。 Reference Example 2-5

2- (2-Methylhydrazono) -2- (methylthio) acetic acid ethyl (compound (VI-2))
To a solution obtained by dissolving 4.47 g (16.1 mmol) of compound (XV-1) in 13 ml of dioxane, 23 ml (92 mmol) of 4.0 M hydrogen chloride dioxane solution was added. The mixture was stirred at room temperature for 2 hours. Saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture to make it alkaline, and the mixture was extracted twice with ethyl acetate. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1) to obtain 1.95 g (yield 68%) of compound (VI-2) in E form (light yellow solid) and compound (VI-2). 0.63 g (yield 22%) of Z-form was obtained.

E-2- (2-Methylhydrazono) -2- (methylthio) acetic acid ethyl
¹ H NMR (CDCl ₃ ) δ ppm: 1.35 (3H, t, J = 7.1 Hz), 2.29 (3H, s), 3.21 (3H, d, J = 3.9 Hz), 4 .26 (2H, q, J = 7.1 Hz), 9.96 (1H, brs).

Z-2- (2-methylhydrazono) -2- (methylthio) acetic acid ethyl
¹ H NMR (CDCl ₃ ) δ ppm: 1.36 (3H, t, J = 7.2 Hz), 2.28 (3H, s), 3.33 (3H, d, J = 4.1 Hz), 4 .33 (2H, q, J = 7.2 Hz), 7.32 (1H, brs).

２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−メチルヒドラゾノ］−２−（メチルチオ）酢酸エチル（化合物（ＩＩ−５））
化合物（ＶＩ−２）のＥ体と化合物（Ｖ−１）とを参考例１−４に準じて反応させ、化合物（ＩＩ−５）をオイルとして得た（幾何異性体約２：１の混合物）。
主要物の¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１７（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．４０（３Ｈ，ｔ，Ｊ＝７．２Ｈｚ），２．２９（３Ｈ，ｓ），２．４９（３Ｈ，ｓ），２．５４（４Ｈ，ｑ，Ｊ＝７．６Ｈｚ），３．３９（３Ｈ，ｓ），３．８４（２Ｈ，ｓ），４．４０（３Ｈ，ｑ，Ｊ＝７．２Ｈｚ），６．８８（２Ｈ，ｓ）． Reference Example 2-6

2- [2- (2,6-Diethyl-4-methylphenyl) acetyl-2-methylhydrazono] -2- (methylthio) acetate (compound (II-5))
The E-form of compound (VI-2) and compound (V-1) were reacted according to Reference Example 1-4 to obtain compound (II-5) as an oil (mixture of about 2: 1 geometric isomer) ).
¹ H NMR (CDCl ₃ ) δ ppm of main product: 1.17 (6H, t, J = 7.6 Hz), 1.40 (3H, t, J = 7.2 Hz), 2.29 (3H, s ), 2.49 (3H, s), 2.54 (4H, q, J = 7.6 Hz), 3.39 (3H, s), 3.84 (2H, s), 4.40 (3H, q, J = 7.2 Hz), 6.88 (2H, s).

Reference Example 2-7
Compound (V-1) 780 mg (3.47 mmol), pyridine 0.3 ml and 4-dimethylaminopyridine 3 mg were added to a solution of compound (VI-2) Z form 540 mg (2.83 mmol) in toluene 5 ml. The mixture was stirred for 1 hour with heating under reflux. The reaction mixture was cooled to room temperature, tert-butyl methyl ether was added, the mixture was washed successively with 2N hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 4: 1) to obtain 1.11 g (yield 99%) of compound (II-5) as an oil. The geometric isomer ratio of this compound was about 2: 1, which was the same as the geometric isomer ratio in Reference Example 2-6.

２−［２−メチル−２−（２，４，６−トリメチルフェニル）アセチルヒドラゾノ］−２−（メチルチオ）酢酸エチル（化合物（ＩＩ−４））
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．３８（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），２．２１（６Ｈ，ｓ），２．２５（３Ｈ，ｓ），２．４９（３Ｈ，ｓ），３．２５（３Ｈ，ｓ），３．９４（２Ｈ，ｓ），４．３６（２Ｈ，ｑ，Ｊ＝７．１Ｈｚ），６．８６（２Ｈ，ｓ）。 The following compounds were obtained according to Reference Example 2.

2- [2-Methyl-2- (2,4,6-trimethylphenyl) acetylhydrazono] -2- (methylthio) acetic acid ethyl (compound (II-4))
¹ H NMR (CDCl ₃ ) δ ppm: 1.38 (3H, t, J = 7.1 Hz), 2.21 (6H, s), 2.25 (3H, s), 2.49 (3H, s ), 3.25 (3H, s), 3.94 (2H, s), 4.36 (2H, q, J = 7.1 Hz), 6.86 (2H, s).

２−［２−メチル−２−（２，４，６−トリエチルフェニル）アセチルヒドラゾノ］−２−（メチルチオ）酢酸エチル（化合物（ＩＩ−６））（幾何異性体約３：１の混合物）
主要物の¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１３〜１．２９（９Ｈ，ｍ），１．３３〜１．４２（３Ｈ，ｍ），２．４９（３Ｈ，ｓ），２．５１〜２．６６（６Ｈ，ｍ），３．２６（３Ｈ，ｓ），４．０１（２Ｈ，ｓ），４．３０〜４．４３（２Ｈ，ｍ），６．９１（２Ｈ，ｓ）。

2- [2-Methyl-2- (2,4,6-triethylphenyl) acetylhydrazono] -2- (methylthio) acetate (compound (II-6)) (mixture of about 3: 1 geometric isomers)
¹ H NMR (CDCl ₃ ) δ ppm of main product: 1.13 to 1.29 (9H, m), 1.33 to 1.42 (3H, m), 2.49 (3H, s), 2. 51 to 2.66 (6H, m), 3.26 (3H, s), 4.01 (2H, s), 4.30 to 4.43 (2H, m), 6.91 (2H, s) .

２−［２−メチル−２−（２−エチル−４，６−ジメチルフェニル）アセチルヒドラゾノ］−２−（メチルチオ）酢酸エチル（幾何異性体混合物）
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１１−１．２２（３Ｈ，ｍ），１．３３−１．４５（３Ｈ，ｍ），２．２１（３Ｈ，ｓ），２．２７（３Ｈ，ｓ），２．４９（３Ｈ，ｓ），２．４６−２．６６（２Ｈ，ｍ），３．２６（３Ｈ，ｓ），３．９６（２Ｈ，ｓ），４．２６−４．４５（２Ｈ，ｍ），６．８７（２Ｈ，ｓ）．

Ethyl 2- [2-methyl-2- (2-ethyl-4,6-dimethylphenyl) acetylhydrazono] -2- (methylthio) acetate (geometric isomer mixture)
¹ H NMR (CDCl ₃ ) δ ppm: 1.11-1.22 (3H, m), 1.33-1.45 (3H, m), 2.21 (3H, s), 2.27 (3H , S), 2.49 (3H, s), 2.46-2.66 (2H, m), 3.26 (3H, s), 3.96 (2H, s), 4.26-4. 45 (2H, m), 6.87 (2H, s).

２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−メチルヒドラゾノ］−２−（ドデシルチオ）酢酸エチルの合成 Reference example 3

Synthesis of ethyl 2- [2- (2,6-diethyl-4-methylphenyl) acetyl-2-methylhydrazono] -2- (dodecylthio) acetate

Ｚ−２−（２−メチルヒドラゾノ）−２−（ドデシルチオ）酢酸エチル
化合物（ＸＶＩＩ−１）２．６１ｇ（１５．８ｍｍｏｌ）をｔｅｒｔ−ブチルメチルエーテル１５ｍｌに溶解した溶液に、１−ドデカンチオール３．２１ｇ（１５．８ｍｍｏｌ）を加え、氷冷した。この溶液に６０％水素化ナトリウム６９８ｍｇ（１７．４ｍｍｏｌ）を加え、５分撹拌した。この反応液に水を加え、ｔｅｒｔ−ブチルメチルエーテルで２回抽出し、合わせた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝４：１）で精製し、Ｚ−２−（２−メチルヒドラゾノ）−２−（ドデシルチオ）酢酸エチル４．５２ｇ（収率８６％）をオイルとして得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８８（３Ｈ，ｔ，Ｊ＝６．８Ｈｚ），１．１８−１．３９（１８Ｈ，ｍ），１．４８−１．５９（５Ｈ，ｍ），２．７６（２Ｈ，ｔ，Ｊ＝７．４Ｈｚ），３．３３（３Ｈ，ｄ，Ｊ＝４．１Ｈｚ），４．３２（２Ｈ，ｑ，Ｊ＝７．２Ｈｚ），７．３９（１Ｈ，ｄ，Ｊ＝４．１Ｈｚ）． Reference Example 3-1

Z-2- (2-methylhydrazono) -2- (dodecylthio) acetic acid ethyl compound (XVII-1) 2.61 g (15.8 mmol) dissolved in tert-butyl methyl ether 15 ml was dissolved in 1-dodecanethiol. 3.21 g (15.8 mmol) was added and ice-cooled. To this solution, 698 mg (17.4 mmol) of 60% sodium hydride was added and stirred for 5 minutes. Water was added to the reaction mixture, and the mixture was extracted twice with tert-butyl methyl ether. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 4: 1), and 4.52 g (yield 86%) of ethyl Z-2- (2-methylhydrazono) -2- (dodecylthio) acetate was obtained as an oil. Got as.
¹ H NMR (CDCl ₃ ) δ ppm: 0.88 (3H, t, J = 6.8 Hz), 1.18-1.39 (18H, m), 1.48-1.59 (5H, m) , 2.76 (2H, t, J = 7.4 Hz), 3.33 (3H, d, J = 4.1 Hz), 4.32 (2H, q, J = 7.2 Hz), 7.39 ( 1H, d, J = 4.1 Hz).

２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−メチルヒドラゾノ］−２−（ドデシルチオ）酢酸エチル
参考例２−７に準じて２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−メチルヒドラゾノ］−２−（ドデシルチオ）酢酸エチル（幾何異性体約２：１の混合物）を得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８４−０．９１（３Ｈ，ｍ），１．１１−１．４５（２７Ｈ，ｍ），１．６０−１．７７（２Ｈ，ｍ），２．２９（２Ｈ，ｓ），２．３０（１Ｈ，ｓ），２．４９−２．５９（４Ｈ，ｍ），２．９２−３．０９（２Ｈ，ｍ），３．２４（１Ｈ，ｓ），３．３９（２Ｈ，ｓ），３．８４（１．４Ｈ，ｓ），３．９５（０．６Ｈ，ｓ），４．３２−４．４３（２Ｈ，ｍ），６．８７（１．４Ｈ，ｓ），６．８９（０．６Ｈ，ｓ）． Reference Example 3-2

2- [2- (2,6-Diethyl-4-methylphenyl) acetyl-2-methylhydrazono] -2- (dodecylthio) acetic acid ethyl 2- [2- (2,6 -Diethyl-4-methylphenyl) acetyl-2-methylhydrazono] -2- (dodecylthio) acetic acid ethyl acetate (mixture of about 2: 1 geometric isomers) was obtained.
¹ H NMR (CDCl ₃ ) δ ppm: 0.84-0.91 (3H, m), 1.11-1.45 (27H, m), 1.60-1.77 (2H, m), 2 .29 (2H, s), 2.30 (1H, s), 2.49-2.59 (4H, m), 2.92-3.09 (2H, m), 3.24 (1H, s) ), 3.39 (2H, s), 3.84 (1.4H, s), 3.95 (0.6H, s), 4.32-4.43 (2H, m), 6.87 ( 1.4H, s), 6.89 (0.6H, s).

２−［２−（２，４，６−トリメチルフェニル）アセチル−２−メチルヒドラゾノ］−２−（ドデシルチオ）酢酸エチル（幾何異性体約２：１の混合物）
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８４−０．９２（３Ｈ，ｍ），１．１７−１．４４（２１Ｈ，ｍ），１．５５−１．８０（２Ｈ，ｍ），２．１８（２Ｈ，ｓ），２．２１（４Ｈ，ｓ），２．２５（２Ｈ，ｓ），２．２８（１Ｈ，ｓ），２．９５（１．４Ｈ，ｔ，Ｊ＝７．４Ｈｚ），３．０５（０．６Ｈ，ｔ，Ｊ＝７．４Ｈｚ），３．２４（１Ｈ，ｓ），３．３９（２Ｈ，ｓ），３．７９（１．４Ｈ，ｓ），３．９０（０．６Ｈ，ｓ），４．３１−４．４３（２Ｈ，ｍ），６．８４（１．４Ｈ，ｓ），６．８６（０．６Ｈ，ｓ）． The following compounds were obtained according to Reference Example 3.

2- [2- (2,4,6-Trimethylphenyl) acetyl-2-methylhydrazono] -2- (dodecylthio) acetate (mixture of about 2: 1 geometric isomers)
¹ H NMR (CDCl ₃ ) δ ppm: 0.84-0.92 (3H, m), 1.17-1.44 (21H, m), 1.55-1.80 (2H, m), 2 .18 (2H, s), 2.21 (4H, s), 2.25 (2H, s), 2.28 (1H, s), 2.95 (1.4 H, t, J = 7.4 Hz) ), 3.05 (0.6 H, t, J = 7.4 Hz), 3.24 (1 H, s), 3.39 (2 H, s), 3.79 (1.4 H, s), 3. 90 (0.6H, s), 4.31-4.43 (2H, m), 6.84 (1.4H, s), 6.86 (0.6H, s).

２−［２−（２−ブロモ−４，６−ジメチルフェニル）アセチル−２−メチルヒドラゾノ］−２−（ドデシルチオ）酢酸エチル（幾何異性体約２：１の混合物）
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８５−０．９１（３Ｈ，ｍ），１．１７−１．４４（２１Ｈ，ｍ），１．５５−１．８０（２Ｈ，ｍ），２．２５（２Ｈ，ｓ），２．２６（２Ｈ，ｓ），２．２７（１Ｈ，ｓ），２．２８（１Ｈ，ｓ），２．９６（１．４Ｈ，ｔ，Ｊ＝７．４Ｈｚ），３．０７（０．６Ｈ，ｔ，Ｊ＝７．３Ｈｚ），３．２５（１Ｈ，ｓ），３．４１（２Ｈ，ｓ），３．９８（０．６Ｈ，ｓ），３．９９（１．４Ｈ，ｓ），４．３２−４．４３（２Ｈ，ｍ），６．９３（０．７Ｈ，ｓ），６．９５（０．３Ｈ，ｓ），７．２５（０．７Ｈ，ｓ），７．２６（０．３Ｈ，ｓ）．

2- [2- (2-Bromo-4,6-dimethylphenyl) acetyl-2-methylhydrazono] -2- (dodecylthio) acetate (mixture of about 2: 1 geometric isomers)
¹ H NMR (CDCl ₃ ) δ ppm: 0.85-0.91 (3H, m), 1.17-1.44 (21H, m), 1.55-1.80 (2H, m), 2 .25 (2H, s), 2.26 (2H, s), 2.27 (1H, s), 2.28 (1H, s), 2.96 (1.4 H, t, J = 7.4 Hz) ), 3.07 (0.6 H, t, J = 7.3 Hz), 3.25 (1 H, s), 3.41 (2 H, s), 3.98 (0.6 H, s), 3. 99 (1.4H, s), 4.32-4.43 (2H, m), 6.93 (0.7H, s), 6.95 (0.3H, s), 7.25 (0. 7H, s), 7.26 (0.3H, s).

２−［２−（４−クロロ−２−トリフルオロメチルフェニル）アセチル−２−メチルヒドラゾノ］−２−（ドデシルチオ）酢酸エチル（幾何異性体約３：１の混合物）
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８４−０．９２（３Ｈ，ｍ），１．１９−１．４１（２１Ｈ，ｍ），１．４８−１．７１（２Ｈ，ｍ），２．８４−３．００（２Ｈ，ｍ），３．２３（０．７５Ｈ，ｓ），３．３９（２．２５Ｈ，ｓ），３．９８（１．５Ｈ，ｓ），４．０８（０．５Ｈ，ｓ），４．３１−４．３９（２Ｈ，ｍ），７．２３−７．３２（１Ｈ，ｍ），７．４３−７．５１（１Ｈ，ｍ），７．６１−７．６５（１Ｈ，ｍ）．

2- [2- (4-Chloro-2-trifluoromethylphenyl) acetyl-2-methylhydrazono] -2- (dodecylthio) acetate (mixture of geometric isomers about 3: 1)
¹ H NMR (CDCl ₃ ) δ ppm: 0.84-0.92 (3H, m), 1.19-1.41 (21H, m), 1.48-1.71 (2H, m), 2 .84-3.00 (2H, m), 3.23 (0.75H, s), 3.39 (2.25H, s), 3.98 (1.5H, s), 4.08 (0 .5H, s), 4.31-4.39 (2H, m), 7.23-7.32 (1H, m), 7.43-7.51 (1H, m), 7.61-7 .65 (1H, m).

２−［２−（２−トリフルオロメトキシフェニル）アセチル−２−メチルヒドラゾノ］−２−（ドデシルチオ）酢酸エチル（幾何異性体約３：１の混合物）
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８５−０．９２（３Ｈ，ｍ），１．１８−１．４１（２１Ｈ，ｍ），１．４８−１．７１（２Ｈ，ｍ），２．８４−３．００（２Ｈ， ｍ），３．２４（０．７５Ｈ，ｓ），３．３９（２．２５Ｈ，ｓ），３．８９（１．５Ｈ，ｓ），３．９９（０．５Ｈ，ｓ），４．２９−４．４１（２Ｈ，ｍ），７．１４−７．５０（４Ｈ，ｍ）．

2- [2- (2-Trifluoromethoxyphenyl) acetyl-2-methylhydrazono] -2- (dodecylthio) acetate ethyl (a mixture of geometric isomers about 3: 1)
¹ H NMR (CDCl ₃ ) δ ppm: 0.85-0.92 (3H, m), 1.18-1.41 (21H, m), 1.48-1.71 (2H, m), 2 .84-3.00 (2H, m), 3.24 (0.75H, s), 3.39 (2.25H, s), 3.89 (1.5H, s), 3.99 (0 .5H, s), 4.29-4.41 (2H, m), 7.14-7.50 (4H, m).

２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−ベンジルヒドラゾノ］−２−（ドデシルチオ）酢酸エチルの合成 Reference example 4

Synthesis of ethyl 2- [2- (2,6-diethyl-4-methylphenyl) acetyl-2-benzylhydrazono] -2- (dodecylthio) acetate

２−（２−ベンジルヒドラゾノ）酢酸エチル
４７％グリオキシル酸エチルのトルエン溶液（ポリマー型）２９．２ｇ（１３４．５ｍｍｏｌ）をＴＨＦ２００ｍｌに溶解した溶液に、ベンジルヒドラジン一塩酸塩２１．３ｇ（１３４．５ｍｍｏｌ）およびトリエチルアミン２０．６ｍｌ（１４８ｍｍｏｌ）を加え、室温で一晩撹拌した。この反応液に酢酸エチルを加え、水洗し、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２：１）で精製し、Ｅ−２−（２−ベンジルヒドラゾノ）酢酸エチル（Ｅ：Ｚ＝４：１の混合物）１４．９ｇ（収率５３％）をオイルとして得た。
Ｅ体の¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．３２（３Ｈ，ｔ，Ｊ ７．１Ｈｚ），４．２６（２Ｈ，ｑ，Ｊ＝７．１Ｈｚ），４．４０（２Ｈ，ｄ，Ｊ＝４．３Ｈｚ），６．７７（１Ｈ，ｓ），６．８４（１Ｈ，ｂｒｓ），７．２３−７．４０（５Ｈ，ｍ）． Reference Example 4-1

2- (2-Benzylhydrazono) acetic acid 21.3 g (134. 5 mmol) and 20.6 ml (148 mmol) of triethylamine were added and stirred overnight at room temperature. Ethyl acetate was added to the reaction mixture, washed with water, washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1), and 14.9 g of ethyl E-2- (2-benzylhydrazono) acetate (a mixture of E: Z = 4: 1) (yield) 53%) was obtained as an oil.
¹ H NMR (CDCl ₃ ) δ ppm of E form: 1.32 (3H, t, J 7.1 Hz), 4.26 (2H, q, J = 7.1 Hz), 4.40 (2H, d, J = 4.3 Hz), 6.77 (1H, s), 6.84 (1H, brs), 7.23-7.40 (5H, m).

２−クロロ−２−（２−ベンジルヒドラゾノ）酢酸エチル
参考例１−２に準じて、２−クロロ−２−（２−ベンジルヒドラゾノ）酢酸エチルをＥ：Ｚ＝８：１のオイル状の混合物として得た（収率５６％）。
Ｚ体の¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．３７（３Ｈ，ｔ，Ｊ＝７．２Ｈｚ），４．３５（２Ｈ，ｑ，Ｊ＝７．２Ｈｚ），４．７０（２Ｈ，ｄ，Ｊ＝４．８Ｈｚ），６．７１（１Ｈ，ｂｒｓ），７．２８−７．４０（５Ｈ，ｍ）． Reference Example 4-2

2-Chloro-2- (2-benzylhydrazono) ethyl acetate According to Reference Example 1-2, ethyl 2-chloro-2- (2-benzylhydrazono) acetate was obtained as an oil with E: Z = 8: 1 (Yield 56%).
¹ H NMR (CDCl ₃ ) δ ppm of Z form: 1.37 (3H, t, J = 7.2 Hz), 4.35 (2H, q, J = 7.2 Hz), 4.70 (2H, d , J = 4.8 Hz), 6.71 (1H, brs), 7.28-7.40 (5H, m).

Ｚ−２−（２−ベンジルヒドラゾノ）−２−（ドデシルチオ）酢酸エチル
参考例３−１に準じて、Ｚ−２−（２−ベンジルヒドラゾノ）−２−（ドデシルチオ）酢酸エチルをオイル状の混合物として得た（収率７８％）。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８８（３Ｈ，ｔ，Ｊ＝６．６Ｈｚ），１．１４−１．５３（２３Ｈ，ｍ），２．７６（２Ｈ，ｔ，Ｊ＝７．４Ｈｚ），４．３３（２Ｈ，ｑ，Ｊ＝７．２Ｈｚ），４．７６（２Ｈ，ｄ，Ｊ＝４．８Ｈｚ），７．２４−７．３９（５Ｈ，ｍ），７．６３（１Ｈ，ｔ，Ｊ＝４．８Ｈｚ）． Reference Example 4-3

Z-2- (2-benzylhydrazono) -2- (dodecylthio) ethyl acetate According to Reference Example 3-1, ethyl Z-2- (2-benzylhydrazono) -2- (dodecylthio) acetate was oily. (Yield 78%).
¹ H NMR (CDCl ₃ ) δ ppm: 0.88 (3H, t, J = 6.6 Hz), 1.14-1.53 (23H, m), 2.76 (2H, t, J = 7. 4 Hz), 4.33 (2H, q, J = 7.2 Hz), 4.76 (2H, d, J = 4.8 Hz), 7.24-7.39 (5H, m), 7.63 ( 1H, t, J = 4.8 Hz).

２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−ベンジルヒドラゾノ］−２−（ドデシルチオ）酢酸エチル
参考例２−７に準じて、２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−ベンジルヒドラゾノ］−２−（ドデシルチオ）酢酸エチルをオイル状の幾何異性体混合物として得た（収率８３％）。
Ｅ体の¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８８（３Ｈ，ｔ，Ｊ＝６．８Ｈｚ），１．０７−１．７１（２９Ｈ，ｍ），２．２８（２．４Ｈ，ｓ），２．３２（０．６Ｈ，ｓ），２．５１（３．２Ｈ，ｑ，Ｊ＝７．５Ｈｚ），２．６５（０．８Ｈ，ｑ，Ｊ＝７．６Ｈｚ），２．８６（１．６Ｈ，ｔ，Ｊ＝７．４Ｈｚ），２．９７（０．４Ｈ，ｔ，Ｊ＝７．４Ｈｚ），３．７９（０．４Ｈ，ｓ），３．８０（１．６Ｈ，ｓ），４．１５（０．４Ｈ，ｑ，Ｊ＝７．０Ｈｚ），４．３６（１．６Ｈ，ｑ，Ｊ＝７．２Ｈｚ），５．１１（１．６Ｈ，ｓ），５．２９（０．４Ｈ，ｓ），６．８７（１．６Ｈ，ｓ），６．９３（０．４Ｈ，ｓ），７．１９−７．４０（５Ｈ，ｍ）． Reference Example 4-4

2- [2- (2,6-Diethyl-4-methylphenyl) acetyl-2-benzylhydrazono] -2- (dodecylthio) acetate according to Reference Example 2-7, 2- [2- (2, Ethyl 6-diethyl-4-methylphenyl) acetyl-2-benzylhydrazono] -2- (dodecylthio) acetate was obtained as an oily geometric isomer mixture (yield 83%).
¹ H NMR (CDCl ₃ ) δ ppm of E form: 0.88 (3H, t, J = 6.8 Hz), 1.07-1.71 (29H, m), 2.28 (2.4H, s ), 2.32 (0.6 H, s), 2.51 (3.2 H, q, J = 7.5 Hz), 2.65 (0.8 H, q, J = 7.6 Hz), 2.86 (1.6 H, t, J = 7.4 Hz), 2.97 (0.4 H, t, J = 7.4 Hz), 3.79 (0.4 H, s), 3.80 (1.6 H, s), 4.15 (0.4 H, q, J = 7.0 Hz), 4.36 (1.6 H, q, J = 7.2 Hz), 5.11 (1.6 H, s), 5. 29 (0.4H, s), 6.87 (1.6H, s), 6.93 (0.4H, s), 7.19-7.40 (5H, m).

２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−（シクロプロピルメチル）ヒドラゾノ］−２−（ドデシルチオ）酢酸エチルの合成 Reference Example 5

Synthesis of ethyl 2- [2- (2,6-diethyl-4-methylphenyl) acetyl-2- (cyclopropylmethyl) hydrazono] -2- (dodecylthio) acetate

Ｅ−２−（２−ｔ−ブトキシカルボニル−２−（シクロプロピルメチル）ヒドラゾノ）酢酸エチル
６０％水素化ナトリウム２．１０ｇ（５２．５ｍｍｏｌ）を無水テトラヒドロフラン５０ｍｌおよび無水ＤＭＦ５０ｍｌの混合溶媒に縣濁させ、これに（ブロモメチル）シクロプロパン７．０４ｇ（５２．１ｍｍｏｌ）を加え、氷冷した。この混合物に化合物（Ｘ−１）１０．２ｇ（４７．４ｍｍｏｌ）をゆっくり加えた。得られた混合物を６５℃で３．５時間攪拌した。この反応液を室温まで冷却した後、反応液に水を加え、ｔｅｒｔ−ブチルメチルエーテルで２回抽出した。合わせた有機層を水洗し、無水硫酸マグネシウムで乾燥し、減圧濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝３：１）で精製し、Ｅ−２−（２−ｔ−ブトキシカルボニル−２−（シクロプロピルメチル）ヒドラゾノ）酢酸エチル９．３８ｇ（収率７３％）をオイルとして得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δｐｐｍ：０．３１−０．３７（２Ｈ，ｍ），０．４８−０．５５（２Ｈ，ｍ），０．９８−１．１１（１Ｈ，ｍ），１．３６（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），１．５６（９Ｈ，ｓ），３．７４（２Ｈ，ｄ，Ｊ＝６．８Ｈｚ），４．３２（２Ｈ，ｑ，Ｊ＝７．１Ｈｚ），７．３２（１Ｈ，ｓ）． Reference Example 5-1

E-2- (2-t-butoxycarbonyl-2- (cyclopropylmethyl) hydrazono) ethyl acetate 60% sodium hydride (2.10 g, 52.5 mmol) was suspended in a mixed solvent of anhydrous tetrahydrofuran (50 ml) and anhydrous DMF (50 ml). To this was added 7.04 g (52.1 mmol) of (bromomethyl) cyclopropane, and the mixture was ice-cooled. To this mixture, 10.2 g (47.4 mmol) of compound (X-1) was slowly added. The resulting mixture was stirred at 65 ° C. for 3.5 hours. After cooling this reaction liquid to room temperature, water was added to the reaction liquid and extracted twice with tert-butyl methyl ether. The combined organic layers were washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1), and 9.38 g (yield 73) of ethyl E-2- (2-t-butoxycarbonyl-2- (cyclopropylmethyl) hydrazono) acetate. %) As an oil.
¹ H NMR (CDCl ₃ ) δ ppm: 0.31-0.37 (2H, m), 0.48-0.55 (2H, m), 0.98-1.11 (1H, m), 36 (3H, t, J = 7.1 Hz), 1.56 (9H, s), 3.74 (2H, d, J = 6.8 Hz), 4.32 (2H, q, J = 7.1 Hz) ), 7.32 (1H, s).

Ｚ−２−クロロ−２−（２−ｔ−ブトキシカルボニル−２−（シクロプロピルメチル）ヒドラゾノ）酢酸エチル
参考例１−２に準じて、Ｚ−２−クロロ−２−（２−ｔ−ブトキシカルボニル−２−（シクロプロピルメチル）ヒドラゾノ）酢酸エチルをオイルとして得た（収率７０％）。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．２８−０．３４（２Ｈ，ｍ），０．４７−０．５３（２Ｈ，ｍ），１．０７−１．１８（１Ｈ，ｍ），１．３９（３Ｈ，ｔ，Ｊ＝７．２Ｈｚ），１．５２（９Ｈ，ｓ），３．８３（２Ｈ，ｄ，Ｊ＝７．０Ｈｚ），４．３８（２Ｈ，ｑ，Ｊ＝７．２Ｈｚ）． Reference Example 5-2

Z-2-Chloro-2- (2-t-butoxycarbonyl-2- (cyclopropylmethyl) hydrazono) ethyl acetate According to Reference Example 1-2, Z-2-chloro-2- (2-t-butoxy) Carbonyl-2- (cyclopropylmethyl) hydrazono) ethyl acetate was obtained as an oil (yield 70%).
¹ H NMR (CDCl ₃ ) δ ppm: 0.28-0.34 (2H, m), 0.47-0.53 (2H, m), 1.07-1.18 (1H, m), 1 .39 (3H, t, J = 7.2 Hz), 1.52 (9H, s), 3.83 (2H, d, J = 7.0 Hz), 4.38 (2H, q, J = 7. 2 Hz).

Ｚ−２−（２−ｔ−ブトキシカルボニル−２−（シクロプロピルメチル）ヒドラゾノ）−２−（ドデシルチオ）酢酸エチル
参考例３−１に準じて、Ｚ−２−（２−ｔ−ブトキシカルボニル−２−（シクロプロピルメチル）ヒドラゾノ）−２−（ドデシルチオ）酢酸エチルをオイルとして得た（収率８７％）。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．２３−０．２９（２Ｈ，ｍ），０．４３−０．５０（２Ｈ，ｍ），０．８８（３Ｈ，ｔ，Ｊ＝６．９Ｈｚ），１．０２−１．１２（１Ｈ，ｍ），１．２１−１．６４（２３Ｈ，ｍ），１．４９（９Ｈ，ｓ），２．８５（２Ｈ，ｔ，Ｊ＝７．５Ｈｚ），３．４９（２Ｈ，ｄ，Ｊ＝７．２Ｈｚ），４．３７（２Ｈ，ｑ，Ｊ＝７．１Ｈｚ）． Reference Example 5-3

Z-2- (2-t-butoxycarbonyl-2- (cyclopropylmethyl) hydrazono) -2- (dodecylthio) acetic acid ethyl according to Reference Example 3-1, Z-2- (2-t-butoxycarbonyl- Ethyl 2- (cyclopropylmethyl) hydrazono) -2- (dodecylthio) acetate was obtained as an oil (yield 87%).
¹ H NMR (CDCl ₃ ) δ ppm: 0.23-0.29 (2H, m), 0.43-0.50 (2H, m), 0.88 (3H, t, J = 6.9 Hz) , 1.02-1.12 (1H, m), 1.21-1.64 (23H, m), 1.49 (9H, s), 2.85 (2H, t, J = 7.5 Hz) 3.49 (2H, d, J = 7.2 Hz), 4.37 (2H, q, J = 7.1 Hz).

２−（２−（シクロプロピルメチル）ヒドラゾノ）−２−（ドデシルチオ）酢酸エチル
Ｚ−２−（２−ｔ−ブトキシカルボニル−２−（シクロプロピルメチル）ヒドラゾノ）−２−（ドデシルチオ）酢酸エチル１０．０ｇ（２１．３ｍｍｏｌ）をジオキサン１０ｍｌに溶解した溶液に、４Ｍ塩化水素ジオキサン溶液１０ｍｌを加え、室温で２時間撹拌した。この反応液を飽和炭酸水素ナトリウム水溶液に加え、ｔｅｒｔ−ブチルメチルエーテルで２回抽出した。合わせた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝９：１）で精製し、Ｅ−２−（２−（シクロプロピルメチル）ヒドラゾノ）−２−（ドデシルチオ）酢酸エチル１．２６ｇ（収率１６％）およびＺ−２−（２−（シクロプロピルメチル）ヒドラゾノ）−２−（ドデシルチオ）酢酸エチル１．３４ｇ（収率１７％）を得た。
Ｅ体の¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δｐｐｍ：０．２０−０．２７（２Ｈ，ｍ），０．４９−０．５６（２Ｈ，ｍ），０．８８（３Ｈ，ｔ，Ｊ＝６．９Ｈｚ），０．９８−１．０９（１Ｈ，ｍ），１．１８−１．４４（２１Ｈ，ｍ），１．５６−１．６７（２Ｈ，ｍ），２．７８（２Ｈ，ｔ，Ｊ ＝７．４Ｈｚ），３．３１（２Ｈ，ｄｄ，Ｊ＝７．０，４．６Ｈｚ），４．２６（２Ｈ，ｑ，Ｊ＝７．２Ｈｚ），１０．２６（１Ｈ，ｔ，Ｊ＝４．６Ｈｚ）．
Ｚ体の¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δｐｐｍ：０．２２−０．２８（２Ｈ，ｍ），０．５２−０．５９（２Ｈ，ｍ），０．８８（３Ｈ，ｔ，Ｊ＝６．７Ｈｚ），１．００−１．１１（１Ｈ，ｍ），１．１８−１．４０（２１Ｈ，ｍ），１．４８−１．５９（２Ｈ，ｍ），２．７８（２Ｈ，ｔ，Ｊ＝７．３Ｈｚ），３．４４（２Ｈ，ｄｄ，Ｊ＝７．１，４．７Ｈｚ），４．３２（２Ｈ，ｑ，Ｊ＝７．１Ｈｚ），７．５８（１Ｈ，ｔ，Ｊ＝４．７Ｈｚ）． Reference Example 5-4

2- (2- (cyclopropylmethyl) hydrazono) -2- (dodecylthio) acetate ethyl Z-2- (2-t-butoxycarbonyl-2- (cyclopropylmethyl) hydrazono) -2- (dodecylthio) acetate 10 To a solution of 0.0 g (21.3 mmol) dissolved in 10 ml of dioxane, 10 ml of 4M hydrogen chloride dioxane solution was added and stirred at room temperature for 2 hours. This reaction solution was added to a saturated aqueous sodium hydrogen carbonate solution, and extracted twice with tert-butyl methyl ether. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 9: 1) to obtain 1.26 g of ethyl E-2- (2- (cyclopropylmethyl) hydrazono) -2- (dodecylthio) acetate (yield 16%). ) And 1.34 g (17% yield) of ethyl Z-2- (2- (cyclopropylmethyl) hydrazono) -2- (dodecylthio) acetate.
¹ H NMR (CDCl ₃ ) δ ppm of E form: 0.20-0.27 (2H, m), 0.49-0.56 (2H, m), 0.88 (3H, t, J = 6. 9Hz), 0.98-1.09 (1H, m), 1.18-1.44 (21H, m), 1.56-1.67 (2H, m), 2.78 (2H, t, J = 7.4 Hz), 3.31 (2H, dd, J = 7.0, 4.6 Hz), 4.26 (2H, q, J = 7.2 Hz), 10.26 (1H, t, J = 4.6 Hz).
¹ H NMR (CDCl ₃ ) δ ppm of Z form: 0.22 to 0.28 (2H, m), 0.52 to 0.59 (2H, m), 0.88 (3H, t, J = 6. 7Hz), 1.00-1.11 (1H, m), 1.18-1.40 (21H, m), 1.48-1.59 (2H, m), 2.78 (2H, t, J = 7.3 Hz), 3.44 (2H, dd, J = 7.1, 4.7 Hz), 4.32 (2H, q, J = 7.1 Hz), 7.58 (1H, t, J = 4.7 Hz).

２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−（シクロプロピルメチル）ヒドラゾノ］−２−（ドデシルチオ）酢酸エチル
参考例２−７に準じて、２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−（シクロプロピルメチル）ヒドラゾノ］−２−（ドデシルチオ）酢酸エチル（幾何異性体比約５：１）をオイルとして得た（収率８４％）。
主要物の¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．２５−０．３１（２Ｈ，ｍ），０．４３−０．５０（２Ｈ，ｍ），０．８８（３Ｈ，ｔ，Ｊ＝６．７Ｈｚ），１．１２−１．２０（７Ｈ，ｍ），１．２２−１．３４（１９Ｈ，ｍ），１．３６−１．４４（２Ｈ，ｍ），１．６０−１．７０（２Ｈ，ｍ），２．２９（３Ｈ，ｓ），２．５５（４Ｈ，ｑ，Ｊ＝７．６Ｈｚ），２．９６（２Ｈ，ｔ，Ｊ＝７．３Ｈｚ），３．７６（２Ｈ，ｓ），３．７８（２Ｈ，ｄ，Ｊ＝７．１Ｈｚ），４．４０（２Ｈ，ｑ，Ｊ＝７．２Ｈｚ），６．８７（２Ｈ，ｓ）． Reference Example 5-5

2- [2- (2,6-Diethyl-4-methylphenyl) acetyl-2- (cyclopropylmethyl) hydrazono] -2- (dodecylthio) acetate according to Reference Example 2-7, 2- [2- Ethyl (2,6-diethyl-4-methylphenyl) acetyl-2- (cyclopropylmethyl) hydrazono] -2- (dodecylthio) acetate (geometric isomer ratio about 5: 1) was obtained as an oil (yield 84 %).
¹ H NMR (CDCl ₃ ) δ ppm of main product: 0.25-0.31 (2H, m), 0.43-0.50 (2H, m), 0.88 (3H, t, J = 6 .7 Hz), 1.12-1.20 (7 H, m), 1.22-1.34 (19 H, m), 1.36-1.44 (2 H, m), 1.60-1.70 (2H, m), 2.29 (3H, s), 2.55 (4H, q, J = 7.6 Hz), 2.96 (2H, t, J = 7.3 Hz), 3.76 (2H , S), 3.78 (2H, d, J = 7.1 Hz), 4.40 (2H, q, J = 7.2 Hz), 6.87 (2H, s).

４−（２，４，６−トリメチルフェニル）−６−ドデシルチオ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン
２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−ベンジルヒドラゾノ］−２−（ドデシルチオ）酢酸エチルの代わりに、原料として２−［２−（２，４，６−トリメチルフェニル）アセチル−２−メチルヒドラゾノ］−２−（ドデシルチオ）酢酸エチルを用い、製造例１２と同様にして４−（２，４，６−トリメチルフェニル）−６−ドデシルチオ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（収率１７％）を得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８８（３Ｈ，ｔ，Ｊ＝６．８Ｈｚ），１．１９−１．３８（１６Ｈ，ｍ），１．４１−１．５０（２Ｈ，ｍ），１．６９−１．７９（２Ｈ，ｍ），２．０７（６Ｈ，ｓ），２．３１（３Ｈ，ｓ），３．０６（２Ｈ，ｔ，Ｊ＝７．３Ｈｚ），３．７９（３Ｈ，ｓ），５．８２（１Ｈ，ｂｒｓ），６．９８（２Ｈ，ｓ）． Reference Example 6

4- (2,4,6-trimethylphenyl) -6-dodecylthio-5-hydroxy-2-methyl-3 (2H) -pyridazinone 2- [2- (2,6-diethyl-4-methylphenyl) acetyl- 2- [2- (2,4,6-trimethylphenyl) acetyl-2-methylhydrazono] -2- (dodecylthio) acetic acid as a starting material instead of ethyl 2-benzylhydrazono] -2- (dodecylthio) acetate 4- (2,4,6-trimethylphenyl) -6-dodecylthio-5-hydroxy-2-methyl-3 (2H) -pyridazinone (yield 17%) was obtained in the same manner as in Production Example 12 using ethyl. It was.
¹ H NMR (CDCl ₃ ) δ ppm: 0.88 (3H, t, J = 6.8 Hz), 1.19-1.38 (16H, m), 1.41-1.50 (2H, m) 1.69-1.79 (2H, m), 2.07 (6H, s), 2.31 (3H, s), 3.06 (2H, t, J = 7.3 Hz), 3.79. (3H, s), 5.82 (1H, brs), 6.98 (2H, s).

４−（２−トリフルオロメチル−４−クロロフェニル）−６−ドデシルチオ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８８（３Ｈ，ｔ，Ｊ＝６．８Ｈｚ），１．１９−１．３５（１６Ｈ，ｍ），１．３８−１．４８（２Ｈ，ｍ），１．６３−１．７５（２Ｈ，ｍ），２．９９（２Ｈ，ｔ，Ｊ＝７．３Ｈｚ），３．７７（３Ｈ，ｓ），７．２０−７．２４（１Ｈ，ｍ），７．５９−７．６２（１Ｈ，ｍ），７．７６−７．７８（１Ｈ，ｍ）． In the same manner as in Reference Example 6, the following compound was obtained.

4- (2-Trifluoromethyl-4-chlorophenyl) -6-dodecylthio-5-hydroxy-2-methyl-3 (2H) -pyridazinone
¹ H NMR (CDCl ₃ ) δ ppm: 0.88 (3H, t, J = 6.8 Hz), 1.19-1.35 (16H, m), 1.38-1.48 (2H, m) , 1.63-1.75 (2H, m), 2.99 (2H, t, J = 7.3 Hz), 3.77 (3H, s), 7.20-7.24 (1 H, m) , 7.59-7.62 (1H, m), 7.76-7.78 (1H, m).

４−（２−トリフルオロメトキシフェニル）−６−ドデシルチオ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８８（３Ｈ，ｔ，Ｊ＝６．７Ｈｚ），１．２１−１．３６（１６Ｈ，ｍ），１．３７−１．４８（２Ｈ，ｍ），１．６５−１．７５（２Ｈ，ｍ），３．００（２Ｈ，ｔ，Ｊ＝７．３Ｈｚ），３．８０（３Ｈ，ｓ），７．３６−７．４３（３Ｈ，ｍ），７．４５−７．５１（１Ｈ，ｍ）．

4- (2-trifluoromethoxyphenyl) -6-dodecylthio-5-hydroxy-2-methyl-3 (2H) -pyridazinone
¹ H NMR (CDCl ₃ ) δ ppm: 0.88 (3H, t, J = 6.7 Hz), 1.21-1.36 (16H, m), 1.37-1.48 (2H, m) , 1.65-1.75 (2H, m), 3.00 (2H, t, J = 7.3 Hz), 3.80 (3H, s), 7.36-7.43 (3H, m) , 7.45-7.51 (1H, m).

４−（２，６−ジエチル−４−メチルフェニル）−６−ドデシルスルホニル−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノンの合成
４−（２，６−ジエチル−４−メチルフェニル）−６−ドデシルチオ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン４．０ｇ（８．４６ｍｍｏｌ）をＤＭＦ２０ｍｌに溶解した溶液に、タングステン酸ナトリウム二水和物２７９ｍｇ（０．８４６ｍｍｏｌ）水溶液（１０ｍｌ）を加えた。この溶液に６０℃で３０％過酸化水素水２．８７ｇ（２５．３ｍｍｏｌ）をゆっくり滴下した。滴下終了後、１時間撹拌し、室温まで冷却した。この反応液に１Ｍ亜硫酸水素ナトリウム水溶液を９ｍｌ加え、５分撹拌した。この溶液に２Ｎ塩酸１０ｍｌを加え、酢酸エチルで２回抽出した。合わせた有機層を２回水洗し、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮し、４−（２，６−ジエチル−４−メチルフェニル）−６−ドデシルスルホニル−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン４．２７ｇ（収率１００％）をオイルとして得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８８（３Ｈ，ｔ，Ｊ＝６．８Ｈｚ），１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．２０−１．３７（１６Ｈ，ｍ），１．４０−１．５０（２Ｈ，ｍ），１．７７−１．８９（２Ｈ，ｍ），２．２５−２．４２（７Ｈ，ｍ），３．３８−３．４６（２Ｈ，ｍ），３．９０（３Ｈ，ｓ），７．００（２Ｈ，ｓ），８．９０（１Ｈ，ｂｒｓ）． Reference Example 7

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-dodecylsulfonyl-5-hydroxy-2-methyl-3 (2H) -pyridazinone 4- (2,6-diethyl-4-methylphenyl) To a solution of 4.0 g (8.46 mmol) of -6-dodecylthio-5-hydroxy-2-methyl-3 (2H) -pyridazinone in 20 ml of DMF, an aqueous solution of 279 mg (0.846 mmol) of sodium tungstate dihydrate ( 10 ml) was added. To this solution, 2.87 g (25.3 mmol) of 30% aqueous hydrogen peroxide was slowly added dropwise at 60 ° C. After completion of dropping, the mixture was stirred for 1 hour and cooled to room temperature. 9 ml of 1M sodium bisulfite aqueous solution was added to this reaction liquid, and it stirred for 5 minutes. To this solution was added 10 ml of 2N hydrochloric acid, and the mixture was extracted twice with ethyl acetate. The combined organic layer was washed twice with water, washed with saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and 4- (2,6-diethyl-4-methylphenyl) -6-dodecylsulfonyl-5. -Hydroxy-2-methyl-3 (2H) -pyridazinone 4.27 g (yield 100%) was obtained as an oil.
¹ H NMR (CDCl ₃ ) δ ppm: 0.88 (3H, t, J = 6.8 Hz), 1.09 (6H, t, J = 7.6 Hz), 1.20-1.37 (16H, m), 1.40-1.50 (2H, m), 1.77-1.89 (2H, m), 2.25-2.42 (7H, m), 3.38-3.46 ( 2H, m), 3.90 (3H, s), 7.00 (2H, s), 8.90 (1H, brs).

４−（２，４，６−トリメチルフェニル）−６−ドデシルスルホニル−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８８（３Ｈ，ｔ，Ｊ＝６．８Ｈｚ），１．１９−１．３６（１６Ｈ，ｍ），１．４０−１．５０（２Ｈ，ｍ），１．７９−１．８９（２Ｈ，ｍ），２．０７（６Ｈ，ｓ），２．３１（３Ｈ，ｓ），３．３７−３．４４（２Ｈ，ｍ），３．９０（３Ｈ，ｓ），６．９５（２Ｈ，ｓ）． In the same manner as in Reference Example 7, the following compound was obtained.

4- (2,4,6-trimethylphenyl) -6-dodecylsulfonyl-5-hydroxy-2-methyl-3 (2H) -pyridazinone
¹ H NMR (CDCl ₃ ) δ ppm: 0.88 (3H, t, J = 6.8 Hz), 1.19-1.36 (16H, m), 1.40-1.50 (2H, m) , 1.79-1.89 (2H, m), 2.07 (6H, s), 2.31 (3H, s), 3.37-3.44 (2H, m), 3.90 (3H , S), 6.95 (2H, s).

４−（２−ブロモ−４，６−ジメチルフェニル）−６−ドデシルスルホニル−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８８（３Ｈ，ｔ，Ｊ＝６．８Ｈｚ），１．２０−１．３５（１６Ｈ，ｍ），１．３８−１．５２（２Ｈ，ｍ），１．７５−１．９２（２Ｈ，ｍ），２．１３（３Ｈ，ｓ），２．３２（３Ｈ，ｓ），３．３３−３．４７（２Ｈ，ｍ），３．９１（３Ｈ，ｓ），７．０６（１Ｈ，ｓ），７．３４（１Ｈ，ｓ）．

4- (2-Bromo-4,6-dimethylphenyl) -6-dodecylsulfonyl-5-hydroxy-2-methyl-3 (2H) -pyridazinone
¹ H NMR (CDCl ₃ ) δ ppm: 0.88 (3H, t, J = 6.8 Hz), 1.20-1.35 (16H, m), 1.38-1.52 (2H, m) , 1.75-1.92 (2H, m), 2.13 (3H, s), 2.32 (3H, s), 3.33-3.47 (2H, m), 3.91 (3H , S), 7.06 (1H, s), 7.34 (1H, s).

４−（２−トリフルオロメチル−４−クロロフェニル）−６−ドデシルスルホニル−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８８（３Ｈ，ｔ，Ｊ＝６．８Ｈｚ），１．１７−１．５１（１６Ｈ，ｍ），１．４０−１．５２（２Ｈ， ｍ），１．７２−１．９４（２Ｈ，ｍ），３．３０−３．４７（２Ｈ，ｍ）， ３．８９（３Ｈ，ｓ），７．１８−７．２３（１Ｈ，ｍ），７．５８−７．６５（１Ｈ，ｍ），７．７４−７．８０（１Ｈ，ｍ）．

4- (2-trifluoromethyl-4-chlorophenyl) -6-dodecylsulfonyl-5-hydroxy-2-methyl-3 (2H) -pyridazinone
¹ H NMR (CDCl ₃ ) δ ppm: 0.88 (3H, t, J = 6.8 Hz), 1.17-1.51 (16H, m), 1.40-1.52 (2H, m) , 1.72-1.94 (2H, m), 3.30-3.47 (2H, m), 3.89 (3H, s), 7.18-7.23 (1H, m), 7 .58-7.65 (1H, m), 7.74-7.80 (1H, m).

４−（２−トリフルオロメトキシフェニル）−６−ドデシルスルホニル−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８４−０．９１（３Ｈ，ｍ），１．１６−１．５０（１６Ｈ，ｍ），１．３９−１．５１（２Ｈ，ｍ），１．７４−１．９４（２Ｈ，ｍ），３．３１−３．４７（２Ｈ，ｍ），３．９０（３Ｈ，ｓ），７．３２−７．４１（３Ｈ，ｍ），７．４３−７．５１（１Ｈ，ｍ）．

4- (2-trifluoromethoxyphenyl) -6-dodecylsulfonyl-5-hydroxy-2-methyl-3 (2H) -pyridazinone
¹ H NMR (CDCl ₃ ) δ ppm: 0.84-0.91 (3H, m), 1.16-1.50 (16H, m), 1.39-1.51 (2H, m), 1 .74-1.94 (2H, m), 3.31-3.47 (2H, m), 3.90 (3H, s), 7.32-7.41 (3H, m), 7.43 -7.51 (1H, m).

４−（２，６−ジエチル−４−メチルフェニル）−６−ドデシルスルホニル−５−ヒドロキシ−２−ベンジル−３（２Ｈ）−ピリダジノン
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８９（３Ｈ，ｔ，Ｊ＝６．９Ｈｚ），１．０２（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．１６−１．３８（１６Ｈ，ｍ），１．６５−１．７５（２Ｈ，ｍ），２．２３−２．３６（５Ｈ，ｍ），２．６１（２Ｈ，ｔ，Ｊ＝７．６Ｈｚ），３．３０−３．３７（２Ｈ，ｍ），５．４１（２Ｈ，ｓ），６．９０（１Ｈ，ｓ），６．９８（２Ｈ，ｓ），７．２９−７．３６（３Ｈ，ｍ），７．３８−７．４３（２Ｈ，ｍ）．

4- (2,6-Diethyl-4-methylphenyl) -6-dodecylsulfonyl-5-hydroxy-2-benzyl-3 (2H) -pyridazinone
¹ H NMR (CDCl ₃ ) δ ppm: 0.89 (3H, t, J = 6.9 Hz), 1.02 (6H, t, J = 7.6 Hz), 1.16-1.38 (16H, m), 1.65-1.75 (2H, m), 2.23-2.36 (5H, m), 2.61 (2H, t, J = 7.6 Hz), 3.30-3. 37 (2H, m), 5.41 (2H, s), 6.90 (1H, s), 6.98 (2H, s), 7.29-7.36 (3H, m), 7.38 -7.43 (2H, m).

４−（２，６−ジエチル−４−メチルフェニル）−６−ドデシルスルホニル−５−ヒドロキシ−２−シクロプロピルメチル−３（２Ｈ）−ピリダジノン
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．４２−０．４７（２Ｈ，ｍ），０．５４−０．６０（２Ｈ，ｍ），０．８８（３Ｈ，ｔ，Ｊ＝６．８Ｈｚ），１．０９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．２１−１．４９（１９Ｈ，ｍ），１．７８−１．８８（２Ｈ，ｍ），２．２７−２．４２（７Ｈ，ｍ），３．３８−３．４４（２Ｈ，ｍ），４．１４（２Ｈ，ｄ，Ｊ＝７．３Ｈｚ），７．００（２Ｈ，ｓ），８．７７（１Ｈ，ｂｒｓ）．

4- (2,6-Diethyl-4-methylphenyl) -6-dodecylsulfonyl-5-hydroxy-2-cyclopropylmethyl-3 (2H) -pyridazinone
¹ H NMR (CDCl ₃ ) δ ppm: 0.42-0.47 (2H, m), 0.54-0.60 (2H, m), 0.88 (3H, t, J = 6.8 Hz) , 1.09 (6H, t, J = 7.6 Hz), 1.21-1.49 (19H, m), 1.78-1.88 (2H, m), 2.27-2.42 ( 7H, m), 3.38-3.44 (2H, m), 4.14 (2H, d, J = 7.3 Hz), 7.00 (2H, s), 8.77 (1H, brs) .

４−（２，６−ジエチル−４−メチルフェニル）−６−ヒドロキシ−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノンの合成
化合物（Ｉ−３−４）５００ｍｇ（１．１３ｍｍｏｌ）を１，３−ジメチルイミダゾリジノン５ｍｌに溶解した溶液に、２Ｎ水酸化ナトリウム水溶液２．３ｍｌを加え、７０℃で４時間撹拌した。この反応液を室温まで冷却した後、反応液に２Ｎ塩酸５ｍｌを加え、ｔｅｒｔ−ブチルメチルエーテルで２回抽出した。合わせた有機層を２回水洗し、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１：１）で精製し、４−（２，６−ジエチル−４−メチルフェニル）−６−ヒドロキシ−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン３０９ｍｇ（収率７２％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１４（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２９−２．５２（７Ｈ，ｍ），３．６７（３Ｈ，ｓ），４．６１（２Ｈ，ｓ），６．９１（１Ｈ，ｂｒｓ），６．９８（２Ｈ，ｓ），７．０４−７．０９（２Ｈ，ｍ），７．２７−７．３３（３Ｈ，ｍ）． Reference Example 8

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-hydroxy-5-benzyloxy-2-methyl-3 (2H) -pyridazinone Compound (I-3-4) 500 mg (1.13 mmol) Was dissolved in 5 ml of 1,3-dimethylimidazolidinone, 2.3 ml of 2N aqueous sodium hydroxide solution was added, and the mixture was stirred at 70 ° C. for 4 hours. The reaction solution was cooled to room temperature, 5 ml of 2N hydrochloric acid was added to the reaction solution, and the mixture was extracted twice with tert-butyl methyl ether. The combined organic layers were washed twice with water, washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1) to give 4- (2,6-diethyl-4-methylphenyl) -6-hydroxy-5-benzyloxy-2-methyl-3 ( 309 mg (yield 72%) of 2H) -pyridazinone was obtained as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.14 (6H, t, J = 7.6 Hz), 2.29-2.52 (7H, m), 3.67 (3H, s), 4.61 (2H, s), 6.91 (1H, brs), 6.98 (2H, s), 7.04-7.09 (2H, m), 7.27-7.33 (3H, m).

４−（２，６−ジエチル−４−メチルフェニル）−６−ヒドロキシ−５−（４−メトキシベンジル）オキシ−２−メチル−３（２Ｈ）−ピリダジノンの合成 Reference Example 9

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-hydroxy-5- (4-methoxybenzyl) oxy-2-methyl-3 (2H) -pyridazinone

４−（２，６−ジエチル−４−メチルフェニル）−６−ブロモ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（化合物（Ｉ−１９）およびベンジルブロミドの代わりに、原料として４−（２，６−ジエチル−４−メチルフェニル）−６−ドデシルスルホニル−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノンおよび４−メトキシベンジルクロリドを用い、製造例２１と同様にして、４−（２，６−ジエチル−４−メチルフェニル）−６−ドデシルスルホニル−５−（４−メトキシベンジル）オキシ−２−メチル−３（２Ｈ）−ピリダジノンを得た（収率５７％）。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８８（３Ｈ，ｔ，Ｊ＝６．８Ｈｚ），１．１４（６Ｈ，ｔ，Ｊ＝７．５Ｈｚ），１．１７−１．３５（１８Ｈ，ｍ），１．６７−１．７８（２Ｈ，ｍ），２．３０−２．４９（７Ｈ，ｍ），３．２１−３．３０（２Ｈ，ｍ），３．７８（３Ｈ，ｓ），３．９０（３Ｈ，ｓ），４．４８（２Ｈ，ｓ），６．７９（２Ｈ，ｄ，Ｊ＝８．５Ｈｚ），６．９８（２Ｈ，ｄ，Ｊ＝８．５Ｈｚ），７．０５（２Ｈ，ｓ）． Reference Example 9-1

4- (2,6-diethyl-4-methylphenyl) -6-bromo-5-hydroxy-2-methyl-3 (2H) -pyridazinone (compound (I-19) and benzyl bromide instead of 4 Using-(2,6-diethyl-4-methylphenyl) -6-dodecylsulfonyl-5-hydroxy-2-methyl-3 (2H) -pyridazinone and 4-methoxybenzyl chloride in the same manner as in Production Example 21, 4- (2,6-diethyl-4-methylphenyl) -6-dodecylsulfonyl-5- (4-methoxybenzyl) oxy-2-methyl-3 (2H) -pyridazinone was obtained (57% yield).
¹ H NMR (CDCl ₃ ) δ ppm: 0.88 (3H, t, J = 6.8 Hz), 1.14 (6H, t, J = 7.5 Hz), 1.17-1.35 (18H, m), 1.67-1.78 (2H, m), 2.30-2.49 (7H, m), 3.21-3.30 (2H, m), 3.78 (3H, s) , 3.90 (3H, s), 4.48 (2H, s), 6.79 (2H, d, J = 8.5 Hz), 6.98 (2H, d, J = 8.5 Hz), 7 .05 (2H, s).

４−（２，６−ジエチル−４−メチルフェニル）−６−ヒドロキシ−５−（４−メトキシベンジル）オキシ−２−メチル−３（２Ｈ）−ピリダジノン
参考例８と同様にして４−（２，６−ジエチル−４−メチルフェニル）−６−ヒドロキシ−５−（４−メトキシベンジル）オキシ−２−メチル−３（２Ｈ）−ピリダジノンを得た（収率１５％）。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１５（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．３０−２．４０（５Ｈ，ｍ），２．４１−２．５２（２Ｈ，ｍ），３．６７（３Ｈ，ｓ），３．７９（３Ｈ，ｓ），４．５３（２Ｈ，ｓ），６．８１（２Ｈ，ｄ，Ｊ＝８．８Ｈｚ），６．９９（２Ｈ，ｓ），６．９９（２Ｈ，ｄ，Ｊ＝８．８Ｈｚ）． Reference Example 9-2

4- (2,6-diethyl-4-methylphenyl) -6-hydroxy-5- (4-methoxybenzyl) oxy-2-methyl-3 (2H) -pyridazinone 4- (2 , 6-Diethyl-4-methylphenyl) -6-hydroxy-5- (4-methoxybenzyl) oxy-2-methyl-3 (2H) -pyridazinone (yield 15%).
¹ H NMR (CDCl ₃ ) δ ppm: 1.15 (6H, t, J = 7.6 Hz), 2.30-2.40 (5H, m), 2.41-2.52 (2H, m) 3.67 (3H, s), 3.79 (3H, s), 4.53 (2H, s), 6.81 (2H, d, J = 8.8 Hz), 6.99 (2H, s) ), 6.99 (2H, d, J = 8.8 Hz).

４−（２，６−ジエチル−４−メチルフェニル）−５、６−ジヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノンの合成
化合物（Ｉ−４−３）６６０ｍｇ（２．０８ｍｍｏｌ）をトルエン１０ｍｌに加え、この混合物に塩化アルミニウム８３２ｍｇ（６．３４ｍｍｏｌ）を加えた。この混合物を加熱還流下３０分撹拌した。この反応液を室温まで冷却した後、２Ｎ塩酸を加え、酢酸エチルで抽出し、有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをＯＤＳシリカゲルカラムクロマトグラフィー（メタノール：０．５％ギ酸水溶液＝６０：４０）で精製し、４−（２，６−ジエチル−４−メチルフェニル）−５、６−ジヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン２００ｍｇ（収率３３％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０５（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２２−２．３９（７Ｈ，ｍ），３．６０（３Ｈ，ｓ），５．５９（１Ｈ，ｂｒｓ），６．９５（２Ｈ，ｓ），７．９３（１Ｈ，ｓ）． Reference Example 10

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -5,6-dihydroxy-2-methyl-3 (2H) -pyridazinone Compound (I-4-3) 660 mg (2.08 mmol) in toluene 10 ml In addition, 832 mg (6.34 mmol) of aluminum chloride was added to the mixture. This mixture was stirred for 30 minutes under heating to reflux. The reaction mixture was cooled to room temperature, 2N hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by ODS silica gel column chromatography (methanol: 0.5% formic acid aqueous solution = 60: 40) to give 4- (2,6-diethyl-4-methylphenyl) -5,6-dihydroxy-2-methyl- 200 mg (33% yield) of 3 (2H) -pyridazinone was obtained as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.05 (6H, t, J = 7.6 Hz), 2.22-2.39 (7H, m), 3.60 (3H, s), 5.59 (1H, brs), 6.95 (2H, s), 7.93 (1H, s).

４−（２−トリメチルシリルエチニル−４，６−ジメチルフェニル）−６−メトキシ−５−メトキシカルボニルオキシ−２−メチル−３（２Ｈ）−ピリダジノンの合成
原料として、トリブチル（ビニル）すずの代わりにトリブチル（トリメチルシリルエチニル）すずをを用い、製造例１４と同様にし、４−（２−トリメチルシリルエチニル−４，６−ジメチルフェニル）−６−メトキシ−５−メトキシカルボニルオキシ−２−メチル−３（２Ｈ）−ピリダジノン（収率７４％）を得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．０７（９Ｈ，ｓ），２．１２（３Ｈ，ｓ），２．２９（３Ｈ，ｓ），３．７３（３Ｈ，ｓ），３．７７（３Ｈ，ｓ），３．９１（３Ｈ，ｓ），７．０１（１Ｈ，ｓ），７．１９（１Ｈ，ｓ）． Reference Example 11

Synthesis of 4- (2-trimethylsilylethynyl-4,6-dimethylphenyl) -6-methoxy-5-methoxycarbonyloxy-2-methyl-3 (2H) -pyridazinone As a raw material, tributyl (vinyl) instead of tributyl (vinyl) 4- (2-trimethylsilylethynyl-4,6-dimethylphenyl) -6-methoxy-5-methoxycarbonyloxy-2-methyl-3 (2H)-using trimethylsilylethynyl) tin in the same manner as in Production Example 14. Pyridazinone (yield 74%) was obtained.
¹ H NMR (CDCl ₃ ) δ ppm: 0.07 (9H, s), 2.12 (3H, s), 2.29 (3H, s), 3.73 (3H, s), 3.77 ( 3H, s), 3.91 (3H, s), 7.01 (1H, s), 7.19 (1H, s).

４−（２，６−ジエチル−４−メチルフェニル）−６−ビス（４−メトキシベンジル）アミノ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノンの合成 Reference Example 12

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-bis (4-methoxybenzyl) amino-5-hydroxy-2-methyl-3 (2H) -pyridazinone

Ｚ−２−（２−メチルヒドラゾノ）−２−（ビス（４−メトキシベンジル）アミノ）酢酸エチル
化合物（ＸＶＩＩ−１）１７．６ｇ（１０７ｍｍｏｌ）およびビス（４−メトキシベンジル）アミン１２．３ｇ（４７．７ｍｍｏｌ）をｔｅｒｔ−ブチルメチルエーテル１００ｍｌに溶解した溶液に、氷冷下１，８−ジアザビシクロ［５．４．０］−７−ウンデセン１６．８ｇ（１１０ｍｍｏｌ）をゆっくり滴下した。この溶液を室温で２時間撹拌した。この反応液を水、飽和食塩水で順次洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮し、Ｚ−２−（２−メチルヒドラゾノ）−２−（ビス（４−メトキシベンジル）アミノ）酢酸エチル１８．３ｇ（収率９９％）をオイルとして得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．３２（３Ｈ，ｔ，Ｊ＝７．２Ｈｚ），２．８７（３Ｈ，ｄ，Ｊ＝４．１Ｈｚ），３．７８（６Ｈ，ｓ），３．９４（４Ｈ，ｓ），４．２６（２Ｈ，ｑ，Ｊ＝７．２Ｈｚ），６．８１（４Ｈ，ｄ，Ｊ＝８．５Ｈｚ），７．０４（１Ｈ，ｑ，Ｊ＝４．１Ｈｚ），７．１５（４Ｈ，ｄ，Ｊ＝８．５Ｈｚ）． Reference Example 12-1

Z-2- (2-Methylhydrazono) -2- (bis (4-methoxybenzyl) amino) ethyl acetate Compound (XVII-1) 17.6 g (107 mmol) and bis (4-methoxybenzyl) amine 12.3 g To a solution obtained by dissolving (47.7 mmol) in 100 ml of tert-butyl methyl ether, 16.8 g (110 mmol) of 1,8-diazabicyclo [5.4.0] -7-undecene was slowly added dropwise under ice cooling. The solution was stirred at room temperature for 2 hours. The reaction mixture was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and Z-2- (2-methylhydrazono) -2- (bis (4-methoxybenzyl) amino). 18.3 g (99% yield) of ethyl acetate was obtained as an oil.
¹ H NMR (CDCl ₃ ) δ ppm: 1.32 (3H, t, J = 7.2 Hz), 2.87 (3H, d, J = 4.1 Hz), 3.78 (6H, s), 3 .94 (4H, s), 4.26 (2H, q, J = 7.2 Hz), 6.81 (4H, d, J = 8.5 Hz), 7.04 (1H, q, J = 4. 1 Hz), 7.15 (4H, d, J = 8.5 Hz).

２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−メチルヒドラゾノ］−２−（ビス（４−メトキシベンジル）アミノ）酢酸エチル
参考例２−７に準じて、２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−メチルヒドラゾノ］−２−（ビス（４−メトキシベンジル）アミノ）酢酸エチルをオイルとして得た（収率１００％）。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１８（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．３２（３Ｈ，ｔ，Ｊ＝７．２Ｈｚ），２．２９（３Ｈ，ｓ），２．５５（４Ｈ，ｑ，Ｊ＝７．６Ｈｚ），３．１５（３Ｈ，ｓ），３．７１（２Ｈ，ｓ），３．７９（６Ｈ，ｓ），４．２８−４．４２（６Ｈ，ｍ），６．８７（４Ｈ，ｄ，Ｊ＝８．８Ｈｚ），６．８７（２Ｈ，ｓ），７．１９（４Ｈ，ｄ，Ｊ＝８．８Ｈｚ）． Reference Example 12-2

2- [2- (2,6-Diethyl-4-methylphenyl) acetyl-2-methylhydrazono] -2- (bis (4-methoxybenzyl) amino) acetate ethyl according to Reference Example 2-7, 2 -[2- (2,6-diethyl-4-methylphenyl) acetyl-2-methylhydrazono] -2- (bis (4-methoxybenzyl) amino) ethyl acetate was obtained as an oil (yield 100%). .
¹ H NMR (CDCl ₃ ) δ ppm: 1.18 (6H, t, J = 7.6 Hz), 1.32 (3H, t, J = 7.2 Hz), 2.29 (3H, s), 2 .55 (4H, q, J = 7.6 Hz), 3.15 (3H, s), 3.71 (2H, s), 3.79 (6H, s), 4.28-4.42 (6H M), 6.87 (4H, d, J = 8.8 Hz), 6.87 (2H, s), 7.19 (4H, d, J = 8.8 Hz).

４−（２，６−ジエチル−４−メチルフェニル）−６−ビス（４−メトキシベンジル）アミノ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン
製造例１２と同様にして４−（２，６−ジエチル−４−メチルフェニル）−６−ビス（４−メトキシベンジル）アミノ−５−ヒドロキシ−２−メチル−３（２Ｈ）−ピリダジノン（収率８０％）を得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８９（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．９３−２．１２（４Ｈ，ｍ），２．２８（３Ｈ，ｓ），３．７４（３Ｈ，ｓ），３．７７（６Ｈ，ｓ），４．１７（４Ｈ，ｓ），６．５１（１Ｈ，ｓ），６．７９（４Ｈ，ｄ，Ｊ＝８．５Ｈｚ），６．８８（２Ｈ，ｓ），７．１５（４Ｈ，ｄ，Ｊ＝８．５Ｈｚ）． Reference Example 12-3

4- (2,6-diethyl-4-methylphenyl) -6-bis (4-methoxybenzyl) amino-5-hydroxy-2-methyl-3 (2H) -pyridazinone In the same manner as in Production Example 12, 4- ( 2,6-Diethyl-4-methylphenyl) -6-bis (4-methoxybenzyl) amino-5-hydroxy-2-methyl-3 (2H) -pyridazinone (yield 80%) was obtained.
¹ H NMR (CDCl ₃ ) δ ppm: 0.89 (6H, t, J = 7.6 Hz), 1.93-2.12 (4H, m), 2.28 (3H, s), 3.74 (3H, s), 3.77 (6H, s), 4.17 (4H, s), 6.51 (1H, s), 6.79 (4H, d, J = 8.5 Hz), 6. 88 (2H, s), 7.15 (4H, d, J = 8.5 Hz).

４−（２，６−ジエチル−４−メチルフェニル）−６−ヒドロキシメチル−５−（４−メチルフェニルスルホニル）−２−メチル−３（２Ｈ）−ピリダジノンの合成 Reference Example 13

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-hydroxymethyl-5- (4-methylphenylsulfonyl) -2-methyl-3 (2H) -pyridazinone

１−アセトキシ−３−（４−メチルフェニルチオ）アセトン
１−アセトキシ−３−クロロアセトン５．０ｇ（３３．２ｍｍｏｌ）および４−メチルチオフェノール４．１２ｇ（３３．２ｍｍｏｌ）をｔｅｒｔ−ブチルメチルエーテル１００ｍｌに溶解した溶液に、氷冷下トリエチルアミン５．１ｍｌ（３６．６ｍｍｏｌ）をゆっくり滴下した。この溶液を室温で３０分撹拌した。この反応液を水、飽和炭酸水素ナトリウム水溶液、飽和食塩水で順次洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝７：３）で精製し、１−アセトキシ−３−（４−メチルフェニルチオ）アセトン７．７２ｇ（収率９７％）をオイルとして得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：２．１４（３Ｈ，ｓ），２．３２（３Ｈ，ｓ），３．６５（２Ｈ，ｓ），４．８４（２Ｈ，ｓ），７．１２（２Ｈ，ｄ，Ｊ＝８．１Ｈｚ），７．２８（２Ｈ，ｄ，Ｊ＝８．１Ｈｚ）． Reference Example 13-1

1-acetoxy-3- (4-methylphenylthio) acetone 5.0 g (33.2 mmol) of 1-acetoxy-3-chloroacetone and 4.12 g (33.2 mmol) of 4-methylthiophenol were added to 100 ml of tert-butyl methyl ether. To the solution dissolved in (5), 5.1 ml (36.6 mmol) of triethylamine was slowly added dropwise under ice cooling. The solution was stirred at room temperature for 30 minutes. The reaction mixture was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 7: 3) to obtain 7.72 g (yield 97%) of 1-acetoxy-3- (4-methylphenylthio) acetone as an oil.
¹ H NMR (CDCl ₃ ) δ ppm: 2.14 (3H, s), 2.32 (3H, s), 3.65 (2H, s), 4.84 (2H, s), 7.12 ( 2H, d, J = 8.1 Hz), 7.28 (2H, d, J = 8.1 Hz).

１−アセトキシ−３−（４−メチルフェニルスルホニル）アセトン
１−アセトキシ−３−（４−メチルフェニルチオ）アセトン２２．２ｇ（９３．５ｍｍｏｌ）をクロロホルム２００ｍｌに溶解した溶液に、氷冷下７０％ｍ−クロロ過安息香酸５０．７ｇ（２０５ｍｍｏｌ）をゆっくり加えた。この反応液を室温で１時間攪拌した後、減圧下濃縮した。残さに酢酸エチルを加え、亜硫酸水素ナトリウム水溶液、飽和炭酸水素ナトリウム水溶液、飽和食塩水で順次洗浄し、無水硫酸マグネシウムで乾燥し、減圧濃縮し、１−アセトキシ−３−（４−メチルフェニルスルホニル）アセトン２２．７ｇ（収率９０％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：２．１６（３Ｈ，ｓ），２．４６（３Ｈ，ｓ），４．１９（２Ｈ，ｓ），４．９２（２Ｈ，ｓ），７．３８（２Ｈ，ｄ，Ｊ＝８．２Ｈｚ），７．７７（２Ｈ，ｄ，Ｊ＝８．２Ｈｚ）． Reference Example 13-2

1-acetoxy-3- (4-methylphenylsulfonyl) acetone To a solution of 22.2 g (93.5 mmol) of 1-acetoxy-3- (4-methylphenylthio) acetone in 200 ml of chloroform was added 70% under ice cooling. 50.7 g (205 mmol) of m-chloroperbenzoic acid was slowly added. The reaction was stirred at room temperature for 1 hour and then concentrated under reduced pressure. Ethyl acetate was added to the residue, washed successively with aqueous sodium hydrogen sulfite solution, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and 1-acetoxy-3- (4-methylphenylsulfonyl). Acetone 22.7 g (yield 90%) was obtained as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 2.16 (3H, s), 2.46 (3H, s), 4.19 (2H, s), 4.92 (2H, s), 7.38 ( 2H, d, J = 8.2 Hz), 7.77 (2H, d, J = 8.2 Hz).

１−アセトキシ−３−（４−メチルフェニルスルホニル）アセトン１７．５ｇ（６４．７ｍｍｏｌ）をＴＨＦ６０ｍｌに溶解し、氷冷した。この溶液にメチルヒドラジン２．９８ｇ（６４．７ｍｍｏｌ）をゆっくり滴下した。アイスバスをはずし、室温で一晩撹拌した。この反応液にトリエチルアミン１０．８ｍｌ（７７．５ｍｍｏｌ）を加え、次に（２，６−ジエチル−４−メチルフェニル）グリオキシル酸クロライド１５．４ｇ（６４．７ｍｍｏｌ）をＴＨＦ３０ｍｌに溶かした溶液を、ゆっくり加えた。この反応混合物を室温で３時間撹拌した後、加熱還流下１．５時間撹拌した。この反応液を室温まで冷却した後、反応液に水を加え、ｔｅｒｔ−ブチルメチルエーテルで抽出し、有機層を飽和炭酸水素ナトリウム水溶液、飽和食塩水で順次洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さにメタノール７０ｍｌを加え、氷冷した。この溶液に水酸化リチウム一水和物８．１４ｇ（１９４ｍｍｏｌ）を加え、０℃で５時間撹拌した。反応液に２Ｎ塩酸１５０ｍｌを加え、減圧下濃縮し、メタノールを留去した。残さを酢酸エチルで２回抽出し、合わせた有機層を飽和炭酸水素ナトリウム水溶液、飽和食塩水で順次洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１：１）で精製し、４−（２，６−ジエチル−４−メチルフェニル）−６−ヒドロキシメチル−５−（４−メチルフェニルスルホニル）−２−メチル−３（２Ｈ）−ピリダジノン２．５８ｇ（収率９％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．９５（６Ｈ，ｔ，Ｊ＝７．５Ｈｚ），１．９４（４Ｈ，ｑ，Ｊ＝７．５Ｈｚ），２．３２（３Ｈ， ｓ），２．３９（３Ｈ，ｓ），３．７３（１Ｈ，ｔ，Ｊ＝７．０Ｈｚ），３．８２（３Ｈ，ｓ），５．０６（２Ｈ，ｄ，Ｊ＝７．０Ｈｚ），６．７１（２Ｈ，ｓ），７．０４（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ），７．２０（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ）． Reference Example 13-3

17.5 g (64.7 mmol) of 1-acetoxy-3- (4-methylphenylsulfonyl) acetone was dissolved in 60 ml of THF and cooled on ice. To this solution, 2.98 g (64.7 mmol) of methyl hydrazine was slowly added dropwise. The ice bath was removed and the mixture was stirred overnight at room temperature. To this reaction solution was added 10.8 ml (77.5 mmol) of triethylamine, and then a solution of 15.4 g (64.7 mmol) of (2,6-diethyl-4-methylphenyl) glyoxylic acid chloride in 30 ml of THF was slowly added. added. The reaction mixture was stirred at room temperature for 3 hours and then stirred for 1.5 hours under heating to reflux. After cooling the reaction solution to room temperature, water was added to the reaction solution, extracted with tert-butyl methyl ether, the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, Concentrated under reduced pressure. 70 ml of methanol was added to the residue and cooled on ice. To this solution, 8.14 g (194 mmol) of lithium hydroxide monohydrate was added and stirred at 0 ° C. for 5 hours. 150 ml of 2N hydrochloric acid was added to the reaction mixture, and the mixture was concentrated under reduced pressure to distill off methanol. The residue was extracted twice with ethyl acetate, and the combined organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 1: 1) to give 4- (2,6-diethyl-4-methylphenyl) -6-hydroxymethyl-5- (4-methylphenylsulfonyl)- 2.58 g (9% yield) of 2-methyl-3 (2H) -pyridazinone was obtained as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 0.95 (6H, t, J = 7.5 Hz), 1.94 (4H, q, J = 7.5 Hz), 2.32 (3H, s), 2 .39 (3H, s), 3.73 (1H, t, J = 7.0 Hz), 3.82 (3H, s), 5.06 (2H, d, J = 7.0 Hz), 6.71 (2H, s), 7.04 (2H, d, J = 8.3 Hz), 7.20 (2H, d, J = 8.3 Hz).

４−（２，４，６−トリエチルフェニル）−６−ヒドロキシメチル−５−（４−メチルフェニルスルホニル）−２−メチル−３（２Ｈ）−ピリダジノン
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．９５（６Ｈ，ｔ，Ｊ＝７．５Ｈｚ），１．２７（３Ｈ，ｔ，Ｊ＝７．６Ｈｚ）， １．８８−１．９８（４Ｈ，ｍ），２．３８（３Ｈ，ｓ），２．６１（２Ｈ，ｑ，Ｊ＝７．６Ｈｚ），３．７４（１Ｈ，ｔ，Ｊ＝６．６Ｈｚ），３．８２（３Ｈ，ｓ），５．０７（２Ｈ，ｄ，Ｊ＝６．６Ｈｚ），６．７２（２Ｈ，ｓ），７．０２（２Ｈ，ｄ，Ｊ＝８．５Ｈｚ），７．１７（２Ｈ，ｄ，Ｊ＝８．５Ｈｚ）． The following compounds were obtained in the same manner as in Reference Example 13.

4- (2,4,6-triethylphenyl) -6-hydroxymethyl-5- (4-methylphenylsulfonyl) -2-methyl-3 (2H) -pyridazinone
¹ H NMR (CDCl ₃ ) δ ppm: 0.95 (6H, t, J = 7.5 Hz), 1.27 (3H, t, J = 7.6 Hz), 1.88-1.98 (4H, m), 2.38 (3H, s), 2.61 (2H, q, J = 7.6 Hz), 3.74 (1H, t, J = 6.6 Hz), 3.82 (3H, s) , 5.07 (2H, d, J = 6.6 Hz), 6.72 (2H, s), 7.02 (2H, d, J = 8.5 Hz), 7.17 (2H, d, J = 8.5 Hz).

４−（２，６−ジエチル−４−メチルフェニル）−６−メトキシメトキシメチル−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノンの合成 Reference Example 14

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-methoxymethoxymethyl-5-benzyloxy-2-methyl-3 (2H) -pyridazinone

４−（２，６−ジエチル−４−メチルフェニル）−６−メトキシメトキシメチル−５−（４−メチルフェニルスルホニル）−２−メチル−３（２Ｈ）−ピリダジノン
４−（２，６−ジエチル−４−メチルフェニル）−６−ヒドロキシメチル−５−（４−メチルフェニルスルホニル）−２−メチル−３（２Ｈ）−ピリダジノン２．４０ｇ（５．４５ｍｍｏｌ）およびジイソプロピルエチルアミン１０ｍｌ（５７．４ｍｍｏｌ）をＴＨＦ２０ｍｌに溶解した溶液に、クロロメチルメチルエーテル２．４ｍｌ（３１．６ｍｍｏｌ）を加え、加熱還流下４時間撹拌した。この反応液を室温まで冷却した後、反応液に飽和炭酸水素ナトリウム水溶液を加え、酢酸エチルで２回抽出した。合わせた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２：１）で精製し、４−（２，６−ジエチル−４−メチルフェニル）−６−メトキシメトキシメチル−５−（４−メチルフェニルスルホニル）−２−メチル−３（２Ｈ）−ピリダジノン２．１１ｇ（収率８０％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．９３（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），１．８２−１．９５（４Ｈ，ｍ），２．３３（３Ｈ，ｓ），２．３９（３Ｈ，ｓ），３．５０（３Ｈ，ｓ），３．８２（３Ｈ，ｓ），４．８７（２Ｈ，ｓ），５．１０（２Ｈ，ｓ），６．７３（２Ｈ，ｓ），７．０４（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ），７．２５（２Ｈ，ｄ，Ｊ＝８．３Ｈｚ）． Reference Example 14-1

4- (2,6-diethyl-4-methylphenyl) -6-methoxymethoxymethyl-5- (4-methylphenylsulfonyl) -2-methyl-3 (2H) -pyridazinone 4- (2,6-diethyl- 4-methylphenyl) -6-hydroxymethyl-5- (4-methylphenylsulfonyl) -2-methyl-3 (2H) -pyridazinone 2.40 g (5.45 mmol) and diisopropylethylamine 10 ml (57.4 mmol) in THF 20 ml To the solution dissolved in 2, 2.4 ml (31.6 mmol) of chloromethyl methyl ether was added, and the mixture was stirred for 4 hours with heating under reflux. After cooling this reaction liquid to room temperature, saturated sodium hydrogencarbonate aqueous solution was added to the reaction liquid, and ethyl acetate extracted twice. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to give 4- (2,6-diethyl-4-methylphenyl) -6-methoxymethoxymethyl-5- (4-methylphenylsulfonyl). -2-Methyl-3 (2H) -pyridazinone 2.11 g (80% yield) was obtained as a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 0.93 (6H, t, J = 7.6 Hz), 1.82-1.95 (4H, m), 2.33 (3H, s), 2.39 (3H, s), 3.50 (3H, s), 3.82 (3H, s), 4.87 (2H, s), 5.10 (2H, s), 6.73 (2H, s) 7.04 (2H, d, J = 8.3 Hz), 7.25 (2H, d, J = 8.3 Hz).

４−（２，６−ジエチル−４−メチルフェニル）−６−メトキシメトキシメチル−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン
４−（２，６−ジエチル−４−メチルフェニル）−６−メトキシメトキシメチル−５−（４−メチルフェニルスルホニル）−２−メチル−３（２Ｈ）−ピリダジノン２．３８ｇ（４．９１ｍｍｏｌ）およびベンジルアルコール７９７ｍｇ（７．３７ｍｍｏｌ）を無水ＤＭＦ１０ｍｌに溶解した溶液に、５℃で６０％水素化ナトリウム２９４ｍｇ（７．３５ｍｍｏｌ）を加えた。この反応液を０℃で１時間撹拌した。この反応液に水を加え、ｔｅｒｔ−ブチルメチルエーテルで２回抽出し、合わせた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２：１）で精製し、４−（２，６−ジエチル−４−メチルフェニル）−６−メトキシメトキシメチル−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン２．１２ｇ（収率９９％）をオイルとして得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１４（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ）， ２．３２−２．５３（７Ｈ，ｍ），３．３０（３Ｈ，ｓ），３．７９（３Ｈ，ｓ），４．４５（２Ｈ，ｓ），４．５１（２Ｈ，ｓ），４．６３（２Ｈ，ｓ），６．９９（２Ｈ，ｓ），７．０３−７．０９（２Ｈ，ｍ），７．２４−７．３３（３Ｈ，ｍ）． Reference Example 14-2

4- (2,6-diethyl-4-methylphenyl) -6-methoxymethoxymethyl-5-benzyloxy-2-methyl-3 (2H) -pyridazinone 4- (2,6-diethyl-4-methylphenyl) -6-methoxymethoxymethyl-5- (4-methylphenylsulfonyl) -2-methyl-3 (2H) -pyridazinone 2.38 g (4.91 mmol) and 797 mg (7.37 mmol) of benzyl alcohol were dissolved in 10 ml of anhydrous DMF. To the solution was added 294 mg (7.35 mmol) of 60% sodium hydride at 5 ° C. The reaction was stirred at 0 ° C. for 1 hour. Water was added to the reaction mixture, and the mixture was extracted twice with tert-butyl methyl ether. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to give 4- (2,6-diethyl-4-methylphenyl) -6-methoxymethoxymethyl-5-benzyloxy-2-methyl- 2.12 g (99% yield) of 3 (2H) -pyridazinone was obtained as an oil.
¹ H NMR (CDCl ₃ ) δ ppm: 1.14 (6H, t, J = 7.6 Hz), 2.32-2.53 (7H, m), 3.30 (3H, s), 3.79 (3H, s), 4.45 (2H, s), 4.51 (2H, s), 4.63 (2H, s), 6.99 (2H, s), 7.03-7.09 ( 2H, m), 7.24-7.33 (3H, m).

４−（２，６−ジエチル−４−メチルフェニル）−６−ブロモメチル−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノンの合成
化合物（Ｉ−２９）６００ｍｇ（１．５３ｍｍｏｌ）をＴＨＦ８ｍｌに溶解した溶液に、０℃で三臭化リン１６６ｍｇ（０．６１３ｍｍｏｌ）をＴＨＦ０．５ｍｌに溶解した溶液を滴下した。この反応液を０℃で３０分撹拌した。この反応液に飽和炭酸水素ナトリウム水溶液を加え、ｔｅｒｔ−ブチルメチルエーテルで３回抽出し、合わせた有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮して、４−（２，６−ジエチル−４−メチルフェニル）−６−ブロモメチル−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン６８１ｇ（収率９７％）をオイルとして得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．１５（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．３２−２．５４（７Ｈ，ｍ），３．７８（３Ｈ，ｓ），４．４２（２Ｈ，ｓ），４．５０（２Ｈ，ｓ），７．００（２Ｈ，ｓ），７．１１−７．１５（２Ｈ，ｍ），７．２８−７．３２（３Ｈ，ｍ）． Reference Example 15

Synthesis of 4- (2,6-diethyl-4-methylphenyl) -6-bromomethyl-5-benzyloxy-2-methyl-3 (2H) -pyridazinone Compound (I-29) 600 mg (1.53 mmol) was added to THF 8 ml. A solution prepared by dissolving 166 mg (0.613 mmol) of phosphorus tribromide in 0.5 ml of THF was added dropwise to the solution dissolved in 0.degree. The reaction was stirred at 0 ° C. for 30 minutes. Saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted 3 times with tert-butyl methyl ether. The combined organic layers were washed with saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and 4- 681, g (yield 97%) of (2,6-diethyl-4-methylphenyl) -6-bromomethyl-5-benzyloxy-2-methyl-3 (2H) -pyridazinone was obtained as an oil.
¹ H NMR (CDCl ₃ ) δ ppm: 1.15 (6H, t, J = 7.6 Hz), 2.32-2.54 (7H, m), 3.78 (3H, s), 4.42 (2H, s), 4.50 (2H, s), 7.00 (2H, s), 7.11-7.15 (2H, m), 7.28-7.32 (3H, m).

（２，６−ジエチル−４−メチルフェニル）グリオキシル酸クロライドの合成 Reference Example 16

Synthesis of (2,6-diethyl-4-methylphenyl) glyoxylic acid chloride

（２，６−ジエチル−４−メチルフェニル）グリオキシル酸エチル
窒素雰囲気下、室温にて、マグネシウム（切削片状）３５．３１ｇ、無水テトラヒドロフラン６００ｍｌを入れ、攪拌を開始した後、３０℃まで加温し、ジブロモエタン２５．４ｇを２０分かけて滴下した。得られた混合物を３０分間攪拌した後、５０℃に加温し、そこにテトラヒドロフラン１５０ｍｌに溶解させた２，６−ジエチル−４−メチルブロモベンゼン３００．１８ｇを２時間かけて滴下した。得られた混合物を５０℃で、１時間攪拌した後、０℃に冷やし、シュウ酸ジエチル１９２．５ｇを１５分かけて滴下した。得られた混合物を室温で２時間攪拌した。その後、０℃で３．５重量％塩酸を１０００ｍｌ、および濃塩酸６０ｍｌ加えた。その後、有機層を留去し、水層をｔｅｒｔ−ブチルメチルエーテルにて抽出し、有機層を減圧濃縮することで、（２，６−ジエチル−４−メチルフェニル）グリオキシル酸エチル３２０．８２ｇを得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：６．９２（２Ｈ，ｓ），４．３６（２Ｈ，ｑ，Ｊ＝７．１Ｈｚ），２．５２（４Ｈ，ｑ，Ｊ＝７．６Ｈｚ），２．３４（３Ｈ，ｓ），１．３６（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ），１．１６（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ） Reference Example 16-1

Ethyl (2,6-diethyl-4-methylphenyl) glyoxylate In a nitrogen atmosphere, 35.31 g of magnesium (cut pieces) and 600 ml of anhydrous tetrahydrofuran were added at room temperature. After stirring, the mixture was heated to 30 ° C. Then, 25.4 g of dibromoethane was added dropwise over 20 minutes. The resulting mixture was stirred for 30 minutes and then heated to 50 ° C., and 300.18 g of 2,6-diethyl-4-methylbromobenzene dissolved in 150 ml of tetrahydrofuran was added dropwise over 2 hours. The resulting mixture was stirred at 50 ° C. for 1 hour, then cooled to 0 ° C., and 192.5 g of diethyl oxalate was added dropwise over 15 minutes. The resulting mixture was stirred at room temperature for 2 hours. Thereafter, 1000 ml of 3.5% by weight hydrochloric acid and 60 ml of concentrated hydrochloric acid were added at 0 ° C. Thereafter, the organic layer was distilled off, the aqueous layer was extracted with tert-butyl methyl ether, and the organic layer was concentrated under reduced pressure to obtain 320.82 g of ethyl (2,6-diethyl-4-methylphenyl) glyoxylate. Obtained.
¹ H NMR (CDCl ₃ ) δ ppm: 6.92 (2H, s), 4.36 (2H, q, J = 7.1 Hz), 2.52 (4H, q, J = 7.6 Hz), 2 .34 (3H, s), 1.36 (3H, t, J = 7.1 Hz), 1.16 (6H, t, J = 7.6 Hz)

（２，６−ジエチル−４−メチルフェニル）グリオキシル酸
室温にて、テトラヒドロフラン６００ｍｌで希釈した（２，６−ジエチル−４−メチルフェニル）グリオキシル酸エチル３２０．８２ｇを加え、攪拌し、１０℃にて、１０．７重量％水酸化ナトリウム水溶液９００ｍｌを２時間かけて滴下した。得られた混合物を室温にて、１時間攪拌した。その後、有機層を留去し、水層へｔｅｒｔ−ブチルメチルエーテルを加え、洗浄した。有機層を除去した後に、水層へ濃塩酸１８０ｍｌを滴下し、ｔｅｒｔ−ブチルメチルエーテルにて抽出、有機層を減圧濃縮することで、（２，６−ジエチル−４−メチルフェニル）グリオキシル酸１６６．５５ｇを得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：６．９５（２Ｈ，ｓ），２．４９（４Ｈ，ｑ，Ｊ＝７．５Ｈｚ），２．３５（３Ｈ，ｓ），１．１６（６Ｈ，ｔ，Ｊ＝７．５Ｈｚ） Reference Example 16-2

(2,6-Diethyl-4-methylphenyl) glyoxylic acid At room temperature, 320.82 g of ethyl (2,6-diethyl-4-methylphenyl) glyoxylate diluted with 600 ml of tetrahydrofuran was added, stirred, and heated to 10 ° C. Then, 900 ml of a 10.7 wt% aqueous sodium hydroxide solution was added dropwise over 2 hours. The resulting mixture was stirred at room temperature for 1 hour. Thereafter, the organic layer was distilled off, and tert-butyl methyl ether was added to the aqueous layer for washing. After removing the organic layer, 180 ml of concentrated hydrochloric acid was added dropwise to the aqueous layer, extracted with tert-butyl methyl ether, and the organic layer was concentrated under reduced pressure to obtain (2,6-diethyl-4-methylphenyl) glyoxylic acid 166. Obtained .55 g.
¹ H NMR (CDCl ₃ ) δ ppm: 6.95 (2H, s), 2.49 (4H, q, J = 7.5 Hz), 2.35 (3H, s), 1.16 (6H, t , J = 7.5Hz)

（２，６−ジエチル−４−メチルフェニル）グリオキシル酸クロライド
窒素雰囲気下、室温にて、（２，６−ジエチル−４−メチルフェニル）グリオキシル酸０．９４ｇ、トルエン３．０ｍｌ、ジメチルホルムアミド０．２ｍｌを加え、攪拌し５０℃に加熱して、塩化チオニルを０．４５ｍｌ添加した。得られた混合物を５０℃で、２時間攪拌した後、減圧濃縮し、（２，６−ジエチル−４−メチルフェニル）グリオキシル酸クロライドを０．９６ｇ得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：６．９６（２Ｈ，ｓ），２．５３（４Ｈ，ｑ，Ｊ＝７．６Ｈｚ），２．３８（３Ｈ，ｓ），１．１８（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ） Reference Example 16-3

(2,6-diethyl-4-methylphenyl) glyoxylic acid chloride 0.94 g of (2,6-diethyl-4-methylphenyl) glyoxylic acid, 3.0 ml of toluene, dimethylformamide 0. 2 ml was added, stirred and heated to 50 ° C., and 0.45 ml of thionyl chloride was added. The resulting mixture was stirred at 50 ° C. for 2 hours and then concentrated under reduced pressure to obtain 0.96 g of (2,6-diethyl-4-methylphenyl) glyoxylic acid chloride.
¹ H NMR (CDCl ₃ ) δ ppm: 6.96 (2H, s), 2.53 (4H, q, J = 7.6 Hz), 2.38 (3H, s), 1.18 (6H, t , J = 7.6 Hz)

（４−（２，６−ジエチル−４−メチルフェニル）−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン−６−イル）オキシ酢酸の合成
化合物（Ｉ−８−７）を用い、製造例２８と同様にして（４−（２，６−ジエチル−４−メチルフェニル）−５−ベンジルオキシ−２−メチル−３（２Ｈ）−ピリダジノン−６−イル）オキシ酢酸（収率８８％）を固体として得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．０８（６Ｈ，ｔ，Ｊ＝７．６Ｈｚ），２．２０−２．３０（２Ｈ，ｍ），２．３２−２．４３（２Ｈ，ｍ），２．３７（３Ｈ，ｓ），３．６６（３Ｈ，ｓ），４．８５（２Ｈ，ｓ），４．８７（２Ｈ，ｓ），６．９６（２Ｈ，ｓ），７．００−７．０４（２Ｈ，ｍ），７．２０−７．２４（３Ｈ，ｍ）． Reference Example 17

Synthesis of (4- (2,6-diethyl-4-methylphenyl) -5-benzyloxy-2-methyl-3 (2H) -pyridazinon-6-yl) oxyacetic acid Using compound (I-8-7) In the same manner as in Production Example 28, (4- (2,6-diethyl-4-methylphenyl) -5-benzyloxy-2-methyl-3 (2H) -pyridazinon-6-yl) oxyacetic acid (yield 88 %) As a solid.
¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (6H, t, J = 7.6 Hz), 2.20-2.30 (2H, m), 2.32-2.43 (2H, m) , 2.37 (3H, s), 3.66 (3H, s), 4.85 (2H, s), 4.87 (2H, s), 6.96 (2H, s), 7.00- 7.04 (2H, m), 7.20-7.24 (3H, m).

２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−アリルヒドラゾノ］−２−（ドデシルチオ）酢酸エチルの合成
参考例１８−１

Ｅ−２−（２−ｔ−ブトキシカルボニル−２−アリルヒドラゾノ）酢酸エチル
参考例５−１と同様にして、Ｅ−２−（２−ｔ−ブトキシカルボニル−２−アリルヒドラゾノ）酢酸エチルをオイルとして得た（収率７３％）。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δｐｐｍ：１．３５（３Ｈ，ｔ，Ｊ＝７．２Ｈｚ），１．５６（９Ｈ，ｓ），４．３０（２Ｈ，ｑ，Ｊ＝７．２Ｈｚ），４．４４−４．５０（２Ｈ，ｍ），５．０６−５．１５（１Ｈ，ｍ），５．１９−５．２７（１Ｈ，ｍ），５．６４−５．７７（１Ｈ，ｍ），７．０３ （１Ｈ， ｓ）．
参考例１８−２

Ｅ−２−（２−アリルヒドラゾノ）酢酸エチル
Ｅ−２−（２−ｔ−ブトキシカルボニル−２−アリルヒドラゾノ）酢酸エチル８．６５ｇ（３３．７ｍｍｏｌ）をジクロロメタン６０ｍｌに溶解した溶液に、３℃でトリフルオロ酢酸１５ｍｌを加えた。この反応液を室温で１時間撹拌した後、減圧下濃縮した。残さを飽和炭酸水素ナトリウム水溶液３００ｍｌに加え、酢酸エチルで抽出し、有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥し、減圧下濃縮した。残さをシリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝２：１）で精製し、Ｅ−２−（２−アリルヒドラゾノ）酢酸エチル１．８７ｇ（収率３５％）をオイルとして得た。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δｐｐｍ：１．３３（３Ｈ，ｔ，Ｊ＝７．２Ｈｚ），３．８９（２Ｈ，ｔ，Ｊ＝５．１Ｈｚ），４．２８（２Ｈ，ｑ，Ｊ＝７．２Ｈｚ），５．２５−５．３４（２Ｈ，ｍ），５．８０−５．９１（１Ｈ，ｍ），６．５１（１Ｈ，ｂｒｓ），６．７６（１Ｈ，ｓ）．
参考例１８−３

Ｚ−２−クロロ−２−（２−アリルヒドラゾノ）酢酸エチル
参考例１−２と同様にして、Ｚ−２−クロロ−２−（２−アリルヒドラゾノ）酢酸エチルをオイルとして得た（収率３８％）。
Ｚ体の¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：１．３６（３Ｈ，ｔ，Ｊ＝７．２Ｈｚ），４．１１−４．１７（２Ｈ，ｍ），４．３５（２Ｈ，ｑ，Ｊ＝７．２Ｈｚ），５．１９−５．２９（２Ｈ，ｍ），５．８６−５．９９（１Ｈ，ｍ），６．５１（１Ｈ，ｂｒｓ）．
参考例１８−４

Ｚ−２−（２−アリルヒドラゾノ）−２−（ドデシルチオ）酢酸エチル
参考例３−１と同様にして、Ｚ−２−（２−アリルヒドラゾノ）−２−（ドデシルチオ）酢酸エチルをオイルとして得た（収率４０％）。
¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８８（３Ｈ，ｔ，Ｊ＝６．９Ｈｚ），１．１７−１．４２（２１Ｈ，ｍ），１．４８−１．５９（２Ｈ，ｍ），２．７９（２Ｈ，ｔ，Ｊ＝７．４Ｈｚ），４．１６−４．２３（２Ｈ，ｍ），４．３２（２Ｈ，ｑ，Ｊ＝７．１Ｈｚ），５．１６−５．２８（２Ｈ，ｍ），５．８６−５．９９（１Ｈ，ｍ），７．４６（１Ｈ，ｔ，Ｊ＝４．７Ｈｚ）．
参考例１８−５

２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−アリルヒドラゾノ］−２−（ドデシルチオ）酢酸エチル
参考例２−７と同様にして、２−［２−（２，６−ジエチル−４−メチルフェニル）アセチル−２−アリルヒドラゾノ］−２−（ドデシルチオ）酢酸エチルをオイル状の幾何異性体混合物として得た（収率８１％）。
主要物の¹Ｈ ＮＭＲ（ＣＤＣｌ₃）δ ｐｐｍ：０．８８（３Ｈ，ｔ，Ｊ＝６．８Ｈｚ），１．１０−１．４５（２７Ｈ，ｍ），１．５７−１．６９（２Ｈ，ｍ），２．２９（３Ｈ，ｓ），２．５４（４Ｈ，ｑ，Ｊ＝７．６Ｈｚ），２．９５（２Ｈ，ｔ，Ｊ＝７．６Ｈｚ），３．８２（２Ｈ，ｓ），４．３８（２Ｈ，ｑ，Ｊ＝７．２Ｈｚ），４．５７（２Ｈ，ｄ，Ｊ＝５．３Ｈｚ），５．０９−５．２７（２Ｈ，ｍ），５．７７−５．９３（１Ｈ，ｍ），６．８７（２Ｈ，ｓ）． Reference Example 18

Synthesis Reference Example 18-1 for Ethyl 2- [2- (2,6-diethyl-4-methylphenyl) acetyl-2-allylhydrazono] -2- (dodecylthio) acetate

E-2- (2-t-butoxycarbonyl-2-allylhydrazono) ethyl acetate In the same manner as in Reference Example 5-1, ethyl E-2- (2-t-butoxycarbonyl-2-allylhydrazono) acetate was obtained as an oil. (Yield 73%).
¹ H NMR (CDCl ₃ ) δ ppm: 1.35 (3H, t, J = 7.2 Hz), 1.56 (9H, s), 4.30 (2H, q, J = 7.2 Hz), 4. 44-4.50 (2H, m), 5.06-5.15 (1H, m), 5.19-5.27 (1H, m), 5.64-5.77 (1H, m), 7.03 (1H, s).
Reference Example 18-2

E-2- (2-allylhydrazono) ethyl acetate To a solution of 8.65 g (33.7 mmol) of ethyl E-2- (2-t-butoxycarbonyl-2-allylhydrazono) acetate in 60 ml of dichloromethane was added at 3 ° C. 15 ml of fluoroacetic acid was added. The reaction was stirred at room temperature for 1 hour and then concentrated under reduced pressure. The residue was added to 300 ml of a saturated aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1) to obtain 1.87 g (yield 35%) of ethyl E-2- (2-allylhydrazono) acetate as an oil.
¹ H NMR (CDCl ₃ ) δ ppm: 1.33 (3H, t, J = 7.2 Hz), 3.89 (2H, t, J = 5.1 Hz), 4.28 (2H, q, J = 7) .2 Hz), 5.25-5.34 (2H, m), 5.80-5.91 (1H, m), 6.51 (1H, brs), 6.76 (1H, s).
Reference Example 18-3

Z-2-Chloro-2- (2-allylhydrazono) ethyl acetate In the same manner as in Reference Example 1-2, ethyl Z-2-chloro-2- (2-allylhydrazono) acetate was obtained as an oil (yield 38%). ).
¹ H NMR (CDCl ₃ ) δ ppm of Z form: 1.36 (3H, t, J = 7.2 Hz), 4.11-4.17 (2H, m), 4.35 (2H, q, J = 7.2 Hz), 5.19-5.29 (2H, m), 5.86-5.99 (1H, m), 6.51 (1H, brs).
Reference Example 18-4

Z-2- (2-allylhydrazono) -2- (dodecylthio) ethyl acetate In the same manner as in Reference Example 3-1, ethyl Z-2- (2-allylhydrazono) -2- (dodecylthio) acetate was obtained as an oil ( Yield 40%).
¹ H NMR (CDCl ₃ ) δ ppm: 0.88 (3H, t, J = 6.9 Hz), 1.17-1.42 (21H, m), 1.48-1.59 (2H, m) , 2.79 (2H, t, J = 7.4 Hz), 4.16-4.23 (2H, m), 4.32 (2H, q, J = 7.1 Hz), 5.16-5. 28 (2H, m), 5.86-5.99 (1 H, m), 7.46 (1 H, t, J = 4.7 Hz).
Reference Example 18-5

2- [2- (2,6-Diethyl-4-methylphenyl) acetyl-2-allylhydrazono] -2- (dodecylthio) acetate In the same manner as in Reference Example 2-7, 2- [2- (2,6 -Diethyl-4-methylphenyl) acetyl-2-allylhydrazono] -2- (dodecylthio) acetate was obtained as an oily geometric isomer mixture (yield 81%).
¹ H NMR (CDCl ₃ ) δ ppm of main product: 0.88 (3H, t, J = 6.8 Hz), 1.10-1.45 (27H, m), 1.57-1.69 (2H M), 2.29 (3H, s), 2.54 (4H, q, J = 7.6 Hz), 2.95 (2H, t, J = 7.6 Hz), 3.82 (2H, s) ), 4.38 (2H, q, J = 7.2 Hz), 4.57 (2H, d, J = 5.3 Hz), 5.09-5.27 (2H, m), 5.77-5. .93 (1H, m), 6.87 (2H, s).

  Next, formulation examples are shown.

Formulation Example 1
Compound (I-1-1) 10% by weight
Diflufenican 2% by weight
Polyoxyethylene sorbitan monooleate 3% by weight
Carboxymethylcellulose 3% by weight
82% by weight of water
And wet mill until the particle size is 5 microns or less to obtain a formulation.
Compound (I-1-1) is converted from Compound (I-1-2) to Compound (I-1-7), Compound (I-2-1) to Compound (I-2-3), Compound (I-3) -1) to Compound (I-3-4), Compound (I-4-1) to Compound (I-4-6), Compound (I-5-1) to Compound (I-5-9), Compound (I-6-1), Compound (I-6-2), Compound (I-7-1) to Compound (I-7-4), Compound (I-8-1) to Compound (I-8- 9), Compound (I-9-1) to Compound (I-9-10), Compound (I-10-1) to Compound (I-10-3), Compound (I-11), Compound (I- 12-1) to Compound (I-12-4), Compound (I-13-1) to Compound (I-13-6), Compound (I-14) to Compound (I-20), Compound (I- 21-1) to compound (I-21- ), Compound (I-22), Compound (I-23), Compound (I-24-1), Compound (I-24-2), Compound (I-25-1), Compound (I-25-2) ), Compound (I-26-1), Compound (I-26-2), Compound (I-27-1), Compound (I-27-2), Compound (I-28-1), Compound (I) -28-2), compound (I-29) to compound (I-32), compound (I-33-1), compound (I-35-1), compound (I-35-2) and compound (I Instead of -36), each preparation is obtained in the same manner.

Formulation Example 2
Compound (I-1-1) 20% by weight
Diflufenican 5% by weight
Croquinto set mexil 5 wt%
Sodium lignin sulfonate 5% by weight
Polyoxyethylene alkyl ether 5% by weight
5% white carbon
55% by weight of clay
Are mixed and pulverized to obtain a preparation. The prepared preparation is used after appropriately diluted with water.
Compound (I-1-1) is converted from Compound (I-1-2) to Compound (I-1-7), Compound (I-2-1) to Compound (I-2-3), Compound (I-3) -1) to Compound (I-3-4), Compound (I-4-1) to Compound (I-4-6), Compound (I-5-1) to Compound (I-5-9), Compound (I-6-1), Compound (I-6-2), Compound (I-7-1) to Compound (I-7-4), Compound (I-8-1) to Compound (I-8- 9), Compound (I-9-1) to Compound (I-9-10), Compound (I-10-1) to Compound (I-10-3), Compound (I-11), Compound (I- 12-1) to Compound (I-12-4), Compound (I-13-1) to Compound (I-13-6), Compound (I-14) to Compound (I-20), Compound (I- 21-1) to compound (I-21- ), Compound (I-22), Compound (I-23), Compound (I-24-1), Compound (I-24-2), Compound (I-25-1), Compound (I-25-2) ), Compound (I-26-1), Compound (I-26-2), Compound (I-27-1), Compound (I-27-2), Compound (I-28-1), Compound (I) -28-2), compound (I-29) to compound (I-32), compound (I-33-1), compound (I-35-1), compound (I-35-2) and compound (I Instead of -36), each preparation is obtained in the same manner.

Examples of biological tests are shown below.
Test Example 1 Foliage application test to weeds Filled with a commercially available soil in a plastic cup, seeded with blackgrass (Alopecurus myoloides) or Konukagusa (Agrostis alba), covered with about 0.5 cm of soil, then greenhouse Cultivated within. When the weeds grew to the 1-2 leaf stage, the spray solution of the herbicidal composition of the present invention was uniformly sprayed over the entire plant so as to have a predetermined dosage. The spray solution was prepared by dissolving a predetermined amount of each compound in a dimethylformamide solution (2%) of Tween 20 (polyoxyethylene sorbitan fatty acid ester, manufactured by MP Biomedicals, Inc.) and diluting with water. After drug treatment, the plants were placed in a greenhouse for 3 weeks. The herbicidal effect was evaluated in 101 stages from 0 (no action) to 100 (complete death).
The results are shown in Table 20 to Table 23.

  The herbicidal composition of the present invention is useful for controlling weeds.

Claims (14)

Formula (I)

[Wherein, R ¹ is halogen, C _1-6 alkyl group or a C _1-6 1 or more which may have a substituent phenyl C _1-6 alkyl group selected from alkoxy groups, hydrogen, C _{1 -6} alkyl group, C _1-6 haloalkyl group, C _3-8 cycloalkyl group, C _3-8 halocycloalkyl group, (C _1-6 alkyl) C _3-8 cycloalkyl group, (C _3-8 cyclo Alkyl) C _1-6 alkyl group, (C _3-8 cycloalkyl) C _3-8 cycloalkyl group, (C _3-8 halocycloalkyl) C _1-6 alkyl group, {(C _1-6 alkyl) C _3-8 cycloalkyl} C _1-6 alkyl group, (C _1-6 alkoxy) C _1-6 alkyl group, (C _3-8 cycloalkoxy) C _1-6 alkyl group, {(C _1-6 alkoxy) C _1-6 alkoxy} C _1-6 alkyl group, (C _1-6 alkylthio) C _1-6 alkyl group, (C _1-6 alkylsulfinyl) C _1-6 alkyl group, (C _{1- 6} alkylsulfonyl) represents a C _1-6 alkyl group, a C _3-6 alkenyl group, a C _3-6 alkynyl group or a tetrahydropyranyl group,
R ² is halogen, cyano group, nitro group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C _{1-6 1-6} haloalkylthio group, C _1-6 haloalkylsulfinyl group, C _1-6 haloalkylsulfonyl group, C _3-8 cycloalkoxy group, (C _3-8 cycloalkyl) C _1-6 alkoxy group, (C _{1- 6} alkylthio) C _1-6 alkoxy group, (C _1-6 alkoxy) C _1-6 alkoxy group, C _3-6 alkenyloxy group, C _3-6 alkynyloxy group, cyano C _1-6 alkoxy group, (C _1-6 alkoxycarbonyl) C _1-6 alkoxy group, carbamoyl C _1-6 alkoxy group, {(C _1-6 alkyl) aminocarbonyl} C _1-6 alkoxy group, {di (C _1-6 alkyl) aminocarbonyl } C _1-6 alkoxy group, amino group, C _1-6 al Killamino group, di (C _1-6 alkyl) amino group, formylamino group, (C _1-6 alkyl) carbonylamino group, hydroxy C _1-6 alkyl group, (C _1-6 alkoxy) C _1-6 alkyl group , (C _1-6 haloalkoxy) C _1-6 alkyl group, (C _3-8 cycloalkoxy) C _1-6 alkyl group, {(C _3-8 cycloalkyl) C _1-6 alkoxy} C _1-6 Alkyl group, (C _1-6 alkylthio) C _1-6 alkyl group, (C _1-6 haloalkylthio) C _1-6 alkyl group, cyano C _1-6 alkyl group, hydroxyimino C _1-6 alkyl group, ( C _1-6 alkoxyimino) represents a C _1-6 alkyl group, a formyl group or a (C _1-6 alkyl) carbonyl group,
G is hydrogen or the following formula

{Wherein L represents oxygen or sulfur;
R ³ is a C _1-6 alkyl group, C _3-8 cycloalkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _6-10 aryl group, (C _6-10 aryl) C _1-6 Alkyl group, C _1-6 alkoxy group, C _3-8 cycloalkoxy group, C _3-6 alkenyloxy group, C _3-6 alkynyloxy group, C _6-10 aryloxy group, (C _6-10 aryl) C _1-6 alkoxy group, di (C _1-6 alkyl) amino group, di (C _3-6 alkenyl) amino group, (C _1-6 alkyl) (C _6-10 aryl) amino group or 5-6 membered Represents a heteroaryl group,
R ⁴ represents a C _1-6 alkyl group, a C _6-10 aryl group or a di (C _1-6 alkyl) amino group,
R ⁵ and R ⁶ may be the same or different and are a C _1-6 alkyl group, a C _3-8 cycloalkyl group, a C _6-10 aryl group, a C _1-6 alkoxy group, a C _3-8 cycloalkoxy group. , A C _6-10 aryloxy group, a (C _6-10 aryl) C _1-6 alkoxy group, a C _1-6 alkylthio group or a di (C _1-6 alkyl) amino group,
R ⁷ represents hydrogen or a C _1-6 alkyl group,
W is a phenyl group optionally having one or more substituents selected from halogen, a C _1-6 alkyl group or a C _1-6 alkoxy group, a C _1-6 alkoxy group, a C _1-6 alkylthio group, C _1-6 alkyl sulfinyl group or a C _1-6 alkylsulfonyl group (provided ^{that, R 3, R 4, R} 5, any of the groups represented by each of R ⁶ and W have a halogen Well, a C _3-8 cycloalkyl group, a C _6-10 aryl group, an aryl part of a (C _6-10 aryl) C _1-6 alkyl group, a C _3-8 cycloalkoxy group, a C _6-10 aryloxy group, The aryl moiety of (C _6-10 aryl) C _1-6 alkoxy group, the (C _1-6 alkyl) (C _6-10 aryl) amino moiety and the 5-6 membered heteroaryl group are all C _{1. -6} may be substituted by an alkyl group). }
Any one of the groups represented by
Z is halogen, cyano group, nitro group, C _1-6 alkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _1-6 alkoxy group, C _1-6 alkylthio group or C _3-8 cyclo Represents an alkyl group (provided that a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _1-6 alkoxy group and a C _1-6 alkylthio group represented by Z have halogen). And the C _3-8 cycloalkyl group may be substituted with at least one group selected from the group consisting of halogen and C _1-6 alkyl groups),
n represents an integer of 1 to 5 (provided that when n is 2 or more, each Z may be the same or different)], and at least one selected from the following group A: And a herbicidal composition comprising:
Group A:
A group consisting of diflufenican, picolinafen, norflurazon, fluridone, flurochloridone, flurtamone, and beflubutamide. R ¹ represents a methyl group,
R ² is dimethylamino group, methylthio group, methylsulfinyl group, methoxy group, ethoxy group, normal propyloxy group, methoxymethyl group, cyano group, cyanomethyl group, 2,2-difluoroethoxy group, dimethylaminocarbonylmethoxy group, chlorine Represents an atom, bromine atom or fluorine atom,
G represents hydrogen, methoxymethyl group, ethoxymethyl group, acetyl group, propionyl group, pivaloyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, phenoxycarbonyl group or methylsulfonyl group;
The herbicidal composition according to claim 1, wherein Z represents a methyl group, an ethyl group, or a vinyl group, and n represents 3 (provided that each Z may be the same or different). The herbicidal composition according to claim 1 or 2, further comprising at least one compound selected from Group B.
Group B Benoxacol, Croquintoset Mexil, Ciomethrinyl, Dichlormid, Fenchlorazole Ethyl, Fenchlorim, Flurazole, Furirazole, Mefenpyr Diethyl, Oxabetrinyl, Isoxadiphenethyl, Cyprosulfamide, Flxophenim, 1,8-Naphthal The group consisting of acid anhydride and AD-67.   The herbicidal composition according to claim 3, wherein at least one compound selected from Group B is croquintoset mexil or mefenpyr diethyl.   The herbicidal composition according to any one of claims 1 to 4, wherein at least one compound selected from Group A is diflufenican or picolinaphene.   The herbicidal composition according to any one of claims 1 to 4, wherein at least one compound selected from Group A is norflurazon.   The herbicidal composition according to any one of claims 1 to 4, wherein at least one compound selected from Group A is fluridone.   The herbicidal composition according to any one of claims 1 to 4, wherein at least one compound selected from Group A is flurochloridone.   The herbicidal composition according to any one of claims 1 to 4, wherein at least one compound selected from Group A is flurtamone.   The herbicidal composition according to any one of claims 1 to 4, wherein at least one compound selected from Group A is beflubutamide. Formula (I)

[Wherein R ¹ represents a methyl group,
R ² is dimethylamino group, methylthio group, methylsulfinyl group, methoxy group, ethoxy group, normal propyloxy group, methoxymethyl group, cyano group, cyanomethyl group, 2,2-difluoroethoxy group, dimethylaminocarbonylmethoxy group, chlorine Represents an atom, bromine atom or fluorine atom,
G represents hydrogen, methoxymethyl group, ethoxymethyl group, acetyl group, propionyl group, pivaloyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, phenoxycarbonyl group or methylsulfonyl group,
Z represents a methyl group, an ethyl group or a vinyl group, n represents 3 (wherein each Z may be the same or different)], and a pyridazinone compound represented by
A herbicidal composition comprising diflufenican, picolinaphene, or befluftamide. Formula (I)

[Wherein, R ¹ is halogen, C _1-6 alkyl group or a C _1-6 1 or more which may have a substituent phenyl C _1-6 alkyl group selected from alkoxy groups, hydrogen, C _{1 -6} alkyl group, C _1-6 haloalkyl group, C _3-8 cycloalkyl group, C _3-8 halocycloalkyl group, (C _1-6 alkyl) C _3-8 cycloalkyl group, (C _3-8 cyclo Alkyl) C _1-6 alkyl group, (C _3-8 cycloalkyl) C _3-8 cycloalkyl group, (C _3-8 halocycloalkyl) C _1-6 alkyl group, {(C _1-6 alkyl) C _3-8 cycloalkyl} C _1-6 alkyl group, (C _1-6 alkoxy) C _1-6 alkyl group, (C _3-8 cycloalkoxy) C _1-6 alkyl group, {(C _1-6 alkoxy) C _1-6 alkoxy} C _1-6 alkyl group, (C _1-6 alkylthio) C _1-6 alkyl group, (C _1-6 alkylsulfinyl) C _1-6 alkyl group, (C _{1- 6} alkylsulfonyl) represents a C _1-6 alkyl group, a C _3-6 alkenyl group, a C _3-6 alkynyl group or a tetrahydropyranyl group,
R ² is halogen, cyano group, nitro group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C _{1-6 1-6} haloalkylthio group, C _1-6 haloalkylsulfinyl group, C _1-6 haloalkylsulfonyl group, C _3-8 cycloalkoxy group, (C _3-8 cycloalkyl) C _1-6 alkoxy group, (C _{1- 6} alkylthio) C _1-6 alkoxy group, (C _1-6 alkoxy) C _1-6 alkoxy group, C _3-6 alkenyloxy group, C _3-6 alkynyloxy group, cyano C _1-6 alkoxy group, (C _1-6 alkoxycarbonyl) C _1-6 alkoxy group, carbamoyl C _1-6 alkoxy group, {(C _1-6 alkyl) aminocarbonyl} C _1-6 alkoxy group, {di (C _1-6 alkyl) aminocarbonyl } C _1-6 alkoxy group, amino group, C _1-6 al Killamino group, di (C _1-6 alkyl) amino group, formylamino group, (C _1-6 alkyl) carbonylamino group, hydroxy C _1-6 alkyl group, (C _1-6 alkoxy) C _1-6 alkyl group , (C _1-6 haloalkoxy) C _1-6 alkyl group, (C _3-8 cycloalkoxy) C _1-6 alkyl group, {(C _3-8 cycloalkyl) C _1-6 alkoxy} C _1-6 Alkyl group, (C _1-6 alkylthio) C _1-6 alkyl group, (C _1-6 haloalkylthio) C _1-6 alkyl group, cyano C _1-6 alkyl group, hydroxyimino C _1-6 alkyl group, ( C _1-6 alkoxyimino) represents a C _1-6 alkyl group, a formyl group or a (C _1-6 alkyl) carbonyl group,
G is hydrogen or the following formula

{Wherein L represents oxygen or sulfur;
R ³ is a C _1-6 alkyl group, C _3-8 cycloalkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _6-10 aryl group, (C _6-10 aryl) C _1-6 Alkyl group, C _1-6 alkoxy group, C _3-8 cycloalkoxy group, C _3-6 alkenyloxy group, C _3-6 alkynyloxy group, C _6-10 aryloxy group, (C _6-10 aryl) C _1-6 alkoxy group, di (C _1-6 alkyl) amino group, di (C _3-6 alkenyl) amino group, (C _1-6 alkyl) (C _6-10 aryl) amino group or 5-6 membered Represents a heteroaryl group,
R ⁴ represents a C _1-6 alkyl group, a C _6-10 aryl group or a di (C _1-6 alkyl) amino group,
R ⁵ and R ⁶ may be the same or different and are a C _1-6 alkyl group, a C _3-8 cycloalkyl group, a C _6-10 aryl group, a C _1-6 alkoxy group, a C _3-8 cycloalkoxy group. , A C _6-10 aryloxy group, a (C _6-10 aryl) C _1-6 alkoxy group, a C _1-6 alkylthio group or a di (C _1-6 alkyl) amino group,
R ⁷ represents hydrogen or a C _1-6 alkyl group,
W is a phenyl group optionally having one or more substituents selected from halogen, a C _1-6 alkyl group or a C _1-6 alkoxy group, a C _1-6 alkoxy group, a C _1-6 alkylthio group, C _1-6 alkyl sulfinyl group or a C _1-6 alkylsulfonyl group (provided ^{that, R 3, R 4, R} 5, any of the groups represented by each of R ⁶ and W have a halogen Well, a C _3-8 cycloalkyl group, a C _6-10 aryl group, an aryl part of a (C _6-10 aryl) C _1-6 alkyl group, a C _3-8 cycloalkoxy group, a C _6-10 aryloxy group, The aryl moiety of (C _6-10 aryl) C _1-6 alkoxy group, the (C _1-6 alkyl) (C _6-10 aryl) amino moiety and the 5-6 membered heteroaryl group are all C _{1. -6} may be substituted by an alkyl group). }
Any one of the groups represented by
Z is halogen, cyano group, nitro group, C _1-6 alkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _1-6 alkoxy group, C _1-6 alkylthio group or C _3-8 cyclo Represents an alkyl group (provided that a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _1-6 alkoxy group and a C _1-6 alkylthio group represented by Z have halogen). And the C _3-8 cycloalkyl group may be substituted with at least one group selected from the group consisting of halogen and C _1-6 alkyl groups),
n represents an integer of 1 to 5 (provided that, when n is 2 or more, each Z may be the same or different)] and at least one selected from the following group A: A method for controlling weeds, wherein an effective amount of the compound is applied to weeds or soil where weeds grow.
Group A A group consisting of diflufenican, picolinaphene, norflurazon, fluridone, flurochloridone, flurtamone, and beflubutamide. The method for controlling weeds according to claim 12, further comprising at least one compound selected from Group B.
Group B Benoxacol, Croquintoset Mexil, Ciomethrinyl, Dichlormid, Fenchlorazole Ethyl, Fenchlorim, Flurazole, Furirazole, Mefenpyr Diethyl, Oxabetrinyl, Isoxadiphenethyl, Cyprosulfamide, Flxophenim, 1,8-Naphthal The group consisting of acid anhydride and AD-67.   Use of the composition according to any one of claims 1 to 11 for controlling weeds.