JP2012092058A - Harmful animal control composition and method for controlling harmful animal - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for controlling harmful animals, the composition exerting an excellent control effect on harmful animals, and a method for controlling harmful animals.SOLUTION: The harmful animal control composition comprises a fused imidazole compound represented by formula (1) (wherein Aand Arepresent a nitrogen atom or the like; R, R, Rand Rrepresent a halogen atom or the like; Rrepresents an optionally halogenated C1 to C6 chain hydrocarbon group or the like; Rand Rrepresent a halogenated C1 to C4 chain hydrocarbon group or the like; and n represents 0 or 1) and at least one kind of respiration inhibiting compound selected from a group composed of azoxystrobin, orysastrobin, ferimzone, furametpyr, flutolanil or the like.

Description

  The present invention relates to a pest control composition and a pest control method.

So far, various compounds have been studied and put into practical use for the purpose of controlling pests.
Moreover, a certain kind of substituted benzimidazole compound (for example, refer nonpatent literatures 1-3) is known.

Farmaco, Editione Scientifica (1987), 42 (7), 475-90. Heterocycles (1977), 6 (7), 911-27. Chemical & Pharmaceutical Bulletin (1982), 30 (8), 2996.

  An object of the present invention is to provide a pest control composition having an excellent control effect on harmful animals, and a method for controlling harmful animals.

［式中、
Ａ¹及びＡ²は同一または相異なり、窒素原子または=ＣＨ-を表し、
ｍは０、１または２を表し、
Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は同一または相異なり、群Ｘから選ばれる基で置換されていてもよいＣ１−Ｃ６鎖式炭化水素基、群Ｘから選ばれる基で置換されていてもよいＣ３−Ｃ６脂環式炭化水素基、群Ｙから選ばれる基で置換されていてもよいフェニル基、群Ｙから選ばれる基で置換されていてもよいベンジル基、群Ｙから選ばれる基で置換されていてもよい５員複素環基もしくは６員複素環基、-ＯＲ⁸、-ＮＲ⁸Ｒ⁹、-ＮＲ⁸Ｃ(Ｏ)Ｒ⁹、-Ｓ(Ｏ)_mＲ⁸、−ＳＯ_２Ｃｌ、−ＳＯ_２ＮＲ⁸Ｒ⁹、-ＣＯ₂Ｒ¹⁰、-ＣＯＮＲ⁸Ｒ⁹、-ＣＯＮＲ¹⁰ＮＲ¹¹Ｒ¹²、シアノ基、ニトロ基、ハロゲン原子、または水素原子を表し、
Ｒ⁵はハロゲン原子で置換されていてもよいＣ１−Ｃ４鎖式炭化水素基、ハロゲン原子で置換されていてもよいシクロプロピル基、ハロゲン原子で置換されていてもよいシクロプロピルメチル基、-ＯＲ¹³、-ＮＲ¹³Ｒ¹⁴またはシアノ基を表し、
Ｒ⁶及びＲ⁷は同一または相異なり、ハロゲン原子で置換されたＣ１−Ｃ４鎖式炭化水素基、-ＯＲ¹⁵、-Ｓ(Ｏ)_mＲ¹⁵、ハロゲン原子または水素原子を表すか（但し、Ｒ⁶及びＲ⁷は同時にハロゲン原子及び水素原子からなる群から選ばれる基を表さない。）、あるいは、Ｒ⁶とＲ⁷とが結合し、Ｒ⁶とＲ⁷が結合している炭素原子が一緒になって、ハロゲン原子で置換された５員環もしくは６員環を形成してもよく、
Ｒ⁸及びＲ⁹は同一または相異なり、群Ｘから選ばれる基で置換されていてもよいＣ１−Ｃ６鎖式炭化水素基、群Ｘから選ばれる基で置換されていてもよいＣ３−Ｃ６脂環式炭化水素基、群Ｙから選ばれる基で置換されていてもよいフェニル基、群Ｙから選ばれる基で置換されていてもよいベンジル基、群Ｙから選ばれる基で置換されていてもよい５員複素環基もしくは６員複素環基または水素原子を表し（-Ｓ(Ｏ)_mＲ⁸において、ｍは前記と同じ意味を表し、但し、ｍが１または２である場合は、Ｒ⁸は水素原子を表さない。）、
Ｒ¹⁰はハロゲン原子で置換されていてもよいＣ１−Ｃ４アルキル基または水素原子を表し、
Ｒ¹¹及びＲ¹²は同一または相異なり、ハロゲン原子で置換されていてもよいＣ１−Ｃ４アルキル基、Ｃ２−Ｃ５アルコキシカルボニル基または水素原子を表し、
Ｒ¹³及びＲ¹⁴は同一または相異なり、ハロゲン原子で置換されていてもよいＣ１−Ｃ３鎖式炭化水素基、ハロゲン原子で置換されていてもよいシクロプロピル基または水素原子を表し、
Ｒ¹⁵はハロゲン原子で置換されたＣ１−Ｃ４鎖式炭化水素基を表し、
ｎは０または１を表す。
群Ｘ：ハロゲン原子で置換されていてもよいＣ１−Ｃ４アルコキシ基、-ＣＯ₂Ｒ¹⁶（但し、Ｒ¹⁶はハロゲンで置換されていてもよいＣ１−Ｃ４アルキル基を表す。）、シアノ基及びハロゲン原子からなる群。
群Ｙ：ハロゲン原子で置換されていてもよいＣ１−Ｃ４アルキル基、ハロゲン原子で置換されていてもよいＣ１−Ｃ４アルコキシ基、シアノ基、ニトロ基及びハロゲン原子からなる群。］
で示される縮合イミダゾール化合物と、アゾキシストロビン、オリサストロビン、フェリムゾン、フラメトピル、フルトラニル、及び式（Ａ）

で示される化合物からなる群より選ばれる少なくとも１種の呼吸阻害化合物とを含有する有害動物防除組成物。
〔２〕 縮合イミダゾール化合物と呼吸阻害化合物との重量比が、０．１：９９．９〜９９．９：０．１の〔１〕に記載の有害動物防除組成物。
〔３〕 縮合イミダゾール化合物が、式（１）において、
Ａ¹が=ＣＨ-であり、
Ａ²が窒素原子または=ＣＨ-であり、
ｍが０、１または２であり、
Ｒ¹、Ｒ²、Ｒ³及びＲ⁴が同一または相異なり、群Ｘから選ばれる基で置換されていてもよいＣ１−Ｃ６鎖式炭化水素基、-ＯＲ⁸、-Ｓ(Ｏ)_mＲ⁸、-ＣＯ₂Ｒ¹⁰、シアノ基、ニトロ基、ハロゲン原子、または水素原子であり、
Ｒ⁵がハロゲン原子で置換されていてもよいＣ１−Ｃ４鎖式炭化水素基、またはハロゲン原子で置換されていてもよいシクロプロピル基であり、
Ｒ⁶がハロゲン原子で置換されたＣ１−Ｃ４鎖式炭化水素基、-ＯＲ¹⁵または-Ｓ(Ｏ)_mＲ¹⁵であり、
Ｒ⁷が水素原子であり、
Ｒ⁸が群Ｘから選ばれる基で置換されていてもよいＣ１−Ｃ６鎖式炭化水素基、群Ｘから選ばれる基で置換されていてもよいＣ３−Ｃ６脂環式炭化水素基、群Ｙから選ばれる基で置換されていてもよいフェニル基、群Ｙから選ばれる基で置換されていてもよいベンジル基、群Ｙから選ばれる基で置換されていてもよい５員複素環基もしくは６員複素環基または水素原子であり（-Ｓ(Ｏ)_mＲ⁸において、ｍは前記と同じ意味を表し、但し、ｍが１または２である場合は、Ｒ⁸は水素原子を表さない。）、
Ｒ¹⁰がハロゲン原子で置換されていてもよいＣ１−Ｃ４アルキル基または水素原子であり、
Ｒ¹⁵がハロゲン原子で置換されたＣ１−Ｃ４鎖式炭化水素基であり、
ｎが０である〔１〕または〔２〕に記載の有害動物防除組成物。
〔４〕 式（１）

［式中、
Ａ¹及びＡ²は同一または相異なり、窒素原子または=ＣＨ-を表し、
ｍは０、１または２を表し、
Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は同一または相異なり、群Ｘから選ばれる基で置換されていてもよいＣ１−Ｃ６鎖式炭化水素基、群Ｘから選ばれる基で置換されていてもよいＣ３−Ｃ６脂環式炭化水素基、群Ｙから選ばれる基で置換されていてもよいフェニル基、群Ｙから選ばれる基で置換されていてもよいベンジル基、群Ｙから選ばれる基で置換されていてもよい５員複素環基もしくは６員複素環基、-ＯＲ⁸、-ＮＲ⁸Ｒ⁹、-ＮＲ⁸Ｃ(Ｏ)Ｒ⁹、-Ｓ(Ｏ)_mＲ⁸、−ＳＯ_２Ｃｌ、−ＳＯ_２ＮＲ⁸Ｒ⁹、-ＣＯ₂Ｒ¹⁰、-ＣＯＮＲ⁸Ｒ⁹、-ＣＯＮＲ¹⁰ＮＲ¹¹Ｒ¹²、シアノ基、ニトロ基、ハロゲン原子、または水素原子を表し、
Ｒ⁵はハロゲン原子で置換されていてもよいＣ１−Ｃ４鎖式炭化水素基、ハロゲン原子で置換されていてもよいシクロプロピル基、ハロゲン原子で置換されていてもよいシクロプロピルメチル基、-ＯＲ¹³、-ＮＲ¹³Ｒ¹⁴またはシアノ基を表し、
Ｒ⁶及びＲ⁷は同一または相異なり、ハロゲン原子で置換されたＣ１−Ｃ４鎖式炭化水素基、-ＯＲ¹⁵、-Ｓ(Ｏ)_mＲ¹⁵、ハロゲン原子または水素原子を表すか（但し、Ｒ⁶及びＲ⁷は同時にハロゲン原子及び水素原子からなる群から選ばれる基を表さない。）、あるいは、Ｒ⁶とＲ⁷とが結合し、Ｒ⁶とＲ⁷が結合している炭素原子が一緒になって、ハロゲン原子で置換された５員環もしくは６員環を形成してもよく、
Ｒ⁸及びＲ⁹は同一または相異なり、群Ｘから選ばれる基で置換されていてもよいＣ１−Ｃ６鎖式炭化水素基、群Ｘから選ばれる基で置換されていてもよいＣ３−Ｃ６脂環式炭化水素基、群Ｙから選ばれる基で置換されていてもよいフェニル基、群Ｙから選ばれる基で置換されていてもよいベンジル基、群Ｙから選ばれる基で置換されていてもよい５員複素環基もしくは６員複素環基または水素原子を表し（-Ｓ(Ｏ)_mＲ⁸において、ｍは前記と同じ意味を表し、但し、ｍが１または２である場合は、Ｒ⁸は水素原子を表さない。）、
Ｒ¹⁰はハロゲン原子で置換されていてもよいＣ１−Ｃ４アルキル基または水素原子を表し、
Ｒ¹¹及びＲ¹²は同一または相異なり、ハロゲン原子で置換されていてもよいＣ１−Ｃ４アルキル基、Ｃ２−Ｃ５アルコキシカルボニル基または水素原子を表し、
Ｒ¹³及びＲ¹⁴は同一または相異なり、ハロゲン原子で置換されていてもよいＣ１−Ｃ３鎖式炭化水素基、ハロゲン原子で置換されていてもよいシクロプロピル基または水素原子を表し、
Ｒ¹⁵はハロゲン原子で置換されたＣ１−Ｃ４鎖式炭化水素基を表し、
ｎは０または１を表す。
群Ｘ：ハロゲン原子で置換されていてもよいＣ１−Ｃ４アルコキシ基、-ＣＯ₂Ｒ¹⁶（但し、Ｒ¹⁶はハロゲンで置換されていてもよいＣ１−Ｃ４アルキル基を表す。）、シアノ基及びハロゲン原子からなる群。
群Ｙ：ハロゲン原子で置換されていてもよいＣ１−Ｃ４アルキル基、ハロゲン原子で置換されていてもよいＣ１−Ｃ４アルコキシ基、シアノ基、ニトロ基及びハロゲン原子からなる群。］
で示される縮合イミダゾール化合物と、アゾキシストロビン、オリサストロビン、フェリムゾン、フラメトピル、フルトラニル、及び式（Ａ）

で示される化合物からなる群より選ばれる少なくとも１種の呼吸阻害化合物との有効量を、有害動物または有害動物の生息場所に施用する有害動物の防除方法。
〔５〕 縮合イミダゾール化合物が、式（１）において、
Ａ¹が=ＣＨ-であり、
Ａ²が窒素原子または=ＣＨ-であり、
ｍが０、１または２であり、
Ｒ¹、Ｒ²、Ｒ³及びＲ⁴が同一または相異なり、群Ｘから選ばれる基で置換されていてもよいＣ１−Ｃ６鎖式炭化水素基、-ＯＲ⁸、-Ｓ(Ｏ)_mＲ⁸、-ＣＯ₂Ｒ¹⁰、シアノ基、ニトロ基、ハロゲン原子、または水素原子であり、
Ｒ⁵がハロゲン原子で置換されていてもよいＣ１−Ｃ４鎖式炭化水素基、またはハロゲン原子で置換されていてもよいシクロプロピル基であり、
Ｒ⁶がハロゲン原子で置換されたＣ１−Ｃ４鎖式炭化水素基、-ＯＲ¹⁵または-Ｓ(Ｏ)_mＲ¹⁵であり、
Ｒ⁷が水素原子であり、
Ｒ⁸が群Ｘから選ばれる基で置換されていてもよいＣ１−Ｃ６鎖式炭化水素基、群Ｘから選ばれる基で置換されていてもよいＣ３−Ｃ６脂環式炭化水素基、群Ｙから選ばれる基で置換されていてもよいフェニル基、群Ｙから選ばれる基で置換されていてもよいベンジル基、群Ｙから選ばれる基で置換されていてもよい５員複素環基もしくは６員複素環基または水素原子であり（-Ｓ(Ｏ)_mＲ⁸において、ｍは前記と同じ意味を表し、但し、ｍが１または２である場合は、Ｒ⁸は水素原子を表さない。）、
Ｒ¹⁰がハロゲン原子で置換されていてもよいＣ１−Ｃ４アルキル基または水素原子であり、
Ｒ¹⁵がハロゲン原子で置換されたＣ１−Ｃ４鎖式炭化水素基であり、
ｎが０である〔４〕に記載の有害動物の防除方法。
〔６〕 式（１）

［式中、
Ａ¹及びＡ²は同一または相異なり、窒素原子または=ＣＨ-を表し、
ｍは０、１または２を表し、
Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は同一または相異なり、群Ｘから選ばれる基で置換されていてもよいＣ１−Ｃ６鎖式炭化水素基、群Ｘから選ばれる基で置換されていてもよいＣ３−Ｃ６脂環式炭化水素基、群Ｙから選ばれる基で置換されていてもよいフェニル基、群Ｙから選ばれる基で置換されていてもよいベンジル基、群Ｙから選ばれる基で置換されていてもよい５員複素環基もしくは６員複素環基、-ＯＲ⁸、-ＮＲ⁸Ｒ⁹、-ＮＲ⁸Ｃ(Ｏ)Ｒ⁹、-Ｓ(Ｏ)_mＲ⁸、−ＳＯ_２Ｃｌ、−ＳＯ_２ＮＲ⁸Ｒ⁹、-ＣＯ₂Ｒ¹⁰、-ＣＯＮＲ⁸Ｒ⁹、-ＣＯＮＲ¹⁰ＮＲ¹¹Ｒ¹²、シアノ基、ニトロ基、ハロゲン原子、または水素原子を表し、
Ｒ⁵はハロゲン原子で置換されていてもよいＣ１−Ｃ４鎖式炭化水素基、ハロゲン原子で置換されていてもよいシクロプロピル基、ハロゲン原子で置換されていてもよいシクロプロピルメチル基、-ＯＲ¹³、-ＮＲ¹³Ｒ¹⁴またはシアノ基を表し、
Ｒ⁶及びＲ⁷は同一または相異なり、ハロゲン原子で置換されたＣ１−Ｃ４鎖式炭化水素基、-ＯＲ¹⁵、-Ｓ(Ｏ)_mＲ¹⁵、ハロゲン原子または水素原子を表すか（但し、Ｒ⁶及びＲ⁷は同時にハロゲン原子及び水素原子からなる群から選ばれる基を表さない。）、あるいは、Ｒ⁶とＲ⁷とが結合し、Ｒ⁶とＲ⁷が結合している炭素原子が一緒になって、ハロゲン原子で置換された５員環もしくは６員環を形成してもよく、
Ｒ⁸及びＲ⁹は同一または相異なり、群Ｘから選ばれる基で置換されていてもよいＣ１−Ｃ６鎖式炭化水素基、群Ｘから選ばれる基で置換されていてもよいＣ３−Ｃ６脂環式炭化水素基、群Ｙから選ばれる基で置換されていてもよいフェニル基、群Ｙから選ばれる基で置換されていてもよいベンジル基、群Ｙから選ばれる基で置換されていてもよい５員複素環基もしくは６員複素環基または水素原子を表し（-Ｓ(Ｏ)_mＲ⁸において、ｍは前記と同じ意味を表し、但し、ｍが１または２である場合は、Ｒ⁸は水素原子を表さない。）、
Ｒ¹⁰はハロゲン原子で置換されていてもよいＣ１−Ｃ４アルキル基または水素原子を表し、
Ｒ¹¹及びＲ¹²は同一または相異なり、ハロゲン原子で置換されていてもよいＣ１−Ｃ４アルキル基、Ｃ２−Ｃ５アルコキシカルボニル基または水素原子を表し、
Ｒ¹³及びＲ¹⁴は同一または相異なり、ハロゲン原子で置換されていてもよいＣ１−Ｃ３鎖式炭化水素基、ハロゲン原子で置換されていてもよいシクロプロピル基または水素原子を表し、
Ｒ¹⁵はハロゲン原子で置換されたＣ１−Ｃ４鎖式炭化水素基を表し、
ｎは０または１を表す。
群Ｘ：ハロゲン原子で置換されていてもよいＣ１−Ｃ４アルコキシ基、-ＣＯ₂Ｒ¹⁶（但し、Ｒ¹⁶はハロゲンで置換されていてもよいＣ１−Ｃ４アルキル基を表す。）、シアノ基及びハロゲン原子からなる群。
群Ｙ：ハロゲン原子で置換されていてもよいＣ１−Ｃ４アルキル基、ハロゲン原子で置換されていてもよいＣ１−Ｃ４アルコキシ基、シアノ基、ニトロ基及びハロゲン原子からなる群。］
で示される縮合イミダゾール化合物と、アゾキシストロビン、オリサストロビン、フェリムゾン、フラメトピル、フルトラニル、及び式（Ａ）

で示される化合物からなる群より選ばれる少なくとも１種の呼吸阻害化合物との有効量を、植物または植物を栽培する土壌に施用する有害動物の防除方法。
〔７〕 縮合イミダゾール化合物が、式（１）において、
Ａ¹が=ＣＨ-であり、
Ａ²が窒素原子または=ＣＨ-であり、
ｍが０、１または２であり、
Ｒ¹、Ｒ²、Ｒ³及びＲ⁴が同一または相異なり、群Ｘから選ばれる基で置換されていてもよいＣ１−Ｃ６鎖式炭化水素基、-ＯＲ⁸、-Ｓ(Ｏ)_mＲ⁸、-ＣＯ₂Ｒ¹⁰、シアノ基、ニトロ基、ハロゲン原子、または水素原子であり、
Ｒ⁵がハロゲン原子で置換されていてもよいＣ１−Ｃ４鎖式炭化水素基、またはハロゲン原子で置換されていてもよいシクロプロピル基であり、
Ｒ⁶がハロゲン原子で置換されたＣ１−Ｃ４鎖式炭化水素基、-ＯＲ¹⁵または-Ｓ(Ｏ)_mＲ¹⁵であり、
Ｒ⁷が水素原子であり、
Ｒ⁸が群Ｘから選ばれる基で置換されていてもよいＣ１−Ｃ６鎖式炭化水素基、群Ｘから選ばれる基で置換されていてもよいＣ３−Ｃ６脂環式炭化水素基、群Ｙから選ばれる基で置換されていてもよいフェニル基、群Ｙから選ばれる基で置換されていてもよいベンジル基、群Ｙから選ばれる基で置換されていてもよい５員複素環基もしくは６員複素環基または水素原子であり（-Ｓ(Ｏ)_mＲ⁸において、ｍは前記と同じ意味を表し、但し、ｍが１または２である場合は、Ｒ⁸は水素原子を表さない。）、
Ｒ¹⁰がハロゲン原子で置換されていてもよいＣ１−Ｃ４アルキル基または水素原子であり、
Ｒ¹⁵がハロゲン原子で置換されたＣ１−Ｃ４鎖式炭化水素基であり、
ｎが０である〔６〕に記載の有害動物の防除方法。 As a result of intensive studies, the present inventors have composed of a condensed imidazole compound represented by the following formula (1), an azoxystrobin, orissastrobin, ferrimzone, furametopyr, flutolanil, and a compound represented by the following formula (A). By using in combination with at least one respiratory-inhibiting compound selected from the group, the present inventors have found that it has an excellent controlling effect on harmful animals, and has led to the present invention.
That is, the present invention has the following configuration.
[1] Formula (1)

[Where:
A ¹ and A ² are the same or different and represent a nitrogen atom or ═CH—,
m represents 0, 1 or 2;
R ¹ , R ² , R ³ and R ⁴ are the same or different and are substituted with a group selected from group X, a C1-C6 chain hydrocarbon group which may be substituted with a group selected from group X; A C3-C6 alicyclic hydrocarbon group, a phenyl group optionally substituted with a group selected from group Y, a benzyl group optionally substituted with a group selected from group Y, a group selected from group Y in substituted heterocycle may also be 5-membered optionally heterocyclic group or 6-membered heterocyclic ^{group, -OR 8, -NR 8 R 9} , -NR 8 C (O) R 9, -S (O) m R 8, -SO ₂ Cl, —SO ₂ NR ⁸ R ⁹ , —CO ₂ R ¹⁰ , —CONR ⁸ R ⁹ , —CONR ¹⁰ NR ¹¹ R ¹² , a cyano group, a nitro group, a halogen atom, or a hydrogen atom,
R ⁵ is a C1-C4 chain hydrocarbon group optionally substituted with a halogen atom, a cyclopropyl group optionally substituted with a halogen atom, a cyclopropylmethyl group optionally substituted with a halogen atom, —OR ¹³ represents —NR ¹³ R ¹⁴ or a cyano group,
R ⁶ and R ⁷ are the same or different and each represents a C1-C4 chain hydrocarbon group substituted with a halogen atom, —OR ¹⁵ , —S (O) _m R ¹⁵ , a halogen atom or a hydrogen atom (provided that R ⁶ and R ⁷ does not represent a group selected from the group consisting of a halogen atom and a hydrogen atom at the same time.), or bonded to R ⁶ and R ^7, the carbon atom to which R ⁶ and R ⁷ are bound Together may form a 5- or 6-membered ring substituted with a halogen atom,
R ⁸ and R ⁹ are the same or different and are a C1-C6 chain hydrocarbon group optionally substituted with a group selected from group X, or a C3-C6 fatty acid optionally substituted with a group selected from group X A cyclic hydrocarbon group, a phenyl group which may be substituted with a group selected from group Y, a benzyl group which may be substituted with a group selected from group Y, or a group selected from group Y Represents a good 5-membered heterocyclic group or a 6-membered heterocyclic group or a hydrogen atom (in —S (O) _m R ⁸ , m represents the same meaning as described above, provided that when m is 1 or 2, ⁸ does not represent a hydrogen atom)
R ¹⁰ represents a C1-C4 alkyl group which may be substituted with a halogen atom or a hydrogen atom,
R ¹¹ and R ¹² are the same or different and each represents a C1-C4 alkyl group, a C2-C5 alkoxycarbonyl group or a hydrogen atom which may be substituted with a halogen atom;
R ¹³ and R ¹⁴ are the same or different and represent a C1-C3 chain hydrocarbon group which may be substituted with a halogen atom, a cyclopropyl group which may be substituted with a halogen atom, or a hydrogen atom,
R ¹⁵ represents a C1-C4 chain hydrocarbon group substituted with a halogen atom,
n represents 0 or 1.
Group X: C1-C4 alkoxy group optionally substituted with a halogen atom, —CO ₂ R ¹⁶ (wherein R ¹⁶ represents a C1-C4 alkyl group optionally substituted with halogen), a cyano group, and A group consisting of halogen atoms.
Group Y: A group consisting of a C1-C4 alkyl group optionally substituted with a halogen atom, a C1-C4 alkoxy group optionally substituted with a halogen atom, a cyano group, a nitro group, and a halogen atom. ]
A condensed imidazole compound represented by formula (1), azoxystrobin, oryastrostrobin, ferrimzone, furametopyr, flutolanil, and formula (A)

A pest control composition comprising at least one respiratory inhibitory compound selected from the group consisting of compounds represented by:
[2] The harmful animal control composition according to [1], wherein the weight ratio of the condensed imidazole compound and the respiratory inhibitory compound is 0.1: 99.9 to 99.9: 0.1.
[3] The condensed imidazole compound is represented by the formula (1):
A ¹ is = CH-
A ² is a nitrogen atom or = CH-,
m is 0, 1 or 2;
R ¹ , R ² , R ³ and R ⁴ are the same or different and may be substituted with a group selected from group X, a C1-C6 chain hydrocarbon group, —OR ⁸ , —S (O) _m R ⁸ , —CO ₂ R ¹⁰ , a cyano group, a nitro group, a halogen atom, or a hydrogen atom,
R ⁵ is a C1-C4 chain hydrocarbon group which may be substituted with a halogen atom, or a cyclopropyl group which may be substituted with a halogen atom;
R ⁶ is a C1-C4 chain hydrocarbon group substituted with a halogen atom, —OR ¹⁵ or —S (O) _m R ¹⁵ ;
R ⁷ is a hydrogen atom,
R ⁸ is a C1-C6 chain hydrocarbon group optionally substituted with a group selected from group X, a C3-C6 alicyclic hydrocarbon group optionally substituted with a group selected from group X, group Y A phenyl group optionally substituted with a group selected from: a benzyl group optionally substituted with a group selected from group Y; a 5-membered heterocyclic group optionally substituted with a group selected from group Y; or 6 A membered heterocyclic group or a hydrogen atom (in —S (O) _m R ⁸ , m represents the same meaning as described above, provided that when m is 1 or 2, R ⁸ does not represent a hydrogen atom. ),
R ¹⁰ is a C1-C4 alkyl group which may be substituted with a halogen atom or a hydrogen atom,
R ¹⁵ is a C1-C4 chain hydrocarbon group substituted with a halogen atom,
The harmful animal control composition according to [1] or [2], wherein n is 0.
[4] Formula (1)

[Where:
A ¹ and A ² are the same or different and represent a nitrogen atom or ═CH—,
m represents 0, 1 or 2;
R ¹ , R ² , R ³ and R ⁴ are the same or different and are substituted with a group selected from group X, a C1-C6 chain hydrocarbon group which may be substituted with a group selected from group X; A C3-C6 alicyclic hydrocarbon group, a phenyl group optionally substituted with a group selected from group Y, a benzyl group optionally substituted with a group selected from group Y, a group selected from group Y in substituted heterocycle may also be 5-membered optionally heterocyclic group or 6-membered heterocyclic ^{group, -OR 8, -NR 8 R 9} , -NR 8 C (O) R 9, -S (O) m R 8, -SO ₂ Cl, —SO ₂ NR ⁸ R ⁹ , —CO ₂ R ¹⁰ , —CONR ⁸ R ⁹ , —CONR ¹⁰ NR ¹¹ R ¹² , a cyano group, a nitro group, a halogen atom, or a hydrogen atom,
R ⁵ is a C1-C4 chain hydrocarbon group optionally substituted with a halogen atom, a cyclopropyl group optionally substituted with a halogen atom, a cyclopropylmethyl group optionally substituted with a halogen atom, —OR ¹³ represents —NR ¹³ R ¹⁴ or a cyano group,
R ⁶ and R ⁷ are the same or different and each represents a C1-C4 chain hydrocarbon group substituted with a halogen atom, —OR ¹⁵ , —S (O) _m R ¹⁵ , a halogen atom or a hydrogen atom (provided that R ⁶ and R ⁷ does not represent a group selected from the group consisting of a halogen atom and a hydrogen atom at the same time.), or bonded to R ⁶ and R ^7, the carbon atom to which R ⁶ and R ⁷ are bound Together may form a 5- or 6-membered ring substituted with a halogen atom,
R ⁸ and R ⁹ are the same or different and are a C1-C6 chain hydrocarbon group optionally substituted with a group selected from group X, or a C3-C6 fatty acid optionally substituted with a group selected from group X A cyclic hydrocarbon group, a phenyl group which may be substituted with a group selected from group Y, a benzyl group which may be substituted with a group selected from group Y, or a group selected from group Y Represents a good 5-membered heterocyclic group or a 6-membered heterocyclic group or a hydrogen atom (in —S (O) _m R ⁸ , m represents the same meaning as described above, provided that when m is 1 or 2, ⁸ does not represent a hydrogen atom)
R ¹⁰ represents a C1-C4 alkyl group which may be substituted with a halogen atom or a hydrogen atom,
R ¹¹ and R ¹² are the same or different and each represents a C1-C4 alkyl group, a C2-C5 alkoxycarbonyl group or a hydrogen atom which may be substituted with a halogen atom;
R ¹³ and R ¹⁴ are the same or different and represent a C1-C3 chain hydrocarbon group which may be substituted with a halogen atom, a cyclopropyl group which may be substituted with a halogen atom, or a hydrogen atom,
R ¹⁵ represents a C1-C4 chain hydrocarbon group substituted with a halogen atom,
n represents 0 or 1.
Group X: C1-C4 alkoxy group optionally substituted with a halogen atom, —CO ₂ R ¹⁶ (wherein R ¹⁶ represents a C1-C4 alkyl group optionally substituted with halogen), a cyano group, and A group consisting of halogen atoms.
Group Y: A group consisting of a C1-C4 alkyl group optionally substituted with a halogen atom, a C1-C4 alkoxy group optionally substituted with a halogen atom, a cyano group, a nitro group, and a halogen atom. ]
A condensed imidazole compound represented by formula (1), azoxystrobin, oryastrostrobin, ferrimzone, furametopyr, flutolanil, and formula (A)

A method for controlling harmful animals, which comprises applying an effective amount with at least one respiratory-inhibiting compound selected from the group consisting of the compounds represented by the above to harmful animals or habitats of harmful animals.
[5] The condensed imidazole compound is represented by the formula (1):
A ¹ is = CH-
A ² is a nitrogen atom or = CH-,
m is 0, 1 or 2;
R ¹ , R ² , R ³ and R ⁴ are the same or different and may be substituted with a group selected from group X, a C1-C6 chain hydrocarbon group, —OR ⁸ , —S (O) _m R ⁸ , —CO ₂ R ¹⁰ , a cyano group, a nitro group, a halogen atom, or a hydrogen atom,
R ⁵ is a C1-C4 chain hydrocarbon group which may be substituted with a halogen atom, or a cyclopropyl group which may be substituted with a halogen atom;
R ⁶ is a C1-C4 chain hydrocarbon group substituted with a halogen atom, —OR ¹⁵ or —S (O) _m R ¹⁵ ;
R ⁷ is a hydrogen atom,
R ⁸ is a C1-C6 chain hydrocarbon group optionally substituted with a group selected from group X, a C3-C6 alicyclic hydrocarbon group optionally substituted with a group selected from group X, group Y A phenyl group optionally substituted with a group selected from: a benzyl group optionally substituted with a group selected from group Y; a 5-membered heterocyclic group optionally substituted with a group selected from group Y; or 6 A membered heterocyclic group or a hydrogen atom (in —S (O) _m R ⁸ , m represents the same meaning as described above, provided that when m is 1 or 2, R ⁸ does not represent a hydrogen atom. ),
R ¹⁰ is a C1-C4 alkyl group which may be substituted with a halogen atom or a hydrogen atom,
R ¹⁵ is a C1-C4 chain hydrocarbon group substituted with a halogen atom,
The method for controlling harmful animals according to [4], wherein n is 0.
[6] Formula (1)

[Where:
A ¹ and A ² are the same or different and represent a nitrogen atom or ═CH—,
m represents 0, 1 or 2;
R ¹ , R ² , R ³ and R ⁴ are the same or different and are substituted with a group selected from group X, a C1-C6 chain hydrocarbon group which may be substituted with a group selected from group X; A C3-C6 alicyclic hydrocarbon group, a phenyl group optionally substituted with a group selected from group Y, a benzyl group optionally substituted with a group selected from group Y, a group selected from group Y in substituted heterocycle may also be 5-membered optionally heterocyclic group or 6-membered heterocyclic ^{group, -OR 8, -NR 8 R 9} , -NR 8 C (O) R 9, -S (O) m R 8, -SO ₂ Cl, —SO ₂ NR ⁸ R ⁹ , —CO ₂ R ¹⁰ , —CONR ⁸ R ⁹ , —CONR ¹⁰ NR ¹¹ R ¹² , a cyano group, a nitro group, a halogen atom, or a hydrogen atom,
R ⁵ is a C1-C4 chain hydrocarbon group optionally substituted with a halogen atom, a cyclopropyl group optionally substituted with a halogen atom, a cyclopropylmethyl group optionally substituted with a halogen atom, —OR ¹³ represents —NR ¹³ R ¹⁴ or a cyano group,
R ⁶ and R ⁷ are the same or different and each represents a C1-C4 chain hydrocarbon group substituted with a halogen atom, —OR ¹⁵ , —S (O) _m R ¹⁵ , a halogen atom or a hydrogen atom (provided that R ⁶ and R ⁷ does not represent a group selected from the group consisting of a halogen atom and a hydrogen atom at the same time.), or bonded to R ⁶ and R ^7, the carbon atom to which R ⁶ and R ⁷ are bound Together may form a 5- or 6-membered ring substituted with a halogen atom,
R ⁸ and R ⁹ are the same or different and are a C1-C6 chain hydrocarbon group optionally substituted with a group selected from group X, or a C3-C6 fatty acid optionally substituted with a group selected from group X A cyclic hydrocarbon group, a phenyl group which may be substituted with a group selected from group Y, a benzyl group which may be substituted with a group selected from group Y, or a group selected from group Y Represents a good 5-membered heterocyclic group or a 6-membered heterocyclic group or a hydrogen atom (in —S (O) _m R ⁸ , m represents the same meaning as described above, provided that when m is 1 or 2, ⁸ does not represent a hydrogen atom)
R ¹⁰ represents a C1-C4 alkyl group which may be substituted with a halogen atom or a hydrogen atom,
R ¹¹ and R ¹² are the same or different and each represents a C1-C4 alkyl group, a C2-C5 alkoxycarbonyl group or a hydrogen atom which may be substituted with a halogen atom;
R ¹³ and R ¹⁴ are the same or different and represent a C1-C3 chain hydrocarbon group which may be substituted with a halogen atom, a cyclopropyl group which may be substituted with a halogen atom, or a hydrogen atom,
R ¹⁵ represents a C1-C4 chain hydrocarbon group substituted with a halogen atom,
n represents 0 or 1.
Group X: C1-C4 alkoxy group optionally substituted with a halogen atom, —CO ₂ R ¹⁶ (wherein R ¹⁶ represents a C1-C4 alkyl group optionally substituted with halogen), a cyano group, and A group consisting of halogen atoms.
Group Y: A group consisting of a C1-C4 alkyl group optionally substituted with a halogen atom, a C1-C4 alkoxy group optionally substituted with a halogen atom, a cyano group, a nitro group, and a halogen atom. ]
A condensed imidazole compound represented by formula (1), azoxystrobin, oryastrostrobin, ferrimzone, furametopyr, flutolanil, and formula (A)

A method for controlling harmful animals, which comprises applying an effective amount of at least one respiration-inhibiting compound selected from the group consisting of the compounds represented by the above to plants or soil for cultivating plants.
[7] The condensed imidazole compound is represented by the formula (1):
A ¹ is = CH-
A ² is a nitrogen atom or = CH-,
m is 0, 1 or 2;
R ¹ , R ² , R ³ and R ⁴ are the same or different and may be substituted with a group selected from group X, a C1-C6 chain hydrocarbon group, —OR ⁸ , —S (O) _m R ⁸ , —CO ₂ R ¹⁰ , a cyano group, a nitro group, a halogen atom, or a hydrogen atom,
R ⁵ is a C1-C4 chain hydrocarbon group which may be substituted with a halogen atom, or a cyclopropyl group which may be substituted with a halogen atom;
R ⁶ is a C1-C4 chain hydrocarbon group substituted with a halogen atom, —OR ¹⁵ or —S (O) _m R ¹⁵ ;
R ⁷ is a hydrogen atom,
R ⁸ is a C1-C6 chain hydrocarbon group optionally substituted with a group selected from group X, a C3-C6 alicyclic hydrocarbon group optionally substituted with a group selected from group X, group Y A phenyl group optionally substituted with a group selected from: a benzyl group optionally substituted with a group selected from group Y; a 5-membered heterocyclic group optionally substituted with a group selected from group Y; or 6 A membered heterocyclic group or a hydrogen atom (in —S (O) _m R ⁸ , m represents the same meaning as described above, provided that when m is 1 or 2, R ⁸ does not represent a hydrogen atom. ),
R ¹⁰ is a C1-C4 alkyl group which may be substituted with a halogen atom or a hydrogen atom,
R ¹⁵ is a C1-C4 chain hydrocarbon group substituted with a halogen atom,
The method for controlling harmful animals according to [6], wherein n is 0.

  The pest control composition according to the present invention has an excellent control effect on pests.

  The pest control composition according to the present invention (hereinafter sometimes referred to as “the present composition”) may be referred to as a condensed imidazole compound represented by the formula (1) (hereinafter referred to as “the present active compound”). )) And at least one respiratory inhibitory compound selected from the group consisting of azoxystrobin, orissastrobin, ferrimzone, furametopyr, flutolanil, and a compound represented by formula (A) (hereinafter referred to as “the present respiratory inhibitory compound”) In some cases) as an active ingredient.

The active compound will be described.
Examples of the substituent in the active compound include the following. In the present invention, “halogen atom” means a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
In this specification, for example, the description of “C2-C5” represented by “C2-C5 alkoxycarbonyl group” means that the number of carbon atoms constituting the entire alkoxycarbonyl group is in the range of 2-5. .

Examples of the “C1-C6 chain hydrocarbon group optionally substituted with a group selected from group X” represented by R ¹ , R ² , R ³ or R ⁴ include a methyl group, an ethyl group, a propyl group, Isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, methoxymethyl group, ethoxymethyl group, propoxymethyl group, isopropoxymethyl group, 2-methoxyethyl group, 2- Ethoxyethyl group, 2-propoxyethyl group, 2-isopropoxyethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, cyanomethyl group, dicyanomethyl group, 1- Cyanoethyl group, 1,1-dicyanoethyl group, 2-cyanoethyl group, trifluoromethyl A C1-C6 alkyl group optionally substituted with a group selected from group X such as a group, 2,2,2-trifluoroethyl group and pentafluoroethyl group;
Vinyl group, 1-propenyl group, 2-propenyl group, 1-methylvinyl group, 2-methyl-1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 1- A C2-C6 alkenyl group optionally substituted with a group selected from group X such as a hexenyl group, 1,1-difluoroallyl group, pentafluoroallyl group;
Substituted with a group selected from group X such as ethynyl group, propargyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 1-hexynyl group and 4,4,4-trifluoro-2-butynyl group And an optionally substituted C2-C6 alkynyl group.

Examples of the “C3-C6 alicyclic hydrocarbon group optionally substituted with a group selected from group X” represented by R ¹ , R ² , R ³ or R ⁴ include a cyclopropyl group, a cyclobutyl group and a cyclopentyl group. Groups and cyclohexyl groups.

Examples of the “phenyl group optionally substituted with a group selected from group Y” represented by R ¹ , R ² , R ³ or R ⁴ include a phenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4- Chlorophenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2- (trifluoromethyl) phenyl group, 3 -(Trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group, 2-cyanophenyl group, 3-cyanophenyl group and 4 -A cyanophenyl group etc. are mentioned.

Examples of the “benzyl group optionally substituted with a group selected from group Y” represented by R ¹ , R ² , R ³ , R ⁴ , R ⁸ or R ⁹ include a benzyl group, 2-chlorobenzyl group, Examples include 3-chlorobenzyl group, 4-chlorobenzyl group, 2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, 2-methoxybenzyl group, 3-methoxybenzyl group and 4-methoxybenzyl group. .

The “heterocyclic group” in the “5-membered heterocyclic group or 6-membered heterocyclic group optionally substituted with a group selected from group Y” represented by R ¹ , R ² , R ³ or R ⁴ is heterocycle Represents a ring compound residue, and examples of the “5-membered heterocyclic group or 6-membered heterocyclic group optionally substituted with a group selected from group Y” include pyrrolidin-1-yl group and tetrahydrofuran-2-yl group 5-membered saturated heterocyclic groups such as;
6-membered saturated heterocyclic groups such as piperidyl group, morpholyl group, thiomorpholyl group and 4-methylpiperazin-1-yl group;
Pyrazol-1-yl group, 3-chloro-pyrazol-1-yl group, 3-bromopyrazol-1-yl group, 3-nitropyrazol-1-yl group, 3-methylpyrazol-1-yl group, 3- (Trifluoromethyl) pyrazol-1-yl group, 4-methylpyrazol-1-yl group, 4-chloropyrazol-1-yl group, 4-bromopyrazol-1-yl group, 4-cyanopyrazol-1-yl Group, imidazol-1-yl group, 4- (trifluoromethylimidazole) -1-yl group, pyrrol-1-yl group, 1,2,4-triazol-1-yl group, 3-chloro-1,2 , 4-triazol-1-yl group, 1,2,3,4-tetrazol-1-yl group, 1,2,3,5-tetrazol-1-yl group, 2-thienyl group and 3-thienyl group, etc. 5-membered aromatic Heterocyclic group;
Examples thereof include 6-membered aromatic heterocyclic groups such as 2-pyridyl group, 3-pyridyl group and 4-pyridyl group.

Examples of the “C1-C4 chain hydrocarbon group optionally substituted with a halogen atom” represented by R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a sec-butyl group. A C1-C4 alkyl group optionally substituted with a halogen atom such as a tert-butyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group and a pentafluoroethyl group;
A C2-C4 alkenyl group optionally substituted with a halogen atom such as a vinyl group, an allyl group, or a 3,3-difluoroallyl group;
Examples thereof include C2-C4 alkynyl groups which may be substituted with halogen atoms such as propargyl group and 4,4,4-trifluoro-2-butynyl group.

Examples of the “C1-C4 chain hydrocarbon group substituted with a halogen atom” represented by R ⁶ or R ⁷ include, for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, 2,2,2-trifluoroethyl Group, pentafluoroethyl group, heptafluoropropyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, heptafluoroisopropyl group, nonafluorobutyl group, nonafluoroisobutyl group, nonafluoro-sec -Butyl group and nonafluoro-tert-butyl group.

R ⁶ and R ⁷ and are attached, R ⁶ and as a "5- or 6-membered ring substituted with halogen atom" R ⁷ carbon atom attached is shown together, for example the following Examples include rings represented by formulas (a) to (j). (Here, A ⁶ represents a carbon atom to which R ⁶ is bonded, and A ⁷ represents a carbon atom to which R ⁷ is bonded.)

Examples of the “C1-C6 chain hydrocarbon group optionally substituted with a group selected from group X” represented by R ⁸ or R ⁹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Isobutyl group, sec-butyl group, tert-butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, Pentyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, hexyl group, fluoromethyl group, Difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, pen A C1-C6 alkyl group optionally substituted with a group selected from group X such as a tafluoroethyl group and a 1-methyl-2,2,2-trifluoroethyl group;
2-propenyl group, 3,3-dichloro-2-propenyl group, 3,3-difluoro-2-propenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 2-butenyl group, A C3-C6 alkenyl group optionally substituted with a group selected from Group X such as 3-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group;
Substituted with a group selected from group X such as propargyl group, 1-methyl-2-propynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-butynyl group and 1-methyl-3-butynyl group And an optionally substituted C3-C6 alkynyl group.

Examples of the “C3-C6 alicyclic hydrocarbon group optionally substituted with a group selected from group X” represented by R ⁸ or R ⁹ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and 2 -A cyclohexenyl group is mentioned.

Examples of the “phenyl group optionally substituted with a group selected from group Y” represented by R ⁸ and R ⁹ include a 2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, Examples include 4- (trifluoromethyl) phenyl group, 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, 2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group and the like.

Examples of the “5-membered heterocyclic group or 6-membered heterocyclic group optionally substituted with a group selected from group Y” represented by R ⁸ or R ⁹ include 5-thienyl group and 3-thienyl group. A membered aromatic heterocyclic group;
Examples thereof include 6-membered aromatic heterocyclic groups such as 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrimidinyl group and 4-pyrimidinyl group.

Examples of the “C1-C4 alkyl group optionally substituted with a halogen atom” represented by R ¹⁰ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples thereof include a butyl group, a trifluoromethyl group, and a pentafluoroethyl group.

Examples of the “C1-C4 alkyl group optionally substituted with a halogen atom” represented by R ¹¹ or R ¹² include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a sec-butyl group. , Tert-butyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group and the like.

Examples of the “C2-C5 alkoxycarbonyl group” represented by R ¹¹ or R ¹² include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, and a sec-butoxycarbonyl group. Examples include a nyl group and a tert-butoxycarbonyl group.

Examples of the “C1-C3 chain hydrocarbon group optionally substituted with a halogen atom” represented by R ¹³ or R ¹⁴ include, for example, methyl group, ethyl group, propyl group, isopropyl group, fluoromethyl group, difluoromethyl group A C1-C3 alkyl group optionally substituted with a halogen atom such as a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and a pentafluoroethyl group;
A C2-C3 alkenyl group optionally substituted with a halogen atom such as a vinyl group, 2-propenyl group, 3,3-difluoro-2-propenyl group, and 3,3-dichloro-2-propenyl group;
Examples thereof include C2-C3 alkynyl groups which may be substituted with halogen atoms such as ethynyl group and propargyl group.

Examples of the “C1-C4 chain hydrocarbon group substituted with a halogen atom” represented by R ¹⁵ include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a penta Fluoroethyl group, heptafluoropropyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, heptafluoroisopropyl group, nonafluorobutyl group, nonafluoroisobutyl group, nonafluoro-sec-butyl group And a C1-C4 alkyl group substituted with a halogen atom such as a nonafluoro-tert-butyl group;
A C2-C4 alkenyl group substituted with a halogen atom such as a 3,3-difluoroallyl group and a pentafluoroallyl group;
A C2-C4 alkynyl group substituted with a halogen atom such as a 4,4,4-trifluoro-2-butynyl group can be mentioned.

Examples of the “C1-C4 alkyl group optionally substituted with a halogen atom” represented by R ¹⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples thereof include a butyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and a pentafluoroethyl group.

As an aspect of this active compound used for this invention, the following are mentioned, for example.
In formula (1), A ¹ is ═CH—, A ² is a nitrogen atom or ═CH—, m is 0, 1 or 2, and R ¹ , R ² , R ³ and R ⁴ are the same. Or, differently, a C1-C6 chain hydrocarbon group optionally substituted with a group selected from group X, —OR ⁸ , —S (O) _m R ⁸ , —CO ₂ R ¹⁰ , a cyano group, a nitro group , A halogen atom, or a hydrogen atom, and R ⁵ is a C1-C4 chain hydrocarbon group that may be substituted with a halogen atom, or a cyclopropyl group that may be substituted with a halogen atom, and R ⁶ is A C1-C4 chain hydrocarbon group substituted with a halogen atom, —OR ¹⁵ or —S (O) _m R ¹⁵ , R ⁷ is a hydrogen atom, and R ⁸ is substituted with a group selected from group X An optionally substituted C1-C6 chain hydrocarbon group, a C3-C6 alicyclic carbon optionally substituted with a group selected from group X A hydrogen group, a phenyl group optionally substituted with a group selected from group Y, a benzyl group optionally substituted with a group selected from group Y, and a 5-membered optionally substituted with a group selected from group Y A heterocyclic group, a 6-membered heterocyclic group, or a hydrogen atom (in —S (O) _m R ⁸ , m represents the same meaning as described above; provided that when m is 1 or 2, R ⁸ is hydrogen. R ¹⁰ is a C1-C4 alkyl group optionally substituted with a halogen atom or a hydrogen atom, and R ¹⁵ is a C1-C4 chain hydrocarbon group substituted with a halogen atom. A condensed imidazole compound wherein n is 0;

In formula (1), A ¹ is —CH═, and R ¹ , R ² , R ³ and R ⁴ are the same or different and may be substituted with a halogen atom, a C1-C6 chain hydrocarbon group, _{^{-OR 8, -S (O) m}} R 8, -CO 2 R 10, a halogen atom or a hydrogen atom, R ⁸ is a substituted C1-C6 may be chain hydrocarbon group with a halogen atom, R ¹⁰ is a C1-C4 alkyl group which may be substituted with a halogen atom, and R ⁵ may be substituted with a C1-C4 chain hydrocarbon group which may be substituted with a halogen atom or a halogen atom. cyclopropyl group, R ⁶ is a C1-C4 chain hydrocarbon group or -OR ¹⁵ substituted with a halogen atom, R ⁷ is a hydrogen atom, C1-C4 which R ¹⁵ is substituted with a halogen atom Condensed imidazole which is a chain hydrocarbon group and n is 0 Compound;

In the formula (1), A ¹ is —CH═, and R ¹ , R ² , R ³ and R ⁴ are the same or different and may be a C1-C6 alkyl group which may be substituted with a halogen atom, a halogen atom C1-C6 alkoxy group which may be substituted, C1-C6 alkylthio group which may be substituted with halogen atom, C1-C6 alkylsulfinyl group which may be substituted with halogen atom, substituted with halogen atom A C1-C6 alkylsulfonyl group, a (C1-C4 alkoxy) carbonyl group optionally substituted with a halogen atom, a halogen atom or a hydrogen atom, and R ⁵ may be substituted with a halogen atom. A C1-C4 alkyl group which is an alkyl group or a cyclopropyl group optionally substituted with a halogen atom, and R ⁶ is substituted with a halogen atom Or a condensed imidazole compound which is a C1-C4 alkoxy group optionally substituted with a halogen atom, R ⁷ is a hydrogen atom, and n is 0;

In Formula (1), A ¹ is —CH═, R ¹ is a hydrogen atom, R ² is a hydrogen atom, and R ³ and R ⁴ are the same or different, and may be substituted with a halogen atom. A good C1-C6 alkyl group, a C1-C6 alkoxy group optionally substituted with a halogen atom, a C1-C6 alkylthio group optionally substituted with a halogen atom, a C1-C6 alkyl optionally substituted with a halogen atom A sulfinyl group, a C1-C6 alkylsulfonyl group optionally substituted with a halogen atom, a (C1-C4 alkoxy) carbonyl group optionally substituted with a halogen atom, a halogen atom or a hydrogen atom, and R ⁵ is a halogen atom in substituted substituted by C1-C4 may be an alkyl group or a halogen atom are also good cyclopropyl group, R ⁶ is a halogen atom Substituted with substituted C1-C4 alkyl group or a halogen atom are also be C1-C4 alkoxy group, R ⁷ is a hydrogen atom, fused imidazole compounds wherein n is 0;

In formula (1), A ¹ is —CH═, R ¹ is a hydrogen atom, R ² is a hydrogen atom, and R ³ is a C1-C6 alkyl group optionally substituted with a halogen atom, halogen C1-C6 alkoxy group optionally substituted with an atom, C1-C6 alkylthio group optionally substituted with a halogen atom, C1-C6 alkylsulfinyl group optionally substituted with a halogen atom, substituted with a halogen atom An optionally substituted C1-C6 alkylsulfonyl group, a (C1-C4 alkoxy) carbonyl group optionally substituted with a halogen atom, a halogen atom or a hydrogen atom, R ⁴ is a hydrogen atom, and R ⁵ is a halogen atom substituted in substituted substituted by C1-C4 may be an alkyl group or a halogen atom are also good cyclopropyl group, R ⁶ is a halogen atom The a C1-C4 alkyl group or optionally substituted C1-C4 alkoxy group a halogen atom, R ⁷ is a hydrogen atom, fused imidazole compounds wherein n is 0;

In Formula (1), A ¹ is —CH═, A ¹ is a nitrogen atom, R ¹ is a hydrogen atom, R ² is a hydrogen atom, and R ³ is substituted with a halogen atom. A good C1-C6 alkyl group, a C1-C6 alkoxy group optionally substituted with a halogen atom, a C1-C6 alkylthio group optionally substituted with a halogen atom, a C1-C6 alkyl optionally substituted with a halogen atom A sulfinyl group, a C1-C6 alkylsulfonyl group optionally substituted with a halogen atom, a (C1-C4 alkoxy) carbonyl group optionally substituted with a halogen atom, a halogen atom or a hydrogen atom, and R ⁴ is a hydrogen atom R ⁵ is a C1-C4 alkyl group which may be substituted with a halogen atom or a cyclopropyl group which may be substituted with a halogen atom, and R ⁶ Is a C1-C4 alkyl group substituted with a halogen atom or a C1-C4 alkoxy group optionally substituted with a halogen atom, R ⁷ is a hydrogen atom, and n is 0.

Next, the manufacturing method of this active compound which is an active ingredient in this invention composition is demonstrated.
The active compound can be produced, for example, by the following (Production Method 1) to (Production Method 28).

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ａ¹及びＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばテトラヒドロフラン（以下、ＴＨＦと記す場合がある。）、エチレングリコールジメチルエーテル、１，４−ジオキサンなどのエーテル類、ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、クロロベンゼン等のハロゲン化炭化水素類、酢酸エチル、酢酸ブチル等のエステル類、アセトニトリルなどのニトリル類、Ｎ，Ｎ−ジメチルホルムアミド（以下、ＤＭＦと記す場合がある。）等の酸アミド類、ジメチルスルホキシド（以下、ＤＭＳＯと記す場合がある。）等のスルホキシド類、ピリジン、キノリン等の含窒素芳香族化合物類及びこれらの混合物が挙げられる。
化合物（２）１モルに対して、化合物（３）が通常１〜３モルの割合で用いられる。
該反応の反応温度は、通常３０〜２００℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物に水を注加した後、有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４）を単離することができる。単離された化合物（４）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 1)
Among the active compounds, compound (4) in which n is 0 can be produced by reacting compound (2) and compound (3) in the presence of a base.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include tetrahydrofuran (hereinafter sometimes referred to as THF), ethers such as ethylene glycol dimethyl ether and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and toluene. , Aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, N, N-dimethylformamide (hereinafter sometimes referred to as DMF) ), Sulfoxides such as dimethyl sulfoxide (hereinafter sometimes referred to as DMSO), nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
The compound (3) is usually used at a ratio of 1 to 3 moles relative to 1 mole of the compound (2).
The reaction temperature is usually in the range of 30 to 200 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4) can be isolated by performing post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer. The isolated compound (4) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ａ¹及びＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばＴＨＦ、エチレングリコールジメチルエーテル、１，４−ジオキサンなどのエーテル類、ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、クロロベンゼン等のハロゲン化炭化水素類、酢酸エチル、酢酸ブチル等のエステル類、アセトニトリルなどのニトリル類、ＤＭＦ等の酸アミド類、ＤＭＳＯ等のスルホキシド類、ピリジン、キノリン等の含窒素芳香族化合物類及びこれらの混合物が挙げられる。
該反応は、必要に応じて塩基を添加して行うこともできる。
反応に用いられる塩基としては、炭酸水素ナトリウム、炭酸水素カリウム等の炭酸水素塩類、炭酸ナトリウム、炭酸カリウム等の炭酸塩類、亜硫酸ナトリウム、亜硫酸カリウム等の亜硫酸塩類及びこれらの混合物が挙げられる。
化合物（２）１モルに対して、化合物（５）が通常１〜３モルの割合で用いられる。
塩基を添加して行う場合は、化合物（２）１モルに対して、塩基は通常１〜５モルの割合で用いられる。
該反応の反応温度は、通常３０〜２００℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物に水を注加した後、有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４）を単離することができる。単離された化合物（４）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 2)
Among the active compounds, compound (4) in which n is 0 can be produced by reacting compound (2) with compound (5).

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as toluene and xylene, and chlorobenzene. Halogenated hydrocarbons such as ethyl acetate, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF, sulfoxides such as DMSO, nitrogen-containing aromatic compounds such as pyridine and quinoline, and the like Of the mixture.
This reaction can also be carried out by adding a base as necessary.
Examples of the base used in the reaction include hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, carbonates such as sodium carbonate and potassium carbonate, sulfites such as sodium sulfite and potassium sulfite, and mixtures thereof.
The compound (5) is usually used at a ratio of 1 to 3 moles relative to 1 mole of the compound (2).
When performing by adding a base, a base is normally used in the ratio of 1-5 mol with respect to 1 mol of compounds (2).
The reaction temperature is usually in the range of 30 to 200 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4) can be isolated by performing post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer. The isolated compound (4) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ａ¹及びＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばＴＨＦ、エチレングリコールジメチルエーテル、１，４−ジオキサンなどのエーテル類、ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、クロロベンゼン等のハロゲン化炭化水素類、酢酸エチル、酢酸ブチル等のエステル類、アセトニトリルなどのニトリル類、ＤＭＦ等の酸アミド類、ＤＭＳＯ等のスルホキシド類、ピリジン、キノリン等の含窒素芳香族化合物類及びこれらの混合物が挙げられる。
反応に用いられる脱水縮合剤としては、１−エチル−３−（３−ジメチルアミノプロピル）カルボジイミド塩酸塩（以下、ＷＳＣと記す場合がある。）、１，３−ジシクロヘキシルカルボジイミド等のカルボジイミド類が挙げられる。
該反応は、必要に応じて触媒を加えて行うこともできる。
反応に用いられる触媒としては、１−ヒドロキシベンゾトリアゾール等が挙げられる。化合物（２）１モルに対して、化合物（６）が通常１〜３モルの割合、脱水縮合剤が通常１〜５モルの割合、触媒が通常０．０１〜０．１モルの割合で用いられる。
該反応の反応温度は、通常３０〜２００℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物に水を注加した後、有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４）を単離することができる。単離された化合物（４）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 3)
Among the compounds, compound (4) in which n is 0 can be produced by reacting compound (2) and compound (6) in the presence of a dehydration condensing agent.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as toluene and xylene, and chlorobenzene. Halogenated hydrocarbons such as ethyl acetate, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF, sulfoxides such as DMSO, nitrogen-containing aromatic compounds such as pyridine and quinoline, and the like Of the mixture.
Examples of the dehydration condensing agent used in the reaction include carbodiimides such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (hereinafter sometimes referred to as WSC) and 1,3-dicyclohexylcarbodiimide. It is done.
This reaction can also be performed by adding a catalyst as needed.
Examples of the catalyst used for the reaction include 1-hydroxybenzotriazole. The compound (6) is usually used in a proportion of 1 to 3 moles, the dehydration condensing agent is usually used in a proportion of 1 to 5 moles, and the catalyst is usually used in a proportion of 0.01 to 0.1 moles relative to 1 mole of the compound (2). It is done.
The reaction temperature is usually in the range of 30 to 200 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4) can be isolated by performing post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer. The isolated compound (4) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ａ¹及びＡ²は前記と同じ意味を表す］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばＴＨＦ、エチレングリコールジメチルエーテル、１，４−ジオキサンなどのエーテル類、ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、クロロベンゼン等のハロゲン化炭化水素類、酢酸エチル、酢酸ブチル等のエステル類、アセトニトリルなどのニトリル類、ＤＭＦ等の酸アミド類、ＤＭＳＯ等のスルホキシド類及びこれらの混合物が挙げられる。
該反応は必要に応じて、酸または脱水剤を用いることができる。反応に用いられる酸としては、ｐ−トルエンスルホン酸等のスルホン酸類、酢酸等のカルボン酸類が挙げられ、反応に用いられる脱水剤としては、オキシ塩化リン、無水酢酸、トリフルオロ酢酸無水物等が挙げられる。
化合物（７）１モルに対して、脱水剤が通常１モル〜過剰量の割合で用いられる。
該反応の反応温度は、通常３０〜２００℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４）を単離することができる。単離された化合物（４）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production Method 4)
Among the compounds, compound (4) in which n is 0 can be produced by dehydrating condensation of compound (7).

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , A ¹ and A ² represent the same meaning as described above]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as toluene and xylene, and chlorobenzene. And halogenated hydrocarbons such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF, sulfoxides such as DMSO, and mixtures thereof.
In the reaction, an acid or a dehydrating agent can be used as necessary. Examples of the acid used in the reaction include sulfonic acids such as p-toluenesulfonic acid, and carboxylic acids such as acetic acid. Examples of the dehydrating agent used in the reaction include phosphorus oxychloride, acetic anhydride, trifluoroacetic anhydride, and the like. Can be mentioned.
The dehydrating agent is usually used in a proportion of 1 mol to excess with respect to 1 mol of the compound (7).
The reaction temperature is usually in the range of 30 to 200 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ａ¹及びＡ²は前記と同じ意味を表し、Ｒ³¹は塩素原子またはフッ素原子を表し、Ｒ³²は群Ｘから選ばれる基で置換されていてもよいＣ１−Ｃ６鎖式炭化水素基、群Ｘから選ばれる基で置換されていてもよいＣ３−Ｃ６脂環式炭化水素基、群Ｙから選ばれる基で置換されていてもよいフェニル基、群Ｙから選ばれる基で置換されていてもよいベンジル基、群Ｙから選ばれる基で置換されていてもよい５員複素環基もしくは６員複素環基を表す。］
該反応は、通常溶媒の存在下で行われるが、化合物（９）を溶媒量用いてもよい。
反応に用いられる溶媒としては、例えばＴＨＦ、エチレングリコールジメチルエーテル、１，４−ジオキサンなどのエーテル類、トルエン、キシレン等の芳香族炭化水素類、アセトニトリル等のニトリル類、ＤＭＦ等の酸アミド類、ＤＭＳＯ等のスルホキシド類及びこれらの混合物が挙げられる。
反応に用いられる塩基としては、例えば水素化ナトリウム等のアルカリ金属水素化物類が挙げられる。
化合物（８）１モルに対して、化合物（９）が通常１モル〜過剰量の割合、塩基が通常１〜１０モルの割合で用いられる。
該反応の反応温度は、通常０〜１５０℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ａ）を単離することができる。単離された化合物（４−ａ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 5)
Among the compounds (4), the compound (4-a) can be produced by reacting the compound (8) and the compound (9) in the presence of a base.

[Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , A ¹ and A ² represent the same meaning as described above, R ³¹ represents a chlorine atom or a fluorine atom, and R ³² represents a group A C1-C6 chain hydrocarbon group optionally substituted with a group selected from X, a C3-C6 alicyclic hydrocarbon group optionally substituted with a group selected from Group X, a group selected from Group Y A phenyl group optionally substituted with, a benzyl group optionally substituted with a group selected from group Y, a 5-membered heterocyclic group or a 6-membered heterocyclic group optionally substituted with a group selected from group Y Represents. ]
The reaction is usually performed in the presence of a solvent, but compound (9) may be used in an amount of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, acid amides such as DMF, DMSO, and the like. And sulfoxides such as these and mixtures thereof.
Examples of the base used for the reaction include alkali metal hydrides such as sodium hydride.
The compound (9) is usually used in a proportion of 1 mol to excess and the base is usually used in a proportion of 1 to 10 mol with respect to 1 mol of the compound (8).
The reaction temperature is usually in the range of 0 to 150 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4-a) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-a) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ³¹、Ｒ³²、Ａ¹及びＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばＴＨＦ、エチレングリコールジメチルエーテル、１，４−ジオキサンなどのエーテル類、トルエン、キシレン等の芳香族炭化水素類、アセトニトリル等のニトリル類、ＤＭＦ等の酸アミド類、ＤＭＳＯ等のスルホキシド類及びこれらの混合物が挙げられる。
反応に用いられる塩基としては、例えば水素化ナトリウム等のアルカリ金属水素化物類等が挙げられる。
化合物（８）１モルに対して、化合物（１０）が通常１〜１０モルの割合、塩基が通常１〜１０モルの割合で用いられる。
該反応の反応温度は、通常０〜１５０℃の範囲であり、反応時間は通常０．５〜２４時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｂ）を単離することができる。単離された化合物（４−ｂ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 6)
Among the compounds (4), the compound (4-b) can be produced by reacting the compound (8) and the compound (10) in the presence of a base.

[Wherein, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ³¹ , R ³² , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, acid amides such as DMF, DMSO, and the like. And sulfoxides such as these and mixtures thereof.
Examples of the base used for the reaction include alkali metal hydrides such as sodium hydride.
The compound (10) is usually used in a proportion of 1 to 10 mol and the base is usually used in a proportion of 1 to 10 mol with respect to 1 mol of the compound (8).
The reaction temperature is usually in the range of 0 to 150 ° C., and the reaction time is usually in the range of 0.5 to 24 hours.
After completion of the reaction, the compound (4-b) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-b) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ³²、Ａ¹及びＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばジクロロメタン、クロロホルム等の脂肪族ハロゲン化炭化水素類、メタノール、エタノール等のアルコール類、酢酸、水及びこれらの混合物が挙げられる。
反応に用いられる酸化剤としては、例えば過ヨウ素酸ナトリウムが挙げられる。
化合物（４−ｂ）１モルに対して、酸化剤が通常１〜３モルの割合で用いられる。
該反応の反応温度は、通常−２０〜８０℃の範囲であり、反応時間は通常０．１〜１２時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を必要に応じて還元剤（例えば亜硫酸ナトリウム、チオ硫酸ナトリウム）の水溶液、塩基（例えば炭酸水素ナトリウム）の水溶液で洗浄し、乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｃ）を単離することができる。単離された化合物（４−ｃ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 7)
Among the compounds (4), the compound (4-c) can be produced by reacting the compound (4-b) in the presence of an oxidizing agent.

[Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ³² , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
As an oxidizing agent used for reaction, sodium periodate is mentioned, for example.
An oxidizing agent is normally used in the ratio of 1-3 mol with respect to 1 mol of compounds (4-b).
The reaction temperature of the reaction is usually in the range of -20 to 80 ° C, and the reaction time is usually in the range of 0.1 to 12 hours.
After completion of the reaction, the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried, The compound (4-c) can be isolated by performing post-treatment operations such as concentration. The isolated compound (4-c) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ³²、Ａ¹及びＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばジクロロメタン、クロロホルム等の脂肪族ハロゲン化炭化水素類、酢酸、水及びこれらの混合物が挙げられる。
反応に用いられる酸化剤としては、例えば３−クロロ過安息香酸等のカルボン酸過酸化物が挙げられる。
化合物（４−ｂ）１モルに対して、酸化剤が通常２〜４モルの割合で用いられる。
該反応の反応温度は、通常−２０〜３０℃の範囲であり、反応時間は通常０．１〜１２時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を必要に応じて還元剤（例えば亜硫酸ナトリウム、チオ硫酸ナトリウム）の水溶液、塩基（例えば炭酸水素ナトリウム）の水溶液で洗浄し、乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｄ）を単離することができる。単離された化合物（４−ｄ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 8)
Among the compounds (4), the compound (4-d) can be produced by reacting the compound (4-b) in the presence of an oxidizing agent.

[Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ³² , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, acetic acid, water, and mixtures thereof.
Examples of the oxidizing agent used in the reaction include carboxylic acid peroxides such as 3-chloroperbenzoic acid.
An oxidizing agent is normally used in the ratio of 2-4 mol with respect to 1 mol of compounds (4-b).
The reaction temperature of the reaction is usually in the range of -20 to 30 ° C, and the reaction time is usually in the range of 0.1 to 12 hours.
After completion of the reaction, the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried, The compound (4-d) can be isolated by performing post-treatment operations such as concentration. The isolated compound (4-d) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ａ¹およびＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われるが、化合物（１２）を溶媒量用いてもよい。
反応に用いられる溶媒としては、例えばＴＨＦ、エチレングリコールジメチルエーテル、１，４−ジオキサンなどのエーテル類、トルエン、キシレン等の芳香族炭化水素類、アセトニトリル等のニトリル類、ＤＭＦ等の酸アミド類、ＤＭＳＯ等のスルホキシド類、ピリジン、キノリン等の含窒素芳香族化合物類及びこれらの混合物が挙げられる。
該反応は、必要に応じて塩基を加えて行うこともできる。
反応に用いられる塩基としては、例えば水素化ナトリウム等のアルカリ金属水素化物類、炭酸カリウム等の炭酸塩類、トリエチルアミン、ジイソプロピルエチルアミン等の第３級アミン類及びピリジン、４−ジメチルアミノピリジン等の含窒素芳香族化合物類等が挙げられる。
化合物（１１）１モルに対して、化合物（１２）または化合物（１３）が通常１〜１０モルの割合、塩基が通常１〜１０モルの割合で用いられる。
該反応の反応温度は、通常０〜１２０℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｅ）を単離することができる。単離された化合物（４−ｅ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 9)
Among the compounds (4), the compound (4-e) is produced by reacting the compound (11) with an acid anhydride represented by the compound (12) or an acid chloride represented by the compound (13). can do.

[Wherein, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent, but the amount of the compound (12) may be used.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, acid amides such as DMF, DMSO, and the like. And sulfoxides such as pyridine, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
This reaction can also be performed by adding a base as necessary.
Examples of the base used in the reaction include alkali metal hydrides such as sodium hydride, carbonates such as potassium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing compounds such as pyridine and 4-dimethylaminopyridine. Aromatic compounds etc. are mentioned.
The compound (12) or the compound (13) is usually used in a proportion of 1 to 10 mol and the base is usually used in a proportion of 1 to 10 mol with respect to 1 mol of the compound (11).
The reaction temperature is usually in the range of 0 to 120 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4-e) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-e) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ａ¹およびＡ²は前記と同じ意味を表し、
Ｌは臭素原子または沃素原子を表し、
Ｒ^3xは群Ｙから選ばれる基で置換されていてもよいフェニル基、群Ｙから選ばれる基で置換されていてもよい５芳香族複素環基もしくは６員芳香族複素環基（但し、ピリジン環と炭素原子上で結合する芳香族複素環基に限る）を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばＴＨＦ、エチレングリコールジメチルエーテル、１，４−ジオキサンなどのエーテル類、メタノール、エタノール等のアルコール類、ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、ＤＭＦ等の酸アミド類、水及びこれらの混合物等が挙げられる。
反応に用いられるパラジウム化合物としては、酢酸パラジウム、テトラキストリフェニルホスフィンパラジウム、｛１，１’−ビス（ジフェニルホスフィノ）フェロセン｝ジクロロパラジウム塩化メチレン錯体及びビス（トリフェニルホスフィン）パラジウムジクロライド等が挙げられる。
化合物（１４）１モルに対して、化合物（１５）または化合物（１６）が通常０．５〜５モルの割合、パラジウム化合物が通常０．００１〜０．１モルの割合で用いられる。
該反応には必要に応じて塩基（酢酸ナトリウム、酢酸カリウム、炭酸カリウム、リン酸三カリウム、炭酸水素ナトリウム等の無機塩類が挙げられる。）及び／または相関移動触媒（テトラブチルアンモニウムブロミド、ベンジルトリエチルアンモニウムブロミド等の第四級アンモニウム塩が挙げられる。）の存在下で行うこともできる。
該反応の反応温度は、通常５０〜１２０℃の範囲であり、反応時間は通常０．５〜２４時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｆ）を単離することができる。単離された化合物（４−ｆ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 10)
Among the compounds (4), the compound (4-f) is obtained by reacting the boronic acid compound represented by the compound (14) and the compound (15) or the tin compound represented by the compound (16) in the presence of the palladium compound. It can manufacture by making it react.

[Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , A ¹ and A ² represent the same meaning as described above,
L represents a bromine atom or an iodine atom,
R ^3x is a phenyl group optionally substituted with a group selected from group Y, a 5-aromatic heterocyclic group or a 6-membered aromatic heterocyclic group optionally substituted with a group selected from group Y (provided that pyridine An aromatic heterocyclic group bonded to a ring and a carbon atom). ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used for the reaction include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, alcohols such as methanol and ethanol, aliphatic hydrocarbons such as hexane, heptane and octane, toluene, xylene and the like. Aromatic hydrocarbons, acid amides such as DMF, water, and mixtures thereof.
Examples of the palladium compound used in the reaction include palladium acetate, tetrakistriphenylphosphine palladium, {1,1′-bis (diphenylphosphino) ferrocene} dichloropalladium methylene chloride complex, and bis (triphenylphosphine) palladium dichloride. .
The compound (15) or the compound (16) is usually used in a proportion of 0.5 to 5 mol and the palladium compound is usually used in a proportion of 0.001 to 0.1 mol with respect to 1 mol of the compound (14).
In the reaction, a base (inorganic salts such as sodium acetate, potassium acetate, potassium carbonate, tripotassium phosphate, sodium hydrogencarbonate, etc.) and / or phase transfer catalyst (tetrabutylammonium bromide, benzyltriethyl, etc.) are optionally used. And a quaternary ammonium salt such as ammonium bromide).
The reaction temperature of the reaction is usually in the range of 50 to 120 ° C., and the reaction time is usually in the range of 0.5 to 24 hours.
After completion of the reaction, the compound (4-f) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-f) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ³¹、Ａ¹およびＡ²は前記と同じ意味を表し、
Ｒ^3yは群Ｙから選ばれる基で置換されていてもよい５員複素環基もしくは６員複素環基（但し、ピリジン環と窒素原子上で結合する複素環基に限る）を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばＴＨＦ、エチレングリコールジメチルエーテル、１，４−ジオキサンなどのエーテル類、トルエン、キシレン等の芳香族炭化水素類、アセトニトリル等のニトリル類、ＤＭＦ等の酸アミド類、ＤＭＳＯ等のスルホキシド類及びこれらの混合物が挙げられる。
反応に用いられる塩基としては、例えば水素化ナトリウム等のアルカリ金属水素化物類、炭酸カリウム等の炭酸塩類等が挙げられる。
化合物（８）１モルに対して、化合物（１７）が通常１〜１０モルの割合、塩基が通常１〜１０モルの割合で用いられる。
該反応の反応温度は、通常０〜１００℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｇ）を単離することができる。単離された化合物（４−ｇ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 11)
Among the compounds (4), the compound (4-g) can be produced by reacting the compound (8) and the compound (17) in the presence of a base.

[Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ³¹ , A ¹ and A ² represent the same meaning as described above,
R ^3y represents a 5-membered heterocyclic group or a 6-membered heterocyclic group which may be substituted with a group selected from Group Y (however, limited to a heterocyclic group bonded to the pyridine ring on the nitrogen atom). ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, acid amides such as DMF, DMSO, and the like. And sulfoxides such as these and mixtures thereof.
Examples of the base used in the reaction include alkali metal hydrides such as sodium hydride and carbonates such as potassium carbonate.
The compound (17) is usually used in a proportion of 1 to 10 mol and the base is usually used in a proportion of 1 to 10 mol with respect to 1 mol of the compound (8).
The reaction temperature is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4-g) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-g) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ａ¹及びＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばジクロロメタン、クロロホルム等の脂肪族ハロゲン化炭化水素類、酢酸、水及びこれらの混合物が挙げられる。
反応に用いられる酸化剤としては、例えば３−クロロ過安息香酸等のカルボン酸の過酸化物及び過酸化水素水等が挙げられる。
化合物（４）１モルに対して、酸化剤が通常１〜３モルの割合で用いられる。
該反応の反応温度は、通常４０〜１００℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を必要に応じて還元剤（例えば亜硫酸ナトリウム、チオ硫酸ナトリウム）の水溶液、塩基（例えば炭酸水素ナトリウム）の水溶液で洗浄し、乾燥、濃縮する等の後処理操作を行うことにより、化合物（１７）を単離することができる。単離された化合物（１８）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 12)
Among the compounds, compound (18) wherein n is 1 can be produced by reacting compound (4) in the presence of an oxidizing agent.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, acetic acid, water, and mixtures thereof.
Examples of the oxidizing agent used in the reaction include peroxides of carboxylic acids such as 3-chloroperbenzoic acid and hydrogen peroxide.
An oxidizing agent is normally used in the ratio of 1-3 mol with respect to 1 mol of compounds (4).
The reaction temperature of the reaction is usually in the range of 40 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried, The compound (17) can be isolated by performing post-treatment operations such as concentration. The isolated compound (18) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ³¹、Ｒ³²、Ａ¹及びＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばＴＨＦ、エチレングリコールジメチルエーテル、１，４−ジオキサンなどのエーテル類、トルエン、キシレン等の芳香族炭化水素類、アセトニトリル等のニトリル類、ＤＭＦ等の酸アミド類、ＤＭＳＯ等のスルホキシド類及びこれらの混合物が挙げられる。
反応に用いられる塩基としては、例えば水素化ナトリウム等のアルカリ金属水素化物類等が挙げられる。
化合物（２１）１モルに対して、化合物（１０）が通常１〜１０モルの割合、塩基が通常１〜１０モルの割合で用いられる。
該反応の反応温度は、通常０〜１００℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｈ）を単離することができる。単離された化合物（４−ｈ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 13)
Among the compounds (4), the compound (4-h) can be produced by reacting the compound (21) and the compound (10) in the presence of a base.

[Wherein, R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ³¹ , R ³² , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, acid amides such as DMF, DMSO, and the like. And sulfoxides such as these and mixtures thereof.
Examples of the base used for the reaction include alkali metal hydrides such as sodium hydride.
The compound (10) is usually used in a proportion of 1 to 10 mol and the base is usually used in a proportion of 1 to 10 mol with respect to 1 mol of the compound (21).
The reaction temperature is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4-h) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-h) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ³²、Ａ¹及びＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばジクロロメタン、クロロホルム等の脂肪族ハロゲン化炭化水素類、メタノール、エタノール等のアルコール類、ＴＨＦ、エチレングリコールジメチルエーテル、１，４−ジオキサンなどのエーテル類、酢酸、水及びこれらの混合物が挙げられる。
反応に用いられる酸化剤としては、例えば過ヨウ素酸ナトリウムが挙げられる。
化合物（４−ｈ）１モルに対して、酸化剤が通常１〜３モルの割合で用いられる。
該反応の反応温度は、通常−２０〜８０℃の範囲であり、反応時間は通常０．１〜１２時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を必要に応じて還元剤（例えば亜硫酸ナトリウム、チオ硫酸ナトリウム）の水溶液、塩基（例えば炭酸水素ナトリウム）の水溶液で洗浄し、乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｊ）を単離することができる。単離された化合物（４−ｊ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 14)
Among the compounds (4), the compound (4-j) can be produced by reacting the compound (4-h) in the presence of an oxidizing agent.

[Wherein R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ³² , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, ethers such as THF, ethylene glycol dimethyl ether, and 1,4-dioxane, acetic acid, water, and the like. These mixtures are mentioned.
As an oxidizing agent used for reaction, sodium periodate is mentioned, for example.
An oxidizing agent is normally used in the ratio of 1-3 mol with respect to 1 mol of compounds (4-h).
The reaction temperature of the reaction is usually in the range of -20 to 80 ° C, and the reaction time is usually in the range of 0.1 to 12 hours.
After completion of the reaction, the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried, The compound (4-j) can be isolated by performing post-treatment operations such as concentration. The isolated compound (4-j) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ³²、Ａ¹及びＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばジクロロメタン、クロロホルム等の脂肪族ハロゲン化炭化水素類、酢酸、水及びこれらの混合物が挙げられる。
反応に用いられる酸化剤としては、例えば３−クロロ過安息香酸等のカルボン酸過酸化物が挙げられる。
化合物（４−ｈ）１モルに対して、酸化剤が通常２〜４モルの割合で用いられる。
該反応の反応温度は、通常−２０〜３０℃の範囲であり、反応時間は通常０．１〜１２時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を必要に応じて還元剤（例えば亜硫酸ナトリウム、チオ硫酸ナトリウム）の水溶液、塩基（例えば炭酸水素ナトリウム）の水溶液で洗浄し、乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｋ）を単離することができる。単離された化合物（４−ｋ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 15)
Among the compounds (4), the compound (4-k) can be produced by reacting the compound (4-h) in the presence of an oxidizing agent.

[Wherein R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ³² , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, acetic acid, water, and mixtures thereof.
Examples of the oxidizing agent used in the reaction include carboxylic acid peroxides such as 3-chloroperbenzoic acid.
An oxidizing agent is normally used in the ratio of 2-4 mol with respect to 1 mol of compounds (4-h).
The reaction temperature of the reaction is usually in the range of -20 to 30 ° C, and the reaction time is usually in the range of 0.1 to 12 hours.
After completion of the reaction, the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried, The compound (4-k) can be isolated by performing post-treatment operations such as concentration. The isolated compound (4-k) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ³²、Ａ¹及びＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばジクロロメタン、クロロホルム等の脂肪族ハロゲン化炭化水素類、酢酸、水及びこれらの混合物が挙げられる。
反応に用いられる酸化剤としては、例えば３−クロロ過安息香酸等のカルボン酸過酸化物が挙げられる。
化合物（４−ｊ）１モルに対して、酸化剤が通常１〜３モルの割合で用いられる。
該反応の反応温度は、通常−２０〜３０℃の範囲であり、反応時間は通常０．１〜１２時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を必要に応じて還元剤（例えば亜硫酸ナトリウム、チオ硫酸ナトリウム）の水溶液、塩基（例えば炭酸水素ナトリウム）の水溶液で洗浄し、乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｋ）を単離することができる。単離された化合物（４−ｋ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production Method 16)
Among the compounds (4), the compound (4-k) can be produced by reacting the compound (4-j) in the presence of an oxidizing agent.

[Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ³² , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, acetic acid, water, and mixtures thereof.
Examples of the oxidizing agent used in the reaction include carboxylic acid peroxides such as 3-chloroperbenzoic acid.
An oxidizing agent is normally used in the ratio of 1-3 mol with respect to 1 mol of compounds (4-j).
The reaction temperature of the reaction is usually in the range of -20 to 30 ° C, and the reaction time is usually in the range of 0.1 to 12 hours.
After completion of the reaction, the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried, The compound (4-k) can be isolated by performing post-treatment operations such as concentration. The isolated compound (4-k) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ³¹、Ａ¹、及びＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばＴＨＦ、エチレングリコールジメチルエーテル、１，４−ジオキサンなどのエーテル類、ＤＭＦ、１−メチル−２−ピロリジノン等の酸アミド類、ＤＭＳＯ等のスルホキシド類及びこれらの混合物が挙げられる。
反応に用いられるシアン化物としては例えば、シアン化ナトリウムおよびシアン化カリウム等が挙げられる。
該反応は、必要に応じて触媒を加えて行うこともできる。
反応に用いられる触媒としては例えば１５−クラウン−５、１８−クラウン−６等のクラウンエーテル類が挙げられる。
化合物（８）１モルに対して、シアン化物が通常１〜３モルの割合、触媒が通常０．０１〜０．５モルの割合で用いられる。
該反応の反応温度は、通常０〜２００℃の範囲であり、反応時間は通常０．１〜１２時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｐ）を単離することができる。単離された化合物（４−ｐ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production Method 17)
Among compounds (4), compound (4-p) can be produced by reacting compound (8) with cyanide.

[Wherein, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ³¹ , A ¹ , and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, and 1,4-dioxane, acid amides such as DMF and 1-methyl-2-pyrrolidinone, sulfoxides such as DMSO, and mixtures thereof. Can be mentioned.
Examples of the cyanide used in the reaction include sodium cyanide and potassium cyanide.
This reaction can also be performed by adding a catalyst as needed.
Examples of the catalyst used in the reaction include crown ethers such as 15-crown-5 and 18-crown-6.
The cyanide is usually used in a proportion of 1 to 3 mol and the catalyst is usually used in a proportion of 0.01 to 0.5 mol with respect to 1 mol of the compound (8).
The reaction temperature of the reaction is usually in the range of 0 to 200 ° C., and the reaction time is usually in the range of 0.1 to 12 hours.
After completion of the reaction, the compound (4-p) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-p) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ａ¹及びＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばメタノール、エタノール等のアルコール類、水及びこれらの混合物が挙げられる。
反応に用いられる塩基としては例えば、水酸化ナトリウム、水酸化カリウム、水酸化バリウム等のアルカリ金属もしくはアルカリ土類金属の水酸化物類が挙げられる。
化合物（４−ｐ）１モルに対して、塩基が通常１〜３モルの割合で用いられる。
該反応の反応温度は、通常０〜１５０℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、酸析または反応混合物を酸により中和し、有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｑ）を単離することができる。単離された化合物（４−ｑ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 18)
Among the compounds (4), the compound (4-q) can be produced by hydrolyzing the compound (4-p) in the presence of a base.

[Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include alcohols such as methanol and ethanol, water, and mixtures thereof.
Examples of the base used in the reaction include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, and barium hydroxide.
The base is usually used in a proportion of 1 to 3 mol per 1 mol of the compound (4-p).
The reaction temperature is usually in the range of 0 to 150 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4-q) is isolated by performing post-treatment operations such as acid precipitation or neutralization of the reaction mixture with an acid, extraction with an organic solvent, and drying and concentration of the organic layer. be able to. The isolated compound (4-q) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ａ¹及びＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばＤＭＳＯ等のスルホキシド類、水及びこれらの混合物が挙げられる。
反応に用いられる塩基としては例えば、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム等のアルカリ金属もしくはアルカリ土類金属の水酸化物類、炭酸ナトリウム、炭酸カリウム等の炭酸塩類が挙げられる。
化合物（４−ｐ）１モルに対して、過酸化水素が通常１〜５モルの割合、塩基が通常１〜５モルの割合で用いられる。
該反応の反応温度は、通常０〜１００℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｒ）を単離することができる。単離された化合物（４−ｒ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production Method 19)
Among the compounds (4), the compound (4-r) can be produced by reacting the compound (4-p) with hydrogen peroxide in the presence of a base.

[Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include sulfoxides such as DMSO, water, and mixtures thereof.
Examples of the base used in the reaction include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, and carbonates such as sodium carbonate and potassium carbonate.
Hydrogen peroxide is usually used in a proportion of 1 to 5 mol and a base is usually used in a proportion of 1 to 5 mol with respect to 1 mol of compound (4-p).
The reaction temperature is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4-r) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-r) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ａ¹及びＡ²は前記と同じ意味を表す。］
該反応は、通常塩基の存在下に行われ、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばＴＨＦ、エチレングリコールジメチルエーテル、１，４−ジオキサンなどのエーテル類、トルエン、キシレン等の芳香族炭化水素類、アセトニトリル等のニトリル類、ＤＭＦ等の酸アミド類、ＤＭＳＯ等のスルホキシド類、ピリジン、キノリン等の含窒素芳香族化合物類、水及びこれらの混合物が挙げられる。
反応に用いられる塩基としては例えば、炭酸カリウム等の炭酸塩類、トリエチルアミン、ジイソプロピルエチルアミン等の第３級アミン類及びピリジン、４−ジメチルアミノピリジン等の含窒素芳香族化合物類が挙げられる。
化合物（２２）１モルに対して、化合物（２３）が通常１モル〜過剰量の割合、塩基が通常１モル〜過剰量で用いられる。化合物（２３）を過剰に用いる場合は、上記の塩基を使用しないで反応を行うこともできる。またトリエチルアミン、ジイソプロピルエチルアミン等の液体の第３級アミン類またはピリジン等の液体の含窒素芳香族化合物類等を塩基として過剰量使用する場合は、上記の溶媒を使用しないで反応を行うこともできる。
該反応の反応温度は、通常０〜１００℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｓ）を単離することができる。単離された化合物（４−ｓ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 20)
Among the compounds (4), the compound (4-s) can be produced by reacting the compound (22) and the compound (23).

[Wherein, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a base, and usually in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, acid amides such as DMF, DMSO, and the like. Sulfoxides such as pyridine, nitrogen-containing aromatic compounds such as pyridine and quinoline, water, and mixtures thereof.
Examples of the base used in the reaction include carbonates such as potassium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.
The compound (23) is usually used in a proportion of 1 mol to excess and the base is usually used in 1 mol to excess with respect to 1 mol of the compound (22). When compound (23) is used in excess, the reaction can also be carried out without using the above base. In addition, when an excess amount of a liquid tertiary amine such as triethylamine or diisopropylethylamine or a liquid nitrogen-containing aromatic compound such as pyridine is used as a base, the reaction can be carried out without using the above solvent. .
The reaction temperature is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4-s) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-s) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ａ¹およびＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばＴＨＦ、エチレングリコールジメチルエーテル、１，４−ジオキサンなどのエーテル類、ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、クロロベンゼン等のハロゲン化炭化水素類、酢酸エチル、酢酸ブチル等のエステル類、アセトニトリルなどのニトリル類、ＤＭＦ等の酸アミド類、ＤＭＳＯ等のスルホキシド類、ピリジン、キノリン等の含窒素芳香族化合物類及びこれらの混合物が挙げられる。
反応に用いられる脱水縮合剤としてはＷＳＣ、１，３−ジシクロヘキシルカルボジイミド等のカルボジイミド類が挙げられる。
該反応は、必要に応じて触媒を加えて行うこともできる。
反応に用いられる触媒としては、１−ヒドロキシベンゾトリアゾール等が挙げられる。
化合物（４−ｑ）１モルに対して、化合物（２３）が通常１〜３モルの割合、脱水縮合剤が通常１〜５モルの割合、触媒が通常０．０１〜０．１モルの割合で用いられる。
該反応の反応温度は、通常０〜１００℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｑ）を単離することができる。単離された化合物（４−ｓ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 21)
Among the compounds (4), the compound (4-s) can be produced by reacting the compound (4-q) and the compound (23) in the presence of a dehydration condensing agent.

[Wherein, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as toluene and xylene, and chlorobenzene. Halogenated hydrocarbons such as ethyl acetate, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF, sulfoxides such as DMSO, nitrogen-containing aromatic compounds such as pyridine and quinoline, and the like Of the mixture.
Examples of the dehydrating condensing agent used in the reaction include carbodiimides such as WSC and 1,3-dicyclohexylcarbodiimide.
This reaction can also be performed by adding a catalyst as needed.
Examples of the catalyst used for the reaction include 1-hydroxybenzotriazole.
The proportion of compound (23) is usually 1 to 3 mol, the proportion of dehydration condensing agent is usually 1 to 5 mol, and the proportion of catalyst is usually 0.01 to 0.1 mol with respect to 1 mol of compound (4-q). Used in
The reaction temperature is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4-q) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-s) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ａ¹およびＡ²は前記と同じ意味を表し、Ｒ³³はハロゲン原子で置換されていてもよいＣ１−Ｃ４アルキル基を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えば１，４−ジオキサンなどのエーテル類、ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、クロロベンゼン等のハロゲン化炭化水素類、及びこれらの混合物が挙げられる。
反応に用いられる酸としては例えば、塩酸、硫酸等の鉱酸類およびｐ−トルエンスルホン酸等の有機酸類が挙げられる。
化合物（４−ｑ）１モルに対して、化合物（２４）が通常１モル〜過剰量の割合、酸が通常０．０１モル〜１モルで用いられる。
化合物（２４）を過剰に用いる場合は、上記の溶媒を使用しないで反応を行うこともできる。
該反応の反応温度は、通常０〜２００℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｔ）を単離することができる。単離された化合物（４−ｔ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 22)
Among the compounds (4), the compound (4-t) can be produced by reacting the compound (4-q) with the compound (24) in the presence of an acid.

[Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , A ¹ and A ² represent the same meaning as described above, and R ³³ may be substituted with a halogen atom. Represents an alkyl group. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as toluene and xylene, and halogenated hydrocarbons such as chlorobenzene. And mixtures thereof.
Examples of the acid used for the reaction include mineral acids such as hydrochloric acid and sulfuric acid, and organic acids such as p-toluenesulfonic acid.
The compound (24) is usually used in a proportion of 1 mol to excess and the acid is usually used in an amount of 0.01 mol to 1 mol with respect to 1 mol of the compound (4-q).
When compound (24) is used in excess, the reaction can be carried out without using the above solvent.
The reaction temperature of the reaction is usually in the range of 0 to 200 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4-t) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-t) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ³¹、Ａ¹、及びＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては例えば、ＴＨＦ、エチレングリコールジメチルエーテル、１，４−ジオキサンなどのエーテル類、トルエン、キシレン等の芳香族炭化水素類、アセトニトリル等のニトリル類、ＤＭＦ等の酸アミド類、ＤＭＳＯ等のスルホキシド類、ピリジン、キノリン等の含窒素芳香族化合物類、水及びこれらの混合物が挙げられる。
化合物（８）１モルに対して、水硫化ナトリウム等の硫黄化剤が通常１モル〜３モルの割合で用いられる。
該反応の反応温度は、通常０〜１５０℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、酸析または反応混合物を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｕ）を単離することができる。単離された化合物（４−ｕ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production Method 23)
Among the compounds (4), the compound (4-u) can be produced by reacting the compound (8) with a sulfurizing agent such as sodium hydrosulfide.

[Wherein, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ³¹ , A ¹ , and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, acid amides such as DMF, DMSO, and the like. Sulfoxides such as pyridine, nitrogen-containing aromatic compounds such as pyridine and quinoline, water, and mixtures thereof.
A sulfurizing agent such as sodium hydrosulfide is usually used at a ratio of 1 mol to 3 mol with respect to 1 mol of the compound (8).
The reaction temperature is usually in the range of 0 to 150 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4-u) can be isolated by performing post-treatment operations such as acid precipitation or extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-u) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ³²、Ａ¹、Ａ²およびＬは前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては例えば、ＴＨＦ、エチレングリコールジメチルエーテル、１，４−ジオキサンなどのエーテル類、トルエン、キシレン等の芳香族炭化水素類、アセトニトリル等のニトリル類、ＤＭＦ等の酸アミド類、ＤＭＳＯ等のスルホキシド類、及びこれらの混合物が挙げられる。
反応に用いられる塩基としては例えば、水素化ナトリウム、水素化カリウム、水素化カルシウム等のアルカリ金属もしくはアルカリ土類金属の水素化物、炭酸ナトリウム、炭酸カリウム等の無機塩基、または、トリエチルアミン等の有機塩基等が挙げられる。
化合物（４−ｕ）１モルに対して、塩基が通常１〜３モルの割合で用いられる。
該反応の反応温度は、通常０〜１００℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｗ）を単離することができる。単離された化合物（４−ｗ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 24)
Among the compounds (4), the compound (4-w) can be produced by reacting the compound (4-u) and the compound (25) in the presence of a base.

[Wherein, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ³² , A ¹ , A ² and L represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, acid amides such as DMF, DMSO, and the like. And the like, and mixtures thereof.
Examples of the base used in the reaction include alkali metal or alkaline earth metal hydrides such as sodium hydride, potassium hydride and calcium hydride, inorganic bases such as sodium carbonate and potassium carbonate, or organic bases such as triethylamine. Etc.
The base is usually used in a proportion of 1 to 3 mol per 1 mol of the compound (4-u).
The reaction temperature is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4-w) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-w) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ａ¹及びＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えば塩化メチレン、クロロホルム等のハロゲン化炭化水素類、クロロベンゼン等の芳香族ハロゲン化物類、トルエン、キシレン等の芳香族炭化水素類、及びこれらの混合物が挙げられる。
化合物（４−ｕ）１モルに対して、硝酸カリウム等の酸化剤が通常１〜５モルの割合、トリメチルシリルクロリド等の塩素化剤が通常１〜５モルの割合で用いられる。
該反応の反応温度は、通常０〜１５０℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｗ）を単離することができる。単離された化合物（４−ｗ）は、再結晶等によりさらに精製することもできる。 (Production method 25)
Among the compounds (4), the compound (4-w) can be produced by reacting the compound (4-u) with a chlorinating agent such as trimethylsilyl chloride in the presence of an oxidizing agent such as potassium nitrate.

[Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include halogenated hydrocarbons such as methylene chloride and chloroform, aromatic halides such as chlorobenzene, aromatic hydrocarbons such as toluene and xylene, and mixtures thereof.
An oxidizing agent such as potassium nitrate is usually used at a ratio of 1 to 5 moles, and a chlorinating agent such as trimethylsilyl chloride is usually used at a ratio of 1 to 5 moles relative to 1 mole of the compound (4-u).
The reaction temperature is usually in the range of 0 to 150 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4-w) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-w) can be further purified by recrystallization or the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ａ¹およびＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われ、通常塩基の存在下で行われる。
反応に用いられる溶媒としては、例えばＴＨＦ、エチレングリコールジメチルエーテル、１，４−ジオキサンなどのエーテル類、トルエン、キシレン等の芳香族炭化水素類、及びこれらの混合物が挙げられる。
反応に用いられる塩基としては例えば、炭酸ナトリウム、炭酸カリウム等の無機塩基、または、トリエチルアミン、ジイソプロピルエチルアミン等の有機塩基類、ピリジン、キノリン等の含窒素芳香族化合物類が挙げられる。
化合物（４−ｗ）１モルに対して、化合物（２３）が通常１モル〜過剰量の割合、塩基が通常１モル〜過剰量の割合で用いられる。
化合物（２３）を過剰に用いる場合は、上記の塩基を使用しないで反応を行うこともできる。
該反応の反応温度は、通常０〜１００℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｙ）を単離することができる。単離された化合物（４−ｙ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production Method 26)
Among the compounds (4), the compound (4-y) can be produced by reacting the compound (4-w) with the compound (23).

[Wherein, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually carried out in the presence of a solvent and usually in the presence of a base.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, and mixtures thereof.
Examples of the base used in the reaction include inorganic bases such as sodium carbonate and potassium carbonate, organic bases such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and quinoline.
The compound (23) is usually used in a proportion of 1 mol to excess and the base is usually used in a proportion of 1 mol to excess with respect to 1 mol of the compound (4-w).
When compound (23) is used in excess, the reaction can also be carried out without using the above base.
The reaction temperature is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4-y) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4-y) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ａ¹及びＡ²は前記と同じ意味を表す。］
該反応は、通常水素雰囲気下、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばヘキサン、ヘプタン、オクタン等の脂肪族炭化水素類、メタノール、エタノール等のアルコール類、酢酸エチル、酢酸ブチル等のエステル類、及びこれらの混合物が挙げられる。
反応に用いられる遷移金属触媒としては、例えばパラジウム炭素等のパラジウム触媒等が挙げられる。
化合物（２６）１モルに対して、触媒が通常０．０１モル〜０．１の割合で用いられる。
該反応の反応温度は、通常０〜１００℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物をろ過することによって触媒を除去したり、有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｚ）を単離することができる。単離された化合物（４−ｚ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production Method 27)
Among the compounds (4), the compound (4-z) can be produced by reacting the compound (26) with hydrogen in the presence of a transition metal catalyst.

[Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in a hydrogen atmosphere and usually in the presence of a solvent.
Examples of the solvent used in the reaction include aliphatic hydrocarbons such as hexane, heptane, and octane, alcohols such as methanol and ethanol, esters such as ethyl acetate and butyl acetate, and mixtures thereof.
As a transition metal catalyst used for reaction, palladium catalysts, such as palladium carbon, etc. are mentioned, for example.
The catalyst is usually used in the proportion of 0.01 mol to 0.1 with respect to 1 mol of the compound (26).
The reaction temperature is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4-z) is isolated by performing post-treatment operations such as removing the catalyst by filtering the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer. can do. The isolated compound (4-z) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ³²、Ａ¹及びＡ²は前記と同じ意味を表す。］
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばジクロロメタン、クロロホルム等の脂肪族ハロゲン化炭化水素類、酢酸、水及びこれらの混合物が挙げられる。
反応に用いられる酸化剤としては、例えば３−クロロ過安息香酸等のカルボン酸過酸化物が挙げられる。
化合物（４−ｃ）１モルに対して、酸化剤が通常１〜３モルの割合で用いられる。
該反応の反応温度は、通常−２０〜３０℃の範囲であり、反応時間は通常０．１〜１２時間の範囲である。
反応終了後は、反応混合物を有機溶媒で抽出し、有機層を必要に応じて還元剤（例えば亜硫酸ナトリウム、チオ硫酸ナトリウム）の水溶液、塩基（例えば炭酸水素ナトリウム）の水溶液で洗浄し、乾燥、濃縮する等の後処理操作を行うことにより、化合物（４−ｄ）を単離することができる。単離された化合物（４−ｄ）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 28)
Among the compounds (4), the compound (4-d) can be produced by reacting the compound (4-c) in the presence of an oxidizing agent.

[Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ³² , A ¹ and A ² represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, acetic acid, water, and mixtures thereof.
Examples of the oxidizing agent used in the reaction include carboxylic acid peroxides such as 3-chloroperbenzoic acid.
An oxidizing agent is normally used in the ratio of 1-3 mol with respect to 1 mol of compounds (4-c).
The reaction temperature of the reaction is usually in the range of -20 to 30 ° C, and the reaction time is usually in the range of 0.1 to 12 hours.
After completion of the reaction, the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried, The compound (4-d) can be isolated by performing post-treatment operations such as concentration. The isolated compound (4-d) can be further purified by chromatography, recrystallization and the like.

［式中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ａ¹及びＡ²は前記と同じ意味を表す。］
（工程Ｍ１−１）
化合物（Ｍ２）は、化合物（Ｍ１）とニトロ化剤の存在下で反応させることにより製造することができる。
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばクロロホルム等の脂肪族ハロゲン化炭化水素類、酢酸、濃硫酸、濃硝酸、水及びこれらの混合物が挙げられる。
反応に用いられるニトロ化剤としては、例えば濃硝酸等が挙げられる。
化合物（Ｍ１）１モルに対して、ニトロ化剤が通常１〜３モルの割合で用いられる。
該反応の反応温度は、通常−１０〜１００℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を水に注加し、有機溶媒で抽出し、有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（Ｍ２）を単離することができる。単離された化合物（Ｍ２）は、クロマトグラフィー、再結晶等によりさらに精製することもできる。 The intermediate of the active compound can be produced, for example, by the following method.
(Intermediate production method 1)
Compound (2) can be produced by the following method.

[Wherein, R ⁵ , R ⁶ , R ⁷ , A ¹ and A ² represent the same meaning as described above. ]
(Process M1-1)
Compound (M2) can be produced by reacting compound (M1) with a nitrating agent.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as chloroform, acetic acid, concentrated sulfuric acid, concentrated nitric acid, water, and mixtures thereof.
Examples of the nitrating agent used in the reaction include concentrated nitric acid.
The nitrating agent is usually used at a ratio of 1 to 3 moles relative to 1 mole of the compound (M1).
The reaction temperature of the reaction is usually in the range of −10 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M2) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M2) can be further purified by chromatography, recrystallization and the like.

(Process M1-2)
Compound (2) can be produced by reacting compound (M2) with hydrogen in the presence of a hydrogenation catalyst.
The reaction is usually performed in a hydrogen atmosphere at 1 to 100 atm, usually in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF and 1,4-dioxane, esters such as ethyl acetate and butyl acetate, alcohols such as methanol and ethanol, water, and a mixture thereof.
Examples of the hydrogenation catalyst used in the reaction include transition metal compounds such as palladium carbon, palladium hydroxide, Raney nickel, and platinum oxide.
Hydrogen is usually used in a proportion of 3 mol and a hydrogenation catalyst is usually used in a proportion of 0.001 to 0.5 mol with respect to 1 mol of the compound (M1).
This reaction can also be carried out by adding an acid (such as a base) as necessary.
The reaction temperature of the reaction is usually in the range of -20 to 100 ° C, and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (2) can be isolated by performing post-treatment operations such as filtration of the reaction mixture, extraction with an organic solvent as necessary, and drying and concentration of the organic layer. The isolated compound (2) can be further purified by chromatography, recrystallization and the like.

  The active compound contained in the composition of the present invention may be one type or two or more types. Preferably they are 1 type or more and 3 types or less.

The respiratory inhibition compound used in combination with the active compound in the composition of the present invention will be described.
Azoxystrobin is number 52 in “The Pesticide Manual, Fifteenth Edition” (edited by Clive Tomlin, published by The British Crop Protection Council and The Royal Society of Chemistry, 2009). And is commercially available.
Orisatrobin is described in No. 634 of “The Pesticide Manual, Fifteenth Edition” (edited by Clive Tomlin, published by The British Crop Protection Council and The Royal Society of Chemistry, 2009). And are commercially available.
Ferimzone is described in No. 374 of “The Pesticide Manual, Fifteenth Edition” (edited by Clive Tomlin, published by The British Crop Protection Council and The Royal Society of Chemistry, 2009). And are commercially available.
Frametopil is listed in No. 436 of “The Pesticide Manual, Fifteenth Edition” (edited by Clive Tomlin, published by The British Crop Protection Council and The Royal Society of Chemistry, 2009). And are commercially available.
Flutolanil is described in No. 421 of “The Pesticide Manual, Fifteenth Edition” (edited by Clive Tomlin, published by The British Crop Protection Council and The Royal Society of Chemistry, 2009). And are commercially available.
The compound represented by the formula (A) is a compound described in International Publication No. 03/10149 pamphlet, and can be produced, for example, by the method described in the publication.
The respiratory inhibition compound contained in the composition of the present invention may be one kind or two or more kinds. Preferably they are 1 type or more and 3 types or less.

The active compound and the respiratory inhibition compound may exist in geometric isomers and / or stereoisomers, and the present invention includes each of these isomers and mixtures of these isomers.
In addition, the active compound and the respiratory inhibition compound may form an agrochemically acceptable salt. Examples of such salts include inorganic bases (for example, alkali metals such as sodium, potassium and lithium, alkaline earth metals such as calcium and magnesium, ammonia), and organic bases (for example, pyridine, collidine, triethylamine, triethanol). Amines), inorganic acids (eg hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, sulfuric acid, perchloric acid etc.), organic acids (eg formic acid, acetic acid, tartaric acid, malic acid, citric acid, oxalic acid) , Succinic acid, benzoic acid, picric acid, methanesulfonic acid, p-toluenesulfonic acid and the like). In the present invention, the active compound or the respiratory inhibition compound includes salts thereof.

  In the composition of the present invention, the ratio between the active compound and the respiratory inhibitory compound is a weight ratio (= active compound: respiratory inhibitory compound), usually 0.1: 99.9 to 99.9: 0.1. , Preferably in the range of 20:80 to 80:20.

In general, the composition of the present invention contains a carrier to be described later, and is a preparation that can be taken by an agrochemical or animal medicine.
The composition of the present invention comprises dissolving or dispersing the active compound and the respiratory inhibiting compound in a suitable liquid carrier, mixing or adsorbing the active compound and the respiratory inhibiting compound with a suitable solid carrier or ointment base, For example, the following dosage forms can be prepared by a known method such as mixing or dispersing the active compound and the respiratory inhibiting compound in a suitable gaseous carrier.
The above dosage forms include emulsions, liquids, microemulsions, flowables, oils, wettable powders, granular wettable powders, powders, granules, fine granules, seed coating agents, seed soaking agents, smoke agents, tablets, Microcapsules, sprays, aerosols, carbon dioxide preparations, heat transpiration agents such as mosquito coils, electric mosquito mats, liquid electric mosquito traps, EW agents, ointments, poison baits, capsules, pellets, films, injections, coating agents, Examples include resin preparations and shampoo preparations.
In the preparation, if necessary, auxiliary agents for formulation such as emulsifiers, suspending agents, spreading agents, penetrating agents, wetting agents, thickening agents, stabilizers, fixing agents, binders, dispersing agents, coloring agents and the like. It may be added.

  Examples of the liquid carrier include water, alcohols (methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol, phenoxyethanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), aromatic hydrocarbons (Toluene, xylene, ethylbenzene, dodecylbenzene, phenylxylylethane, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, isopropyl myristate, Ethyl oleate, diisopropyl adipate, diisobutyl adipate, propylene glycol monomethyl ether acetate, etc.), nitriles (acetonitrile, isobutyro Tolyl), ethers (diisopropyl ether, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, etc. ), Acid amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), sulfoxides (dimethylsulfoxide, etc.), propylene carbonate and vegetable oil (Soybean oil, cottonseed oil, etc.).

  Examples of solid carriers used for formulation include clays (kaolin clay, diatomaceous earth, bentonite, fusami clay, acidic clay), synthetic hydrous silicon oxide, talc, ceramics, and other inorganic minerals (sericite, quartz, sulfur). , Activated carbon, calcium carbonate, hydrated silica, etc.), fine fertilizers such as chemical fertilizers (ammonium sulfate, phosphorous acid, ammonium nitrate, urea, ammonium chloride, etc.) and granular materials.

  Examples of the gaseous carrier include fluorocarbon, butane gas, LPG (liquefied petroleum gas), dimethyl ether, and carbon dioxide gas.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyethylene glycol fatty acid ester, and the like, and alkyl sulfonates, alkyl benzene sulfonates, alkyl sulfates, and the like. An ionic surfactant is mentioned.

  Examples of other adjuvants for preparation include fixing agents, dispersants, colorants and stabilizers, such as casein, gelatin, saccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, Synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.), PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (2-tert- And a mixture of butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol).

  In addition to the present active compound and the present respiratory inhibitory compound, the composition of the present invention comprises an insecticide, acaricide, nematicide, fungicide, plant hormone agent, plant growth regulator, herbicide, synergist or safener. An agent may be contained.

The content ratio of the active compound and the respiratory inhibition compound in the composition of the present invention is usually 0.01 to 95% by weight, preferably about 0.1 to 90% by weight, more preferably, based on the total amount of the composition of the present invention. About 5 to 70% by weight.
Specifically, when the composition of the present invention is in the form of an emulsion, solution, wettable powder, or granular wettable powder, the content is usually about 1 to 90% by weight with respect to the total amount of the composition of the present invention. %, Preferably about 5 to 50% by weight. When the composition of the present invention is in the form of oil or powder, the content is usually about 0.1 to 50% by weight, preferably about 0.1 to 20% by weight. When the composition of the present invention is in the form of granules, the content is usually about 0.1 to 50% by weight, preferably about 0.5 to 20% by weight.
The other pesticidal active ingredient (for example, insecticide, herbicide, acaricide and / or fungicide) blended in the composition of the present invention is preferably about 1 to 80% by weight based on the total amount of the composition of the present invention. More preferably, it is about 1 to 20% by weight.
The content of additives other than the above active ingredients varies depending on the type or content of the pesticidal active ingredient or the dosage form of the preparation, but is usually about 0.001 to 99.9% by weight, preferably about 1 to 99% by weight. is there. For example, the surfactant is usually about 1 to 20% by weight, preferably about 1 to 15% by weight, the flow aid is about 1 to 20% by weight, and the carrier is about 1 to 90% by weight with respect to the total amount of the composition of the present invention. %, Preferably about 1 to 70% by weight can be added. In the case of a liquid preparation, the surfactant is usually added in an amount of about 1 to 20% by weight, preferably about 1 to 10% by weight, and about 20 to 90% by weight of water based on the total amount of the composition of the present invention. . In addition, emulsions, wettable powders, granular wettable powders, and the like can be sprayed by appropriately increasing the dilution with water or the like (for example, about 100 to 5000 times).

  Examples of harmful animals for which the composition of the present invention exhibits a controlling effect include the following harmful arthropods and harmful gastropods.

  Hemiptera: Pepper (Laodelphax striatellus), brown planthopper (Nilaparvata lugens), leafhopper (Sogatella furcifera) and other species, Nephotettix cincticeps, Nephotettip Leafhoppers, cotton aphids (Aphis gossypii), peach aphids (Myzus persicae), radish aphids (Brevicoryne brassicae), snowy aphids (Aphis spiraecola), tulip mustard aphids (Macrosiphum euphorbiae), potato aphids Aphids such as aphids (Rhopalosiphum padi), citrus aphids (Toxoptera citricidus), peach beetles (Hyalopterus pruni), Nezara antennata, hosohelika Bugs such as Riptortus clavetus, Leptocorisa chinensis, Eysarcoris parvus, Halyomorpha mista, Trialeurodes vaporarioa, desmale taba, desm citri), whiteflies such as honey beetle (Aleurocanthus spiniferus), Aonidiella aurantii, sanhoze scale (Comstockaspis perniciosa), citrus snow scale (Unaspis citri), ceroplastes rubens pur, sisel ), Scale insects (Planococcus kraunhiae), scale insects (Pseudococcus longispinis), scale insects (Pseudaulacaspis pentagona), and other species such as scale insects (Cimex lec) tularius) and other bed bugs and whales.

  Lepidopterous insects: Chilo suppressalis, Tryporyza incertulas, Cnaphalocrocis medinalis, Notarcha derogata, Plodia interpunctella, Odaltrihis, Ostrinia furnacalis, Ostrinia furnacalis Common moths such as Pediasia teterrellus, Spodoptera litura, Spodoptera exigua, Pseudaletia separata, Mamestra brassicae, Mamestra brassicae, Agrotis ipsila, Agrotis ipsila Heliotis genus, Helicoberpa genus moths, white butterflies (Pieris rapae) squirrels, Adoxofies genus, Grapholita molesta, bean squirrel (Leguminivora glycinivorella), azoxa yam Moth (Matsumuraeses azukivora), apple wolfberry (Adoxophyes orana fasciata), tea wolfberry (Adoxophyes honmai.), Chamonaki (Homona magnanima), midarekamonmon (Archips fuscocupreanus), codling moth (Cydia moth) , Chasohosuga (Caloptilia theivora), Kinsohosoga (Phyllonorycter ringoneella), etc ), Spits such as Pectinophora gossypiella, Potatoes such as Phthhorimaea operculella, Hitritria such as Hyphantria cunea, Hiros such as Tinea translucens, Tineola bisselliella, etc.

  Thrips of the order: Thrips parmi, Scirtothrips dorsalis, Thrips tabaci, and ella F.

  Diptera: Culex pipiens pallens, Culex tritaeniorhynchus, Culex quinquefasciatus, etc., Aedes aegypti, Aedes albopictus, etc. Genus Anopheles, Chironomidae, Musca domestica, Muscina stabulans, and other houseflies, Drosophila, Drosophila, Drosophila, Delia platura, Delia antiqua, Drosophila (Agromyza oryzae), rice leaflet (Hydrellia griseola), tomato leaffly, (Liriomyza sativae), leafworm (Liriomyza trifolii), leafworm (Chromatomyia horticola) and other leafhoppers (Chromatomyia horticola), Flies, fruit flies (Dacus cucurbitae), fruit flies such as Ceratitis capitata, fruit flies, fruit flies such as Megaselia spiracularis trigonus) and other species such as flies and flies.

  Coleoptera: Western corn root worms (Diabrotica virgifera virgifera), Southern corn root worms (Diabrotica undecimpunctata howardi), corn root worms, Anomala cuprea, Anomala rufocuprea, Japanese beetle (Popillia japonica) Moss, maize weevil (Sitophilus zeamais), rice weevil (Lissorhoptrus oryzophilus), weevil (Callosobruchuys chienensis), weevil (Echinocnemus squameus), cotton weevil (Anthonomus grandis), tussophyllum tuss Tenebrio molitor, Tribolium castaneum and other species, Oulema oryzae, Aulacophora femoralis, Phyllotreta striolata, co Leaf beetles such as Leptinotarsa decemlineata, beetles such as Anthrenus verbasci, beetles such as Dermestes maculates, beetles such as tobacco larva (Lasioderma serricorne) Epiracuna, Caterpillars such as Lyctus brunneus, Tomicus piniperda, Nagashimushi, Leopardia, Anoplophora malasiaca, etc. (Paederus fuscipes) etc.

  Pterodoptera: Locusta migratoria, Gryllotalpa africana, Oxya yezoensis, Oxya japonica, crickets, etc.

  Lepidoptera: Cat fleas (Ctenocephalides felis), Dog fleas (Ctenocephalides canis), Human fleas (Pulex irritans), Xenopsylla cheopis, etc.

  Lice pests: white lice (Pediculus humanus corporis), white lice (Phthirus pubis), cattle lice (Haematopinus eurysternus), sheep lice (Dalmalinia ovis), pig lice (Haematopinus suis), etc.

  Hymenopteran pests: Monomorium pharaosis, Formica fusca japonica, Ruriari (Ochetellus glaber), Apricot worm (Pristomyrmex pungens), Pheidole noda, Acromyrmex spp., Opis sp (len) Such as ants, hornets, scallops, bees (Athalia rosae), Japanese bees (Athalia japonica), and the like.

Cockroach eye insects: German cockroach (Blattella germanica), Black cockroach (Periplaneta fuliginosa), American cockroach (Periplaneta americana), Great cockroach (Periplaneta brunnea), Great cockroach (Blatta orientalis), etc.
Termite insect pests: Yamato termite (Reticulitermes speratus), termite (Coptotermes formosanus), American white termite (Incisitermes minor), scallop termite (Cryptotermes domesticus), taiwan termite (Odontotermes formosanus), red ant termite (hunsterm termite) Glyptotermes satsumensis, Glyptotermes nakajimai, Caterpillar (Glyptotermes fudamcus), White termite (Glyptotermes kodamai), Ants (Glyptotermes kushimensis), Japanese termites (pants) miyatakei), white termite (Reticulitermes flaviceps amamianus), common termite (Reticulitermes sp.), white termite (Nasutitermes takasagoensis), white termite (Pericapri) termes nitobei), Sinocapritermes mushae, Reticuliterumes flavipes, Reticulitermes hesperus, Reticulitermes virginicus, Reticulitermes tibialis, Heterotermes aureus, Zootermopsis nevadensis and the like.

  Acarid pests: Nite spider mite (Tetranychus urticae), Kanzawa spider mite (Tetranychus kanzawai), Scarlet spider mite (Panonychus citri) Apple spider mite (Panonychus ulmi), Oligonicus spp. Tomato rustic mites (Aculops lycopersici), Chinese radish mites (Calacarus carinatus), Chinese radish mites (Acaphylla theavagrans), Green radish mites (Eriophyes chibaensis), Apple rustic mites (Aculus schlechtendali), mussels photicid mites Scarlet mites (Brevipalpus phoenicis) and other spider mites, mosquito spider mites (Haemaphysalis longicornis), Scarlet tick (Haemaphysalis flava), Dermacentor taiwanicus, Scarlet mite ( Tick such as Ixodes ovatus, Tickling tick (Ixodes persulcatus), Black-legged tick (Ixodes scapularis), Tick (Boophilus microplus), Rhipicephalus sanguineus, Tyrophagus putrescentia, Tyrophagus putrescentia ) And other mites, Dermatophagoides farinae, Dermatophagoides ptrenyssnus, etc. ), Cucumbers such as Ornithonyssus sylvairum, dermatoyssus gallinae, and tsutsugamushi such as Leptotrombidium akamushi. Spiders such as Chiracanthium japonicum and Latrodectus hasseltii.

Lip and limb class: Thereuonema hilgendorfi, Scolopendra subspinipes, etc.
Double-legged class: Japanese red millipede (Oxidus gracilis), Japanese red millipede (Nedyopus tambanus).
Isopods: Armadillidium vulgare, etc.
Gastropods: Limax marginatus, Limax flavus, etc.

The pest control method according to the present invention (hereinafter sometimes referred to as the “control method of the present invention”) is to apply an effective amount of the active compound and the respiratory inhibition compound to the pest or the habitat of the pest. Apply.
In the control method of the present invention, an effective amount of the present active compound and the present respiratory inhibiting compound is applied to a plant, soil for cultivating a plant, hydroponics solution, medium or the like.
Pests can be controlled by the control method of the present invention.
In the control method of the present invention, the active compound and the respiratory inhibitory compound can be applied as they are without adding any other components, and the active compound and the respiratory inhibitory compound can be used together with the above-mentioned insecticides, acaricides, Other drugs such as nematicides and bactericides may be applied, or the active compound and the respiratory inhibition compound may be used in combination with natural enemy organisms or natural enemy microorganisms. The active compound and the respiratory inhibition compound may be applied separately at the same time, but are usually applied as the composition of the present invention from the viewpoint of simplicity during application.
Examples of habitats of harmful animals include plants, paddy fields, dry fields, fields, tea gardens, orchards, non-agricultural lands, houses, seedling trays and seedling boxes, seedling culture soil and seedling mats, hydroponic liquids in hydroponic farms, etc. It is done.
Examples of plants to be applied include foliage, seeds, seed pods, bulbs, and seedlings. Here, the bulb means a bulb, a bulb, a rhizome, a tuber, a tuberous root, and a root support body.
In the control method of the present invention, the active compound and the respiratory inhibition compound can be applied to harmful animals, harmful animal habitats, etc. by contacting or ingesting the above harmful animals in the same manner as conventional harmful animal control agents. can do.
Examples of such application methods include spraying treatment, soil treatment, seed treatment, and hydroponic liquid treatment.
The above-mentioned spraying treatment, for example, exerts a controlling effect on harmful animals by spraying active ingredients (this active compound and this respiratory inhibiting compound) on the surface of plants such as foliage spray, trunk spray, etc. or harmful animals themselves. It is a processing method.
The above-mentioned soil treatment is, for example, a treatment that directly controls harmful animals by giving an active ingredient to the rhizosphere of the plant to be protected, or controls the harmful animals by penetrating and transferring the active ingredients to the inside of the plant. Is the method.
Specifically, the above-mentioned soil treatment includes planting hole treatment, plant source treatment, grooving treatment, rowing treatment, rowing treatment, full surface treatment, side row treatment, water surface treatment, other soil spraying treatment, and other irrigation. Processing, seedling box processing, seedling tray processing, seedbed processing, bed soil mixing processing, and the like can be mentioned.
The seed treatment is, for example, a treatment method that exerts a controlling effect on harmful animals by treating the seed, seed pod or bulb of the plant to be protected directly or in the vicinity thereof with an active ingredient. Specific examples of the seed treatment include spraying, smearing, dipping, impregnation, coating, film coating, and pellet coating.
The above-mentioned hydroponic liquid treatment means, for example, that the plant is harmful by treating the hydroponic liquid etc. with the active ingredient in order to infiltrate and transfer the active ingredient from the root of the plant to be protected to the inside of the plant. This is a treatment method that protects animals from damage. Specific examples of the hydroponic liquid treatment include mixing a hydroponic liquid and mixing a hydroponic liquid.

The pest control method of the present invention can be carried out on agricultural land such as fields, paddy fields, lawns, orchards, or non-agricultural land.
When this active compound and this respiratory inhibitory compound are used for the control of harmful animals in the agricultural field, the doses of this active compound and this respiratory inhibitory compound are the type and extent of harmful animals to be controlled, their occurrence, Although it can be changed over a wide range according to the application time, application place, application method, weather conditions, etc., it is generally 1 to 10,000 g per 10,000 m ² .
Emulsions, wettable powders, flowables and the like are usually diluted with water so that the concentration of the active compound and the respiratory inhibitory compound is 0.01 to 10000 ppm. Apply as is.

  The active compound, the respiratory inhibition compound and the water dilution thereof may be sprayed directly on harmful animals or plants, or may be subjected to the soil treatment described above.

  The active compound and the respiratory inhibiting compound can be applied by a method such as wrapping around a plant as a resin preparation processed into a sheet or string, stretching it in the vicinity of the plant, or laying it on the stock soil.

The composition of the present invention can be used in farmland where the following “crop” is cultivated.
Agricultural crops: corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, sugar beet, rapeseed, sunflower, sugarcane, tobacco, etc. Vegetables: Solanum vegetables (eggplants, tomatoes, peppers, peppers, potatoes, etc.), cucurbits (cucumbers, pumpkins, zucchini, watermelons, melons, etc.), cruciferous vegetables (radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage) , Mustard, broccoli, cauliflower, etc.), asteraceae vegetables (burdock, shungiku, artichokes, lettuce, etc.), liliaceae vegetables (leek, onion, garlic, asparagus), celery family vegetables (carrot, parsley, celery, American scallop, etc.) ), Red crustacean vegetables (spinach, chard, etc.), persimmon vegetables (perilla, mint, basil, etc.), strawberry, sweet potato, yam, taro, etc.
Fruit trees: berries (apples, pears, Japanese pears, quince, quince, etc.), nuclear fruits (peaches, plums, nectarines, ume, sweet cherry, apricots, prunes, etc.), citrus (satsuma mandarin, orange, lemon, lime, grapefruit) ), Nuts (chestnut, walnut, hazel, almond, pistachio, cashew nut, macadamia nut, etc.), berries (blueberry, cranberry, blackberry, raspberry, etc.), grape, oyster, olive, loquat, banana, coffee, Date palm, coconut palm, etc.
Trees other than fruit trees: tea, mulberry, flowering trees (Satsuki, camellia, hydrangea, sasanqua, shikimi, sakura, yurinoki, crape myrtle, eustoma, etc.), roadside trees (ash, birch, dogwood, eucalyptus, ginkgo, lilac, maple, oak) , Poplar, redwood, fu, sycamore, zelkova, black beetle, cinnamon, tsuga, rat, pine, spruce, yew), oil trees (Jatrophacurcas, oil palm), etc.
Lawn: Shiba (Nasis, Pleurotus, etc.), Bermudagrass (Neurodonidae, etc.), Bentgrass (Oleoptera, Hykonukagusa, Odonoptera, etc.), Bluegrass (Nagahagusa, Oosuzunokatabira, etc.), Fescue (Oonishi nokegusa, Drosophila, etc.) , Grass, etc.), ryegrass (rat, wheat, etc.), anemonefish, blue whale, etc.
Other: Flowers, foliage plants, etc.

  “Crop” also includes genetically modified crops.

When this active compound and this respiratory inhibiting compound are used for the control of harmful animals (eg flies, mosquitoes, cockroaches) living in the house, the dosage of this active compound and this respiratory inhibiting compound should be applied on the surface. When it is applied, it is usually 0.01 to 1000 mg per 1 m ^{2 of} processing area, and when applied to a space, it is usually 0.01 to 500 mg per 1 m ^{3 of} processing space.
Emulsions, wettable powders, and flowables are usually diluted with water so that the concentration of the active compound and respiratory inhibitory compound is 0.1 to 1000 ppm, and then applied to oils, aerosols, smoke agents, poison baits. Apply the agent as it is.

  Hereinafter, the present invention will be described in more detail with reference to production examples of the active compound, reference production examples thereof, formulation examples, and test examples, but the present invention is not limited thereto.

本活性化合物［１］
¹H-NMR (CDCl₃) δ: δ8.90-8.87(m, 2H), 8.08(s, 1H), 7.74-7.70(m, 3H), 4.03(s, 3H) The production of this active compound will be shown as production examples.
Production Example 1
0.59 g of 1,1,3,3-tetrafluoro-N-methyl-1,3-dihydroisobenzofuran-5,6-diamine, 0.63 g of sodium hydroxy-pyridin-4-yl-methanesulfonate and 5 ml of DMF The mixture was heated and stirred at 120 ° C. for 1 hour. After cooling to room temperature, saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted 3 times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 5,5,7,7-tetrafluoro-1-methyl-2- (pyridin-4-yl) -5,7-dihydro-1H-furo [3 ′, 4 ′. : 4,5] benzo [1,2-d] imidazole (hereinafter referred to as the present active compound [1]) 0.71 g was obtained.

The active compound [1]
¹ H-NMR (CDCl ₃ ) δ: δ8.90-8.87 (m, 2H), 8.08 (s, 1H), 7.74-7.70 (m, 3H), 4.03 (s, 3H)

本活性化合物［２］
¹H-NMR (CDCl₃) δ: 8.85(dd, J=4.4, 1.5Hz, 2H), 7.93(d, J=8.5Hz, 1H), 7.75-7.71(m, 3H), 7.61(dd, J=8.7, 1.3Hz, 1H), 3.99(s, 3H) Production Example 2
In place of 1,1,3,3-tetrafluoro-N-methyl-1,3-dihydroisobenzofuran-5,6-diamine, N2-methyl-4-trifluoromethylbenzene-1,2-diamine was used, In accordance with the method described in Production Example 1, 1-methyl-2- (pyridin-4-yl) -6-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [2]) is obtained. It was.

The active compound [2]
¹ H-NMR (CDCl ₃ ) δ: 8.85 (dd, J = 4.4, 1.5Hz, 2H), 7.93 (d, J = 8.5Hz, 1H), 7.75-7.71 (m, 3H), 7.61 (dd, J = 8.7, 1.3Hz, 1H), 3.99 (s, 3H)

本活性化合物［３］
¹H-NMR (CDCl₃) δ: 8.86-8.84(m, 2H), 8.14-8.13(m, 1H), 7.74-7.71(m, 2H), 7.66-7.62(m, 1H), 7.53(d, J=8.0Hz, 1H), 3.98 (s, 3H) Production Example 3
In place of 1,1,3,3-tetrafluoro-N-methyl-1,3-dihydroisobenzofuran-5,6-diamine, N1-methyl-4-trifluoromethylbenzene-1,2-diamine was used, In accordance with the method described in Production Example 1, 1-methyl-2- (pyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [3]) is obtained. It was.

The active compound [3]
¹ H-NMR (CDCl ₃ ) δ: 8.86-8.84 (m, 2H), 8.14-8.13 (m, 1H), 7.74-7.71 (m, 2H), 7.66-7.62 (m, 1H), 7.53 (d, J = 8.0Hz, 1H), 3.98 (s, 3H)

本活性化合物［４］
¹H-NMR (CDCl₃) δ: 8.73-8.71(m, 1H), 8.68-8.65(m, 1H), 8.15(d, J=0.7Hz, 1H), 7.72(t, J=5.4Hz, 1H), 7.65(dd, J=8.7, 0.7Hz, 1H), 7.56(d, J=8.7Hz, 1H), 3.85(d, J=2.9Hz, 3H) Production Example 4
A mixture of 1.90 g of N1-methyl-4-trifluoromethylbenzene-1,2-diamine, 1.49 g of 3-fluoropyridine-4-carbaldehyde, 3.12 g of sodium hydrogen sulfite and 20 ml of DMF was added at 80 ° C. The mixture was stirred with heating for 1 hour, and then stirred at 120 ° C. for 2 hours. After cooling to room temperature, saturated aqueous ammonium chloride solution was added, and the mixture was extracted 3 times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [4]). 1.83 g was obtained.

The active compound [4]
¹ H-NMR (CDCl ₃ ) δ: 8.73-8.71 (m, 1H), 8.68-8.65 (m, 1H), 8.15 (d, J = 0.7Hz, 1H), 7.72 (t, J = 5.4Hz, 1H ), 7.65 (dd, J = 8.7, 0.7Hz, 1H), 7.56 (d, J = 8.7Hz, 1H), 3.85 (d, J = 2.9Hz, 3H)

本活性化合物［５］
¹H-NMR (CDCl₃) δ: 8.83(s, 1H), 8.72(dd, J=4.8, 0.5Hz, 1H), 8.15-8.13(m, 1H), 7.66(dd, J=8.6, 1.6Hz, 1H), 7.57-7.53(m, 2H), 3.77(s, 3H) Production Example 5
Using 3-chloropyridine-4-carbaldehyde instead of 3-fluoropyridine-4-carbaldehyde according to the method described in Production Example 4, 2- (3-chloropyridin-4-yl) -1- Methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [5]) was obtained.

The active compound [5]
¹ H-NMR (CDCl ₃ ) δ: 8.83 (s, 1H), 8.72 (dd, J = 4.8, 0.5Hz, 1H), 8.15-8.13 (m, 1H), 7.66 (dd, J = 8.6, 1.6Hz , 1H), 7.57-7.53 (m, 2H), 3.77 (s, 3H)

本活性化合物［６］
¹H-NMR (CDCl₃) δ: 8.70(d, J=0.7Hz, 1H), 8.64(d, J=5.1Hz, 1H), 8.13-8.12(m, 1H), 7.66-7.62(m, 1H), 7.54-7.51(m, 1H), 7.33(d, J=4.6Hz, 1H), 3.72(s, 3H), 2.33(s, 3H) Production Example 6
A mixture of 0.38 g of N1-methyl-4-trifluoromethylbenzene-1,2-diamine, 0.33 g of 3-methylisonicotinic acid, 0.46 g of WSC and 10 ml of pyridine was heated and stirred at 120 ° C. for 5 hours. After cooling to room temperature, water was added and extracted three times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. A mixture of 0.57 g of p-toluenesulfonic acid monohydrate and 10 ml of toluene was added to the residue, and the mixture was stirred with heating at 80 ° C. for 1 hour and 120 ° C. for 2 hours. After cooling to room temperature, saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted 3 times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 1-methyl-2- (3-methylpyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the active compound [6]). 0.48 g was obtained.

The active compound [6]
¹ H-NMR (CDCl ₃ ) δ: 8.70 (d, J = 0.7Hz, 1H), 8.64 (d, J = 5.1Hz, 1H), 8.13-8.12 (m, 1H), 7.66-7.62 (m, 1H ), 7.54-7.51 (m, 1H), 7.33 (d, J = 4.6Hz, 1H), 3.72 (s, 3H), 2.33 (s, 3H)

本活性化合物［７］
¹H-NMR (CDCl₃) δ: 8.73(s, 1H), 8.64(d, J=4.8Hz, 1H), 8.13-8.12(m, 1H), 7.66-7.62(m, 1H), 7.52(d, J=8.5Hz, 1H), 7.29(d, J=5.1Hz, 1H), 3.70(s, 3H), 2.69(q, J=7.6Hz, 2H), 1.13(t, J=7.6Hz, 3H) Production Example 7
2- (3-Ethylpyridin-4-yl) -1-methyl-5-trifluoro was used according to the method described in Preparation Example 6 using 3-ethylisonicotinic acid instead of 3-methylisonicotinic acid. 0.47 g of methyl-1H-benzimidazole (hereinafter referred to as the present active compound [7]) was obtained.

The active compound [7]
¹ H-NMR (CDCl ₃ ) δ: 8.73 (s, 1H), 8.64 (d, J = 4.8Hz, 1H), 8.13-8.12 (m, 1H), 7.66-7.62 (m, 1H), 7.52 (d , J = 8.5Hz, 1H), 7.29 (d, J = 5.1Hz, 1H), 3.70 (s, 3H), 2.69 (q, J = 7.6Hz, 2H), 1.13 (t, J = 7.6Hz, 3H )

本活性化合物［８］
¹H-NMR (CDCl₃) δ: 8.53(s, 1H), 8.48(d, J=4.8Hz, 1H), 8.11(s, 1H), 7.61 (d, J=8.7Hz, 1H), 7.53(d, J=4.6Hz, 1H), 7.51(d, J=8.9 Hz, 1H), 3.98(s, 3H), 3.73(s, 3H) Production Example 8
To a mixture of 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole 0.30 g and DMF 10 ml was added sodium methoxide 0.16 g under ice cooling, The mixture was warmed to room temperature and stirred for 1.5 hours. Saturated aqueous ammonium chloride solution was added, and the mixture was extracted 3 times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 2- (3-methoxypyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [8]). 0.28 g was obtained.

The active compound [8]
¹ H-NMR (CDCl ₃ ) δ: 8.53 (s, 1H), 8.48 (d, J = 4.8Hz, 1H), 8.11 (s, 1H), 7.61 (d, J = 8.7Hz, 1H), 7.53 ( d, J = 4.6Hz, 1H), 7.51 (d, J = 8.9 Hz, 1H), 3.98 (s, 3H), 3.73 (s, 3H)

本活性化合物［９］
¹H-NMR (CDCl₃) δ: 8.50(s, 1H), 8.45(d, J=4.6Hz, 1H), 8.12-8.11(m, 1H), 7.62(dd, J=8.5, 1.5Hz, 1H), 7.54(d, J=4.6Hz, 1H), 7.52(d, J=8.5Hz, 1H), 4.24(q, J=7.0Hz, 2H), 3.75(s, 3H), 1.37(t, J=7.0Hz, 3H) Production Example 9
2- (3-Ethoxypyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole was used in accordance with the method described in Production Example 8 using sodium ethoxide instead of sodium methoxide. (Hereinafter referred to as the present active compound [9]).

The active compound [9]
¹ H-NMR (CDCl ₃ ) δ: 8.50 (s, 1H), 8.45 (d, J = 4.6Hz, 1H), 8.12-8.11 (m, 1H), 7.62 (dd, J = 8.5, 1.5Hz, 1H ), 7.54 (d, J = 4.6Hz, 1H), 7.52 (d, J = 8.5Hz, 1H), 4.24 (q, J = 7.0Hz, 2H), 3.75 (s, 3H), 1.37 (t, J = 7.0Hz, 3H)

本活性化合物［１０］
¹H-NMR (CDCl₃) δ: 8.51(s, 1H), 8.45(d, J=4.7, 1H), 8.11(d, J=0.7Hz, 1H), 7.62(d, J=8.7Hz, 1H), 7.54(d, J=4.7Hz, 1H), 7.52(d, J=8.7Hz, 1H), 4.11(t, J=6.6Hz, 2H), 3.74(d, J=0.7Hz, 3H), 1.80-1.69(m, 2H), 0.91(t, J=7.2Hz, 3H) Production Example 10
To a mixture of 0.36 g of 1-propanol and 6 ml of DMF, 0.24 g of 60% sodium hydride (oil) was added under ice-cooling and stirred for 10 minutes. After adding 0.35 g of 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole, the mixture was warmed to room temperature and further stirred for 1 hour. Saturated aqueous ammonium chloride solution was added, and the mixture was extracted 3 times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 1-methyl-2- (3-propoxypyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the active compound [10]). 0.36 g was obtained.

The active compound [10]
¹ H-NMR (CDCl ₃ ) δ: 8.51 (s, 1H), 8.45 (d, J = 4.7, 1H), 8.11 (d, J = 0.7Hz, 1H), 7.62 (d, J = 8.7Hz, 1H ), 7.54 (d, J = 4.7Hz, 1H), 7.52 (d, J = 8.7Hz, 1H), 4.11 (t, J = 6.6Hz, 2H), 3.74 (d, J = 0.7Hz, 3H), 1.80-1.69 (m, 2H), 0.91 (t, J = 7.2Hz, 3H)

本活性化合物［１１］
¹H-NMR (CDCl₃) δ: 8.51(s, 1H), 8.43(dd, J=4.8, 1.6Hz, 1H), 8.12(s, 1H), 7.62(d, J=8.5Hz, 1H), 7.55(dd, J=4.8, 1.3Hz, 1H), 7.52(d, J=8.5Hz, 1H), 4.72-4.64(m, 1H), 3.75(d, J=2.0Hz, 3H), 1.29(dd, J=6.1, 1.7Hz, 6H) Production Example 11
2- (3-Isopropoxypyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzen was used according to the method described in Preparation Example 10 using 2-propanol instead of 1-propanol. Imidazole (hereinafter referred to as the present active compound [11]) was obtained.

The active compound [11]
¹ H-NMR (CDCl ₃ ) δ: 8.51 (s, 1H), 8.43 (dd, J = 4.8, 1.6Hz, 1H), 8.12 (s, 1H), 7.62 (d, J = 8.5Hz, 1H), 7.55 (dd, J = 4.8, 1.3Hz, 1H), 7.52 (d, J = 8.5Hz, 1H), 4.72-4.64 (m, 1H), 3.75 (d, J = 2.0Hz, 3H), 1.29 (dd , J = 6.1, 1.7Hz, 6H)

本活性化合物［１２］
¹H-NMR (CDCl₃) δ: 8.58(s, 1H), 8.54(d, J=4.9Hz, 1H), 8.13-8.10(m, 1H), 7.64-7.59(m, 2H), 7.53(d, J=8.5Hz, 1H), 3.77(s, 3H), 1.12(s, J=4.8, 1.6Hz, 9H) Production Example 12
2- (3-tert-Butoxypyridin-4-yl) -1-methyl-5-trifluoromethyl-1H was used according to the method described in Production Example 10 using tert-butyl alcohol instead of 1-propanol. -Benzimidazole (hereinafter referred to as the present active compound [12]) was obtained.

The active compound [12]
¹ H-NMR (CDCl ₃ ) δ: 8.58 (s, 1H), 8.54 (d, J = 4.9Hz, 1H), 8.13-8.10 (m, 1H), 7.64-7.59 (m, 2H), 7.53 (d , J = 8.5Hz, 1H), 3.77 (s, 3H), 1.12 (s, J = 4.8, 1.6Hz, 9H)

本活性化合物［１３］
¹H-NMR (CDCl₃) δ: 8.59(d, J=4.6Hz, 1H), 8.55(s, 1H), 8.12(s, 1H), 7.66-7.60(m, 2H), 7.54(d, J=8.5Hz, 1H), 4.47(q, J=7.9Hz, 2H), 3.76(s, 3H) Production Example 13
In accordance with the method described in Production Example 10 using 1,2,2-trifluoroethanol instead of 1-propanol, 1-methyl-2- [3- (2,2,2-trifluoroethoxy)- Pyridin-4-yl] -5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [13]) was obtained.

The active compound [13]
¹ H-NMR (CDCl ₃ ) δ: 8.59 (d, J = 4.6Hz, 1H), 8.55 (s, 1H), 8.12 (s, 1H), 7.66-7.60 (m, 2H), 7.54 (d, J = 8.5Hz, 1H), 4.47 (q, J = 7.9Hz, 2H), 3.76 (s, 3H)

本活性化合物［１４］
¹H-NMR (CDCl₃) δ: 8.56(d, J=4.6Hz, 1H), 8.52(s, 1H), 8.13-8.11(m, 1H), 7.66-7.62(m, 1H), 7.60(d, J=4.6Hz, 1H), 7.54(d, J=8.0Hz, 1H), 5.97(tt, J=54.7, 3.9Hz, 1H), 4.37(td, J=13.0, 3.9Hz, 2H), 3.75(s, 3H) Production Example 14
2,2-Difluoroethanol was used instead of 1-propanol, and 2- [3- (2,2-difluoroethoxy) -pyridin-4-yl] -1-methyl was prepared according to the method described in Preparation Example 10. -5-Trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [14]) was obtained.

The active compound [14]
¹ H-NMR (CDCl ₃ ) δ: 8.56 (d, J = 4.6Hz, 1H), 8.52 (s, 1H), 8.13-8.11 (m, 1H), 7.66-7.62 (m, 1H), 7.60 (d , J = 4.6Hz, 1H), 7.54 (d, J = 8.0Hz, 1H), 5.97 (tt, J = 54.7, 3.9Hz, 1H), 4.37 (td, J = 13.0, 3.9Hz, 2H), 3.75 (s, 3H)

本活性化合物［１５］
¹H-NMR (CDCl₃) δ: 8.52(s, 1H), 8.50(s, 1H), 8.13-8.10(m, 1H), 7.63(dd, J=8.5, 1.4Hz, 1H), 7.60(d, J=4.8Hz, 1H), 7.53(d, J=8.5Hz, 1H), 4.75-4.60(m, 2H), 4.44-4.33(m, 2H), 3.76(s, 3H) Production Example 15
2- [3- (2-Fluoroethoxy) -pyridin-4-yl] -1-methyl-5-trimethyl is used according to the method described in Preparation Example 10 using 2-fluoroethanol instead of 1-propanol. Fluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [15]) was obtained.

The active compound [15]
¹ H-NMR (CDCl ₃ ) δ: 8.52 (s, 1H), 8.50 (s, 1H), 8.13-8.10 (m, 1H), 7.63 (dd, J = 8.5, 1.4Hz, 1H), 7.60 (d , J = 4.8Hz, 1H), 7.53 (d, J = 8.5Hz, 1H), 4.75-4.60 (m, 2H), 4.44-4.33 (m, 2H), 3.76 (s, 3H)

本活性化合物［１６］
¹H-NMR (CDCl₃) δ: 8.58(s, 1H), 8.47(d, J=4.6Hz, 1H), 8.12(d, J=0.7Hz, 1H), 7.60(dd, J= 8.5, 1.5Hz, 1H), 7.57(d, J=4.6Hz, 1H), 7.46(d, J=8.5Hz, 1H), 7.32-7.22(m, 5H), 5.21(s, 2H), 3.69(s, 3H) Production Example 16
2- (3-Benzyloxypyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole was used according to the method described in Preparation Example 10 using benzyl alcohol instead of 1-propanol. (Hereinafter referred to as the present active compound [16]).

The active compound [16]
¹ H-NMR (CDCl ₃ ) δ: 8.58 (s, 1H), 8.47 (d, J = 4.6Hz, 1H), 8.12 (d, J = 0.7Hz, 1H), 7.60 (dd, J = 8.5, 1.5 Hz, 1H), 7.57 (d, J = 4.6Hz, 1H), 7.46 (d, J = 8.5Hz, 1H), 7.32-7.22 (m, 5H), 5.21 (s, 2H), 3.69 (s, 3H )

本活性化合物［１７］
¹H-NMR (CDCl₃) δ: 8.70(s, 1H), 8.60(d, J=4.8Hz, 1H), 8.15-8.13(m, 1H), 7.64(dd, J=8.5, 1.7Hz, 1H), 8.53(d, J=8.5Hz, 1H), 8.38(d, J=4.8Hz, 1H), 3.74(s, 3H), 2.47(s, 3H) Production Example 17
1-Methyl-2- (3-methylthiopyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole was used according to the method described in Production Example 8 using methyl mercaptan sodium instead of sodium methoxide. (Hereinafter referred to as the present active compound [17]).

The active compound [17]
¹ H-NMR (CDCl ₃ ) δ: 8.70 (s, 1H), 8.60 (d, J = 4.8Hz, 1H), 8.15-8.13 (m, 1H), 7.64 (dd, J = 8.5, 1.7Hz, 1H ), 8.53 (d, J = 8.5Hz, 1H), 8.38 (d, J = 4.8Hz, 1H), 3.74 (s, 3H), 2.47 (s, 3H)

本活性化合物［１８］
¹H-NMR (CDCl₃) δ: 9.51(s, 1H), 8.96(d, J=4.8Hz, 1H), 8.14-8.12(m, 1H), 7.68(dd, J=8.8, 1.3Hz, 1H), 7.57(d, J=8.5Hz, 1H), 7.48(d, J=4.8Hz, 1H), 3.91(s, 3H), 3.18(s, 3H) Production Example 18
To a mixture of 1-methyl-2- (3-methylthiopyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole (0.49 g), methanol (5 ml) and water (10 ml) was added sodium periodate (0.65 g) under ice cooling. And then stirred at 40 ° C. for 1 hour. After cooling to room temperature, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium thiosulfate solution were added, and the mixture was extracted 3 times with chloroform. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue is subjected to silica gel column chromatography and described as 2- (3-methanesulfinylpyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the active compound [18]). ) 0.48 g was obtained.

The active compound [18]
¹ H-NMR (CDCl ₃ ) δ: 9.51 (s, 1H), 8.96 (d, J = 4.8Hz, 1H), 8.14-8.12 (m, 1H), 7.68 (dd, J = 8.8, 1.3Hz, 1H ), 7.57 (d, J = 8.5Hz, 1H), 7.48 (d, J = 4.8Hz, 1H), 3.91 (s, 3H), 3.18 (s, 3H)

本活性化合物［１９］
¹H-NMR (CDCl₃) δ: 9.45(s, 1H), 9.09(d, J=4.8Hz, 1H), 8.08(s, 1H), 7.66(d, J=8.2Hz, 1H), 7.55(d, J=8.2Hz, 1H), 7.51 (d, J=4.8Hz, 1H), 3.68(s, 3H), 3.34(s, 3H) Production Example 19
To a mixture of 1-methyl-2- (3-methylthiopyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole (0.60 g) and chloroform (9 ml), 69% 3-chloroperbenzoic acid 1. After adding 40 g, the mixture was stirred at room temperature for 2 hours. Thereafter, a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium thiosulfate solution were added, and the mixture was extracted three times with chloroform. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and described as 2- (3-methanesulfonylpyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the active compound [19]). ) 0.52 g was obtained.

The active compound [19]
¹ H-NMR (CDCl ₃ ) δ: 9.45 (s, 1H), 9.09 (d, J = 4.8Hz, 1H), 8.08 (s, 1H), 7.66 (d, J = 8.2Hz, 1H), 7.55 ( d, J = 8.2Hz, 1H), 7.51 (d, J = 4.8Hz, 1H), 3.68 (s, 3H), 3.34 (s, 3H)

本活性化合物［２０］
¹H-NMR (CDCl₃) δ: 8.76(s, 1H), 8.62(d, J=5.1Hz, 1H), 8.14-8.12(m, 1H), 7.65-7.62(m, 1H), 7.53(dd, J=8.7, 0.5Hz, 1H), 7.41(d, J=4.8Hz, 1H), 3.72(d, J=0.5Hz, 3H), 2.87(q, J=7.2Hz, 2H), 1.23(t, J=7.2Hz, 3H) Production Example 20
2- (3-Ethylthiopyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzen in accordance with the method described in Production Example 8 using ethyl mercaptan sodium instead of sodium methoxide Imidazole (hereinafter referred to as the present active compound [20]) was obtained.

The active compound [20]
¹ H-NMR (CDCl ₃ ) δ: 8.76 (s, 1H), 8.62 (d, J = 5.1Hz, 1H), 8.14-8.12 (m, 1H), 7.65-7.62 (m, 1H), 7.53 (dd , J = 8.7, 0.5Hz, 1H), 7.41 (d, J = 4.8Hz, 1H), 3.72 (d, J = 0.5Hz, 3H), 2.87 (q, J = 7.2Hz, 2H), 1.23 (t , J = 7.2Hz, 3H)

本活性化合物［２１］
¹H-NMR (CDCl₃) δ: 9.40 (s, 1H), 8.95(d, J=5.1Hz, 1H), 8.12-8.10(m, 1H), 7.68(dd, J=8.8, 1.3Hz, 1H), 7.57(d, J=8.8Hz, 1H), 7.49(d, J=5.1Hz, 1H), 3.89(s, 3H), 3.56-3.46(m, 1H), 3.21-3.10(m, 1H), 1.39(t, J=7.4Hz, 3H) Production Example 21
Instead of 1-methyl-2- (3-methylthiopyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole, 2- (3-ethylthiopyridin-4-yl) -1-methyl-5 2- (3-ethanesulfinylpyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole was prepared using trifluoromethyl-1H-benzimidazole according to the method described in Production Example 18. (Hereinafter referred to as the present active compound [21]).

The active compound [21]
¹ H-NMR (CDCl ₃ ) δ: 9.40 (s, 1H), 8.95 (d, J = 5.1Hz, 1H), 8.12-8.10 (m, 1H), 7.68 (dd, J = 8.8, 1.3Hz, 1H ), 7.57 (d, J = 8.8Hz, 1H), 7.49 (d, J = 5.1Hz, 1H), 3.89 (s, 3H), 3.56-3.46 (m, 1H), 3.21-3.10 (m, 1H) , 1.39 (t, J = 7.4Hz, 3H)

本活性化合物［２２］
¹H-NMR (CDCl₃) δ: 9.38(s, 1H), 9.08(d, J=4.9Hz, 1H), 8.09-8.06(m, 1H), 7.66(dd, J=8.4, 1.3Hz, 1H), 7.54(d, J=8.4Hz, 1H), 7.51(dd, J=4.9, 0.7Hz, 1H), 3.67(s, 3H), 3.45(q, J=7.4Hz, 2H), 1.29(t, J=7.4Hz, 3H) Production Example 22
Instead of 1-methyl-2- (3-methylthiopyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole, 2- (3-ethylthiopyridin-4-yl) -1-methyl-5 Using trifluoromethyl-1H-benzimidazole, 2- (3-ethanesulfonylpyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole according to the method described in Preparation Example 19 (Hereinafter referred to as the present active compound [22]).

The active compound [22]
¹ H-NMR (CDCl ₃ ) δ: 9.38 (s, 1H), 9.08 (d, J = 4.9Hz, 1H), 8.09-8.06 (m, 1H), 7.66 (dd, J = 8.4, 1.3Hz, 1H ), 7.54 (d, J = 8.4Hz, 1H), 7.51 (dd, J = 4.9, 0.7Hz, 1H), 3.67 (s, 3H), 3.45 (q, J = 7.4Hz, 2H), 1.29 (t , J = 7.4Hz, 3H)

本活性化合物［２３］
¹H-NMR (CDCl₃) δ: 8.83(s, 1H), 8.66(d, J=4.8Hz, 1H), 8.14-8.11(m, 1H), 7.64(dd, J=8.4, 1.3Hz, 1H), 7.53(d, J=8.4Hz, 1H), 7.45(d, J=4.8Hz, 1H), 3.70(s, 3H), 3.31(sep, J=6.7Hz, 1H), 1.17(d, J=6.7Hz, 6H) Production Example 23
2- (3-Isopropylthiopyridin-4-yl) -1-methyl-5-trifluoromethyl-1H- was used according to the method described in Production Example 10 except that 2-propanethiol was used instead of 1-propanol. Benzimidazole (hereinafter referred to as the present active compound [23]) was obtained.

The active compound [23]
¹ H-NMR (CDCl ₃ ) δ: 8.83 (s, 1H), 8.66 (d, J = 4.8Hz, 1H), 8.14-8.11 (m, 1H), 7.64 (dd, J = 8.4, 1.3Hz, 1H ), 7.53 (d, J = 8.4Hz, 1H), 7.45 (d, J = 4.8Hz, 1H), 3.70 (s, 3H), 3.31 (sep, J = 6.7Hz, 1H), 1.17 (d, J = 6.7Hz, 6H)

本活性化合物［２４］
¹H-NMR (CDCl₃) δ: 8.35(dd, J=5.3, 1.9Hz, 2H), 8.11(s, 1H), 7.80-7.77(m, 2H), 7.64(dd, J=8.5, 1.4Hz, 1H), 7.52(d, J=8.5Hz, 1H), 4.00(s, 3H) Production Example 24
After adding 0.52 g of 69% 3-chloroperbenzoic acid to a mixture of 0.42 g of 1-methyl-2- (pyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole and 8 ml of chloroform, The mixture was stirred with heating at ° C for 2 hours. After cooling to room temperature, saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted 3 times with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 1-methyl-2- (1-oxypyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the active compound [24]). 0.36 g was obtained.

The active compound [24]
¹ H-NMR (CDCl ₃ ) δ: 8.35 (dd, J = 5.3, 1.9Hz, 2H), 8.11 (s, 1H), 7.80-7.77 (m, 2H), 7.64 (dd, J = 8.5, 1.4Hz , 1H), 7.52 (d, J = 8.5Hz, 1H), 4.00 (s, 3H)

本活性化合物［２５］
¹H-NMR (CDCl₃) δ: 8.31(dd, J=5.4, 1.6Hz, 1H), 8.22-8.19(m, 1H), 8.13-8.11(m, 1H), 7.72(dd, J=8.3, 6.9Hz, 1H), 7.67-7.63(m, 1H), 7.55(d, J=8.7Hz, 1H), 3.86(d, J=2.7Hz, 3H) Production Example 25
Instead of 1-methyl-2- (pyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole, 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl- According to the method described in Production Example 24, using 1H-benzimidazole, 2- (3-fluoro-1-oxypyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole ( Hereinafter referred to as the present active compound [25]).

The active compound [25]
¹ H-NMR (CDCl ₃ ) δ: 8.31 (dd, J = 5.4, 1.6Hz, 1H), 8.22-8.19 (m, 1H), 8.13-8.11 (m, 1H), 7.72 (dd, J = 8.3, 6.9Hz, 1H), 7.67-7.63 (m, 1H), 7.55 (d, J = 8.7Hz, 1H), 3.86 (d, J = 2.7Hz, 3H)

本活性化合物［２６］
¹H-NMR(CDCl₃) δ: 8.45(dd, J=5.1, 0.7Hz, 1H), 8.14(d, J=0.7Hz, 1H), 7.67-7.63(m, 2H), 7.54(d, J=8.5Hz, 1H), 7.40-7.38(m,1H), 4.00(s,3H) Production Example 26
Using 2-fluoropyridine-4-carbaldehyde instead of 3-fluoropyridine-4-carbaldehyde according to the method described in Production Example 4, 2- (2-fluoropyridin-4-yl) -1- Methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [26]) was obtained.

The active compound [26]
¹ H-NMR (CDCl ₃ ) δ: 8.45 (dd, J = 5.1, 0.7Hz, 1H), 8.14 (d, J = 0.7Hz, 1H), 7.67-7.63 (m, 2H), 7.54 (d, J = 8.5Hz, 1H), 7.40-7.38 (m, 1H), 4.00 (s, 3H)

本活性化合物［２７］
¹H-NMR(CDCl₃) δ: 8.61(dd, J=5.1, 0.7Hz, 1H), 8.13(t, J=0.7Hz, 1H), 7.79(dd, J=1.5, 0.7Hz, 1H), 7.66(dd, J=5.1, 1.5Hz, 1H), 7.64(d, J=1.0Hz, 1H), 7.54(d, J=8.5Hz, 1H), 3.99(s, 3H) Production Example 27
Using 2-chloropyridine-4-carbaldehyde instead of 3-fluoropyridine-4-carbaldehyde, according to the method described in Production Example 4, 2- (2-chloropyridin-4-yl) -1- Methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [27]) was obtained.

The active compound [27]
¹ H-NMR (CDCl ₃ ) δ: 8.61 (dd, J = 5.1, 0.7Hz, 1H), 8.13 (t, J = 0.7Hz, 1H), 7.79 (dd, J = 1.5, 0.7Hz, 1H), 7.66 (dd, J = 5.1, 1.5Hz, 1H), 7.64 (d, J = 1.0Hz, 1H), 7.54 (d, J = 8.5Hz, 1H), 3.99 (s, 3H)

本活性化合物［２８］
¹H-NMR (CDCl₃) δ: 8.70(d, J=2.0Hz, 1H), 8.64(dd, J=4.9, 1.0Hz, 1H), 8.12-8.11(m, 1H), 7.76-7.70(m, 2H), 7.63(dd, J=8.7, 1.3Hz, 1H), 3.67-3.59(m, 1H), 1.13-1.06(m, 2H), 0.74-0.67(m, 2H) Production Example 28
Instead of N1-methyl-4-trifluoromethylbenzene-1,2-diamine, N1-cyclopropyl-4-trifluoromethylbenzene-1,2-diamine is used instead of 3-methylisonicotinic acid. 1-Cyclopropyl-2- (3-fluoropyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as this activity) was prepared using isonicotinic acid according to the method described in Production Example 6. Compound (28)) was obtained.

The active compound [28]
¹ H-NMR (CDCl ₃ ) δ: 8.70 (d, J = 2.0Hz, 1H), 8.64 (dd, J = 4.9, 1.0Hz, 1H), 8.12-8.11 (m, 1H), 7.76-7.70 (m , 2H), 7.63 (dd, J = 8.7, 1.3Hz, 1H), 3.67-3.59 (m, 1H), 1.13-1.06 (m, 2H), 0.74-0.67 (m, 2H)

本活性化合物［２９］
¹H-NMR (CDCl₃) δ: 8.70(s, 1H), 8.59(dd, J=4.8, 0.5Hz, 1H), 8.13-8.10(m, 1H), 7.73(d, J=8.5Hz, 1H), 7.64-7.60(m, 1H), 7.40(d, J= 4.8Hz, 1H), 3.57-3.50(m, 1H), 2.49(s, 3H), 1.03-0.96(m, 2H), 0.76-0.70(m, 2H) Production Example 29
Instead of 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole, 1-cyclopropyl-2- (3-fluoropyridin-4-yl) -5 1-Cyclopropyl-2- (3-methylthiopyridin-4-yl) was used according to the method described in Production Example 4 except that trifluoromethyl-1H-benzimidazole was replaced with sodium methoxide and methyl mercaptan sodium was used. -5-Trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [29]) was obtained.

The active compound [29]
¹ H-NMR (CDCl ₃ ) δ: 8.70 (s, 1H), 8.59 (dd, J = 4.8, 0.5Hz, 1H), 8.13-8.10 (m, 1H), 7.73 (d, J = 8.5Hz, 1H ), 7.64-7.60 (m, 1H), 7.40 (d, J = 4.8Hz, 1H), 3.57-3.50 (m, 1H), 2.49 (s, 3H), 1.03-0.96 (m, 2H), 0.76- 0.70 (m, 2H)

本活性化合物［３０］
¹H-NMR (CDCl₃) δ: 9.52(s, 1H), 8.94(d, J=5.1Hz, 1H), 8.09 (d, J=0.7Hz, 1H), 7.76(d, J=8.7Hz, 1H), 7.72(d, J=5.1Hz, 1H), 7.66(dd, J=8.6, 1.6Hz, 1H), 3.63-3.57(m, 1H), 3.21(s, 3H), 1.34-1.23(m, 1H), 1.14-1.05(m, 1H), 1.01-0.93(m, 1H), 0.67-0.59(m, 1H) Production Example 30
Instead of 1-methyl-2- (3-methylthiopyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole, 1-cyclopropyl-2- (3-methylthiopyridin-4-yl) -5 1-Cyclopropyl-2- (3-methanesulfinylpyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole was prepared using trifluoromethyl-1H-benzimidazole according to the method described in Production Example 18. (Hereinafter referred to as the present active compound [30]).

The active compound [30]
¹ H-NMR (CDCl ₃ ) δ: 9.52 (s, 1H), 8.94 (d, J = 5.1Hz, 1H), 8.09 (d, J = 0.7Hz, 1H), 7.76 (d, J = 8.7Hz, 1H), 7.72 (d, J = 5.1Hz, 1H), 7.66 (dd, J = 8.6, 1.6Hz, 1H), 3.63-3.57 (m, 1H), 3.21 (s, 3H), 1.34-1.23 (m , 1H), 1.14-1.05 (m, 1H), 1.01-0.93 (m, 1H), 0.67-0.59 (m, 1H)

本活性化合物［３１］
¹H-NMR (CDCl₃) δ: 9.45(s, 1H), 9.06(d, J=4.8Hz, 1H), 8.06-8.04(m, 1H), 7.75(d, J=8.7Hz, 1H), 7.66-7.62(m, 1H), 7.56(d, J=4.8Hz, 1H), 3.50 (s, 3H), 3.43-3.37(m, 1H), 0.97-0.93(m, 4H) Production Example 31
Instead of 1-methyl-2- (3-methylthiopyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole, 1-cyclopropyl-2- (3-methylthiopyridin-4-yl) -5 1-Cyclopropyl-2- (3-methanesulfonylpyridin-4-yl) -5-trifluoromethyl-1H-benzen was prepared according to the method described in Preparation Example 19 using trifluoromethyl-1H-benzimidazole. Imidazole (hereinafter referred to as the present active compound [31]) was obtained.

The active compound [31]
¹ H-NMR (CDCl ₃ ) δ: 9.45 (s, 1H), 9.06 (d, J = 4.8Hz, 1H), 8.06-8.04 (m, 1H), 7.75 (d, J = 8.7Hz, 1H), 7.66-7.62 (m, 1H), 7.56 (d, J = 4.8Hz, 1H), 3.50 (s, 3H), 3.43-3.37 (m, 1H), 0.97-0.93 (m, 4H)

本活性化合物［３２］
¹H-NMR (CDCl₃) δ: 8.77(s, 1H), 8.61(d, J=4.8Hz, 1H), 8.12-8.09(m, 1H), 7.73(d, J=8.7Hz, 1H), 7.62(dd, J=8.7, 1.6Hz, 1H), 7.42(d, J=4.8Hz, 1H), 3.58-3.52(m, 1H), 2.90(q, J=7.4Hz, 2H), 1.23(t, J=7.4Hz, 3H), 0.98(dd, J=12.8, 7.0Hz, 2H), 0.74-0.67(m, 2H) Production Example 32
Instead of 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole, 1-cyclopropyl-2- (3-fluoropyridin-4-yl) -5 1-Cyclopropyl-2- (3-ethylthiopyridin-4-yl) was used according to the method described in Production Example 4 except that trifluoromethyl-1H-benzimidazole was replaced with sodium methoxide and ethyl mercaptan sodium was used. ) -5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [32]) was obtained.

The active compound [32]
¹ H-NMR (CDCl ₃ ) δ: 8.77 (s, 1H), 8.61 (d, J = 4.8Hz, 1H), 8.12-8.09 (m, 1H), 7.73 (d, J = 8.7Hz, 1H), 7.62 (dd, J = 8.7, 1.6Hz, 1H), 7.42 (d, J = 4.8Hz, 1H), 3.58-3.52 (m, 1H), 2.90 (q, J = 7.4Hz, 2H), 1.23 (t , J = 7.4Hz, 3H), 0.98 (dd, J = 12.8, 7.0Hz, 2H), 0.74-0.67 (m, 2H)

本活性化合物［３３］
¹H-NMR (CDCl₃) δ: 9.41(s, 1H), 8.93 (d, J=5.1Hz, 1H), 8.08(d, J=0.7Hz, 1H), 7.77-7.74(m, 1H), 7.71(d, J=5.1Hz, 1H), 7.68-7.64(m, 1H), 3.64-3.53(m, 2H), 3.24-3.14(m, 1H), 1.43(t, J=7.4Hz, 3H), 1.32-1.23(m, 1H), 1.13-1.05(m, 1H), 0.97-0.89(m, 1H),0.67-0.60(m, 1H) Production Example 33
1-cyclopropyl-2- (3-ethylthiopyridin-4-yl) -5 instead of 1-methyl-2- (3-methylthiopyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole 1-cyclopropyl-2- (3-ethanesulfinylpyridin-4-yl) -5-trifluoromethyl-1H-benzen in accordance with the method described in Production Example 18 using -trifluoromethyl-1H-benzimidazole Imidazole (hereinafter referred to as the present active compound [33]) was obtained.

The active compound [33]
¹ H-NMR (CDCl ₃ ) δ: 9.41 (s, 1H), 8.93 (d, J = 5.1Hz, 1H), 8.08 (d, J = 0.7Hz, 1H), 7.77-7.74 (m, 1H), 7.71 (d, J = 5.1Hz, 1H), 7.68-7.64 (m, 1H), 3.64-3.53 (m, 2H), 3.24-3.14 (m, 1H), 1.43 (t, J = 7.4Hz, 3H) , 1.32-1.23 (m, 1H), 1.13-1.05 (m, 1H), 0.97-0.89 (m, 1H), 0.67-0.60 (m, 1H)

本活性化合物［３４］
¹H-NMR (CDCl₃) δ: 9.38(s, 1H), 9.05(d, J=4.8Hz, 1H), 8.05-8.03(m, 1H), 7.74(dd, J=8.5, 0.5Hz, 1H), 7.65-7.62(m, 1H), 7.56(d, J=4.8Hz, 1H), 3.65(q, J=7.4Hz, 2H), 3.43-3.36(m, 1H), 1.33(t, J=7.4Hz, 3H), 0.97-0.92(m, 4H) Production Example 34
1-cyclopropyl-2- (3-ethylthiopyridin-4-yl) -5 instead of 1-methyl-2- (3-methylthiopyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole 1-cyclopropyl-2- (3-ethanesulfonylpyridin-4-yl) -5-trifluoromethyl-1H— using -trifluoromethyl-1H-benzimidazole according to the method described in Preparation Example 19 Benzimidazole (hereinafter referred to as the present active compound [34]) was obtained.

The active compound [34]
¹ H-NMR (CDCl ₃ ) δ: 9.38 (s, 1H), 9.05 (d, J = 4.8Hz, 1H), 8.05-8.03 (m, 1H), 7.74 (dd, J = 8.5, 0.5Hz, 1H ), 7.65-7.62 (m, 1H), 7.56 (d, J = 4.8Hz, 1H), 3.65 (q, J = 7.4Hz, 2H), 3.43-3.36 (m, 1H), 1.33 (t, J = 7.4Hz, 3H), 0.97-0.92 (m, 4H)

本活性化合物［３５］
¹H-NMR (CDCl₃) δ: 8.88(dd, J=4.5, 1.7Hz, 2H), 8.75(d, J=1.9Hz, 1H), 8.35(d, J=1.9Hz, 1H), 7.79(dd, J=4.5, 1.7Hz, 2H), 4.09(s, 3H) Production Example 35
In place of 1,1,3,3-tetrafluoro-N-methyl-1,3-dihydroisobenzofuran-5,6-diamine, N2-methyl-5-trifluoromethylpyridine-2,3-diamine was used, In accordance with the method described in Production Example 1, 3-methyl-2- (pyridin-4-yl) -6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the active compound [35] ] Was obtained.

The active compound [35]
¹ H-NMR (CDCl ₃ ) δ: 8.88 (dd, J = 4.5, 1.7Hz, 2H), 8.75 (d, J = 1.9Hz, 1H), 8.35 (d, J = 1.9Hz, 1H), 7.79 ( dd, J = 4.5, 1.7Hz, 2H), 4.09 (s, 3H)

本活性化合物［３６］
¹H-NMR (CDCl₃) δ: 8.77(s, 1H), 8.76(s, 1H), 8.69(d, J=4.8Hz, 1H), 8.37(s, 1H), 7.72-7.71(m, 1H), 3.94(d, J=2.7Hz, 3H) Production Example 36
A mixture of 5.51 g of N2-methyl-5-trifluoromethylpyridine-2,3-diamine, 6.10 g of 3-fluoroisonicotinic acid, 8.28 g of WSC and 58 ml of pyridine was heated and stirred at 120 ° C. for 3 hours. After cooling to room temperature, water was added and extracted three times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 2- (3-fluoropyridin-4-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the active compound). [Indicated as [36].) 6.77 g was obtained.

The active compound [36]
¹ H-NMR (CDCl ₃ ) δ: 8.77 (s, 1H), 8.76 (s, 1H), 8.69 (d, J = 4.8Hz, 1H), 8.37 (s, 1H), 7.72-7.71 (m, 1H ), 3.94 (d, J = 2.7Hz, 3H)

本活性化合物［３７］
¹H-NMR (CDCl₃) δ: 8.86(s, 1H), 8.78-8.76(m, 1H), 8.74(d, J=4.9Hz, 1H), 8.37(t, J=1.0Hz, 1H), 7.54(dd, J=4.9, 0.7Hz, 1H), 3.85(s, 3H) Production Example 37
Using 3-chloroisonicotinic acid instead of 3-fluoroisonicotinic acid, and according to the method described in Preparation Example 36, 2- (3-chloropyridin-4-yl) -3-methyl-6-trifluoro Methyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the active compound [37]) was obtained.

The active compound [37]
¹ H-NMR (CDCl ₃ ) δ: 8.86 (s, 1H), 8.78-8.76 (m, 1H), 8.74 (d, J = 4.9Hz, 1H), 8.37 (t, J = 1.0Hz, 1H), 7.54 (dd, J = 4.9, 0.7Hz, 1H), 3.85 (s, 3H)

本活性化合物［３８］
¹H-NMR (CDCl₃) δ: 8.73(d, J=1.9Hz, 1H), 8.56(s, 1H), 8.50(d, J=4.7Hz, 1H), 8.33(d, J=1.9Hz, 1H), 7.53(d, J=4.7Hz, 1H), 4.40(s, 3H), 3.82(s, 3H) Production Example 38
Instead of 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole, 2- (3-fluoropyridin-4-yl) -3-methyl-6-tri 2- (3-Methoxypyridin-4-yl) -3-methyl-6-trifluoromethyl was prepared according to the method described in Production Example 8 using fluoromethyl-3H-imidazo [4,5-b] pyridine. -3H-imidazo [4,5-b] pyridine (hereinafter referred to as the active compound [38]) was obtained.

The active compound [38]
¹ H-NMR (CDCl ₃ ) δ: 8.73 (d, J = 1.9Hz, 1H), 8.56 (s, 1H), 8.50 (d, J = 4.7Hz, 1H), 8.33 (d, J = 1.9Hz, 1H), 7.53 (d, J = 4.7Hz, 1H), 4.40 (s, 3H), 3.82 (s, 3H)

本活性化合物［３９］
¹H-NMR (CDCl₃) δ: 8.73(d, J=1.3Hz, 1H), 8.57(s, 1H), 8.47(d, J=4.8Hz, 1H), 8.33(d, J=1.3Hz, 1H), 7.54(d, J=4.8Hz, 1H), 4.27(q, J=7.0Hz, 2H), 3.84(s, 3H), 1.38(t, J=7.0Hz, 3H) Production Example 39
Instead of 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole, 2- (3-fluoropyridin-4-yl) -3-methyl-6-tri Fluoromethyl-3H-imidazo [4,5-b] pyridine was replaced by sodium ethoxide instead of sodium methoxide and 2- (3-ethoxypyridin-4-yl) according to the method described in Preparation Example 8. ) -3-Methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present active compound [39]) was obtained.

The active compound [39]
¹ H-NMR (CDCl ₃ ) δ: 8.73 (d, J = 1.3Hz, 1H), 8.57 (s, 1H), 8.47 (d, J = 4.8Hz, 1H), 8.33 (d, J = 1.3Hz, 1H), 7.54 (d, J = 4.8Hz, 1H), 4.27 (q, J = 7.0Hz, 2H), 3.84 (s, 3H), 1.38 (t, J = 7.0Hz, 3H)

本活性化合物［４０］
¹H-NMR (CDCl₃) δ: 8.74-8.72(m, 1H), 8.54(s, 1H), 8.47(d, J=4.8Hz, 1H), 8.34-8.32(m, 1H), 7.53(d, J=4.8Hz, 1H), 4.14(t, J=6.8Hz, 2H), 3.83(s, 3H), 1.81-1.71(m, 2H), 0.92(t, J=7.4Hz, 3H) Production Example 40
Instead of 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole, 2- (3-fluoropyridin-4-yl) -3-methyl-6-tri 3-methyl-2- (3-propoxypyridin-4-yl) -6-trifluoromethyl was prepared according to the method described in Preparation Example 10 using fluoromethyl-3H-imidazo [4,5-b] pyridine. -3H-imidazo [4,5-b] pyridine (hereinafter referred to as the active compound [40]) was obtained.

The active compound [40]
¹ H-NMR (CDCl ₃ ) δ: 8.74-8.72 (m, 1H), 8.54 (s, 1H), 8.47 (d, J = 4.8Hz, 1H), 8.34-8.32 (m, 1H), 7.53 (d , J = 4.8Hz, 1H), 4.14 (t, J = 6.8Hz, 2H), 3.83 (s, 3H), 1.81-1.71 (m, 2H), 0.92 (t, J = 7.4Hz, 3H)

本活性化合物［４１］
¹H-NMR (CDCl₃) δ: 8.74-8.72(m, 1H), 8.53(s, 1H), 8.44(d, J=4.6Hz, 1H), 8.34-8.32(m, 1H), 7.54(d, J=4.8Hz, 1H), 4.78-4.72(m, 1H), 3.84(s, 3H), 1.32(s, 3H), 1.31(s, 3H) Production Example 41
Instead of 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole, 2- (3-fluoropyridin-4-yl) -3-methyl-6-tri Fluoromethyl-3H-imidazo [4,5-b] pyridine was replaced with 1-propanol using 2-propanol, and 2- (3-isopropoxypyridine-4- Yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present active compound [41]).

The active compound [41]
¹ H-NMR (CDCl ₃ ) δ: 8.74-8.72 (m, 1H), 8.53 (s, 1H), 8.44 (d, J = 4.6Hz, 1H), 8.34-8.32 (m, 1H), 7.54 (d , J = 4.8Hz, 1H), 4.78-4.72 (m, 1H), 3.84 (s, 3H), 1.32 (s, 3H), 1.31 (s, 3H)

本活性化合物［４２］
¹H-NMR (CDCl₃) δ: 8.75-8.72(m, 1H), 8.61(s, 1H), 8.56(d, J=4.8Hz, 1H), 8.35-8.32(m, 1H), 7.60(d, J=4.8Hz, 1H), 3.87(s, 3H), 1.15(s, 9H) Production Example 42
Instead of 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole, 2- (3-fluoropyridin-4-yl) -3-methyl-6-tri Fluoromethyl-3H-imidazo [4,5-b] pyridine was replaced with 1-propanol, and tert-butyl alcohol was used, and 2- (3-tert-butoxypyridine- 4-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present active compound [42]) was obtained.

The active compound [42]
¹ H-NMR (CDCl ₃ ) δ: 8.75-8.72 (m, 1H), 8.61 (s, 1H), 8.56 (d, J = 4.8Hz, 1H), 8.35-8.32 (m, 1H), 7.60 (d , J = 4.8Hz, 1H), 3.87 (s, 3H), 1.15 (s, 9H)

本活性化合物［４３］
¹H-NMR (CDCl₃) δ: 8.76(d, J=1.9Hz, 1H), 8.62(d, J=4.8Hz, 1H), 8.57(s, 1H), 8.35(d, J=1.9Hz, 1H), 7.61(d, J=4.8Hz, 1H), 4.52(q, J=7.9Hz, 2H), 3.85(s, 3H) Production Example 43
Instead of 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole, 2- (3-fluoropyridin-4-yl) -3-methyl-6-tri In accordance with the method described in Preparation Example 10, substituting 3-methyl-2 for fluoromethyl-3H-imidazo [4,5-b] pyridine using 2,2,2-trifluoroethanol instead of 1-propanol -[3- (2,2,2-trifluoroethoxy) -pyridin-4-yl] -6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the active compound [43]) I wrote.)

The active compound [43]
¹ H-NMR (CDCl ₃ ) δ: 8.76 (d, J = 1.9Hz, 1H), 8.62 (d, J = 4.8Hz, 1H), 8.57 (s, 1H), 8.35 (d, J = 1.9Hz, 1H), 7.61 (d, J = 4.8Hz, 1H), 4.52 (q, J = 7.9Hz, 2H), 3.85 (s, 3H)

本活性化合物［４４］
¹H-NMR (CDCl₃) δ: 8.76-8.74(m, 1H), 8.58(d, J=4.6Hz, 1H), 8.55(s, 1H), 8.34-8.33(m, 1H), 7.58(d, J=4.9Hz, 1H), 5.98(tt, J=54.6, 3.8Hz, 1H), 4.38(td, J=12.9, 3.8Hz, 2H), 3.84(s, 3H) Production Example 44
Instead of 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole, 2- (3-fluoropyridin-4-yl) -3-methyl-6-tri Fluoromethyl-3H-imidazo [4,5-b] pyridine was replaced with 1-propanol and 2,2-difluoroethanol was used, and 2- [3- (2, 2-Difluoroethoxy) -pyridin-4-yl] -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present active compound [44]) was obtained. .

The active compound [44]
¹ H-NMR (CDCl ₃ ) δ: 8.76-8.74 (m, 1H), 8.58 (d, J = 4.6Hz, 1H), 8.55 (s, 1H), 8.34-8.33 (m, 1H), 7.58 (d , J = 4.9Hz, 1H), 5.98 (tt, J = 54.6, 3.8Hz, 1H), 4.38 (td, J = 12.9, 3.8Hz, 2H), 3.84 (s, 3H)

本活性化合物［４５］
¹H-NMR (CDCl₃) δ: 8.76-8.73(m, 1H), 8.54(t, J=4.8Hz, 2H), 8.34-8.32(m, 1H), 7.58(dd, J=4.8, 0.6Hz, 1H), 4.76-4.73(m, 1H), 4.64-4.61(m, 1H), 4.47-4.44(m, 1H), 4.41-4.37(m, 1H), 3.86(s, 3H) Production Example 45
Instead of 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole, 2- (3-fluoropyridin-4-yl) -3-methyl-6-tri Fluoromethyl-3H-imidazo [4,5-b] pyridine was replaced with 1-propanol, 2-fluoroethanol was used, and 2- [3- (2-fluoroethoxy) was prepared according to the method described in Preparation Example 10. ) -Pyridin-4-yl] -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present active compound [45]).

The active compound [45]
¹ H-NMR (CDCl ₃ ) δ: 8.76-8.73 (m, 1H), 8.54 (t, J = 4.8Hz, 2H), 8.34-8.32 (m, 1H), 7.58 (dd, J = 4.8, 0.6Hz , 1H), 4.76-4.73 (m, 1H), 4.64-4.61 (m, 1H), 4.47-4.44 (m, 1H), 4.41-4.37 (m, 1H), 3.86 (s, 3H)

本活性化合物［４６］
¹H-NMR (CDCl₃) δ: 8.74-8.72(m, 1H), 8.56(s, 1H), 8.49(d, J=4.3 Hz, 1H), 8.34-8.32(m, 1H), 7.56(d, J=4.8Hz, 1H), 4.33-4.29(m, 2H), 3.87(s, 3H), 3.67-3.64(m, 2H), 3.32(s, 3H) Production Example 46
Instead of 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole, 2- (3-fluoropyridin-4-yl) -3-methyl-6-tri Fluoromethyl-3H-imidazo [4,5-b] pyridine was replaced with 1-propanol using 2-methoxyethanol, and 2- [3- (2-methoxyethoxy) according to the method described in Preparation Example 10. ) -Pyridin-4-yl] -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the active compound [46]).

The active compound [46]
¹ H-NMR (CDCl ₃ ) δ: 8.74-8.72 (m, 1H), 8.56 (s, 1H), 8.49 (d, J = 4.3 Hz, 1H), 8.34-8.32 (m, 1H), 7.56 (d , J = 4.8Hz, 1H), 4.33-4.29 (m, 2H), 3.87 (s, 3H), 3.67-3.64 (m, 2H), 3.32 (s, 3H)

本活性化合物［４７］
¹H-NMR (CDCl₃) δ: 8.74-8.72(m, 1H), 8.56(s, 1H), 8.49(d, J=4.8Hz, 1H), 8.33-8.31(m, 1H), 7.56(d, J=4.6Hz, 1H), 4.34-4.29(m, 2H), 3.88(s, 3H), 3.71-3.66(m, 2H), 3.45(q, J=7.0Hz, 2H), 1.14 (t, J=7.0Hz, 3H) Production Example 47
Instead of 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole, 2- (3-fluoropyridin-4-yl) -3-methyl-6-tri Fluoromethyl-3H-imidazo [4,5-b] pyridine was replaced with 1-propanol and 2-ethoxyethanol was used, and 2- [3- (2-ethoxyethoxy) was prepared according to the method described in Preparation Example 10. ) -Pyridin-4-yl] -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the active compound [47]).

The active compound [47]
¹ H-NMR (CDCl ₃ ) δ: 8.74-8.72 (m, 1H), 8.56 (s, 1H), 8.49 (d, J = 4.8Hz, 1H), 8.33-8.31 (m, 1H), 7.56 (d , J = 4.6Hz, 1H), 4.34-4.29 (m, 2H), 3.88 (s, 3H), 3.71-3.66 (m, 2H), 3.45 (q, J = 7.0Hz, 2H), 1.14 (t, (J = 7.0Hz, 3H)

本活性化合物［４８］
¹H-NMR (CDCl₃) δ: 8.75(d, J=1.4, 1H), 8.73(s, 1H), 8.62(d, J=4.9, 1H), 8.36(d, J=1.4, 1H), 7.37(d, J=4.9, 1H), 3.82(s, 3H), 2.51(s, 3H) Production Example 48
Instead of 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole, 2- (3-fluoropyridin-4-yl) -3-methyl-6-tri 3-methyl-2- (3-methylthiopyridine) was prepared according to the method described in Production Example 8 using fluoromethyl-3H-imidazo [4,5-b] pyridine in place of sodium methoxide and methyl mercaptan sodium. -4-yl) -6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present active compound [48]) was obtained.

The active compound [48]
¹ H-NMR (CDCl ₃ ) δ: 8.75 (d, J = 1.4, 1H), 8.73 (s, 1H), 8.62 (d, J = 4.9, 1H), 8.36 (d, J = 1.4, 1H), 7.37 (d, J = 4.9, 1H), 3.82 (s, 3H), 2.51 (s, 3H)

本活性化合物［４９］
¹H-NMR (CDCl₃) δ: 9.55(s, 1H), 9.00(d, J=4.9Hz, 1H), 8.80-8.79(m, 1H), 8.38-8.37(m, 1H), 7.55(d, J=4.9Hz, 1H), 4.02(s, 3H), 3.20(s, 3H) Production Example 49
Instead of 1-methyl-2- (3-methylthiopyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole, 3-methyl-2- (3-methylthiopyridin-4-yl) -6-tri 2- (3-Methanesulfinylpyridin-4-yl) -3-methyl-6-trifluoro, using fluoromethyl-3H-imidazo [4,5-b] pyridine, according to the method described in Preparation Example 18. Methyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present active compound [49]) was obtained.

The active compound [49]
¹ H-NMR (CDCl ₃ ) δ: 9.55 (s, 1H), 9.00 (d, J = 4.9Hz, 1H), 8.80-8.79 (m, 1H), 8.38-8.37 (m, 1H), 7.55 (d , J = 4.9Hz, 1H), 4.02 (s, 3H), 3.20 (s, 3H)

本活性化合物［５０］
¹H-NMR (CDCl₃) δ: 9.47(s, 1H), 9.12(d, J=4.8Hz, 1H), 8.79-8.77(m, 1H), 8.32-8.31(m, 1H), 7.52(d, J=4.8 Hz, 1H), 3.77(s, 3H), 3.36(s, 3H) Production Example 50
Instead of 1-methyl-2- (3-methylthiopyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole, 3-methyl-2- (3-methylthiopyridin-4-yl) -6-tri 2- (3-Methanesulfonylpyridin-4-yl) -3-methyl-6-trifluoro is used according to the method described in Preparation Example 19 using fluoromethyl-3H-imidazo [4,5-b] pyridine. Methyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the active compound [50]) was obtained.

The active compound [50]
¹ H-NMR (CDCl ₃ ) δ: 9.47 (s, 1H), 9.12 (d, J = 4.8Hz, 1H), 8.79-8.77 (m, 1H), 8.32-8.31 (m, 1H), 7.52 (d , J = 4.8 Hz, 1H), 3.77 (s, 3H), 3.36 (s, 3H)

本活性化合物［５１］
¹H-NMR (CDCl₃) δ: 8.79(s, 1H), 8.76-8.75(m, 1H), 8.65(d, J=4.9Hz, 1H), 8.35(d, J=2.0Hz, 1H), 7.40(dd, J=4.9, 0.7Hz, 1H), 3.81(s, 3H), 2.92(q, J=7.4Hz, 2H), 1.26(t, J=7.4Hz, 3H) Production Example 51
Instead of 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole, 2- (3-fluoropyridin-4-yl) -3-methyl-6-tri Fluoromethyl-3H-imidazo [4,5-b] pyridine was replaced with sodium methoxide using ethyl mercaptan sodium and 2- (3-ethylthiopyridine-4- Yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present active compound [51]).

The active compound [51]
¹ H-NMR (CDCl ₃ ) δ: 8.79 (s, 1H), 8.76-8.75 (m, 1H), 8.65 (d, J = 4.9Hz, 1H), 8.35 (d, J = 2.0Hz, 1H), 7.40 (dd, J = 4.9, 0.7Hz, 1H), 3.81 (s, 3H), 2.92 (q, J = 7.4Hz, 2H), 1.26 (t, J = 7.4Hz, 3H)

本活性化合物［５２］
¹H-NMR (CDCl₃) δ: 9.43(s, 1H), 8.98(dd, J=5.1, 0.7Hz, 1H), 8.81-8.78(m, 1H), 8.37-8.34(m, 1H), 7.55(d, J=5.1Hz, 1H), 4.00(s, 3H), 3.58-3.48(m, 1H), 3.24-3.13(m, 1H), 1.42(t, J=7.5Hz, 3H) Production Example 52
Instead of 1-methyl-2- (3-methylthiopyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole, 2- (3-ethylthiopyridin-4-yl) -3-methyl-6- Using trifluoromethyl-3H-imidazo [4,5-b] pyridine, according to the method described in Preparation Example 18, 2- (3-ethanesulfinylpyridin-4-yl) -3-methyl-6-tri Fluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present active compound [52]) was obtained.

The active compound [52]
¹ H-NMR (CDCl ₃ ) δ: 9.43 (s, 1H), 8.98 (dd, J = 5.1, 0.7Hz, 1H), 8.81-8.78 (m, 1H), 8.37-8.34 (m, 1H), 7.55 (d, J = 5.1Hz, 1H), 4.00 (s, 3H), 3.58-3.48 (m, 1H), 3.24-3.13 (m, 1H), 1.42 (t, J = 7.5Hz, 3H)

本活性化合物［５３］
¹H-NMR (CDCl₃) δ: 9.40(s, 1H), 9.11(d, J=4.9Hz, 1H), 8.79-8.76(m, 1H), 8.32-8.30(m, 1H), 7.52(dd, J=4.9, 0.7Hz, 1H), 3.76(s, 3H), 3.47(q, J=7.4 Hz, 2H), 1.32(t, J=7.4Hz, 3H) Production Example 53
Instead of 1-methyl-2- (3-methylthiopyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole, 2- (3-ethylthiopyridin-4-yl) -3-methyl-6- Using trifluoromethyl-3H-imidazo [4,5-b] pyridine, according to the method described in Preparation Example 19, 2- (3-ethanesulfonylpyridin-4-yl) -3-methyl-6-tri Fluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present active compound [53]) was obtained.

The active compound [53]
¹ H-NMR (CDCl ₃ ) δ: 9.40 (s, 1H), 9.11 (d, J = 4.9Hz, 1H), 8.79-8.76 (m, 1H), 8.32-8.30 (m, 1H), 7.52 (dd , J = 4.9, 0.7Hz, 1H), 3.76 (s, 3H), 3.47 (q, J = 7.4 Hz, 2H), 1.32 (t, J = 7.4Hz, 3H)

本活性化合物［５４］
¹H-NMR (CDCl₃) δ: 9.01(s, 1H), 8.80(d, J=5.0Hz, 1H), 8.79-8.77(m, 1H), 8.38-8.36(m, 1H), 7.46(d, J=5.0Hz, 1H), 3.80(s, 3H), 3.42(q, J=9.5Hz, 2H) Production Example 54
Instead of 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole, 2- (3-fluoropyridin-4-yl) -3-methyl-6-tri In accordance with the method described in Preparation Example 10 except that 2,2,2-trifluoroethanethiol is used instead of 1-propanol instead of fluoromethyl-3H-imidazo [4,5-b] pyridine, 3-methyl- 2- [3- (2,2,2-trifluoroethylthio) pyridin-4-yl] -6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the active compound [54] Was obtained.)

The active compound [54]
¹ H-NMR (CDCl ₃ ) δ: 9.01 (s, 1H), 8.80 (d, J = 5.0Hz, 1H), 8.79-8.77 (m, 1H), 8.38-8.36 (m, 1H), 7.46 (d , J = 5.0Hz, 1H), 3.80 (s, 3H), 3.42 (q, J = 9.5Hz, 2H)

本活性化合物［５５］
¹H-NMR (CDCl₃) δ: 8.74(s, 1H), 8.37(d, J=6.5Hz, 2H), 8.33(s, 1H), 7.88(d, J=6.5Hz, 2H), 4.12(s, 3H) Production Example 55
Instead of 1-methyl-2- (pyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole, 3-methyl-2- (pyridin-4-yl) -6-trifluoromethyl-3H-imidazo According to the method described in Preparation Example 24, using [4,5-b] pyridine, 3-methyl-2- (1-oxypyridin-4-yl) -6-trifluoromethyl-3H-imidazo [4 , 5-b] pyridine (hereinafter referred to as the present active compound [55]).

The active compound [55]
¹ H-NMR (CDCl ₃ ) δ: 8.74 (s, 1H), 8.37 (d, J = 6.5Hz, 2H), 8.33 (s, 1H), 7.88 (d, J = 6.5Hz, 2H), 4.12 ( s, 3H)

本活性化合物［５６］
¹H-NMR(CDCl₃) δ: 8.77(d, J=1.2Hz, 1H), 8.35(d, J=2.0Hz, 1H), 8.33(dd, J=5.6, 1.7Hz, 1H), 8.24-8.20(m, 1H), 7.73(dd, J=8.5, 6.8Hz, 1H), 3.96(d, J=3.2Hz, 3H) Production Example 56
Instead of 1-methyl-2- (pyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole, 2- (3-fluoropyridin-4-yl) -3-methyl-6-trifluoromethyl- 2- (3-Fluoro-1-oxypyridin-4-yl) -3-methyl-6-trifluoroacetate using 3H-imidazo [4,5-b] pyridine according to the method described in Preparation Example 24 Methyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present active compound [56]) was obtained.

The active compound [56]
¹ H-NMR (CDCl ₃ ) δ: 8.77 (d, J = 1.2Hz, 1H), 8.35 (d, J = 2.0Hz, 1H), 8.33 (dd, J = 5.6, 1.7Hz, 1H), 8.24- 8.20 (m, 1H), 7.73 (dd, J = 8.5, 6.8Hz, 1H), 3.96 (d, J = 3.2Hz, 3H)

本活性化合物［５７］
¹H-NMR(CDCl₃) δ： 8.85(m, 1H), 8.75(m, 1H), 8.68(d, J=4.9Hz, 1H), 8.34(m, 1H), 7.43(dd, J=4.9, 0.7Hz, 1H), 3.79(s, 3H), 3.40-3.33(m, 1H)1.20(d, J=6.8Hz ,6H) Production Example 57
0.20 g of the active compound [36] (2- (3-fluoropyridin-4-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine), 2-propane To a mixture of 0.08 g of thiol and 1 ml of DMF was added 0.08 g of 60% sodium hydride (oil) under water cooling, and the mixture was stirred at room temperature for 3 hours. Thereafter, a saturated aqueous ammonium chloride solution was poured into the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed successively with a saturated aqueous ammonium chloride solution and a saturated aqueous sodium chloride solution, dried over sodium sulfate, and concentrated under reduced pressure. The obtained solid was washed with hexane to obtain 0.17 g of a compound represented by the formula [57] (hereinafter referred to as the present active compound [57]).

The active compound [57]
¹ H-NMR (CDCl ₃ ) δ: 8.85 (m, 1H), 8.75 (m, 1H), 8.68 (d, J = 4.9 Hz, 1H), 8.34 (m, 1H), 7.43 (dd, J = 4.9 , 0.7Hz, 1H), 3.79 (s, 3H), 3.40-3.33 (m, 1H) 1.20 (d, J = 6.8Hz, 6H)

本活性化合物［５８］
¹H-NMR (CDCl₃) δ: 8.97 （m, 1H）, 8.81（d, J=4.9Hz, 1H）, 8.75（m, 1H）, 8.34（m, 1H）, 7.55（dd, J=4.9, 0.7Hz）, 3.76（s, 3H）, 1.13（s, 9H） Production Example 58
In place of 2-propanethiol, 0.09 g of 2-methyl-2-propanethiol was used, and according to the method described in Production Example 57, a compound represented by formula [58] (hereinafter referred to as this active compound [58] and 0.19 g was obtained.

The active compound [58]
¹ H-NMR (CDCl ₃ ) δ: 8.97 (m, 1H), 8.81 (d, J = 4.9Hz, 1H), 8.75 (m, 1H), 8.34 (m, 1H), 7.55 (dd, J = 4.9 , 0.7Hz), 3.76 (s, 3H), 1.13 (s, 9H)

本活性化合物［５９］
¹H-NMR (CDCl₃)δ: 8.79(m, 1H), 8.75(m, 1H), 8.64(d, J=4.9Hz, 1H), 8.35(m, 1H), 7.39(dd, J=4.9, 0.7Hz), 3.81(s, 3H), 2.86(t, J=7.3Hz, 2H), 1.63-1.56(m, 2H), 0.94(t, J=7.3Hz, 3H) Production Example 59
Using 0.08 g of 1-propanethiol instead of 2-propanethiol, and a compound represented by the formula [59] according to the method described in Production Example 57 (hereinafter referred to as the present active compound [59]) 0 .22 g was obtained.

The active compound [59]
¹ H-NMR (CDCl ₃ ) δ: 8.79 (m, 1H), 8.75 (m, 1H), 8.64 (d, J = 4.9Hz, 1H), 8.35 (m, 1H), 7.39 (dd, J = 4.9 , 0.7Hz), 3.81 (s, 3H), 2.86 (t, J = 7.3Hz, 2H), 1.63-1.56 (m, 2H), 0.94 (t, J = 7.3Hz, 3H)

本活性化合物［６０］
¹H-NMR (CDCl₃) δ: 8.73(m, 1H), 8.55(s, 1H), 8.50(d, J=4.9Hz, 1H), 8.32(m, 1H), 7.54(d, J=4.6Hz, 1H), 4.34(t, J=6.5Hz, 2H), 3.87(s, H), 2.79(t, J=6.6Hz, 2H), 2.01(s, 3H) Production Example 60
To a mixture of 0.20 g of this active compound [36], 0.09 g of 2- (methylthio) ethanol and 1 ml of DMF was added 0.04 g of 60% sodium hydride (oil) under ice cooling, and the mixture was stirred for 4 hours under ice cooling. Thereafter, a saturated aqueous ammonium chloride solution was poured into the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed successively with a saturated aqueous ammonium chloride solution and a saturated aqueous sodium chloride solution, dried over sodium sulfate, and concentrated under reduced pressure. The obtained solid was washed with hexane to obtain 0.22 g of a compound represented by the formula [60] (hereinafter referred to as the present active compound [60]).

The active compound [60]
¹ H-NMR (CDCl ₃ ) δ: 8.73 (m, 1H), 8.55 (s, 1H), 8.50 (d, J = 4.9Hz, 1H), 8.32 (m, 1H), 7.54 (d, J = 4.6 Hz, 1H), 4.34 (t, J = 6.5Hz, 2H), 3.87 (s, H), 2.79 (t, J = 6.6Hz, 2H), 2.01 (s, 3H)

本活性化合物［６１］
¹H-NMR (CDCl₃) δ: 8.78(s, 1H), 8.75(m, H), 8.64(d, J=4.8Hz, 1H), 8.35(m, 1H), 7.39(d, J=4.8Hz, 1H), 3.81(s, 3H), 2.89(t, J=7.5Hz, 2H), 1.57-1.51(2m, H), 1.39-1.30(m, 2H), 0.85(t, J=7.4Hz, 3H) Production Example 61
In place of 2-propanethiol, 0.09 g of 1-butanethiol was used, and a compound represented by the formula [61] (hereinafter referred to as the present active compound [61]) 0 according to the method described in Production Example 57 .23 g was obtained.

The active compound [61]
¹ H-NMR (CDCl ₃ ) δ: 8.78 (s, 1H), 8.75 (m, H), 8.64 (d, J = 4.8Hz, 1H), 8.35 (m, 1H), 7.39 (d, J = 4.8 Hz, 1H), 3.81 (s, 3H), 2.89 (t, J = 7.5Hz, 2H), 1.57-1.51 (2m, H), 1.39-1.30 (m, 2H), 0.85 (t, J = 7.4Hz , 3H)

本活性化合物［６２］
¹H-NMR (CDCl₃) δ: 8.90(s, 1H), 8.79(d, J=5.1Hz, 1H), 8.75(m, 1H), 8.34(m, 1H), 7.38(d, J=5.6Hz, 1H), 4.55(s, 2H), 3.80(s, 3H), 3.22(s, 3H) Production Example 62
To a mixture of 0.18 g of 3-methoxyisonicotinic acid and 2 ml of pyridine, 0.32 g of WSC and 0.20 g of N2-methyl-5-trifluoromethylpyridine-2,3-diamine were sequentially added, and the mixture was heated to reflux for 6 hours. Thereafter, 0.20 g of WSC was added to the reaction mixture, and the mixture was heated to reflux for 4 hours. The reaction mixture was allowed to cool to room temperature, water was added, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, dried over sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel preparative thin layer chromatography to obtain 0.15 g of a compound represented by the formula [62] (hereinafter referred to as the present active compound [62]).

The active compound [62]
¹ H-NMR (CDCl ₃ ) δ: 8.90 (s, 1H), 8.79 (d, J = 5.1Hz, 1H), 8.75 (m, 1H), 8.34 (m, 1H), 7.38 (d, J = 5.6 Hz, 1H), 4.55 (s, 2H), 3.80 (s, 3H), 3.22 (s, 3H)

本活性化合物［６３］
¹H-NMR (CDCl₃)δ: 8.94(m, 1H), 8.78(d, J=4.9Hz, 1H), 8.12(m, 1H), 7.64(dd, J=8.5, 1.5Hz, 1H), 7.58(dd, J=4.9, 0.7Hz, 1H), 7.53(d, J=8.3Hz), 3.67(s, 3H), 1.11(s, 9H) Production Example 63
To a mixture of 0.20 g of this active compound [4], 0.09 g of 2-methyl-2-propanethiol and 1 ml of DMF, 0.04 g of 60% sodium hydride (oil) is added under ice cooling, and the mixture is cooled for 2 hours under ice cooling. Stir. Then, it heated up to room temperature and stirred for 1 hour. Water was poured into the reaction mixture under ice cooling, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed successively with water and saturated aqueous sodium chloride solution, dried over sodium sulfate, and concentrated under reduced pressure. The resulting solid was washed with hexane to obtain 0.19 g of a compound represented by the formula [63] (hereinafter referred to as the present active compound [63]).

The active compound [63]
¹ H-NMR (CDCl ₃ ) δ: 8.94 (m, 1H), 8.78 (d, J = 4.9Hz, 1H), 8.12 (m, 1H), 7.64 (dd, J = 8.5, 1.5Hz, 1H), 7.58 (dd, J = 4.9, 0.7Hz, 1H), 7.53 (d, J = 8.3Hz), 3.67 (s, 3H), 1.11 (s, 9H)

本活性化合物［６４］
¹H-NMR (CDCl₃) δ: 8.76(s, 1H), 8.61(d, J=4.9Hz, 1H), 8.13(m, 1H), 7.64(dd, J=8.4, 1.3Hz, 1H), 7.53(d, J=8.3Hz, 1H), 7.40(dd, J=4.9, 0.7Hz, 1H), 3.72(s, 3H), 2.84(t, J=7.4Hz, 2H), 1.55-1.49(m, 2H), 1.37-1.28(m, 2H), 0.84(t, 3H) Production Example 64
In place of 2-methyl-2-propanethiol, 0.09 g of 1-butanethiol was used, and according to the method described in Production Example 63, a compound represented by formula [64] (hereinafter referred to as this active compound [64] and 0.15 g was obtained.

The active compound [64]
¹ H-NMR (CDCl ₃ ) δ: 8.76 (s, 1H), 8.61 (d, J = 4.9Hz, 1H), 8.13 (m, 1H), 7.64 (dd, J = 8.4, 1.3Hz, 1H), 7.53 (d, J = 8.3Hz, 1H), 7.40 (dd, J = 4.9, 0.7Hz, 1H), 3.72 (s, 3H), 2.84 (t, J = 7.4Hz, 2H), 1.55-1.49 (m , 2H), 1.37-1.28 (m, 2H), 0.84 (t, 3H)

本活性化合物［６５］
¹H-NMR (CDCl₃)δ: 8.77-8.76(m, 1H), 8.49-8.48(m, 1H), 8.37-8.36(1H, m), 7.72-7.70(m, 1H), 7.47-7.46(m, 1H), 4.11(s, 3H) Production Example 65
1.50 g of WSC was added to a mixture of 1.00 g of N2-methyl-5-trifluoromethylpyridine-2,3-diamine, 0.78 g of 2-fluoroisonicotinic acid and 5 ml of pyridine, and the mixture was heated to reflux for 2 hours. After cooling the reaction mixture to room temperature, water was added. The resulting crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 1.44 g of a compound represented by the formula [65] (hereinafter referred to as the present active compound [65]).

The active compound [65]
¹ H-NMR (CDCl ₃ ) δ: 8.77-8.76 (m, 1H), 8.49-8.48 (m, 1H), 8.37-8.36 (1H, m), 7.72-7.70 (m, 1H), 7.47-7.46 ( m, 1H), 4.11 (s, 3H)

本活性化合物［６６］
¹H-NMR (CDCl₃)δ: 8.74(d, J=1.2Hz, 1H), 8.66(dd, J=5.1, 0.6Hz, 1H), 8.34(d, J=1.2Hz, 1H), 7.65(dd, J=1.5, 0.7Hz, 1H), 7.42(dd, J=5.1, 1.5Hz, 1H), 4.06(s, 3H), 2.65(s, 3H) Production Example 66
0.18 g of methyl mercaptan sodium was added to a mixture of 0.70 g of the active compound [65] and 2 ml of THF under ice cooling, and the mixture was stirred at room temperature for 1 hour. To the reaction mixture, 0.08 g of methyl mercaptan sodium was added and stirred for 5 hours, then 2 ml of DMF was added and stirred for 1 hour, and water was poured under ice cooling. The resulting crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 0.61 g of a compound represented by the formula [66] (hereinafter referred to as the present active compound [66]).

The active compound [66]
¹ H-NMR (CDCl ₃ ) δ: 8.74 (d, J = 1.2Hz, 1H), 8.66 (dd, J = 5.1, 0.6Hz, 1H), 8.34 (d, J = 1.2Hz, 1H), 7.65 ( dd, J = 1.5, 0.7Hz, 1H), 7.42 (dd, J = 5.1, 1.5Hz, 1H), 4.06 (s, 3H), 2.65 (s, 3H)

本活性化合物［６７］
¹H-NMR (CDCl₃)δ: 8.73(d, J=1.5Hz, 1H), 8.53(s, 1H), 8.47(d, J=4.9Hz, 1H), 8.33(d, J=1.5Hz, 1H), 7.49(d, J=4.9Hz, 1H), 3.83(s, 3H), 3.81(s, 2H), 0.85(s, 9H) Production Example 67
According to the method described in Production Example 60, using 0.09 g of 2,2-dimethyl-1-propanol instead of 2- (methylthio) ethanol, the compound represented by formula [67] (hereinafter referred to as the active compound [ 67].) 0.17 g was obtained.

The active compound [67]
¹ H-NMR (CDCl ₃ ) δ: 8.73 (d, J = 1.5Hz, 1H), 8.53 (s, 1H), 8.47 (d, J = 4.9Hz, 1H), 8.33 (d, J = 1.5Hz, 1H), 7.49 (d, J = 4.9Hz, 1H), 3.83 (s, 3H), 3.81 (s, 2H), 0.85 (s, 9H)

本活性化合物［６８］
¹H-NMR (CDCl₃)δ: 8.73(d, J=1.5Hz, 1H), 8.53(s, 1H), 8.47(d, J=4.9Hz, 1H), 8.33(d, J=2.0Hz, 1H), 7.51(d, J=4.9Hz, 1H), 3.94(d, J=6.6Hz, 2H), 3.83(s, 3H), 2.05-1.95(m, 1H), 0.88(d, J=6.8Hz, 6H) Production Example 68
According to the method described in Production Example 60, using 0.07 g of 2-methyl-1-propanol instead of 2- (methylthio) ethanol, the compound represented by formula [68] (hereinafter referred to as this active compound [68]) 0.21 g was obtained.

The active compound [68]
¹ H-NMR (CDCl ₃ ) δ: 8.73 (d, J = 1.5Hz, 1H), 8.53 (s, 1H), 8.47 (d, J = 4.9Hz, 1H), 8.33 (d, J = 2.0Hz, 1H), 7.51 (d, J = 4.9Hz, 1H), 3.94 (d, J = 6.6Hz, 2H), 3.83 (s, 3H), 2.05-1.95 (m, 1H), 0.88 (d, J = 6.8 Hz, 6H)

本活性化合物［６９］
¹H-NMR (CDCl₃)δ: 8.87(dd, J=4.9, 0.7Hz, 1H), 8.77(d, J=1.5Hz, 1H), 8.49(dd, J=1.7, 0.7Hz, 1H), 8.37(d, J=1.5Hz, 1H), 7.99(dd, J=4.9, 1.7Hz, 1H), 4.16(3H, s), 2.95(3H, s) Production Example 69
0.16 g of sodium periodate was added to a mixture of 0.20 g of the active compound [66], 3 ml of methanol, 1 ml of water and 0.4 ml of THF, and the mixture was stirred at about 60 ° C. for 8 hours. Thereafter, the reaction mixture was allowed to cool to room temperature, and water was poured under ice cooling. The precipitated crystals were collected by filtration, washed with water, dissolved in chloroform, washed successively with a saturated aqueous sodium thiosulfate solution, a saturated aqueous sodium bicarbonate solution, and brine, dried over sodium sulfate, and concentrated under reduced pressure. The resulting solid was washed with t-butyl methyl ether to obtain 0.17 g of a compound represented by the formula [69] (hereinafter referred to as the present active compound [69]).

The active compound [69]
¹ H-NMR (CDCl ₃ ) δ: 8.87 (dd, J = 4.9, 0.7Hz, 1H), 8.77 (d, J = 1.5Hz, 1H), 8.49 (dd, J = 1.7, 0.7Hz, 1H), 8.37 (d, J = 1.5Hz, 1H), 7.99 (dd, J = 4.9, 1.7Hz, 1H), 4.16 (3H, s), 2.95 (3H, s)

本活性化合物［７０］
¹H-NMR (CDCl₃)δ: 8.98(dd, J=4.9, 0.7Hz, 1H), 8.79(d, J=1.2Hz, 1H), 8.58(dd, J=1.5, 0.7Hz, 1H), 8.39(d, J=1.5Hz, 1H), 8.14(dd, J=5.0, 1.6Hz, 1H), 4.15(s, 3H), 3.33(s, 3H) Production Example 70
The active compound [66] (0.20 g) was dissolved in chloroform (2 ml), and 65% 3-chloroperbenzoic acid (0.39 g) was added under ice cooling, followed by stirring at room temperature for 4 hours. The reaction mixture was diluted with chloroform, washed successively with saturated aqueous sodium hydrogen carbonate solution, saturated aqueous sodium thiosulfate solution and brine, dried over sodium sulfate, and concentrated under reduced pressure. The resulting solid was washed with hexane to obtain 0.18 g of a compound represented by the formula [70] (hereinafter referred to as the present active compound [70]).

The active compound [70]
¹ H-NMR (CDCl ₃ ) δ: 8.98 (dd, J = 4.9, 0.7Hz, 1H), 8.79 (d, J = 1.2Hz, 1H), 8.58 (dd, J = 1.5, 0.7Hz, 1H), 8.39 (d, J = 1.5Hz, 1H), 8.14 (dd, J = 5.0, 1.6Hz, 1H), 4.15 (s, 3H), 3.33 (s, 3H)

本活性化合物［７１］
¹H-NMR (CDCl₃)δ: 8.79-8.77(m, 2H), 8.59(d, J=4.9Hz,1H), 8.38(d, J=2.0Hz, 1H), 7.39(d, J=5.0, 1H), 4.37(brs, 1H), 3.91(s, 3H) Production Example 71
The active compound [36] (5.0 g) was dissolved in DMF (20 ml), 70% sodium hydrosulfide (3.38 g) was added, and the mixture was stirred at about 80 ° C. for 5 hr. The reaction mixture was allowed to cool to room temperature, poured into ice water, and concentrated hydrochloric acid was added until the pH reached about 3. The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 5.2 g of a compound represented by the formula [71] (hereinafter referred to as the present active compound [71]).

The active compound [71]
¹ H-NMR (CDCl ₃ ) δ: 8.79-8.77 (m, 2H), 8.59 (d, J = 4.9Hz, 1H), 8.38 (d, J = 2.0Hz, 1H), 7.39 (d, J = 5.0 , 1H), 4.37 (brs, 1H), 3.91 (s, 3H)

本活性化合物［７２］
¹H-NMR (CDCl₃)δ: 9.54(s, 1H), 9.18(d, J=4.9Hz, 1H), 8.79(m, 1H), 8.38(m, 1H), 7.60(d, J=4.9, 1H) ,3.76(s ,3H) Production Example 72
0.70 g of trimethylsilyl chloride was added to a mixture of 0.40 g of the active compound [71], 0.52 g of potassium nitrate and 8 ml of chloroform, and the mixture was heated to reflux for 5 hours. The reaction mixture was allowed to cool to room temperature and diluted with chloroform. Unnecessary substances were filtered off, and the filtrate was concentrated under reduced pressure to obtain 0.36 g of a compound represented by the formula [72] (hereinafter referred to as the present active compound [72]).

The active compound [72]
¹ H-NMR (CDCl ₃ ) δ: 9.54 (s, 1H), 9.18 (d, J = 4.9Hz, 1H), 8.79 (m, 1H), 8.38 (m, 1H), 7.60 (d, J = 4.9 , 1H), 3.76 (s, 3H)

本活性化合物［７３］
¹H-NMR (CDCl₃)δ: 9.39(d, J=0.5Hz, 1H), 9.07(d, J=4.9Hz, 1H), 8.79(m, 1H), 8.33(m, 1H), 7.52(dd, J=4.9, 0.7Hz, 1H), 6.29(brq, J=5.0Hz, 1H), 3.87(s, 3H), 2.81(d, J=5.4Hz, 3H) Production Example 73
The active compound [72] (0.15 g) was suspended in THF (2 ml), 40% aqueous methylamine solution (0.1 g) was added, and the mixture was stirred at room temperature for 2 hr. The reaction mixture was concentrated under reduced pressure, and the obtained residue was subjected to silica gel column chromatography to obtain 95 mg of a compound represented by the formula [73] (hereinafter referred to as the present active compound [73]).

The active compound [73]
¹ H-NMR (CDCl ₃ ) δ: 9.39 (d, J = 0.5Hz, 1H), 9.07 (d, J = 4.9Hz, 1H), 8.79 (m, 1H), 8.33 (m, 1H), 7.52 ( dd, J = 4.9, 0.7Hz, 1H), 6.29 (brq, J = 5.0Hz, 1H), 3.87 (s, 3H), 2.81 (d, J = 5.4Hz, 3H)

本活性化合物［７４］
¹H-NMR (CDCl₃)δ: 9.16(s, 1H), 9.05(d, J=5.1Hz, 1H), 8.81(m, 1H), 8.44(m, 1H), 7.73(dd, J=5.1, 0.7Hz, 1H), 4.01(s, 3H) Production Example 74
To a mixture of 4.5 g of the active compound [36], 0.40 g of 18-crown-6-ether and 25 ml of THF, 0.89 g of sodium cyanide was added and heated to reflux for 1 hour. The reaction mixture was allowed to cool to room temperature, and cold water was poured under ice cooling. The resulting crystals are collected by filtration, dissolved in ethyl acetate, added with silica gel and activated carbon, filtered and concentrated under reduced pressure to give a compound of the formula [74] (hereinafter referred to as the present active compound [74]). 49 g was obtained.

The active compound [74]
¹ H-NMR (CDCl ₃ ) δ: 9.16 (s, 1H), 9.05 (d, J = 5.1Hz, 1H), 8.81 (m, 1H), 8.44 (m, 1H), 7.73 (dd, J = 5.1 , 0.7Hz, 1H), 4.01 (s, 3H)

本活性化合物［７５］
¹H-NMR (DMSO-D₆)δ: 13.66(brs, 1H), 9.25(d, J=0.5Hz, 1H), 9.01(d, J=4.8Hz, 1H), 8.83(d, J=1.4Hz, 1H), 8.59(d, J=1.4Hz, 1H), 7.77(dd, J=5.0, 0.6Hz, 1H), 3.65(s, 3H) Production Example 75
This active compound [74] (2.46 g) was suspended in ethanol (30 ml), 2N aqueous sodium hydroxide solution (15 ml) was added, and the mixture was heated to reflux for 5 hr. The reaction mixture was allowed to cool to room temperature and then concentrated under reduced pressure. The residue was dissolved in water, washed with toluene, and concentrated hydrochloric acid was added until the pH was about 2. The resulting crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 2.35 g of a compound represented by the formula [75] (hereinafter referred to as the present active compound [75]).

The active compound [75]
¹ H-NMR (DMSO-D ₆ ) δ: 13.66 (brs, 1H), 9.25 (d, J = 0.5Hz, 1H), 9.01 (d, J = 4.8Hz, 1H), 8.83 (d, J = 1.4 Hz, 1H), 8.59 (d, J = 1.4Hz, 1H), 7.77 (dd, J = 5.0, 0.6Hz, 1H), 3.65 (s, 3H)

本活性化合物［７６］
¹H-NMR (CDCl₃) δ: 8.76(d, J=0.5Hz, 1H), 8.57(d, J=4.9Hz, 1H), 8.15(m, 1H), 7.66(dd, J=8.5, 1.2Hz, 1H), 7.55(d, J=8.5Hz, 1H), 7.36(dd, J=4.9, 0.5Hz, 1H), 3.81(s, 3H) Production Example 76
1.0 g of the active compound [4] was used instead of the active compound [36], and the compound represented by the formula [76] (hereinafter referred to as the active compound [76]) was prepared according to the method described in Production Example 71. 0.88 g was obtained.

The active compound [76]
¹ H-NMR (CDCl ₃ ) δ: 8.76 (d, J = 0.5Hz, 1H), 8.57 (d, J = 4.9Hz, 1H), 8.15 (m, 1H), 7.66 (dd, J = 8.5, 1.2 Hz, 1H), 7.55 (d, J = 8.5Hz, 1H), 7.36 (dd, J = 4.9, 0.5Hz, 1H), 3.81 (s, 3H)

本活性化合物［７７］
¹H-NMR (CDCl₃)δ: 9.15(s, 1H), 8.94(d, J=4.9Hz, 1H), 8.79(m, 1H), 8.38(m, 1H), 7.58(dd, J=5.0, 0.6Hz, 1H), 3.82(s, 3H) Production Example 77
The active compound [71] (0.15 g) was suspended in 1 ml of THF, and 0.05 g of 60% sodium hydride (oil) was added under ice cooling, followed by stirring for 10 minutes. To this mixture, 0.63 g of S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate and 1 ml of THF were added and stirred at room temperature for a whole day and night. Water was poured into the reaction mixture and the mixture was extracted with chloroform. The organic layer was washed successively with a saturated aqueous sodium hydrogen carbonate solution and water, dried over sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel preparative thin layer chromatography to obtain 69 mg of a compound represented by the formula [77] (hereinafter referred to as the present active compound [77]).

The active compound [77]
¹ H-NMR (CDCl ₃ ) δ: 9.15 (s, 1H), 8.94 (d, J = 4.9Hz, 1H), 8.79 (m, 1H), 8.38 (m, 1H), 7.58 (dd, J = 5.0 , 0.6Hz, 1H), 3.82 (s, 3H)

本活性化合物［７８］
¹H-NMR (CDCl₃) δ: 9.12(s, 1H), 8.91(d, J=4.9Hz, 1H), 8.15-8.14(m, 1H), 7.67(dd, J=8.4, 1.3Hz, 1H), 7.56-7.54(m, 2H), 3.74(s, 3H) Production Example 78
The active compound [76] (0.15 g) was suspended in 2 ml of THF, 0.03 g of 60% sodium hydride (oil) was added, and the mixture was stirred for 15 minutes. 0.27 g of S- (trifluoromethyl) dibenzothiophenium-3-sulfonate was added to the mixture and stirred at room temperature for 8 hours. Water was poured into the reaction mixture and the mixture was extracted with chloroform. The organic layer was washed successively with a saturated aqueous sodium hydrogen carbonate solution and water, dried over sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel preparative thin layer chromatography to obtain 96 mg of a compound represented by the formula [78] (hereinafter referred to as the present active compound [78]).

The active compound [78]
¹ H-NMR (CDCl ₃ ) δ: 9.12 (s, 1H), 8.91 (d, J = 4.9Hz, 1H), 8.15-8.14 (m, 1H), 7.67 (dd, J = 8.4, 1.3Hz, 1H ), 7.56-7.54 (m, 2H), 3.74 (s, 3H)

本活性化合物［７９］
¹H-NMR (CDCl₃)δ: 8.96(s, 1H), 8.77-8.76(m, 2H), 8.37(d, J=2.0Hz, 1H), 7.45(d, J=4.9Hz, 1H), 5.83(tt, J=56.0, 4.3Hz, 1H), 3.80(s, 3H), 3.19(td, J=15.1, 4.1Hz, 2H) Production Example 79
The active compound [71] (0.15 g) was suspended in 2 ml of DMF, 0.04 g of 60% sodium hydride (oil) was added, and the mixture was stirred at about 50 ° C. for 5 minutes. To the mixture, 0.18 g of 1,1-difluoro-2-iodoethane was added and stirred for 3 hours. The reaction mixture is allowed to cool to room temperature, water is added, and the mixture is extracted with t-butyl methyl ether. The organic layer is washed with a saturated aqueous sodium bicarbonate solution and a saturated aqueous sodium chloride solution, dried over sodium sulfate, The bottom was concentrated. The residue was subjected to silica gel column chromatography to obtain 0.10 g of a compound represented by the formula [79] (hereinafter referred to as the present active compound [79]).

The active compound [79]
¹ H-NMR (CDCl ₃ ) δ: 8.96 (s, 1H), 8.77-8.76 (m, 2H), 8.37 (d, J = 2.0Hz, 1H), 7.45 (d, J = 4.9Hz, 1H), 5.83 (tt, J = 56.0, 4.3Hz, 1H), 3.80 (s, 3H), 3.19 (td, J = 15.1, 4.1Hz, 2H)

本活性化合物［８０］
¹H-NMR (CDCl₃)δ: 8.94(s, 1H), 8.74(d, J=4.9Hz, 1H), 8.14(m, 1H), 7.66(dd, J=8.5, 1.5Hz, 1H), 7.55(d, J=8.5Hz, 1H), 7.45(dd, J=4.9, 0.7Hz, 1H), 5.80(tt, J=56, 4.2Hz, 1H), 3.72(s, 3H), 3.15(td, J=15.2, 4.2Hz, 2H) Production Example 80
Instead of the active compound [71], 0.15 g of the active compound [76] was used, and a compound represented by the formula [80] according to the method described in Production Example 79 (hereinafter referred to as the active compound [80]). .) 0.10 g was obtained.

The active compound [80]
¹ H-NMR (CDCl ₃ ) δ: 8.94 (s, 1H), 8.74 (d, J = 4.9Hz, 1H), 8.14 (m, 1H), 7.66 (dd, J = 8.5, 1.5Hz, 1H), 7.55 (d, J = 8.5Hz, 1H), 7.45 (dd, J = 4.9, 0.7Hz, 1H), 5.80 (tt, J = 56, 4.2Hz, 1H), 3.72 (s, 3H), 3.15 (td , J = 15.2, 4.2Hz, 2H)

本活性化合物［８１］
¹H-NMR (CDCl₃)δ: 9.15 (s, 1H), 8.92(d, J=5.1Hz, 1H), 8.76(m, 1H), 8.31(m, 1H), 7.46(dd, J=4.9, 0.7Hz, 1H), 6.82(brs, 1H), 5.85(brs, 1H), 3.81(s, 3H) Production Example 81
The active compound [74] (0.15 g) was suspended in 2 ml of methanol, 0.5 ml of 2N aqueous sodium hydroxide solution and 0.3 ml of 30% aqueous hydrogen peroxide were added, and the mixture was stirred at room temperature for 1 hour. Water was poured into the reaction mixture, and the mixture was extracted with chloroform. The organic layer was washed with a saturated aqueous sodium thiosulfate solution, dried over sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel preparative thin layer chromatography to obtain 29 mg of a compound represented by the formula [81] (hereinafter referred to as the present active compound [81]).

The active compound [81]
¹ H-NMR (CDCl ₃ ) δ: 9.15 (s, 1H), 8.92 (d, J = 5.1Hz, 1H), 8.76 (m, 1H), 8.31 (m, 1H), 7.46 (dd, J = 4.9 , 0.7Hz, 1H), 6.82 (brs, 1H), 5.85 (brs, 1H), 3.81 (s, 3H)

本活性化合物［８２］
¹H-NMR (CDCl₃)δ: 9.13(d, J=0.7Hz, 1H), 8.93(d, J=4.9Hz, 1H), 8.78(m, 1H), 8.38(m, 1H), 7.56(dd, J=4.9, 0.7Hz, 1H), 5.77(tt, J=53.5, 2.9Hz, 1H), 3.80(s, 3H) Production Example 82
The active compound [71] (0.20 g) was suspended in 3 ml of DMF, 0.05 g of 60% sodium hydride (oil) was added under water cooling, and the mixture was stirred at room temperature for 5 minutes. 1-Bromo-1,1,2,2-tetrafluoroethane (0.16 g) was added to the mixture, and the mixture was stirred overnight at room temperature. Water was poured into the reaction mixture under ice-cooling, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed successively with water and saturated aqueous sodium chloride solution, dried over sodium sulfate, and concentrated under reduced pressure. The obtained solid was washed with t-butyl methyl ether to obtain 0.16 g of a compound represented by the formula [82] (hereinafter referred to as the present active compound [82]).

The active compound [82]
¹ H-NMR (CDCl ₃ ) δ: 9.13 (d, J = 0.7Hz, 1H), 8.93 (d, J = 4.9Hz, 1H), 8.78 (m, 1H), 8.38 (m, 1H), 7.56 ( dd, J = 4.9, 0.7Hz, 1H), 5.77 (tt, J = 53.5, 2.9Hz, 1H), 3.80 (s, 3H)

本活性化合物［８３］
¹H-NMR (CDCl₃)δ: 9.10(s,1H), 8.90(d, J=4.9Hz, 1H), 8.14(s, 1H), 7.67(dd, J=8.5, 1.2Hz, 1H), 7.56-7.54(m, 2H), 5.76(tt, J=53.5, 3.2Hz, 1H), 3.72(s, 3H) Production Example 83
Instead of the active compound [71], 0.20 g of the active compound [76] was used, and according to the method described in Preparation Example 82, a compound represented by the formula [83] (hereinafter referred to as the active compound [83] and 0.22 g was obtained.

The active compound [83]
¹ H-NMR (CDCl ₃ ) δ: 9.10 (s, 1H), 8.90 (d, J = 4.9Hz, 1H), 8.14 (s, 1H), 7.67 (dd, J = 8.5, 1.2Hz, 1H), 7.56-7.54 (m, 2H), 5.76 (tt, J = 53.5, 3.2Hz, 1H), 3.72 (s, 3H)

本活性化合物［８４］
¹H-NMR (CDCl₃) δ: 8.90(s, 1H), 8.76(d, J=2.0Hz, 1H), 8.72(d, J=4.9Hz, 1H), 8.35(d, J=2.0Hz, 1H), 7.43(d, J=4.9Hz, 1H), 4.49(dt, J=46.9, 6.0, 2H), 3.81(s, 3H), 3.14(dt, J=20.7, 6.1Hz, 2H) Production Example 84
In place of 1-bromo-1,1,2,2-tetrafluoroethane, 0.16 g of 1-bromo-2-fluoroethane is used and represented by the formula [84] according to the method described in Production Example 82. 0.21 g of a compound (hereinafter referred to as the present active compound [84]) was obtained.

The active compound [84]
¹ H-NMR (CDCl ₃ ) δ: 8.90 (s, 1H), 8.76 (d, J = 2.0Hz, 1H), 8.72 (d, J = 4.9Hz, 1H), 8.35 (d, J = 2.0Hz, 1H), 7.43 (d, J = 4.9Hz, 1H), 4.49 (dt, J = 46.9, 6.0, 2H), 3.81 (s, 3H), 3.14 (dt, J = 20.7, 6.1Hz, 2H)

本活性化合物［８５］
¹H-NMR (CDCl₃) δ: 8.87(s, 1H), 8.69(d, J=4.9Hz, 1H), 8.12(m, 1H), 7.63(dd, J=8.5, 1.7, 1H), 7.54(d, J=8.5Hz, 1H), 7.44(d, J=4.9Hz, 1H), 4.46(dt, J=46.8, 6.1Hz, 2H), 3.72(s, 3H), 3.09(dt, J=21.0, 6.0Hz, 2H)

本活性化合物［８６］
¹H-NMR (CDCl₃) δ: 8.79(s, 1H), 8.67(d, J=4.9Hz, 1H), 8.13(m, 1H), 7.63(dd, J=8.5, 1.2Hz, 1H), 7.52(d, J=8.5Hz, 1H), 7.45(dd, J=4.9, 0.7Hz, 1H), 6.41(dd, J=16.5, 9.4Hz, 1H), 5.44(d, J=16.6Hz, 1H), 5.40(d, J=9.5Hz, 1H), 3.74(s, 3H)． Production Example 85 and Production Example 86
The active compound [76] (0.20 g) was suspended in 3 ml of DMF, 0.05 g of 60% sodium hydride (oil) was added under water cooling, and the mixture was stirred at room temperature for 10 minutes. To the mixture was added 0.16 g of 1-bromo-2-fluoroethane, and the mixture was stirred at room temperature overnight. Water was poured into the reaction mixture under ice cooling, and the resulting crystals were collected by filtration, washed with water, and dried under reduced pressure. The obtained crystals were subjected to silica gel preparative thin-layer chromatography, and 0.12 g of a compound represented by the formula [85] (hereinafter referred to as the present active compound [85]) and a compound represented by the formula [86] ( Hereinafter referred to as the present active compound [86].) 50 mg was obtained.

The active compound [85]
¹ H-NMR (CDCl ₃ ) δ: 8.87 (s, 1H), 8.69 (d, J = 4.9Hz, 1H), 8.12 (m, 1H), 7.63 (dd, J = 8.5, 1.7, 1H), 7.54 (d, J = 8.5Hz, 1H), 7.44 (d, J = 4.9Hz, 1H), 4.46 (dt, J = 46.8, 6.1Hz, 2H), 3.72 (s, 3H), 3.09 (dt, J = (21.0, 6.0Hz, 2H)

The active compound [86]
¹ H-NMR (CDCl ₃ ) δ: 8.79 (s, 1H), 8.67 (d, J = 4.9Hz, 1H), 8.13 (m, 1H), 7.63 (dd, J = 8.5, 1.2Hz, 1H), 7.52 (d, J = 8.5Hz, 1H), 7.45 (dd, J = 4.9, 0.7Hz, 1H), 6.41 (dd, J = 16.5, 9.4Hz, 1H), 5.44 (d, J = 16.6Hz, 1H ), 5.40 (d, J = 9.5Hz, 1H), 3.74 (s, 3H).

本活性化合物［８７］
¹H-NMR (CDCl₃) δ: 9.30(s, 1H), 9.00(d, J=4.9Hz, 1H), 8.76(d, J=1.2Hz, 1H), 8.29(d, J=1.5Hz, 1H), 7.49(d, J=4.9Hz, 1H), 3.73(s, 3H), 2.73(s, 6H) Production Example 87
The active compound [72] (0.16 g) was suspended in 3 ml of THF, 0.2 ml of a 50% aqueous dimethylamine solution was added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure, and the obtained residue was subjected to silica gel preparative thin layer chromatography to obtain 73 mg of a compound represented by the formula [87] (hereinafter referred to as the present active compound [87]).

The active compound [87]
¹ H-NMR (CDCl ₃ ) δ: 9.30 (s, 1H), 9.00 (d, J = 4.9Hz, 1H), 8.76 (d, J = 1.2Hz, 1H), 8.29 (d, J = 1.5Hz, 1H), 7.49 (d, J = 4.9Hz, 1H), 3.73 (s, 3H), 2.73 (s, 6H)

本活性化合物［８８］
¹H-NMR (CDCl₃) δ: 9.47(s, 1H), 9.07(d, J=4.9Hz, 1H), 8.80(d, J=1.7Hz, 1H), 8.33(d, J=2.0Hz, 1H), 7.53(d, J=4.9Hz, 1H), 6.25(brs, 2H), 3.89(s, 3H) Production Example 88
The active compound [72] (0.18 g) was suspended in THF (3 ml), 28% aqueous ammonia (0.2 ml) was added, and the mixture was stirred at room temperature for 2 hr. The reaction mixture was concentrated under reduced pressure, and the obtained residue was subjected to silica gel column chromatography to obtain 74 mg of a compound represented by the formula [88] (hereinafter referred to as the present active compound [88]).

The active compound [88]
¹ H-NMR (CDCl ₃ ) δ: 9.47 (s, 1H), 9.07 (d, J = 4.9Hz, 1H), 8.80 (d, J = 1.7Hz, 1H), 8.33 (d, J = 2.0Hz, 1H), 7.53 (d, J = 4.9Hz, 1H), 6.25 (brs, 2H), 3.89 (s, 3H)

本活性化合物［８９］
¹H-NMR (CDCl₃) δ: 8.79(s, 1H), 8.75(d, J=1.2Hz, 1H), 8.66(d, J=4.9Hz, 1H), 8.36(d, J=1.5Hz, 1H), 7.41(d, J=4.9Hz, 1H), 5.79-5.68(m, 1H), 5.11(dd, J=12.6, 1.1Hz, 1H), 5.08(dd, J=5.5, 1.1Hz, 1H), 3.81(s, 3H), 3.48(dt, J=6.9, 1.1Hz, 2H) Production Example 89
A compound represented by the formula [89] according to the method described in Production Example 82, using 0.16 g of 3-bromo-1-propene instead of 1-bromo-1,1,2,2-tetrafluoroethane. (Hereinafter referred to as the present active compound [89].) 0.13 g was obtained.

The active compound [89]
¹ H-NMR (CDCl ₃ ) δ: 8.79 (s, 1H), 8.75 (d, J = 1.2Hz, 1H), 8.66 (d, J = 4.9Hz, 1H), 8.36 (d, J = 1.5Hz, 1H), 7.41 (d, J = 4.9Hz, 1H), 5.79-5.68 (m, 1H), 5.11 (dd, J = 12.6, 1.1Hz, 1H), 5.08 (dd, J = 5.5, 1.1Hz, 1H ), 3.81 (s, 3H), 3.48 (dt, J = 6.9, 1.1Hz, 2H)

本活性化合物［９０］
¹H-NMR (CDCl₃) δ: 8.77(d, J=0.7Hz, 1H), 8.64(d, J=4.9Hz, 1H), 8.14(m, 1H), 7.64(dd, J=8.5, 1.2Hz, 1H), 7.53(d, J=8.5Hz, 1H), 7.42(dd, J=4.9, 0.7Hz, 1H), 5.77-5.67(m, 1H), 5.12-5.05(m, 2H), 3.72(s, 3H), 3.44(dt, J=7.0, 1.1Hz, 2H) Production Example 90
0.20 g of this active compound [76] was used in place of this active compound [71], and 0.16 g of 3-bromo-1-propene was used in place of 1-bromo-1,1,2,2-tetrafluoroethane. In accordance with the method described in Production Example 82, 0.12 g of a compound represented by the formula [90] (hereinafter referred to as the present active compound [90]) was obtained.

The active compound [90]
¹ H-NMR (CDCl ₃ ) δ: 8.77 (d, J = 0.7Hz, 1H), 8.64 (d, J = 4.9Hz, 1H), 8.14 (m, 1H), 7.64 (dd, J = 8.5, 1.2 Hz, 1H), 7.53 (d, J = 8.5Hz, 1H), 7.42 (dd, J = 4.9, 0.7Hz, 1H), 5.77-5.67 (m, 1H), 5.12-5.05 (m, 2H), 3.72 (s, 3H), 3.44 (dt, J = 7.0, 1.1Hz, 2H)

本活性化合物［９１］
¹H-NMR (CDCl₃) δ: 8.98(d, J=0.5Hz, 1H), 8.76(m, 1H), 8.74(d, J=4.9Hz, 1H), 8.35(m, 1H), 7.44(dd, J=5.5, 0.6Hz, 1H), 3.82(s, 3H), 3.59(d, J=2.7Hz, 2H), 2.23(t, J=2.6Hz, 1H) Production Example 91
A compound represented by the formula [91] according to the method described in Production Example 82, using 0.16 g of 3-bromo-1-propyne instead of 1-bromo-1,1,2,2-tetrafluoroethane. (Hereinafter referred to as the present active compound [91].) 70 mg was obtained.

The active compound [91]
¹ H-NMR (CDCl ₃ ) δ: 8.98 (d, J = 0.5Hz, 1H), 8.76 (m, 1H), 8.74 (d, J = 4.9Hz, 1H), 8.35 (m, 1H), 7.44 ( dd, J = 5.5, 0.6Hz, 1H), 3.82 (s, 3H), 3.59 (d, J = 2.7Hz, 2H), 2.23 (t, J = 2.6Hz, 1H)

本活性化合物［９２］
¹H-NMR (CDCl₃) δ: 8.95(s, 1H), 8.71(d, J=4.9Hz, 1H), 8.13(m, 1H), 7.64(d, J=8.5Hz, 1H), 7.53(d, J=8.5Hz, 1H), 7.44(dd, J=4.9, 0.7Hz, 1H), 3.73(s, 3H), 3.55(d, J=2.4Hz, 2H), 2.21(t, J=2.6Hz, 1H) Production Example 92
0.20 g of the active compound [76] was used in place of the active compound [71], and 0.16 g of 3-bromo-1-propyne in place of 1-bromo-1,1,2,2-tetrafluoroethane In accordance with the method described in Production Example 82, 45 mg of a compound represented by the formula [92] (hereinafter referred to as the present active compound [92]) was obtained.

The active compound [92]
¹ H-NMR (CDCl ₃ ) δ: 8.95 (s, 1H), 8.71 (d, J = 4.9Hz, 1H), 8.13 (m, 1H), 7.64 (d, J = 8.5Hz, 1H), 7.53 ( d, J = 8.5Hz, 1H), 7.44 (dd, J = 4.9, 0.7Hz, 1H), 3.73 (s, 3H), 3.55 (d, J = 2.4Hz, 2H), 2.21 (t, J = 2.6 Hz, 1H)

本活性化合物［９３］
¹H-NMR (CDCl₃) δ: 9.03(d, J=0.7Hz, 1H), 8.85(d, J=4.9Hz, 1H), 8.76(d, J=1.2Hz, 1H), 8.29(d, J=1.5Hz, 1H), 7.41(d, J=5.0, 0.6Hz, 1H), 7.25(brs, 1H), 3.80(s, 3H), 2.86(d, J=4.9Hz, 3H) Production Example 93
0.15 g of the active compound [75] was suspended in 3 ml of chloroform, 1 drop of DMF and 0.29 g of oxalyl chloride were added under ice cooling, and the mixture was stirred at room temperature for 15 minutes. The mixture was concentrated under reduced pressure, the residue was suspended in 3 ml of THF, 0.2 ml of 40% methylamine aqueous solution was added under ice cooling, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was concentrated under reduced pressure, and the residue was subjected to preparative thin layer chromatography on silica gel to obtain 34 mg of a compound represented by the formula [93] (hereinafter referred to as the present active compound [93]).

The active compound [93]
¹ H-NMR (CDCl ₃ ) δ: 9.03 (d, J = 0.7Hz, 1H), 8.85 (d, J = 4.9Hz, 1H), 8.76 (d, J = 1.2Hz, 1H), 8.29 (d, J = 1.5Hz, 1H), 7.41 (d, J = 5.0, 0.6Hz, 1H), 7.25 (brs, 1H), 3.80 (s, 3H), 2.86 (d, J = 4.9Hz, 3H)

本活性化合物［９４］
¹H-NMR (CDCl₃) δ: 9.09(s, 1H), 8.91(d, J=4.9Hz, 1H), 8.75(m, 1H), 8.30(m, 1H), 7.46(dd, J=4.9, 0.7Hz, 1H), 6.47(brs, 1H), 3.80(s, 3H), 3.34-3.27(m, 2H), 1.00(t, J=7.2Hz, 3H) Production Example 94
The active compound [75] (0.15 g) was suspended in chloroform (3 ml), 1 drop of DMF and 0.12 g of oxalyl chloride were added under water cooling, and the mixture was stirred at room temperature for 2 hours and concentrated under reduced pressure. The residue was suspended in 2.5 ml of THF, added to a mixture of 0.5 ml of 70% aqueous ethylamine solution and 2.5 ml of THF, and stirred for 1 hour. The reaction mixture was concentrated under reduced pressure, and the residue was subjected to silica gel preparative thin layer chromatography to obtain 0.10 g of a compound represented by the formula [94] (hereinafter referred to as the present active compound [94]).

The active compound [94]
¹ H-NMR (CDCl ₃ ) δ: 9.09 (s, 1H), 8.91 (d, J = 4.9Hz, 1H), 8.75 (m, 1H), 8.30 (m, 1H), 7.46 (dd, J = 4.9 , 0.7Hz, 1H), 6.47 (brs, 1H), 3.80 (s, 3H), 3.34-3.27 (m, 2H), 1.00 (t, J = 7.2Hz, 3H)

本活性化合物［９５］
¹H-NMR (CDCl₃) δ: 8.87(d, J=5.1Hz, 1H), 8.80(d, J=0.7Hz, 1H), 8.73(m, 1H), 8.28(m, 1H), 7.53(dd, J=5.1, 0.7Hz, 1H), 3.89(s, 3H), 3.01(s, 3H), 3.00(s, 6H) Production Example 95
Using 50% dimethylamine aqueous solution instead of 70% ethylamine aqueous solution, 93 mg of a compound represented by the formula [95] (hereinafter referred to as the present active compound [95]) was obtained according to the method described in Production Example 94. It was.

The active compound [95]
¹ H-NMR (CDCl ₃ ) δ: 8.87 (d, J = 5.1Hz, 1H), 8.80 (d, J = 0.7Hz, 1H), 8.73 (m, 1H), 8.28 (m, 1H), 7.53 ( dd, J = 5.1, 0.7Hz, 1H), 3.89 (s, 3H), 3.01 (s, 3H), 3.00 (s, 6H)

本活性化合物［９６］
¹H-NMR (CDCl₃)δ :8.86(d, J=5.1Hz, 1H), 8.79(d, J=0.7Hz, 1H), 8.73(m, 1H), 8.24(m, 1H), 7.52(dd, J=5.1, 0.7Hz, 1H), 3.89(s, 3H), 3.42(q, J=7.0Hz, 2H), 3.31(q, J=7.2Hz, 2H), 1.15(t, J=7.2Hz, 3H), 0.96(t, J=7.1Hz, 3H) Production Example 96
Using 0.5 ml of diethylamine instead of the 70% aqueous solution of ethylamine, 83 mg of a compound represented by the formula [96] (hereinafter referred to as the active compound [96]) was obtained according to the method described in Production Example 94. .

The active compound [96]
¹ H-NMR (CDCl ₃ ) δ: 8.86 (d, J = 5.1Hz, 1H), 8.79 (d, J = 0.7Hz, 1H), 8.73 (m, 1H), 8.24 (m, 1H), 7.52 ( dd, J = 5.1, 0.7Hz, 1H), 3.89 (s, 3H), 3.42 (q, J = 7.0Hz, 2H), 3.31 (q, J = 7.2Hz, 2H), 1.15 (t, J = 7.2 Hz, 3H), 0.96 (t, J = 7.1Hz, 3H)

本活性化合物［９７］
¹H-NMR (CDCl₃)δ: 8.95(brs, 1H), 8.89(d, J=5.1Hz, 1H), 8.73(m, 1H), 8.30(m, 1H), 7.54(dd, J=5.1, 0.7Hz, 1H), 3.91(s, 3H), 3.56(brs, 3H), 3.23(s, 3H) Production Example 97
To a mixture of 1.0 g of this active compound [75], 0.30 g of N-methoxymethanamine hydrochloride, 20 mg of 1-hydroxybenzotriazole and 10 ml of pyridine, 0.71 g of WSC was added and stirred at room temperature for 5 hours. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over sodium sulfate, and concentrated under reduced pressure. The obtained solid was washed with hexane to obtain 0.13 g of a compound represented by the formula [97] (hereinafter referred to as the present active compound [97]).

The active compound [97]
¹ H-NMR (CDCl ₃ ) δ: 8.95 (brs, 1H), 8.89 (d, J = 5.1Hz, 1H), 8.73 (m, 1H), 8.30 (m, 1H), 7.54 (dd, J = 5.1 , 0.7Hz, 1H), 3.91 (s, 3H), 3.56 (brs, 3H), 3.23 (s, 3H)

本活性化合物［９８］
¹H-NMR (CDCl₃)δ: 9.19(d, J=0.7Hz, 2H), 8.96(d, J=5.1Hz, 1H), 8.79(d, J=1.2Hz, 1H), 8.37(d, J=1.5Hz, 1H), 8.14(brt, J=5.6Hz, 1H), 7.47(dd, J=5.0, 0.6Hz, 1H), 4.23(d, J=5.9Hz, 2H), 3.87(s, 3H) Production Example 98
In place of N-methoxymethanamine hydrochloride, 0.06 g of 2-aminoacetonitrile hydrochloride was used, and a compound of the formula [98] (hereinafter referred to as the active compound [98]) was prepared according to the method described in Production Example 97. 0.12 g was obtained.

The active compound [98]
¹ H-NMR (CDCl ₃ ) δ: 9.19 (d, J = 0.7Hz, 2H), 8.96 (d, J = 5.1Hz, 1H), 8.79 (d, J = 1.2Hz, 1H), 8.37 (d, J = 1.5Hz, 1H), 8.14 (brt, J = 5.6Hz, 1H), 7.47 (dd, J = 5.0, 0.6Hz, 1H), 4.23 (d, J = 5.9Hz, 2H), 3.87 (s, 3H)

本活性化合物［９９］
¹H-NMR (CDCl₃)δ: 9.40(d, J=0.7Hz, 1H), 8.99(d, J=5.1Hz, 1H), 8.74(m, 1H), 8.31(m, 1H), 7.52(dd, J=5.0, 0.6Hz, 1H), 3.81(s, 3H), 3.71(s, 3H) Production Example 99
The active compound [75] (0.20 g) was suspended in 10 ml of methanol, 1 drop of concentrated sulfuric acid was added, and the mixture was heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure, saturated aqueous sodium hydrogen carbonate solution was added to the residue, and the mixture was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium bicarbonate solution, dried over sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 46 mg of a compound represented by the formula [99] (hereinafter referred to as the present active compound [99]).

The active compound [99]
¹ H-NMR (CDCl ₃ ) δ: 9.40 (d, J = 0.7Hz, 1H), 8.99 (d, J = 5.1Hz, 1H), 8.74 (m, 1H), 8.31 (m, 1H), 7.52 ( dd, J = 5.0, 0.6Hz, 1H), 3.81 (s, 3H), 3.71 (s, 3H)

本活性化合物［１００］
¹H-NMR (CDCl₃)δ: 9.41(d, J=0.7Hz, 1H), 8.99(d, J=4.9Hz, 1H), 8.74(m, 1H), 8.31(m, 1H), 7.52(dd, J=4.9, 0.7Hz, 1H), 4.23(q, J=7.2Hz, 2H), 3.70(s, 3H), 1.10(t, J=7.1Hz, 3H) Production Example 100
Using ethanol instead of methanol, 0.16 g of a compound represented by the formula [100] (hereinafter referred to as the present active compound [100]) was obtained according to the method described in Production Example 99.

The active compound [100]
¹ H-NMR (CDCl ₃ ) δ: 9.41 (d, J = 0.7Hz, 1H), 8.99 (d, J = 4.9Hz, 1H), 8.74 (m, 1H), 8.31 (m, 1H), 7.52 ( dd, J = 4.9, 0.7Hz, 1H), 4.23 (q, J = 7.2Hz, 2H), 3.70 (s, 3H), 1.10 (t, J = 7.1Hz, 3H)

本活性化合物［１０１］
¹H-NMR (CDCl₃)δ: 8.83(s, 1H), 8.75(m, 1H), 8.65(d, J=5.1Hz, 1H), 8.35(m, 1H), 7.40(dd, J=4.9, 0.6Hz, 1H), 3.82(s, 3H), 2.82(d, J=7.1Hz, 2H), 0.99-0.89(m, 1H), 0.56-0.51(m, 2H), 0.18-0.14(m, 2H) Production Example 101
This active compound [71] (0.31 g) was suspended in 3 ml of DMF, and 0.07 g of 60% sodium hydride (oil) was added under water cooling, followed by stirring at room temperature for 5 minutes. To the mixture was added 0.27 g of (bromomethyl) cyclopropane, and the mixture was stirred at room temperature for 1 hour. A saturated aqueous sodium chloride solution was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium chloride solution, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to medium pressure preparative liquid chromatography to obtain 0.17 g of a compound represented by the formula [101] (hereinafter referred to as the present active compound [101]).

The active compound [101]
¹ H-NMR (CDCl ₃ ) δ: 8.83 (s, 1H), 8.75 (m, 1H), 8.65 (d, J = 5.1Hz, 1H), 8.35 (m, 1H), 7.40 (dd, J = 4.9 , 0.6Hz, 1H), 3.82 (s, 3H), 2.82 (d, J = 7.1Hz, 2H), 0.99-0.89 (m, 1H), 0.56-0.51 (m, 2H), 0.18-0.14 (m, 2H)

本活性化合物［１０２］
¹H-NMR (CDCl₃)δ: 8.81(s, 1H), 8.63(d, J=4.8Hz, 1H), 8.13(s, 1H), 7.64(dd, J=8.6, 1.3Hz, 1H), 7.53(d, J=8.6Hz, 1H), 7.41(dd, J=4.9, 0.6Hz, 1H), 3.73(s, 3H), 2.77(d, J=7.1Hz, 2H), 0.96-0.86(m, 1H), 0.53-0.49(m, 2H), 0.16-0.12(m, 2H) Production Example 102
This active compound [76] (0.31 g) was suspended in 3 ml of DMF, and 0.07 g of 60% sodium hydride (oil) was added under water cooling, followed by stirring at room temperature for 5 minutes. To the mixture was added 0.27 g of (bromomethyl) cyclopropane, and the mixture was stirred at room temperature for 1 hour. A saturated aqueous sodium chloride solution was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium chloride solution, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to medium pressure preparative liquid chromatography to obtain 0.19 g of a compound represented by the formula [102] (hereinafter referred to as the present active compound [102]).

The active compound [102]
¹ H-NMR (CDCl ₃ ) δ: 8.81 (s, 1H), 8.63 (d, J = 4.8Hz, 1H), 8.13 (s, 1H), 7.64 (dd, J = 8.6, 1.3Hz, 1H), 7.53 (d, J = 8.6Hz, 1H), 7.41 (dd, J = 4.9, 0.6Hz, 1H), 3.73 (s, 3H), 2.77 (d, J = 7.1Hz, 2H), 0.96-0.86 (m , 1H), 0.53-0.49 (m, 2H), 0.16-0.12 (m, 2H)

本活性化合物［１０３］
¹H-NMR (CDCl₃)δ: 8.87(d, J=0.5Hz, 1H), 8.75(d, J=1.5Hz, 1H), 8.67(d, J=4.8Hz, 1H), 8.35(d, J=1.5Hz, 1H), 7.40(dd, J=4.9, 0.6Hz, 1H), 3.81(s, 3H), 3.51(t, J=6.2Hz, 2H), 3.28(s, 3H), 3.07(t, J=6.2Hz, 2H) Production Example 103
In place of (bromomethyl) cyclopropane, 0.28 g of 1-bromo-2-methoxyethane was used, and a compound represented by the formula [103] (hereinafter referred to as the active compound [103]) was prepared according to the method described in Production Example 101. 73 mg was obtained.

The active compound [103]
¹ H-NMR (CDCl ₃ ) δ: 8.87 (d, J = 0.5Hz, 1H), 8.75 (d, J = 1.5Hz, 1H), 8.67 (d, J = 4.8Hz, 1H), 8.35 (d, J = 1.5Hz, 1H), 7.40 (dd, J = 4.9, 0.6Hz, 1H), 3.81 (s, 3H), 3.51 (t, J = 6.2Hz, 2H), 3.28 (s, 3H), 3.07 ( (t, J = 6.2Hz, 2H)

本活性化合物［１０４］
¹H-NMR (CDCl₃)δ: 8.85(s, 1H), 8.65(d, J=5.1Hz, 1H), 8.12(s, 1H), 7.64(dd, J=8.6, 1.3Hz, 1H), 7.53(d, J=8.3Hz, 1H), 7.42(dd, J=4.9, 0.6Hz, 1H), 3.72(s, 3H), 3.47(t, J=6.2Hz, 2H), 3.26(s, 3H), 3.01(t, J=6.3Hz, 2H) Production Example 104
In place of (bromomethyl) cyclopropane, 0.28 g of 1-bromo-2-methoxyethane was used, and the compound represented by the formula [104] (hereinafter referred to as this active compound [104]) was prepared according to the method described in Production Example 102. 0.17 g was obtained.

The active compound [104]
¹ H-NMR (CDCl ₃ ) δ: 8.85 (s, 1H), 8.65 (d, J = 5.1Hz, 1H), 8.12 (s, 1H), 7.64 (dd, J = 8.6, 1.3Hz, 1H), 7.53 (d, J = 8.3Hz, 1H), 7.42 (dd, J = 4.9, 0.6Hz, 1H), 3.72 (s, 3H), 3.47 (t, J = 6.2Hz, 2H), 3.26 (s, 3H ), 3.01 (t, J = 6.3Hz, 2H)

本活性化合物［１０５］
¹H-NMR (CDCl₃)δ: 8.75(m, 1H), 8.63(s, 1H), 8.61(d, J=4.8Hz, 1H), 8.36(m, 1H), 7.37(dd, J=4.9, 0.6Hz, 1H), 3.99-3.89(m, 1H), 3.82(s, 3H), 2.47-2.42(m, 2H), 2.05-1.96(m, 2H) Production Example 105
Using 0.27 g of bromocyclobutane instead of (bromomethyl) cyclopropane, 82 mg of a compound represented by the formula [105] (hereinafter referred to as the present active compound [105]) according to the method described in Production Example 101 was obtained. It was.

The active compound [105]
¹ H-NMR (CDCl ₃ ) δ: 8.75 (m, 1H), 8.63 (s, 1H), 8.61 (d, J = 4.8Hz, 1H), 8.36 (m, 1H), 7.37 (dd, J = 4.9 , 0.6Hz, 1H), 3.99-3.89 (m, 1H), 3.82 (s, 3H), 2.47-2.42 (m, 2H), 2.05-1.96 (m, 2H)

本活性化合物［１０６］
¹H-NMR (CDCl₃)δ: 8.61(s, 1H), 8.58(d, J=5.1Hz, 1H), 8.14(m, 1H), 7.64(d, J=8.6Hz, 1H), 7.53(d, J=8.6Hz, 1H), 7.38(d, J=4.8Hz, 1H), 3.93-3.85(m, 1H), 3.73(s, 3H), 2.46-2.39(m, 2H), 2.07-1.92(m, 4H) Production Example 106
Using 0.27 g of bromocyclobutane instead of (bromomethyl) cyclopropane, 51 mg of a compound represented by the formula [106] (hereinafter referred to as the present active compound [106]) according to the method described in Production Example 102 was obtained. It was.

The active compound [106]
¹ H-NMR (CDCl ₃ ) δ: 8.61 (s, 1H), 8.58 (d, J = 5.1Hz, 1H), 8.14 (m, 1H), 7.64 (d, J = 8.6Hz, 1H), 7.53 ( d, J = 8.6Hz, 1H), 7.38 (d, J = 4.8Hz, 1H), 3.93-3.85 (m, 1H), 3.73 (s, 3H), 2.46-2.39 (m, 2H), 2.07-1.92 (m, 4H)

本活性化合物［１０７］
¹H-NMR (CDCl₃)δ: 8.82(s, 1H), 8.75(m, 1H), 8.63(d, J=5.1Hz, 1H), 8.35(m, 1H), 7.38(d, J=4.8Hz, 1H), 3.80(s, 3H), 3.63-3.56(m, 1H), 2.04-1.98(m, 2H), 1.72-1.64(m, 2H), 1.59-1.48(m, 4H) Production Example 107
A compound represented by the formula [107] according to the method described in Production Example 101 (hereinafter referred to as the present active compound [107]) using 0.30 g of bromocyclopentane instead of (bromomethyl) cyclopropane. 13 g was obtained.

The active compound [107]
¹ H-NMR (CDCl ₃ ) δ: 8.82 (s, 1H), 8.75 (m, 1H), 8.63 (d, J = 5.1Hz, 1H), 8.35 (m, 1H), 7.38 (d, J = 4.8 Hz, 1H), 3.80 (s, 3H), 3.63-3.56 (m, 1H), 2.04-1.98 (m, 2H), 1.72-1.64 (m, 2H), 1.59-1.48 (m, 4H)

本活性化合物［１０８］
¹H-NMR (CDCl₃)δ: 8.80(m, 1H), 8.61(d, J=4.8Hz, 1H), 8.13(m, 1H), 7.63(dd, J=8.3, 1.3Hz, 1H), 7.53(d, J=8.6Hz, 1H), 7.39(dd, J=4.8, 0.8Hz, 1H), 3.71(s, 3H), 3.58-3.52(m, 1H), 2.05-1.95(m, 2H), 1.72-1.62(m, 2H), 1.60-1.46(m, 4H) Production Example 108
A compound represented by the formula [108] according to the method described in Production Example 102 using 0.30 g of bromocyclopentane instead of (bromomethyl) cyclopropane (hereinafter referred to as the present active compound [108]). 30 g was obtained.

The active compound [108]
¹ H-NMR (CDCl ₃ ) δ: 8.80 (m, 1H), 8.61 (d, J = 4.8Hz, 1H), 8.13 (m, 1H), 7.63 (dd, J = 8.3, 1.3Hz, 1H), 7.53 (d, J = 8.6Hz, 1H), 7.39 (dd, J = 4.8, 0.8Hz, 1H), 3.71 (s, 3H), 3.58-3.52 (m, 1H), 2.05-1.95 (m, 2H) , 1.72-1.62 (m, 2H), 1.60-1.46 (m, 4H)

本活性化合物［１０９］
¹H-NMR (CDCl₃)δ: 9.09(s, 1H), 8.89(d, J=4.8Hz, 1H), 8.78(d, J=1.3Hz, 1H), 8.36(d, J=1.5Hz, 1H), 7.51(d, J=4.8Hz, 1H), 3.84(s, 3H), 3.71(s, 2H) Production Example 109
Using 0.24 g of bromoacetonitrile instead of (bromomethyl) cyclopropane, 0.23 g of a compound represented by the formula [109] according to the method described in Production Example 101 (hereinafter referred to as the present active compound [109]) Got.

The active compound [109]
¹ H-NMR (CDCl ₃ ) δ: 9.09 (s, 1H), 8.89 (d, J = 4.8Hz, 1H), 8.78 (d, J = 1.3Hz, 1H), 8.36 (d, J = 1.5Hz, 1H), 7.51 (d, J = 4.8Hz, 1H), 3.84 (s, 3H), 3.71 (s, 2H)

本活性化合物［１１０］
¹H-NMR (CDCl₃)δ: 9.06(m, 1H), 8.86(d, J=4.8Hz, 1H), 8.13(m, 1H), 7.67(dd, J=8.5, 1.1Hz, 1H), 7.56(d, J=8.3Hz, 1H), 7.49(dd, J=4.9, 0.6Hz, 1H), 3.76(s, 3H), 3.69(s, 2H) Production Example 110
Using 0.24 g of bromoacetonitrile instead of (bromomethyl) cyclopropane, 0.24 g of a compound represented by the formula [110] according to the method described in Production Example 102 (hereinafter referred to as the present active compound [110]) Got.

The active compound [110]
¹ H-NMR (CDCl ₃ ) δ: 9.06 (m, 1H), 8.86 (d, J = 4.8Hz, 1H), 8.13 (m, 1H), 7.67 (dd, J = 8.5, 1.1Hz, 1H), 7.56 (d, J = 8.3Hz, 1H), 7.49 (dd, J = 4.9, 0.6Hz, 1H), 3.76 (s, 3H), 3.69 (s, 2H)

本活性化合物［１１１］
¹H-NMR (CDCl₃)δ: 8.94(d, J=0.5Hz, 1H), 8.80(d, J=4.8Hz, 1H), 8.78(d, J=1.3Hz, 1H), 8.36(d, J=1.5Hz, 1H), 7.48(dd, J=4.8, 0.5Hz, 1H), 3.81(s, 3H), 3.04(t, J=7.1Hz, 2H), 2.56(t, J=6.9Hz, 2H) Production Example 111
A compound represented by the formula [111] according to the method described in Production Example 101 using 0.27 g of 3-bromopropiononitrile instead of (bromomethyl) cyclopropane (hereinafter referred to as the active compound [111]). 0.19 g was obtained.

The active compound [111]
¹ H-NMR (CDCl ₃ ) δ: 8.94 (d, J = 0.5Hz, 1H), 8.80 (d, J = 4.8Hz, 1H), 8.78 (d, J = 1.3Hz, 1H), 8.36 (d, J = 1.5Hz, 1H), 7.48 (dd, J = 4.8, 0.5Hz, 1H), 3.81 (s, 3H), 3.04 (t, J = 7.1Hz, 2H), 2.56 (t, J = 6.9Hz, 2H)

本活性化合物［１１２］
¹H-NMR (CDCl₃)δ: 8.92(m, 1H), 8.78(d, J=4.8Hz, 1H), 8.12(m, 1H), 7.66(dd, J=8.5, 1.4Hz, 1H), 7.55(d, J=8.6Hz, 1H), 7.49(dd, J=4.8, 0.8Hz, 1H), 3.73(s, 3H), 2.98(t, J=6.9Hz, 2H), 2.52(t, J=6.9Hz, 2H) Production Example 112
A compound represented by the formula [112] according to the method described in Production Example 102 using 0.27 g of 3-bromopropiononitrile instead of (bromomethyl) cyclopropane (hereinafter referred to as the present active compound [112]). 0.16 g was obtained.

The active compound [112]
¹ H-NMR (CDCl ₃ ) δ: 8.92 (m, 1H), 8.78 (d, J = 4.8Hz, 1H), 8.12 (m, 1H), 7.66 (dd, J = 8.5, 1.4Hz, 1H), 7.55 (d, J = 8.6Hz, 1H), 7.49 (dd, J = 4.8, 0.8Hz, 1H), 3.73 (s, 3H), 2.98 (t, J = 6.9Hz, 2H), 2.52 (t, J = 6.9Hz, 2H)

本活性化合物［１１３］
¹H-NMR (CDCl₃)δ: 8.90(d, J=0.5Hz, 1H), 8.76(d, J=1.3Hz, 1H), 8.72(d, J=5.1Hz, 1H), 8.36(d, J=1.5Hz, 1H), 7.42(dd, J=4.9, 0.6Hz, 1H), 3.83(s, 3H), 3.67(s, 3H), 3.64(s, 2H) Production Example 113
In place of (bromomethyl) cyclopropane, 0.31 g of 2-bromoacetic acid methyl ester was used, and a compound represented by the formula [113] according to the method described in Production Example 101 (hereinafter referred to as this active compound [113]). ) 0.13 g was obtained.

The active compound [113]
¹ H-NMR (CDCl ₃ ) δ: 8.90 (d, J = 0.5Hz, 1H), 8.76 (d, J = 1.3Hz, 1H), 8.72 (d, J = 5.1Hz, 1H), 8.36 (d, J = 1.5Hz, 1H), 7.42 (dd, J = 4.9, 0.6Hz, 1H), 3.83 (s, 3H), 3.67 (s, 3H), 3.64 (s, 2H)

本活性化合物［１１４］
¹H-NMR (CDCl₃)δ: 8.87(m, 1H), 8.70(d, J=4.8Hz, 1H), 8.13(m, 1H), 7.65(dd, J=8.6, 1.3Hz, 1H), 7.54(d, J=8.3Hz, 1H), 7.43(d, J=4.8Hz, 1H), 3.74(s, 3H), 3.64(s, 3H), 3.60(s, 2H) Production Example 114
In place of (bromomethyl) cyclopropane, 0.31 g of 2-bromoacetic acid methyl ester was used and a compound represented by the formula [114] according to the method described in Production Example 102 (hereinafter referred to as the present active compound [114]). 94 mg was obtained.

The active compound [114]
¹ H-NMR (CDCl ₃ ) δ: 8.87 (m, 1H), 8.70 (d, J = 4.8Hz, 1H), 8.13 (m, 1H), 7.65 (dd, J = 8.6, 1.3Hz, 1H), 7.54 (d, J = 8.3Hz, 1H), 7.43 (d, J = 4.8Hz, 1H), 3.74 (s, 3H), 3.64 (s, 3H), 3.60 (s, 2H)

本活性化合物［１１５］
¹H-NMR (CDCl₃) δ: 8.83(dd, J=4.4, 1.7Hz, 2H), 8.12(s, 1H), 7.72(d, J=8.5Hz, 1H), 7.58-7.54(m, 3H), 4.54-4.44(m, 1H), 2.25-2.12(m, 1H), 1.99-1.87(m, 1H), 1.99-1.88(m, 1H), 1.74(d, J=6.8Hz, 3H), 0.66(t, J=7.3Hz, 3H) Production Example 115
A mixture of 0.76 g of N1-sec-butyl-4-trifluoromethylbenzene-1,2-diamine, 0.84 g of hydroxy-pyridin-4-yl-sodium methanesulfonate and 17 ml of DMF was heated and stirred at 120 ° C. for 1 hour. . After cooling to room temperature, saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted 3 times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 0.91 g of 1-sec-butyl-2-pyridin-4-yl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [115]). Got.

The active compound [115]
¹ H-NMR (CDCl ₃ ) δ: 8.83 (dd, J = 4.4, 1.7Hz, 2H), 8.12 (s, 1H), 7.72 (d, J = 8.5Hz, 1H), 7.58-7.54 (m, 3H ), 4.54-4.44 (m, 1H), 2.25-2.12 (m, 1H), 1.99-1.87 (m, 1H), 1.99-1.88 (m, 1H), 1.74 (d, J = 6.8Hz, 3H), 0.66 (t, J = 7.3Hz, 3H)

本活性化合物［１１６］
¹H-NMR (CDCl₃) δ: 8.83(dd, J=4.4, 1.6Hz, 2H), 8.12(s, 1H), 7.65(dd, J=4.4, 1.6Hz, 2H), 7.60(d, J=8.7Hz, 1H), 7.53(d, J=8.7Hz, 1H), 4.16(d, J=7.6Hz, 2H), 2.17-2.04(m, 1H), 0.78(d, J=6.8Hz, 6H) Production Example 116
In accordance with the method described in Production Example 115, using N1-isobutyl-4-trifluoromethylbenzene-1,2-diamine instead of N1-sec-butyl-4-trifluoromethylbenzene-1,2-diamine 1-isobutyl-2-pyridin-4-yl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [116]) was obtained.

The active compound [116]
¹ H-NMR (CDCl ₃ ) δ: 8.83 (dd, J = 4.4, 1.6Hz, 2H), 8.12 (s, 1H), 7.65 (dd, J = 4.4, 1.6Hz, 2H), 7.60 (d, J = 8.7Hz, 1H), 7.53 (d, J = 8.7Hz, 1H), 4.16 (d, J = 7.6Hz, 2H), 2.17-2.04 (m, 1H), 0.78 (d, J = 6.8Hz, 6H )

本活性化合物［１１７］
¹H-NMR (CDCl₃) δ: 8.85(dd, J=4.4, 1.7Hz, 2H), 7.93 (d, J=8.7Hz, 1H), 7.73(s, 1H), 7.67(dd, J=4.4, 1.7Hz, 2H), 7.59(d, J=8.7Hz, 1H), 4.29 (t, J=7.7Hz, 2H), 1.94-1.84(m, 2H), 0.92(t, J=7.4Hz, 3H) Production Example 117
In accordance with the method described in Production Example 115, using N2-propyl-4-trifluoromethylbenzene-1,2-diamine instead of N1-sec-butyl-4-trifluoromethylbenzene-1,2-diamine 1-propyl-2-pyridin-4-yl-6-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [117]) was obtained.

The active compound [117]
¹ H-NMR (CDCl ₃ ) δ: 8.85 (dd, J = 4.4, 1.7Hz, 2H), 7.93 (d, J = 8.7Hz, 1H), 7.73 (s, 1H), 7.67 (dd, J = 4.4 , 1.7Hz, 2H), 7.59 (d, J = 8.7Hz, 1H), 4.29 (t, J = 7.7Hz, 2H), 1.94-1.84 (m, 2H), 0.92 (t, J = 7.4Hz, 3H )

本活性化合物［１１８］
¹H-NMR(CDCl₃) δ: 8.85(dd, J=4.4, 1.7Hz, 2H), 7.93(d, J=8.3Hz, 1H), 7.75(s, 1H), 7.68(dd, J=4.4, 1.7Hz, 2H), 7.60(d, J=8.3Hz, 1H), 4.39(q, J=7.3Hz, 2H), 1.55(t, J=7.3Hz, 3H) Production Example 118
According to the method described in Production Example 115, using N2-ethyl-4-trifluoromethylbenzene-1,2-diamine instead of N1-sec-butyl-4-trifluoromethylbenzene-1,2-diamine 1-ethyl-2-pyridin-4-yl-6-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [118]) was obtained.

The active compound [118]
¹ H-NMR (CDCl ₃ ) δ: 8.85 (dd, J = 4.4, 1.7Hz, 2H), 7.93 (d, J = 8.3Hz, 1H), 7.75 (s, 1H), 7.68 (dd, J = 4.4 , 1.7Hz, 2H), 7.60 (d, J = 8.3Hz, 1H), 4.39 (q, J = 7.3Hz, 2H), 1.55 (t, J = 7.3Hz, 3H)

本活性化合物［１１９］
¹H-NMR(CDCl₃) δ: 8.84(dd, J=4.4, 1.7Hz, 2H), 7.93(d, J=8.3Hz, 1H), 7.88(s, 1H), 7.60-7.56(m, 3H), 4.55-4.45(m, 1H), 2.24-2.13(m, 1H), 2.00-1.90(m, 1H), 1.75(d, J=6.8Hz, 3H), 0.68(t, J=7.4Hz, 3H) Production Example 119
N2-sec-butyl-4-trifluoromethylbenzene-1,2-diamine was used instead of N1-sec-butyl-4-trifluoromethylbenzene-1,2-diamine, and the method described in Production Example 115 was used. Accordingly, 1-sec-butyl-2-pyridin-4-yl-6-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [119]) was obtained.

The active compound [119]
¹ H-NMR (CDCl ₃ ) δ: 8.84 (dd, J = 4.4, 1.7Hz, 2H), 7.93 (d, J = 8.3Hz, 1H), 7.88 (s, 1H), 7.60-7.56 (m, 3H ), 4.55-4.45 (m, 1H), 2.24-2.13 (m, 1H), 2.00-1.90 (m, 1H), 1.75 (d, J = 6.8Hz, 3H), 0.68 (t, J = 7.4Hz, 3H)

本活性化合物［１２０］
¹H-NMR (CDCl₃) δ: 8.51(s, 1H), 8.45(d, J=4.6Hz, 1H), 8.11(s, 1H), 7.62(d, J=8.5Hz, 1H), 7.54-7.50(m, 2H), 4.15(t, J=6.6Hz, 2H), 3.74 (s, 3H), 1.74-1.66(m, 2H), 1.39-1.29(m, 2H), 0.87(t, J=7.4Hz, 3H) Production Example 120
To a mixture of 0.44 g of 1-butanol and 6 ml of DMF was added 0.24 g of 60% sodium hydride (oil) under ice cooling, and the mixture was stirred for 10 minutes. After adding 0.35 g of 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole, the mixture was warmed to room temperature and further stirred for 1.5 hours. Saturated aqueous ammonium chloride solution was added, and the mixture was extracted 3 times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 2- (3-butoxypyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [120]). 0.37 g was obtained.

The active compound [120]
¹ H-NMR (CDCl ₃ ) δ: 8.51 (s, 1H), 8.45 (d, J = 4.6Hz, 1H), 8.11 (s, 1H), 7.62 (d, J = 8.5Hz, 1H), 7.54- 7.50 (m, 2H), 4.15 (t, J = 6.6Hz, 2H), 3.74 (s, 3H), 1.74-1.66 (m, 2H), 1.39-1.29 (m, 2H), 0.87 (t, J = (7.4Hz, 3H)

本活性化合物［１２１］
¹H-NMR (CDCl₃) δ: 8.50(s, 1H), 8.44(d, J=4.9Hz, 1H), 8.11(s, 1H), 7.61(d, J=8.5Hz, 1H), 7.55(d, J=4.9Hz, 1H), 7.51(d, J=8.5Hz, 1H), 5.34(t, J=6.7Hz, 1H), 4.68(d, J=6.7Hz, 2H), 3.73(s, 3H), 1.73(s, 3H), 1.68(s, 3H) Production Example 121
1-Methyl-2- [3- (3-methyl-2-buteneoxy)-was used according to the method described in Production Example 120, using 3-methyl-2-buten-1-ol instead of 1-butanol. Pyridin-4-yl] -5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [121]) was obtained.

The active compound [121]
¹ H-NMR (CDCl ₃ ) δ: 8.50 (s, 1H), 8.44 (d, J = 4.9Hz, 1H), 8.11 (s, 1H), 7.61 (d, J = 8.5Hz, 1H), 7.55 ( d, J = 4.9Hz, 1H), 7.51 (d, J = 8.5Hz, 1H), 5.34 (t, J = 6.7Hz, 1H), 4.68 (d, J = 6.7Hz, 2H), 3.73 (s, 3H), 1.73 (s, 3H), 1.68 (s, 3H)

本活性化合物［１２２］
¹H-NMR (CDCl₃) δ: 8.83(dd, J=4.4, 1.7Hz, 2H), 7.72(br s, 1H), 7.71(dd, J=4.4, 1.7Hz, 2H), 7.43(d, J=8.8Hz, 1H), 7.29(br s, 1H), 3.95(s, 3H) Production Example 122
In accordance with the method described in Production Example 115, using N1-methyl-4-trifluoromethoxybenzene-1,2-diamine instead of N1-sec-butyl-4-trifluoromethylbenzene-1,2-diamine 1-methyl-2-pyridin-4-yl-6-trifluoromethoxy-1H-benzimidazole (hereinafter referred to as the present active compound [122]) was obtained.

The active compound [122]
¹ H-NMR (CDCl ₃ ) δ: 8.83 (dd, J = 4.4, 1.7Hz, 2H), 7.72 (br s, 1H), 7.71 (dd, J = 4.4, 1.7Hz, 2H), 7.43 (d, J = 8.8Hz, 1H), 7.29 (br s, 1H), 3.95 (s, 3H)

本活性化合物［１２３］
¹H-NMR (CDCl₃) δ: 8.69-8.66(m, 2H), 8.11(s, 1H), 7.69(d, J=5.1Hz, 1H), 7.63(d, J=8.1Hz, 1H), 7.52(d, J=8.1Hz, 1H), 4.75 (d, J=47.1Hz, 2H), 4.50(t, J=3.5Hz, 1H), 4.22(d, J=3.5Hz, 1H), 3.80 (s, 3H) Production Example 123
1,3-Difluoroisopropanol was used in place of 1-butanol, and 2- [3- (1-fluoromethyl-vinyloxy) -pyridin-4-yl] -1-methyl was prepared according to the method described in Production Example 120. -5-Trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [123]) was obtained.

The active compound [123]
¹ H-NMR (CDCl ₃ ) δ: 8.69-8.66 (m, 2H), 8.11 (s, 1H), 7.69 (d, J = 5.1Hz, 1H), 7.63 (d, J = 8.1Hz, 1H), 7.52 (d, J = 8.1Hz, 1H), 4.75 (d, J = 47.1Hz, 2H), 4.50 (t, J = 3.5Hz, 1H), 4.22 (d, J = 3.5Hz, 1H), 3.80 ( s, 3H)

本活性化合物［１２４］
¹H-NMR (CDCl₃) δ: 8.43(d, J=4.8Hz, 1H), 8.35(s, 1H), 8.12(s, 1H), 7.62(d, J=8.7Hz, 1H), 7.55(d, J=4.8Hz, 1H), 7.52(d, J=8.7Hz, 1H), 4.85-4.77(m, 1H), 3.76(s, 3H), 2.52-2.43(m, 2H), 2.17-2.07(m, 2H), 1.90-1.80(m, 1H), 1.77-1.66(m, 1H) Production Example 124
2- (3-Cyclobutoxypyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole was used according to the method described in Production Example 120, using cyclobutanol instead of 1-butanol. (Hereinafter referred to as the present active compound [124]).

The active compound [124]
¹ H-NMR (CDCl ₃ ) δ: 8.43 (d, J = 4.8Hz, 1H), 8.35 (s, 1H), 8.12 (s, 1H), 7.62 (d, J = 8.7Hz, 1H), 7.55 ( d, J = 4.8Hz, 1H), 7.52 (d, J = 8.7Hz, 1H), 4.85-4.77 (m, 1H), 3.76 (s, 3H), 2.52-2.43 (m, 2H), 2.17-2.07 (m, 2H), 1.90-1.80 (m, 1H), 1.77-1.66 (m, 1H)

本活性化合物［１２５］
¹H-NMR (CDCl₃) δ: 8.96(s, 1H), 8.80(d, J=4.9Hz, 1H), 8.76(d, J=1.5Hz, 1H), 8.37(d, J=1.5Hz, 1H), 7.56(d, J=4.9Hz, 1H), 3.91(s, 3H), 3.27(s, 1H) Production Example 125
A mixture of 0.29 g of N2-methyl-5-trifluoromethylpyridine-2,3-diamine, 0.27 g of 3-ethynylisonicotinic acid, 0.35 g of WSC and 8 ml of pyridine was heated and stirred at 120 ° C. for 2 hours. After cooling to room temperature, water was added and extracted three times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 2- (3-ethynylpyridin-4-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the active compound). [Indicated as [125].) 0.15 g was obtained.

The active compound [125]
¹ H-NMR (CDCl ₃ ) δ: 8.96 (s, 1H), 8.80 (d, J = 4.9Hz, 1H), 8.76 (d, J = 1.5Hz, 1H), 8.37 (d, J = 1.5Hz, 1H), 7.56 (d, J = 4.9Hz, 1H), 3.91 (s, 3H), 3.27 (s, 1H)

本活性化合物［１２６］
¹H-NMR (CDCl₃) δ: 9.18(s, 1H), 9.05(d, J=4.8Hz, 1H), 8.78(d, J=1.9Hz, 1H), 8.37(d, J=1.9Hz, 1H), 7.52(d, J=4.8Hz, 1H), 3.75(s, 3H) Production Example 126
Using 3-trifluoromethylisonicotinic acid instead of 3-ethynylisonicotinic acid, and according to the method described in Production Example 125, 3-methyl-6-trifluoromethyl-2- (3-trifluoromethylpyridine) -4-yl) -3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present active compound [126]) was obtained.

The active compound [126]
¹ H-NMR (CDCl ₃ ) δ: 9.18 (s, 1H), 9.05 (d, J = 4.8Hz, 1H), 8.78 (d, J = 1.9Hz, 1H), 8.37 (d, J = 1.9Hz, 1H), 7.52 (d, J = 4.8Hz, 1H), 3.75 (s, 3H)

本活性化合物［１２７］
¹H-NMR (CDCl₃) δ: 8.87(d, J=1.9Hz, 1H), 8.78(d, J=1.9 Hz, 1H), 8.49(ddd, J=6.8, 1.9, 0.5Hz, 1H), 8.31(d, J=1.9Hz, 1H), 7.45(d, J=6.8Hz, 1H), 3.80(d, J=0.5Hz, 3H), 3.55(q, J=7.4Hz, 2H), 1.35(t, J=7.4Hz, 3H) Production Example 127
To a mixture of 2- (3-ethylthiopyridin-4-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine 0.34 g and chloroform 10 ml was added 69% under ice-cooling. After adding 0.75 g of 3-chloroperbenzoic acid, the mixture was stirred at room temperature for 2.5 hours and at 40 ° C. for 1.5 hours. Thereafter, a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium thiosulfate solution were added, and the mixture was extracted three times with chloroform. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 2- (3-ethanesulfonyl-1-oxy-pyridin-4-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine. (Hereinafter referred to as the present active compound [127].) 0.20 g was obtained.

The active compound [127]
¹ H-NMR (CDCl ₃ ) δ: 8.87 (d, J = 1.9Hz, 1H), 8.78 (d, J = 1.9 Hz, 1H), 8.49 (ddd, J = 6.8, 1.9, 0.5Hz, 1H), 8.31 (d, J = 1.9Hz, 1H), 7.45 (d, J = 6.8Hz, 1H), 3.80 (d, J = 0.5Hz, 3H), 3.55 (q, J = 7.4Hz, 2H), 1.35 ( (t, J = 7.4Hz, 3H)

本活性化合物［１２８］
¹H-NMR (CDCl₃) δ: 8.72-8.70(m, 1H), 8.61(s, 1H), 8.49(d, J=4.8Hz, 1H), 8.33(d, J=1.7Hz, 1H), 7.55(d, J=4.8Hz, 1H), 7.33-7.24(m, 5H), 5.24(s, 2H), 3.79(s, 3H) Production Example 128
Instead of 1-butanol, benzyl alcohol is replaced with 2- (3-fluoropyridin-4-yl) -1-methyl-5-trifluoromethyl-1H-benzimidazole and 2- (3-fluoropyridine-4- Yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine and 2- (3-benzyloxypyridin-4-yl) according to the method described in Production Example 120 ) -3-Methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present active compound [128]) was obtained.

The active compound [128]
¹ H-NMR (CDCl ₃ ) δ: 8.72-8.70 (m, 1H), 8.61 (s, 1H), 8.49 (d, J = 4.8Hz, 1H), 8.33 (d, J = 1.7Hz, 1H), 7.55 (d, J = 4.8Hz, 1H), 7.33-7.24 (m, 5H), 5.24 (s, 2H), 3.79 (s, 3H)

本活性化合物［１２９］
¹H-NMR (CDCl₃) δ: 12.67(br s, 1H), 8.78(dd, J=2.0, 0.5Hz, 1H), 8.65(s, 1H), 8.35(dd, J=2.0, 0.5Hz, 1H), 8.33(d, J=5.2Hz, 1H), 7.75(dd, J=5.2, 0.5Hz, 1H), 4.32(s, 3H) Production Example 129
1.16 g of 2- (3-benzyloxypyridin-4-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine, 60 ml of ethanol, 0.12 g of 5% palladium carbon The mixture was stirred at room temperature for 3 hours under a hydrogen atmosphere of about 1 atm. Celite (registered trademark) was filtered, and the filtrate was concentrated under reduced pressure to give 4- (3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridin-2-yl] -pyridine-3. 0.27 g of ol (hereinafter referred to as the present active compound [129]) was obtained.

The active compound [129]
¹ H-NMR (CDCl ₃ ) δ: 12.67 (br s, 1H), 8.78 (dd, J = 2.0, 0.5Hz, 1H), 8.65 (s, 1H), 8.35 (dd, J = 2.0, 0.5Hz, 1H), 8.33 (d, J = 5.2Hz, 1H), 7.75 (dd, J = 5.2, 0.5Hz, 1H), 4.32 (s, 3H)

本活性化合物［１３０］
¹H-NMR (CDCl₃) δ: 8.76-8.74(m, 1H), 8.72(d, J=0.5Hz, 1H), 8.67(d, J=4.8Hz, 1H), 8.35(d, J=2.2Hz, 1H), 7.35(d, J=4.8Hz, 1H), 3.80(s, 3H), 2.35(s, 3H) Production Example 130
A mixture of N2-methyl-5-trifluoromethylpyridine-2,3-diamine 0.40 g, 3-methylisonicotinic acid 0.32 g, WSC 0.44 g and pyridine 10 ml was heated and stirred at 120 ° C. for 5 hours. After cooling to room temperature, water was added and extracted three times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. A mixture of 0.60 g of p-toluenesulfonic acid monohydrate and 10 ml of toluene was added to the residue, and the mixture was stirred at 120 ° C. for 1 hour. Toluene was distilled off, 10 ml of phenyl bromide was added, and the mixture was further heated at 150 ° C. for 4 hours. Stir. After cooling to room temperature, water was added and extracted three times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 3-methyl-2- (3-methylpyridin-4-yl) -6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the active compound). [Indicated as [130].) 0.14 g was obtained.

The active compound [130]
¹ H-NMR (CDCl ₃ ) δ: 8.76-8.74 (m, 1H), 8.72 (d, J = 0.5Hz, 1H), 8.67 (d, J = 4.8Hz, 1H), 8.35 (d, J = 2.2 Hz, 1H), 7.35 (d, J = 4.8Hz, 1H), 3.80 (s, 3H), 2.35 (s, 3H)

本活性化合物［１３１］
¹H-NMR (CDCl₃) δ: 8.76-8.74(m, 2H), 8.67(d, J=5.0Hz, 1H), 8.35(d, J=1.9Hz, 1H), 7.31(d, J=5.0Hz, 1H), 3.78(s, 3H), 2.70(q, J=7.6Hz, 2H), 1.14(t, J=7.6Hz, 3H) Production Example 131
A mixture of 0.40 g of N2-methyl-5-trifluoromethylpyridine-2,3-diamine, 0.41 g of 3-ethylisonicotinic acid, 0.44 g of WSC and 10 ml of pyridine was heated and stirred at 120 ° C. for 2.5 hours. After cooling to room temperature, water was added and extracted three times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. A mixture of 0.60 g of p-toluenesulfonic acid monohydrate and 10 ml of toluene was added to the residue, and the mixture was stirred at 120 ° C. for 7 hours. After cooling to room temperature, water was added and extracted three times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 2- (3-ethylpyridin-4-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the active compound). [131].) 0.10 g was obtained.

The active compound [131]
¹ H-NMR (CDCl ₃ ) δ: 8.76-8.74 (m, 2H), 8.67 (d, J = 5.0Hz, 1H), 8.35 (d, J = 1.9Hz, 1H), 7.31 (d, J = 5.0 Hz, 1H), 3.78 (s, 3H), 2.70 (q, J = 7.6Hz, 2H), 1.14 (t, J = 7.6Hz, 3H)

本活性化合物［１３２］
¹H-NMR (CDCl₃) δ: 8.84 (dd, 2H), 8.13 (s, 1H), 7.66 (dd, 2H), 7.61 (dd, 1H), 7.54 (d, 1H), 4.28 (t, 2H), 1.92-1.82 (m, 2H), 0.90 (t, 3H). Production Example 132
A mixture of 0.41 g of N1-propyl-4-trifluoromethylbenzene-1,2-diamine, 0.51 g of isonicotinaldehyde / bisulfite adduct and 4 ml of N, N-dimethylformamide was heated and stirred at 150 ° C. for 1 hour. did. Water was poured into the reaction mixture allowed to cool to room temperature, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over sodium sulfate, and concentrated under reduced pressure to obtain a solid residue. The obtained residue was washed with hexane, and 0.55 g of 1-propyl-2- (pyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [132]). Got.

The active compound [132]
¹ H-NMR (CDCl ₃ ) δ: 8.84 (dd, 2H), 8.13 (s, 1H), 7.66 (dd, 2H), 7.61 (dd, 1H), 7.54 (d, 1H), 4.28 (t, 2H ), 1.92-1.82 (m, 2H), 0.90 (t, 3H).

本活性化合物［１３３］
¹H-NMR (CDCl₃) δ: 8.84 (dd, 2H), 8.12 (d, 1H), 7.74 (d, 1H), 7.58-7.55 (m, 3H), 4.88-4.78 (m, 1H), 1.70 (d, 6H). Production Example 133
A mixture of 0.41 g of N1-isopropyl-4-trifluoromethylbenzene-1,2-diamine, 0.51 g of isonicotinaldehyde / bisulfite adduct and 4 ml of N, N-dimethylformamide was heated and stirred at 150 ° C. for 1 hour. did. Water was poured into the reaction mixture allowed to cool to room temperature, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over sodium sulfate, and concentrated under reduced pressure to obtain a solid residue. The obtained residue was washed with hexane, and 0.50 g of 1-isopropyl-2- (pyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [133]). Got.

The active compound [133]
¹ H-NMR (CDCl ₃ ) δ: 8.84 (dd, 2H), 8.12 (d, 1H), 7.74 (d, 1H), 7.58-7.55 (m, 3H), 4.88-4.78 (m, 1H), 1.70 (d, 6H).

本活性化合物［１３４］
¹H-NMR (CDCl₃) δ: 8.75 (dd, 2H), 8.05 (s, 1H), 7.84 (d, 1H), 7.56 (d, 1H), 7.44 (dd, 2H), 1.67 (s, 9H). Production Example 134
A mixture of 0.47 g of N1-tert-butyl-4-trifluoromethylbenzene-1,2-diamine, 0.51 g of isonicotinaldehyde bisulphite adduct and 5 ml of N, N-dimethylformamide was stirred at 150 ° C. for 10 minutes. Stir with heating. The reaction mixture was ice-cooled, 10% aqueous sodium hydroxide solution was added, and the mixture was extracted with tert-butyl methyl ether. The organic layer was washed with water, dried over sodium sulfate, and concentrated under reduced pressure to obtain a solid residue. The obtained residue was washed with hexane, and 0.26 g of 1-tert-butyl-2- (pyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [134]). .)

The active compound [134]
¹ H-NMR (CDCl ₃ ) δ: 8.75 (dd, 2H), 8.05 (s, 1H), 7.84 (d, 1H), 7.56 (d, 1H), 7.44 (dd, 2H), 1.67 (s, 9H ).

本活性化合物［１３５］
¹H-NMR (CDCl₃) δ: 8.84(dd, J=4.4, 1.7Hz, 2H), 8.14-8.13(m, 1H), 7.68(dd, J=4.4, 1.7Hz, 2H), 7.64-7.60(m, 1H), 7.55(d, J=8.5Hz, 1H), 4.37(q, J=7.2Hz, 2H), 1.53(t, J=7.2Hz, 3H) Production Example 135
A mixture of 1.0 g of N1-ethyl-4-trifluoromethylbenzene-1,2-diamine, 1.05 g of isonicotinic acid chloride hydrochloride and 15 ml of pyridine was heated and stirred at 60 ° C. for 4 hours. Next, 0.94 g of WSC was added and heated and stirred at 80 ° C. for 8 hours. The reaction mixture was cooled to room temperature, poured into water, and extracted twice with ethyl acetate. The combined organic layers were washed with water and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 0.65 g of 1-ethyl-2- (pyridin-4-yl) -5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present active compound [135]). Got.

The active compound [135]
¹ H-NMR (CDCl ₃ ) δ: 8.84 (dd, J = 4.4, 1.7Hz, 2H), 8.14-8.13 (m, 1H), 7.68 (dd, J = 4.4, 1.7Hz, 2H), 7.64-7.60 (m, 1H), 7.55 (d, J = 8.5Hz, 1H), 4.37 (q, J = 7.2Hz, 2H), 1.53 (t, J = 7.2Hz, 3H)

¹H-NMR (CDCl₃) δ: 8.48(s, 1H), 8.28(br s, 1H), 7.65(dd, J=9.0, 2.1Hz, 1H), 6.94(d, J=9.0Hz, 1H), 3.09 (d, J=5.1Hz, 3H) Next, reference production examples are shown for the production of the production intermediate of the active compound.
Reference production example 1
To a mixture of 2.09 g of 4-fluoro-3-nitro-benzotrifluoride and 20 ml of N-methylpyrrolidone, 2.33 g of 40% aqueous methylamine solution was added under ice cooling, and the mixture was warmed to room temperature and stirred for 1 hour. Water was added, and the deposited precipitate was filtered, washed with water, and dried under reduced pressure to obtain 2.0 g of N-methyl-2-nitro-4-trifluoromethylaniline.

¹ H-NMR (CDCl ₃ ) δ: 8.48 (s, 1H), 8.28 (br s, 1H), 7.65 (dd, J = 9.0, 2.1Hz, 1H), 6.94 (d, J = 9.0Hz, 1H) , 3.09 (d, J = 5.1Hz, 3H)

¹H-NMR (CDCl₃) δ: 7.14-7.10(m, 1H), 6.92(d, J=2.0 Hz, 1H), 6.63(d, J=8.3Hz, 1H), 3.73(br s, 1H), 3.34(br s, 2H), 2.90(d, J=5.1Hz, 3H) A mixture of 2.0 g of N-methyl-2-nitro-4-trifluoromethylaniline, 18 ml of ethanol, and 0.20 g of 5% palladium carbon was stirred at room temperature for 3 hours under a hydrogen atmosphere of about 1 atm. Celite (registered trademark) was filtered, and the filtrate was concentrated under reduced pressure to obtain 1.17 g of N1-methyl-4-trifluoromethylbenzene-1,2-diamine.

¹ H-NMR (CDCl ₃ ) δ: 7.14-7.10 (m, 1H), 6.92 (d, J = 2.0 Hz, 1H), 6.63 (d, J = 8.3 Hz, 1H), 3.73 (br s, 1H) , 3.34 (br s, 2H), 2.90 (d, J = 5.1Hz, 3H)

¹H-NMR (CDCl₃) δ: 8.29(d, J=8.9Hz, 1H), 8.09(br s, 1H), 7.10(s, 1H), 6.87(dd, J=8.9, 1.7Hz, 1H), 3.08(d, J=5.1Hz, 3H) Reference production example 2
Using 2-chloro-1-nitro-4-trifluoromethylbenzene instead of 4-fluoro-3-nitro-benzotrifluoride and according to the method described in Reference Production Example 1, N-methyl-2-nitro -5-Trifluoromethylaniline was obtained.

¹ H-NMR (CDCl ₃ ) δ: 8.29 (d, J = 8.9Hz, 1H), 8.09 (br s, 1H), 7.10 (s, 1H), 6.87 (dd, J = 8.9, 1.7Hz, 1H) , 3.08 (d, J = 5.1Hz, 3H)

¹H-NMR (CDCl₃) δ: 6.95(d, J=7.8Hz, 1H), 6.83(s, 1H), 6.72(d, J=7.8Hz, 1H), 3.55(br s, 2H), 3.39(br s, 1H), 2.89(d, J=5.6Hz, 3H) Using N-methyl-2-nitro-5-trifluoromethylaniline instead of N-methyl-2-nitro-4-trifluoromethylaniline, according to the method described in Reference Production Example 1, N2-methyl- 4-trifluoromethylbenzene-1,2-diamine was obtained.

¹ H-NMR (CDCl ₃ ) δ: 6.95 (d, J = 7.8Hz, 1H), 6.83 (s, 1H), 6.72 (d, J = 7.8Hz, 1H), 3.55 (br s, 2H), 3.39 (br s, 1H), 2.89 (d, J = 5.6Hz, 3H)

¹H-NMR (CDCl₃) δ: 8.50(s, 1H), 8.41(br s, 1H), 7.07(s, 1H), 3.13(d, J=4.9Hz, 3H) Reference production example 3
Described in Reference Production Example 1 using 5-chloro-1,1,3,3-tetrafluoro-6-nitro-1,3-dihydro-isobenzofuran instead of 4-fluoro-3-nitro-benzotrifluoride According to the above method, N-methyl- (1,1,3,3-tetrafluoro-6-nitro-1,3-dihydro-isobenzofuran-5-yl) -amine was obtained.

¹ H-NMR (CDCl ₃ ) δ: 8.50 (s, 1H), 8.41 (br s, 1H), 7.07 (s, 1H), 3.13 (d, J = 4.9Hz, 3H)

¹H-NMR (CDCl₃) δ: 6.84(s, 1H), 6.72(s, 1H), 3.83(br s, 1H), 3.65(br s, 2H), 2.94(d, J=5.1Hz, 3H) N-methyl- (1,1,3,3-tetrafluoro-6-nitro-1,3-dihydro-isobenzofuran-5-yl) instead of N-methyl-2-nitro-4-trifluoromethylaniline -According to the method described in Reference Production Example 1, 1,1,3,3-tetrafluoro-N-methyl-1,3-dihydroisobenzofuran-5,6-diamine was obtained using an amine.

¹ H-NMR (CDCl ₃ ) δ: 6.84 (s, 1H), 6.72 (s, 1H), 3.83 (br s, 1H), 3.65 (br s, 2H), 2.94 (d, J = 5.1Hz, 3H )

¹H-NMR(DMSO-d₆) δ: 8.74(d, J=2.4Hz, 1H), 8.58(d, J=4.9Hz, 1H), 7.80-7.77(m, 1H) Reference production example 4
While a mixture of 39.9 ml of diisopropylamine and 257 ml of tetrahydrofuran was cooled in a dry ice-acetone bath, 107 ml of a 2.64M hexane solution of n-butyllithium was added with stirring, followed by stirring for 1.5 hours. Next, 25.0 g of 3-fluoropyridine was added, and the mixture was further stirred for 1.5 hours. After adding crushed dry ice to the reaction mixture, the cooling was stopped and the mixture was stirred until it returned to room temperature. Water was added, and most of hexane and tetrahydrofuran were distilled off under reduced pressure. The residue was washed with tert-butyl methyl ether, and the aqueous layer was recovered. Concentrated hydrochloric acid was added to the obtained aqueous layer under ice-cooling to adjust the pH of the mixture to 3, and the mixture was stirred for 1 hour. The precipitate was collected by filtration and dried under reduced pressure to obtain 32.51 g of 3-fluoroisonicotinic acid.

¹ H-NMR (DMSO-d ₆ ) δ: 8.74 (d, J = 2.4Hz, 1H), 8.58 (d, J = 4.9Hz, 1H), 7.80-7.77 (m, 1H)

¹H-NMR (CDCl₃) δ: 10.09(d, J=1.2Hz, 1H), 8.49(d, J=4.9Hz, 1H), 7.65-7.62(m, 1H), 7.38-7.36(m, 1H) Reference production example 5
0.64 g of 2-fluoro-4-pyridinemethanol, 10 ml of chloroform, desmartin periodinane (1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3 (1H)- On) 2.54 g of the mixture was stirred at room temperature for 30 minutes. Saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted 3 times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.19 g of 2-fluoropyridine-4-carbaldehyde.

¹ H-NMR (CDCl ₃ ) δ: 10.09 (d, J = 1.2Hz, 1H), 8.49 (d, J = 4.9Hz, 1H), 7.65-7.62 (m, 1H), 7.38-7.36 (m, 1H )

¹H-NMR (CDCl₃) δ: 8.34(s, 1H), 7.60(dd, J=8.8, 2.4Hz, 1H), 6.40(d, J=8.8Hz, 1H), 4.89(br s, 1H), 2.97(d, J=5.1Hz, 3H) Reference production example 6
To a mixture of 18.2 g of 2-chloro-5-trifluoromethylpyridine and 100 ml of N-methylpyrrolidone was added 23.3 g of a 40% aqueous methylamine solution, and the mixture was stirred at room temperature for 3 hours. Water was added and extracted three times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 17.3 g of N-methyl- (5-trifluoromethyl-pyridin-2-yl) -amine.

¹ H-NMR (CDCl ₃ ) δ: 8.34 (s, 1H), 7.60 (dd, J = 8.8, 2.4Hz, 1H), 6.40 (d, J = 8.8Hz, 1H), 4.89 (br s, 1H) , 2.97 (d, J = 5.1Hz, 3H)

¹H-NMR (CDCl₃) δ: 8.66-8.64(m, 2H), 8.43(br s, 1H), 3.23(d, J=4.9Hz, 3H) After 12.3 g of nitric acid was added dropwise to a mixture of 17.3 g of N-methyl- (5-trifluoromethyl-pyridin-2-yl) -amine and 100 ml of sulfuric acid, the mixture was heated and stirred at 80 ° C. for 2 hours. After cooling to room temperature, the reaction mixture was poured into water, the deposited precipitate was filtered, washed with water, dried under reduced pressure, and N-methyl- (3-nitro-5-trifluoromethyl-pyridine- 18.8 g of 2-yl) -amine were obtained.

¹ H-NMR (CDCl ₃ ) δ: 8.66-8.64 (m, 2H), 8.43 (br s, 1H), 3.23 (d, J = 4.9Hz, 3H)

¹H-NMR (CDCl₃) δ: 8.04(s, 1H), 6.98(d, J=1.7Hz, 1H), 4.56(br s, 1H), 3.25(br s, 2H), 3.06(d, J=4.9Hz, 3H) As described in Reference Production Example 1, N-methyl-2- (3-nitro-5-trifluoromethyl-pyridin-2-yl) -amine was used instead of N-methyl-2-nitro-4-trifluoromethylaniline. According to the method, N2-methyl-5-trifluoromethylpyridine-2,3-diamine was obtained.

¹ H-NMR (CDCl ₃ ) δ: 8.04 (s, 1H), 6.98 (d, J = 1.7Hz, 1H), 4.56 (br s, 1H), 3.25 (br s, 2H), 3.06 (d, J = 4.9Hz, 3H)

¹H-NMR (CDCl₃) δ: 8.48-8.46(m, 1H), 8.25(br s, 1H), 7.59(dd, J=9.2, 2.2Hz, 1H), 6.94(d, J=9.2Hz, 1H), 3.72-3.62(m, 1H), 1.77-1.61(m, 2H), 1.32(d, J=6.3Hz, 3H), 1.01(t, J=7.6Hz, 3H) Reference production example 7
To a mixture of 4-fluoro-3-nitro-benzotrifluoride 1.05 g and N-methylpyrrolidone 10 ml, 1.10 g of sec-butylamine was added under ice cooling, and the mixture was warmed to room temperature and stirred for 1.5 hours. Water was added, and the deposited precipitate was filtered, washed with water, and dried under reduced pressure to obtain 1.16 g of N-sec-butyl-2-nitro-4-trifluoromethylaniline.

¹ H-NMR (CDCl ₃ ) δ: 8.48-8.46 (m, 1H), 8.25 (br s, 1H), 7.59 (dd, J = 9.2, 2.2Hz, 1H), 6.94 (d, J = 9.2Hz, 1H), 3.72-3.62 (m, 1H), 1.77-1.61 (m, 2H), 1.32 (d, J = 6.3Hz, 3H), 1.01 (t, J = 7.6Hz, 3H)

¹H-NMR (CDCl₃) δ: 7.10-7.06(m, 1H), 6.93(d, J=2.0Hz, 1H), 6.61(d, J=8.3Hz, 1H), 3.56(br s, 1H), 3.47-3.38(m, 1H), 3.30(br s, 2H), 1.71-1.59(m, 1H), 1.58-1.46(m, 1H), 1.21(d, J=6.1Hz, 3H), 0.98(t, J=7.4Hz, 3H) A mixture of 1.16 g of N- (sec-butyl) -2-nitro-4-trifluoromethylaniline, 9 ml of ethanol, and 0.12 g of 5% palladium on carbon was stirred at room temperature under a hydrogen atmosphere of about 1 atm for 5.5 hours. . Celite (registered trademark) was filtered, and the filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.76 g of N1-sec-butyl-4-trifluoromethylbenzene-1,2-diamine.

¹ H-NMR (CDCl ₃ ) δ: 7.10-7.06 (m, 1H), 6.93 (d, J = 2.0Hz, 1H), 6.61 (d, J = 8.3Hz, 1H), 3.56 (br s, 1H) , 3.47-3.38 (m, 1H), 3.30 (br s, 2H), 1.71-1.59 (m, 1H), 1.58-1.46 (m, 1H), 1.21 (d, J = 6.1Hz, 3H), 0.98 ( (t, J = 7.4Hz, 3H)

¹H-NMR (CDCl₃) δ: 8.48-8.46(m, 1H), 8.39(br s, 1H), 7.60(dd, J=9.0, 2.3Hz, 1H), 6.93(d, J=9.0Hz, 1H), 3.17(dd, J=6.8, 5.4Hz, 2H), 2.09-1.98(m, 1H), 1.08(s, 3H), 1.06 (s, 3H) Reference production example 8
N-isobutyl-2-nitro-4-trifluoromethylaniline was obtained in accordance with the method described in Reference Production Example 7 using isobutylamine instead of sec-butylamine.

¹ H-NMR (CDCl ₃ ) δ: 8.48-8.46 (m, 1H), 8.39 (br s, 1H), 7.60 (dd, J = 9.0, 2.3Hz, 1H), 6.93 (d, J = 9.0Hz, 1H), 3.17 (dd, J = 6.8, 5.4Hz, 2H), 2.09-1.98 (m, 1H), 1.08 (s, 3H), 1.06 (s, 3H)

¹H-NMR (CDCl₃) δ: 7.11-7.06(m, 1H), 6.93(d, J=2.0Hz, 1H), 6.62(d, J=8.3Hz, 1H), 3.74(br s, 1H), 3.32(br s, 2H), 2.96(m, 2H), 1.99-1.86(m, 1H), 1.03(s, 3H), 1.01(s, 3H) In accordance with the method described in Reference Production Example 7 using N-isobutyl-2-nitro-4-trifluoromethylaniline instead of N- (sec-butyl) -2-nitro-4-trifluoromethylaniline, N1-isobutyl-4-trifluoromethylbenzene-1,2-diamine was obtained.

¹ H-NMR (CDCl ₃ ) δ: 7.11-7.06 (m, 1H), 6.93 (d, J = 2.0Hz, 1H), 6.62 (d, J = 8.3Hz, 1H), 3.74 (br s, 1H) , 3.32 (br s, 2H), 2.96 (m, 2H), 1.99-1.86 (m, 1H), 1.03 (s, 3H), 1.01 (s, 3H)

¹H-NMR (CDCl₃) δ: 8.28(d, J=8.8Hz, 1H), 8.09(br s, 1H), 7.09(s, 1H), 6.84(dd, J=8.8, 1.7Hz, 1H), 3.34-3.28(m, 2H), 1.85-1.74(m, 2H), 1.08(t, J=7.5Hz, 3H) Reference production example 9
According to the method described in Reference Production Example 7, using 2-chloro-1-nitro-4-trifluorobenzene in place of 4-fluoro-3-nitro-benzotrifluoride and propylamine in place of sec-butylamine. Thus, N-propyl-2-nitro-5-trifluoromethylaniline was obtained.

¹ H-NMR (CDCl ₃ ) δ: 8.28 (d, J = 8.8Hz, 1H), 8.09 (br s, 1H), 7.09 (s, 1H), 6.84 (dd, J = 8.8, 1.7Hz, 1H) , 3.34-3.28 (m, 2H), 1.85-1.74 (m, 2H), 1.08 (t, J = 7.5Hz, 3H)

¹H-NMR (CDCl₃) δ: 6.95-6.92(m, 1H), 6.83(d, J=1.7 Hz, 1H), 6.72(d, J=8.0Hz, 1H), 3.55(br s, 2H), 3.28(br s, 1H), 3.09(t, J=7.1Hz, 2H), 1.76-1.66(m, 2H), 1.05(t, J=7.4Hz, 3H) According to the method described in Reference Production Example 7, using N-propyl-2-nitro-5-trifluoromethylaniline instead of N- (sec-butyl) -2-nitro-4-trifluoromethylaniline, N2-propyl-4-trifluoromethylbenzene-1,2-diamine was obtained.

¹ H-NMR (CDCl ₃ ) δ: 6.95-6.92 (m, 1H), 6.83 (d, J = 1.7 Hz, 1H), 6.72 (d, J = 8.0Hz, 1H), 3.55 (br s, 2H) , 3.28 (br s, 1H), 3.09 (t, J = 7.1Hz, 2H), 1.76-1.66 (m, 2H), 1.05 (t, J = 7.4Hz, 3H)

¹H-NMR (CDCl₃) δ: 8.28(d, J=9.0Hz, 1H), 8.00(br s, 1H), 7.09(s, 1H), 6.85(dd, J=9.0, 1.7Hz, 1H), 3.43-3.35(m, 2H), 1.41(t, J=7.2Hz, 3H) Reference production example 10
According to the method described in Reference Production Example 7, using 2-chloro-1-nitro-4-trifluorobenzene instead of 4-fluoro-3-nitro-benzotrifluoride and ethylamine instead of sec-butylamine. N-ethyl-2-nitro-5-trifluoromethylaniline was obtained.

¹ H-NMR (CDCl ₃ ) δ: 8.28 (d, J = 9.0Hz, 1H), 8.00 (br s, 1H), 7.09 (s, 1H), 6.85 (dd, J = 9.0, 1.7Hz, 1H) , 3.43-3.35 (m, 2H), 1.41 (t, J = 7.2Hz, 3H)

¹H-NMR (CDCl₃) δ: 6.94(dt, J=8.0, 0.9Hz, 1H), 6.84(s, 1H), 6.72(d, J=8.0Hz, 1H), 3.56(br s, 2H), 3.25-3.13(m, 3H), 1.32(t, J=7.0Hz, 3H) According to the method described in Reference Production Example 7, using N-ethyl-2-nitro-5-trifluoromethylaniline instead of N- (sec-butyl) -2-nitro-4-trifluoromethylaniline, N2-ethyl-4-trifluoromethylbenzene-1,2-diamine was obtained.

¹ H-NMR (CDCl ₃ ) δ: 6.94 (dt, J = 8.0, 0.9Hz, 1H), 6.84 (s, 1H), 6.72 (d, J = 8.0Hz, 1H), 3.56 (br s, 2H) , 3.25-3.13 (m, 3H), 1.32 (t, J = 7.0Hz, 3H)

¹H-NMR (CDCl₃) δ: 8.28(d, J=8.9Hz, 1H), 8.07(br s, 1H), 7.09(s, 1H), 6.81(dd, J=8.9, 2.0Hz, 1H), 3.72-3.60(m, 1H), 1.78-1.61(m, 2H), 1.31 (d, J=6.3Hz, 3H), 1.02(t, J=7.4Hz, 3H) Reference production example 11
Using 2-chloro-1-nitro-4-trifluorobenzene instead of 4-fluoro-3-nitro-benzotrifluoride, according to the method described in Reference Production Example 7, N-sec-butyl-2- Nitro-5-trifluoromethylaniline was obtained.

¹ H-NMR (CDCl ₃ ) δ: 8.28 (d, J = 8.9Hz, 1H), 8.07 (br s, 1H), 7.09 (s, 1H), 6.81 (dd, J = 8.9, 2.0Hz, 1H) , 3.72-3.60 (m, 1H), 1.78-1.61 (m, 2H), 1.31 (d, J = 6.3Hz, 3H), 1.02 (t, J = 7.4Hz, 3H)

¹H-NMR (CDCl₃) δ: 6.91(dt, J=8.0, 1.2Hz, 1H), 6.82(d, J=1.2Hz, 1H), 6.72(d, J=8.0Hz, 1H), 3.54(br s, 2H), 3.44-3.34(m, 1H), 3.17(br s, 1H), 1.70-1.46(m, 2H), 0.98(t, J=7.5Hz, 3H) According to the method described in Reference Production Example 7, using N-sec-butyl-2-nitro-5-trifluoromethylaniline instead of N- (sec-butyl) -2-nitro-4-trifluoromethylaniline N2-sec-butyl-4-trifluoromethylbenzene-1,2-diamine was obtained.

¹ H-NMR (CDCl ₃ ) δ: 6.91 (dt, J = 8.0, 1.2Hz, 1H), 6.82 (d, J = 1.2Hz, 1H), 6.72 (d, J = 8.0Hz, 1H), 3.54 ( br s, 2H), 3.44-3.34 (m, 1H), 3.17 (br s, 1H), 1.70-1.46 (m, 2H), 0.98 (t, J = 7.5Hz, 3H)

¹H-NMR (CDCl₃) δ: 8.10-8.01(m, 2H), 7.37(dtd, J=9.3, 1.8, 1.0Hz, 1H), 6.87(d, J=9.3Hz, 1H), 3.05(d, J=5.1Hz, 3H) Reference production example 12
To a mixture of 2.22 g of 2-nitro-4-trifluoromethoxyaniline and 20 ml of DMF, 0.44 g of 60% sodium hydride (oil) was added under ice cooling, and the mixture was stirred for 10 minutes. After adding 1.42 g of methyl iodide, the mixture was warmed to room temperature and further stirred for 1 hour. Saturated aqueous ammonium chloride solution was added, and the mixture was extracted 3 times with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 1.80 g of N-methyl-2-nitro-4-trifluoromethoxyaniline.

¹ H-NMR (CDCl ₃ ) δ: 8.10-8.01 (m, 2H), 7.37 (dtd, J = 9.3, 1.8, 1.0Hz, 1H), 6.87 (d, J = 9.3Hz, 1H), 3.05 (d , J = 5.1Hz, 3H)

¹H-NMR (CDCl₃) δ: 6.72-6.67(m, 1H), 6.61-6.56(m, 2H), 3.42(br s, 2H), 3.30(br s, 1H), 2.86(s, 3H) According to the method described in Reference Production Example 7, using N-methyl-2-nitro-4-trifluoromethoxyaniline instead of N- (sec-butyl) -2-nitro-4-trifluoromethylaniline, N1-methyl-4-trifluoromethoxybenzene-1,2-diamine was obtained.

¹ H-NMR (CDCl ₃ ) δ: 6.72-6.67 (m, 1H), 6.61-6.56 (m, 2H), 3.42 (br s, 2H), 3.30 (br s, 1H), 2.86 (s, 3H)

¹H-NMR (CDCl₃) δ: 8.47 (d, 1H), 8.29 (br s, 1H), 7.61 (dd, 1H), 6.94 (d, 1H), 3.36-3.30 (m, 2H), 1.84-1.74 (m, 2H), 1.07 (t, 3H). Reference production example 13
To a mixture of 5.23 g of 4-fluoro-3-nitro-benzotrifluoride and 25 ml of N-methylpyrrolidone, 3.69 g of n-propylamine was added under ice cooling, and the mixture was warmed to room temperature and stirred for 1 hour. The reaction mixture was poured into water, and the deposited precipitate was filtered, washed with water, and dried under reduced pressure to obtain 2.78 g of N-propyl-2-nitro-4-trifluoromethylaniline.

¹ H-NMR (CDCl ₃ ) δ: 8.47 (d, 1H), 8.29 (br s, 1H), 7.61 (dd, 1H), 6.94 (d, 1H), 3.36-3.30 (m, 2H), 1.84- 1.74 (m, 2H), 1.07 (t, 3H).

¹H-NMR (CDCl₃) δ: 7.09 (dd, 1H), 6.92 (d, 1H), 6.63 (d, 1H), 3.66 (br s, 1H), 3.32 (br s, 2H), 3.11 (t, 2H), 1.75-1.65 (m, 2H), 1.03 (t, 3H). A mixture of 2.48 g of N-propyl-2-nitro-4-trifluoromethylaniline, 30 ml of ethyl acetate and 5% palladium on carbon (catalytic amount) was stirred at room temperature for 1.5 hours under a hydrogen atmosphere of about 1 atm. After filtration through Celite (registered trademark), the obtained filtrate was washed with water, dried over sodium sulfate, concentrated under reduced pressure, and 1.91 g of N1-propyl-4-trifluoromethylbenzene-1,2-diamine. Got.

¹ H-NMR (CDCl ₃ ) δ: 7.09 (dd, 1H), 6.92 (d, 1H), 6.63 (d, 1H), 3.66 (br s, 1H), 3.32 (br s, 2H), 3.11 (t , 2H), 1.75-1.65 (m, 2H), 1.03 (t, 3H).

Reference production example 14
A saturated solution was prepared from 150 g of water and 80 g of sodium bisulfite. 150 ml of this saturated solution was ice-cooled, and 17.0 g of isonicotinaldehyde and 20 ml of ethanol were added. The deposited precipitate was filtered and washed with water to obtain 24.9 g of an isonicotinaldehyde / bisulfite adduct.

¹H-NMR (CDCl₃) δ: 8.47 (d, 1H), 8.22 (br s, 1H), 7.60 (dd, 1H), 6.95 (d, 1H), 3.94-3.82 (m, 1H), 1.36 (d, 6H). Reference production example 15
To a mixture of 5.23 g of 4-fluoro-3-nitro-benzotrifluoride and 25 ml of N-methylpyrrolidone, 3.69 g of isopropylamine was added under ice cooling, and the mixture was warmed to room temperature and stirred for 1 hour. The reaction mixture was poured into water, and the deposited precipitate was filtered, washed with water, and dried under reduced pressure to obtain 5.90 g of N-isopropyl-2-nitro-4-trifluoromethylaniline.

¹ H-NMR (CDCl ₃ ) δ: 8.47 (d, 1H), 8.22 (br s, 1H), 7.60 (dd, 1H), 6.95 (d, 1H), 3.94-3.82 (m, 1H), 1.36 ( d, 6H).

¹H-NMR (CDCl₃) δ: 7.08 (dd, 1H), 6.93 (d, 1H), 6.63 (d, 1H), 3.65 (br s, 1H), 3.54 (br s, 1H), 3.31 (br s, 2H), 1.25 (d, 6H). A mixture of 5.46 g of N-isopropyl-2-nitro-4-trifluoromethylaniline, 30 ml of ethyl acetate and 5% palladium on carbon (catalytic amount) was stirred at room temperature for 1.5 hours under a hydrogen atmosphere of about 1 atm. After filtration through Celite (registered trademark), the obtained filtrate was washed with water, dried over sodium sulfate, concentrated under reduced pressure, and 4.35 g of N1-isopropyl-4-trifluoromethylbenzene-1,2-diamine. Got.

¹ H-NMR (CDCl ₃ ) δ: 7.08 (dd, 1H), 6.93 (d, 1H), 6.63 (d, 1H), 3.65 (br s, 1H), 3.54 (br s, 1H), 3.31 (br s, 2H), 1.25 (d, 6H).

¹H-NMR (CDCl₃) δ: 8.61 (br s, 1H), 8.48 (d, 1H), 7.56 (dd, 1H), 7.18 (d, 1H), 1.53 (s, 9H). Reference Production Example 16
To a mixture of 5.22 g of 4-fluoro-3-nitro-benzotrifluoride and 25 ml of N-methylpyrrolidone, 3.88 g of tert-butylamine was added at room temperature and stirred for 2 hours. The reaction mixture was poured into water, and the deposited precipitate was filtered, washed with water, and dried under reduced pressure to obtain 5.35 g of N-tert-butyl-2-nitro-4-trifluoromethylaniline. .

¹ H-NMR (CDCl ₃ ) δ: 8.61 (br s, 1H), 8.48 (d, 1H), 7.56 (dd, 1H), 7.18 (d, 1H), 1.53 (s, 9H).

¹H-NMR (CDCl₃) δ: 7.03 (d, 1H), 6.94 (s, 1H), 6.89 (d, 1H), 3.54 (br s, 1H), 3.40 (br s, 2H), 1.39 (s, 9H). A mixture of 5.25 g of N-tert-butyl-2-nitro-4-trifluoromethylaniline, 20 ml of ethyl acetate and 5% palladium on carbon (catalytic amount) was stirred at room temperature for 9 hours under a hydrogen atmosphere of about 1 atm. After filtration through Celite (registered trademark), the obtained filtrate was washed with water, dried over sodium sulfate, and then concentrated under reduced pressure to obtain a residue. The obtained residue was subjected to silica gel chromatography to obtain 4.82 g of N1-tert-butyl-4-trifluoromethylbenzene-1,2-diamine.

¹ H-NMR (CDCl ₃ ) δ: 7.03 (d, 1H), 6.94 (s, 1H), 6.89 (d, 1H), 3.54 (br s, 1H), 3.40 (br s, 2H), 1.39 (s , 9H).

  Next, formulation examples are shown. In the following examples, parts represent parts by weight unless otherwise specified.

Formulation Example 1
1 part of the compound of any one of the above-mentioned active compounds [1] to [135] and 9 parts of any one compound of the respiratory inhibitory compound, 35 parts of xylene and N, N-dimethylformamide 35 14 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate are mixed and stirred well to obtain 10% emulsions.

Formulation Example 2
4 parts of sodium lauryl sulfate, 2 parts of calcium lignin sulfonate, 20 parts of synthetic silicon hydroxide fine powder and 54 parts of diatomaceous earth are mixed, and the compound 5 of any one of the above active compounds [1] to [135] is mixed. And 15 parts of any one compound of the respiratory inhibition compound are added and mixed well with stirring to obtain each 20% wettable powder.

Formulation Example 3
1 part of the compound of any one of the above active compounds [1] to [135] and 1 part of any one compound of the respiratory inhibition compound, 1 part of fine powder of synthetic silicon hydroxide and lignin sulfone Add 2 parts of calcium acid, 30 parts of bentonite and 65 parts of kaolin clay and mix well. Next, an appropriate amount of water is added to these mixtures, and the mixture is further stirred, granulated with a granulator, and dried by ventilation to obtain 2% granules.

Formulation Example 4
0.9 part of any one of the above active compounds [1] to [135] and 0.1 part of any one of the respiratory inhibition compounds are dissolved in an appropriate amount of acetone. To this, 5 parts of synthetic silicon hydroxide fine powder, 0.3 part of PAP (isopropyl acid phosphate) and 93.7 parts of fusami clay are stirred and mixed thoroughly, and acetone is removed by evaporation to obtain each 1% powder. .

Formulation Example 5
35 parts of a mixture of polyoxyethylene alkyl ether sulfate ammonium salt and white carbon (weight ratio 1: 1), 8 parts of any one of the above active compounds [1] to [135], and respiratory inhibition Each 10% flowable agent is obtained by mixing 2 parts of any one of the compounds and 55 parts of water and finely pulverizing them by a wet pulverization method.

Formulation Example 6
0.04 part of any one compound of the above active compounds [1] to [135] and 0.06 part of any one compound of the present respiratory inhibition compound, 5 parts of xylene and 5 parts of trichloroethane And is mixed with 89.9 parts of deodorized kerosene to obtain each 0.1% oil.

Formulation Example 7
7 mg of any one of the above active compounds [1] to [135] and 3 mg of any one of the respiratory inhibition compounds are dissolved in 0.5 ml of acetone, and this solution is used as an animal. 5g of solid feed powder (solid feed powder CE-2 for breeding, product of Nippon Claire Co., Ltd.) and mixed uniformly. Then, acetone is evaporated to dryness to obtain each poisonous bait.

Formulation Example 8
0.03 part of any one compound of the present active compounds [1] to [135], 0.07 part of any one compound of the respiratory inhibition compound, neothiozole (Chuo Kasei Co., Ltd.) 49.9 The part is put in an aerosol can, and after mounting an aerosol valve, 25 parts of dimethyl ether and 25 parts of LPG are filled and shaken, and an actuator aerosol is obtained by mounting an actuator.

Formulation Example 9
0.5 part of any one of the above active compounds [1] to [135], 0.1 part of any one of the respiratory inhibiting compounds, BHT (2,6-di-tert- (Butyl-4-methylphenol) 0.01 part, xylene 5 parts, deodorized kerosene 3.39 parts and emulsifier {Atmos 300 (registered trademark of Atmos Chemical)} 1 part mixed and dissolved, 50 parts distilled water Is filled in an aerosol container, and a valve is mounted. Then, 40 parts of a propellant (LPG) is pressurized and filled through the valve to obtain an aqueous aerosol.

Next, the control effect with respect to harmful animals of the composition of the present invention is shown by test examples.
Test Example 1 (Control effect by spraying foliage on Nilaparvata lugens)
As the active compound, the active compound [32], [36], [37], [39], [43], [44], [51], [100], [126], [131] described above is used. Each was formulated by the method of Formulation Example 5 and diluted to a predetermined concentration. In addition, as the respiratory inhibiting compound, azoxystrobin contains a commercially available azoxystrobin wettable powder (trade name: Amister 20 Flowable; manufactured by Syngenta Japan Co., Ltd.), and a 5,000-fold diluted spreading agent dyne. Dilute with water to the desired concentration. Orisatrobin, ferrimzone, furametopyr, flutolanil and a compound represented by the formula (A) (hereinafter referred to as “compound (A)”) were each formulated by the method of Formulation Example 5 and diluted to a predetermined concentration. The diluted solution of each active compound and the diluted solution of each respiratory inhibiting compound were mixed so as to have a predetermined concentration to obtain a test drug solution.
Rice seedlings (2 weeks after sowing, second leaf development stage) planted in 20 ml of a test chemical solution in a plastic cup were sprayed. After the chemicals sprayed on the rice were dried, 20 third-instar larvae of the brown planthopper were released and stored in a greenhouse at 25 ° C., and the number of surviving insects was examined after 5 days. The control value (%) was calculated by the following formula, and the results are shown in Table 1, Table 2, Table 3, Table 4, Table 5, and Table 6.
Control value (%) = {1− (Cb × Tai) / (Cai × Tb)} × 100
In addition, the character in a formula represents the following meaning.
Cb: Number of insects before treatment in the untreated group Cai: Number of insects when observed in the untreated group Tb: Number of insects before treatment in the treated group Tai: Number of insects when observed in the treated group

  As shown in Table 1, the active compounds [32], [36], [37], [39], [43], [44], [51], [100], [126], [131] Each of the compositions composed of azoxystrobin exhibited a high control effect against the brown planthopper (Nilaparvata lugens).

  As shown in Table 2, the active compounds [32], [36], [37], [39], [43], [44], [51], [100], [126], [131] Each of the compositions composed of orissastrobin showed a high control effect against the brown planthopper (Nilaparvata lugens).

  As shown in Table 3, the active compounds [32], [36], [37], [39], [43], [44], [51], [100], [126], [131] A composition comprising each of them and ferrimzone showed a high control effect against the brown planthopper (Nilaparvata lugens).

  As shown in Table 4, the active compounds [32], [36], [37], [39], [43], [44], [51], [100], [126], [131] Each of the compositions composed of flametopil showed a high control effect against the brown planthopper (Nilaparvata lugens).

  As shown in Table 5, the active compounds [32], [36], [37], [39], [43], [44], [51], [100], [126], [131] Each of the compositions composed of flutolanil showed a high control effect against yellow planthopper (Nilaparvata lugens).

  As shown in Table 6, the active compounds [32], [36], [37], [39], [43], [44], [51], [100], [126], [131] Each of the compositions comprising the compound (A) showed a high control effect against the brown planthopper (Nilaparvata lugens).

  According to the present invention, it is possible to provide a pest control composition having high activity and a method capable of effectively controlling pests.

Claims (7)

Formula (1)

[Where:
A ¹ and A ² are the same or different and represent a nitrogen atom or ═CH—,
m represents 0, 1 or 2;
R ¹ , R ² , R ³ and R ⁴ are the same or different and are substituted with a group selected from group X, a C1-C6 chain hydrocarbon group which may be substituted with a group selected from group X; A C3-C6 alicyclic hydrocarbon group, a phenyl group optionally substituted with a group selected from group Y, a benzyl group optionally substituted with a group selected from group Y, a group selected from group Y in substituted heterocycle may also be 5-membered optionally heterocyclic group or 6-membered heterocyclic ^{group, -OR 8, -NR 8 R 9} , -NR 8 C (O) R 9, -S (O) m R 8, -SO ₂ Cl, —SO ₂ NR ⁸ R ⁹ , —CO ₂ R ¹⁰ , —CONR ⁸ R ⁹ , —CONR ¹⁰ NR ¹¹ R ¹² , a cyano group, a nitro group, a halogen atom, or a hydrogen atom,
R ⁵ is a C1-C4 chain hydrocarbon group optionally substituted with a halogen atom, a cyclopropyl group optionally substituted with a halogen atom, a cyclopropylmethyl group optionally substituted with a halogen atom, —OR ¹³ represents —NR ¹³ R ¹⁴ or a cyano group,
R ⁶ and R ⁷ are the same or different and each represents a C1-C4 chain hydrocarbon group substituted with a halogen atom, —OR ¹⁵ , —S (O) _m R ¹⁵ , a halogen atom or a hydrogen atom (provided that R ⁶ and R ⁷ does not represent a group selected from the group consisting of a halogen atom and a hydrogen atom at the same time.), or bonded to R ⁶ and R ^7, the carbon atom to which R ⁶ and R ⁷ are bound Together may form a 5- or 6-membered ring substituted with a halogen atom,
R ⁸ and R ⁹ are the same or different and are a C1-C6 chain hydrocarbon group optionally substituted with a group selected from group X, or a C3-C6 fatty acid optionally substituted with a group selected from group X A cyclic hydrocarbon group, a phenyl group which may be substituted with a group selected from group Y, a benzyl group which may be substituted with a group selected from group Y, or a group selected from group Y Represents a good 5-membered heterocyclic group or a 6-membered heterocyclic group or a hydrogen atom (in —S (O) _m R ⁸ , m represents the same meaning as described above, provided that when m is 1 or 2, ⁸ does not represent a hydrogen atom)
R ¹⁰ represents a C1-C4 alkyl group which may be substituted with a halogen atom or a hydrogen atom,
R ¹¹ and R ¹² are the same or different and each represents a C1-C4 alkyl group, a C2-C5 alkoxycarbonyl group or a hydrogen atom which may be substituted with a halogen atom;
R ¹³ and R ¹⁴ are the same or different and represent a C1-C3 chain hydrocarbon group which may be substituted with a halogen atom, a cyclopropyl group which may be substituted with a halogen atom, or a hydrogen atom,
R ¹⁵ represents a C1-C4 chain hydrocarbon group substituted with a halogen atom,
n represents 0 or 1.
Group X: C1-C4 alkoxy group optionally substituted with a halogen atom, —CO ₂ R ¹⁶ (wherein R ¹⁶ represents a C1-C4 alkyl group optionally substituted with halogen), a cyano group, and A group consisting of halogen atoms.
Group Y: A group consisting of a C1-C4 alkyl group optionally substituted with a halogen atom, a C1-C4 alkoxy group optionally substituted with a halogen atom, a cyano group, a nitro group, and a halogen atom. ]
A condensed imidazole compound represented by formula (1), azoxystrobin, oryastrostrobin, ferrimzone, furametopyr, flutolanil, and formula (A)

A pest control composition comprising at least one respiratory inhibitory compound selected from the group consisting of compounds represented by:   The harmful animal pest control composition according to claim 1, wherein the weight ratio of the condensed imidazole compound and the respiratory inhibitory compound is 0.1: 99.9 to 99.9: 0.1. In the formula (1), the condensed imidazole compound is
A ¹ is = CH-
A ² is a nitrogen atom or = CH-,
m is 0, 1 or 2;
R ¹ , R ² , R ³ and R ⁴ are the same or different and may be substituted with a group selected from group X, a C1-C6 chain hydrocarbon group, —OR ⁸ , —S (O) _m R ⁸ , —CO ₂ R ¹⁰ , a cyano group, a nitro group, a halogen atom, or a hydrogen atom,
R ⁵ is a C1-C4 chain hydrocarbon group which may be substituted with a halogen atom, or a cyclopropyl group which may be substituted with a halogen atom;
R ⁶ is a C1-C4 chain hydrocarbon group substituted with a halogen atom, —OR ¹⁵ or —S (O) _m R ¹⁵ ;
R ⁷ is a hydrogen atom,
R ⁸ is a C1-C6 chain hydrocarbon group optionally substituted with a group selected from group X, a C3-C6 alicyclic hydrocarbon group optionally substituted with a group selected from group X, group Y A phenyl group optionally substituted with a group selected from: a benzyl group optionally substituted with a group selected from group Y; a 5-membered heterocyclic group optionally substituted with a group selected from group Y; or 6 A membered heterocyclic group or a hydrogen atom (in —S (O) _m R ⁸ , m represents the same meaning as described above, provided that when m is 1 or 2, R ⁸ does not represent a hydrogen atom. ),
R ¹⁰ is a C1-C4 alkyl group which may be substituted with a halogen atom or a hydrogen atom,
R ¹⁵ is a C1-C4 chain hydrocarbon group substituted with a halogen atom,
The pest control composition according to claim 1 or 2, wherein n is 0. Formula (1)

[Where:
A ¹ and A ² are the same or different and represent a nitrogen atom or ═CH—,
m represents 0, 1 or 2;
R ¹ , R ² , R ³ and R ⁴ are the same or different and are substituted with a group selected from group X, a C1-C6 chain hydrocarbon group which may be substituted with a group selected from group X; A C3-C6 alicyclic hydrocarbon group, a phenyl group optionally substituted with a group selected from group Y, a benzyl group optionally substituted with a group selected from group Y, a group selected from group Y in substituted heterocycle may also be 5-membered optionally heterocyclic group or 6-membered heterocyclic ^{group, -OR 8, -NR 8 R 9} , -NR 8 C (O) R 9, -S (O) m R 8, -SO ₂ Cl, —SO ₂ NR ⁸ R ⁹ , —CO ₂ R ¹⁰ , —CONR ⁸ R ⁹ , —CONR ¹⁰ NR ¹¹ R ¹² , a cyano group, a nitro group, a halogen atom, or a hydrogen atom,
R ⁵ is a C1-C4 chain hydrocarbon group optionally substituted with a halogen atom, a cyclopropyl group optionally substituted with a halogen atom, a cyclopropylmethyl group optionally substituted with a halogen atom, —OR ¹³ represents —NR ¹³ R ¹⁴ or a cyano group,
R ⁶ and R ⁷ are the same or different and each represents a C1-C4 chain hydrocarbon group substituted with a halogen atom, —OR ¹⁵ , —S (O) _m R ¹⁵ , a halogen atom or a hydrogen atom (provided that R ⁶ and R ⁷ does not represent a group selected from the group consisting of a halogen atom and a hydrogen atom at the same time.), or bonded to R ⁶ and R ^7, the carbon atom to which R ⁶ and R ⁷ are bound Together may form a 5- or 6-membered ring substituted with a halogen atom,
R ⁸ and R ⁹ are the same or different and are a C1-C6 chain hydrocarbon group optionally substituted with a group selected from group X, or a C3-C6 fatty acid optionally substituted with a group selected from group X A cyclic hydrocarbon group, a phenyl group which may be substituted with a group selected from group Y, a benzyl group which may be substituted with a group selected from group Y, or a group selected from group Y Represents a good 5-membered heterocyclic group or a 6-membered heterocyclic group or a hydrogen atom (in —S (O) _m R ⁸ , m represents the same meaning as described above, provided that when m is 1 or 2, ⁸ does not represent a hydrogen atom)
R ¹⁰ represents a C1-C4 alkyl group which may be substituted with a halogen atom or a hydrogen atom,
R ¹¹ and R ¹² are the same or different and each represents a C1-C4 alkyl group, a C2-C5 alkoxycarbonyl group or a hydrogen atom which may be substituted with a halogen atom;
R ¹³ and R ¹⁴ are the same or different and represent a C1-C3 chain hydrocarbon group which may be substituted with a halogen atom, a cyclopropyl group which may be substituted with a halogen atom, or a hydrogen atom,
R ¹⁵ represents a C1-C4 chain hydrocarbon group substituted with a halogen atom,
n represents 0 or 1.
Group X: C1-C4 alkoxy group optionally substituted with a halogen atom, —CO ₂ R ¹⁶ (wherein R ¹⁶ represents a C1-C4 alkyl group optionally substituted with halogen), a cyano group, and A group consisting of halogen atoms.
Group Y: A group consisting of a C1-C4 alkyl group optionally substituted with a halogen atom, a C1-C4 alkoxy group optionally substituted with a halogen atom, a cyano group, a nitro group, and a halogen atom. ]
A condensed imidazole compound represented by formula (1), azoxystrobin, oryastrostrobin, ferrimzone, furametopyr, flutolanil, and formula (A)

A method for controlling harmful animals, which comprises applying an effective amount with at least one respiratory-inhibiting compound selected from the group consisting of the compounds represented by the above to harmful animals or habitats of harmful animals. In the formula (1), the condensed imidazole compound is
A ¹ is = CH-
A ² is a nitrogen atom or = CH-,
m is 0, 1 or 2;
R ¹ , R ² , R ³ and R ⁴ are the same or different and may be substituted with a group selected from group X, a C1-C6 chain hydrocarbon group, —OR ⁸ , —S (O) _m R ⁸ , —CO ₂ R ¹⁰ , a cyano group, a nitro group, a halogen atom, or a hydrogen atom,
R ⁵ is a C1-C4 chain hydrocarbon group which may be substituted with a halogen atom, or a cyclopropyl group which may be substituted with a halogen atom;
R ⁶ is a C1-C4 chain hydrocarbon group substituted with a halogen atom, —OR ¹⁵ or —S (O) _m R ¹⁵ ;
R ⁷ is a hydrogen atom,
R ⁸ is a C1-C6 chain hydrocarbon group optionally substituted with a group selected from group X, a C3-C6 alicyclic hydrocarbon group optionally substituted with a group selected from group X, group Y A phenyl group optionally substituted with a group selected from: a benzyl group optionally substituted with a group selected from group Y; a 5-membered heterocyclic group optionally substituted with a group selected from group Y; or 6 A membered heterocyclic group or a hydrogen atom (in —S (O) _m R ⁸ , m represents the same meaning as described above, provided that when m is 1 or 2, R ⁸ does not represent a hydrogen atom. ),
R ¹⁰ is a C1-C4 alkyl group which may be substituted with a halogen atom or a hydrogen atom,
R ¹⁵ is a C1-C4 chain hydrocarbon group substituted with a halogen atom,
The pest control method according to claim 4, wherein n is 0. Formula (1)

[Where:
A ¹ and A ² are the same or different and represent a nitrogen atom or ═CH—,
m represents 0, 1 or 2;
R ¹ , R ² , R ³ and R ⁴ are the same or different and are substituted with a group selected from group X, a C1-C6 chain hydrocarbon group which may be substituted with a group selected from group X; A C3-C6 alicyclic hydrocarbon group, a phenyl group optionally substituted with a group selected from group Y, a benzyl group optionally substituted with a group selected from group Y, a group selected from group Y in substituted heterocycle may also be 5-membered optionally heterocyclic group or 6-membered heterocyclic ^{group, -OR 8, -NR 8 R 9} , -NR 8 C (O) R 9, -S (O) m R 8, -SO ₂ Cl, —SO ₂ NR ⁸ R ⁹ , —CO ₂ R ¹⁰ , —CONR ⁸ R ⁹ , —CONR ¹⁰ NR ¹¹ R ¹² , a cyano group, a nitro group, a halogen atom, or a hydrogen atom,
R ⁵ is a C1-C4 chain hydrocarbon group optionally substituted with a halogen atom, a cyclopropyl group optionally substituted with a halogen atom, a cyclopropylmethyl group optionally substituted with a halogen atom, —OR ¹³ represents —NR ¹³ R ¹⁴ or a cyano group,
R ⁶ and R ⁷ are the same or different and each represents a C1-C4 chain hydrocarbon group substituted with a halogen atom, —OR ¹⁵ , —S (O) _m R ¹⁵ , a halogen atom or a hydrogen atom (provided that R ⁶ and R ⁷ does not represent a group selected from the group consisting of a halogen atom and a hydrogen atom at the same time.), or bonded to R ⁶ and R ^7, the carbon atom to which R ⁶ and R ⁷ are bound Together may form a 5- or 6-membered ring substituted with a halogen atom,
R ⁸ and R ⁹ are the same or different and are a C1-C6 chain hydrocarbon group optionally substituted with a group selected from group X, or a C3-C6 fatty acid optionally substituted with a group selected from group X A cyclic hydrocarbon group, a phenyl group which may be substituted with a group selected from group Y, a benzyl group which may be substituted with a group selected from group Y, or a group selected from group Y Represents a good 5-membered heterocyclic group or a 6-membered heterocyclic group or a hydrogen atom (in —S (O) _m R ⁸ , m represents the same meaning as described above, provided that when m is 1 or 2, ⁸ does not represent a hydrogen atom)
R ¹⁰ represents a C1-C4 alkyl group which may be substituted with a halogen atom or a hydrogen atom,
R ¹¹ and R ¹² are the same or different and each represents a C1-C4 alkyl group, a C2-C5 alkoxycarbonyl group or a hydrogen atom which may be substituted with a halogen atom;
R ¹³ and R ¹⁴ are the same or different and represent a C1-C3 chain hydrocarbon group which may be substituted with a halogen atom, a cyclopropyl group which may be substituted with a halogen atom, or a hydrogen atom,
R ¹⁵ represents a C1-C4 chain hydrocarbon group substituted with a halogen atom,
n represents 0 or 1.
Group X: C1-C4 alkoxy group optionally substituted with a halogen atom, —CO ₂ R ¹⁶ (wherein R ¹⁶ represents a C1-C4 alkyl group optionally substituted with halogen), a cyano group, and A group consisting of halogen atoms.
Group Y: A group consisting of a C1-C4 alkyl group optionally substituted with a halogen atom, a C1-C4 alkoxy group optionally substituted with a halogen atom, a cyano group, a nitro group, and a halogen atom. ]
A condensed imidazole compound represented by formula (1), azoxystrobin, oryastrostrobin, ferrimzone, furametopyr, flutolanil, and formula (A)

A method for controlling harmful animals, which comprises applying an effective amount of at least one respiration-inhibiting compound selected from the group consisting of the compounds represented by the above to plants or soil for cultivating plants. In the formula (1), the condensed imidazole compound is
A ¹ is = CH-
A ² is a nitrogen atom or = CH-,
m is 0, 1 or 2;
R ¹ , R ² , R ³ and R ⁴ are the same or different and may be substituted with a group selected from group X, a C1-C6 chain hydrocarbon group, —OR ⁸ , —S (O) _m R ⁸ , —CO ₂ R ¹⁰ , a cyano group, a nitro group, a halogen atom, or a hydrogen atom,
R ⁵ is a C1-C4 chain hydrocarbon group which may be substituted with a halogen atom, or a cyclopropyl group which may be substituted with a halogen atom;
R ⁶ is a C1-C4 chain hydrocarbon group substituted with a halogen atom, —OR ¹⁵ or —S (O) _m R ¹⁵ ;
R ⁷ is a hydrogen atom,
R ⁸ is a C1-C6 chain hydrocarbon group optionally substituted with a group selected from group X, a C3-C6 alicyclic hydrocarbon group optionally substituted with a group selected from group X, group Y A phenyl group optionally substituted with a group selected from: a benzyl group optionally substituted with a group selected from group Y; a 5-membered heterocyclic group optionally substituted with a group selected from group Y; or 6 A membered heterocyclic group or a hydrogen atom (in —S (O) _m R ⁸ , m represents the same meaning as described above, provided that when m is 1 or 2, R ⁸ does not represent a hydrogen atom. ),
R ¹⁰ is a C1-C4 alkyl group which may be substituted with a halogen atom or a hydrogen atom,
R ¹⁵ is a C1-C4 chain hydrocarbon group substituted with a halogen atom,
The pest control method according to claim 6, wherein n is 0.