JP4580173B2 - Herbicidal composition containing 3-phenoxy-4-pyridazinol compound - Google Patents

Description

  The present invention relates to a herbicidal composition containing as an active ingredient a 3-phenoxy-4-pyridazinol compound, a salt thereof, an ester derivative thereof and another specific compound having herbicidal activity.

  At present, many herbicides have been put to practical use as paddy field herbicides and are widely used as single agents and mixed agents. However, there are many kinds of paddy field weeds, and the weeds and the growth time of each weed are not uniform, and the generation of perennial weeds is particularly long. Therefore, it is very difficult to control all weeds with a single herbicide application. Therefore, as a herbicide, many kinds of weeds including annual and perennial weeds can be killed, that is, the herbicidal spectrum is wide, effective for weeds that have grown, and the herbicidal effect can be maintained for a certain period of time. In addition, the emergence of highly safe drugs in paddy rice is most demanded.

  General formula (I) which is one active ingredient of the present invention:

［式中、Ｒ¹は、水素原子、ハロゲン原子、Ｃ₁〜Ｃ₆アルキル基、Ｃ₁〜Ｃ₆ハロアルキル基、Ｃ₃〜Ｃ₆シクロアルキル基、Ｃ₂〜Ｃ₆アルケニル基、シアノ基、Ｃ₂〜Ｃ₇アルキルカルボニル基、ジ（Ｃ₁〜Ｃ₆アルキル）カルバモイル基、置換されてよいフェニル基（当該置換基は、下記置換基群Ａから選ばれる置換基である。）、５又は６員複素環基（当該複素環は、環中に、１個の、窒素原子、酸素原子又は硫黄原子を含有し、更に１〜２個の窒素原子を含有してよい。）、Ｃ₁〜Ｃ₆アルコキシ基、置換されてよいフェノキシ基（当該置換基は、下記置換基群Ａから選ばれる置換基である。）又は置換されてよい５又は６員複素環オキシ基｛当該複素環は、環中に、１個の、窒素原子、酸素原子又は硫黄原子を含有し、更に１〜２個の窒素原子を含有してよい。当該置換基は、置換されてよいベンゾイル基（当該置換基は、下記置換基群Ａから選ばれる置換基である。）及びＣ₁〜Ｃ₆アルキル基からなる群から選ばれる置換基である。｝であり、
Ｒ²は、水素原子、ハロゲン原子、Ｃ₁〜Ｃ₆アルキル基、（Ｃ₁〜Ｃ₆アルコキシ）Ｃ₁〜Ｃ₆アルキル基、置換されてよいベンゾイル基（当該置換基は、下記置換基群Ａから選ばれる置換基である。）、Ｃ₂〜Ｃ₇アルコキシカルボニル基、置換されてよいフェノキシ基（当該置換基は、下記置換基群Ａから選ばれる置換基である。）、置換されてよいフェニルチオ基（当該置換基は、下記置換基群Ａから選ばれる置換基である。）又はトリ（Ｃ₁〜Ｃ₆アルキル）ケイ素基であり、
Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、互いに独立して、水素原子、ハロゲン原子、置換されてよいＣ₁〜Ｃ₆アルキル基（当該置換基は、下記置換基群Ｂから選ばれる置換基である。）、置換されてよいＣ₂〜Ｃ₆アルケニル基（当該置換基は、シアノ基又はニトロ基である。）、Ｃ₂〜Ｃ₆アルキニル基、置換されてよいＣ₃〜Ｃ₆シクロアルキル基（当該置換基は、下記置換基群Ｃから選ばれる置換基である。）、Ｃ₄〜Ｃ₁₀ビシクロアルキル基、シアノ基、ホルミル基、Ｃ₂〜Ｃ₇アルキルカルボニル基、置換されてよいベンゾイル基（当該置換基は、下記置換基群Ａから選ばれる置換基である。）、カルボキシル基、Ｃ₂〜Ｃ₇アルコキシカルボニル基、カルバモイル基、ジ（Ｃ₁〜Ｃ₆アルキル）カルバモイル基、置換されてよいフェニル基（当該置換基は、下記置換基群Ａから選ばれる置換基である。）、置換されてよい３〜６員複素環基（当該複素環は、環中に、１個の、窒素原子、酸素原子又は硫黄原子を含有し、更に１〜２個の窒素原子を含有してよく、ベンゼン環と縮合してよい。当該置換基は、下記置換基群Ｅから選ばれる置換基である。）、置換されてよいアミノ基（当該置換基は、下記置換基群Ｄから選ばれる置換基である。）、ニトロ基、水酸基、Ｃ₁〜Ｃ₆アルコキシ基、Ｃ₁〜Ｃ₆ハロアルコキシ基、（Ｃ₁〜Ｃ₆アルコキシ）Ｃ₁〜Ｃ₆アルコキシ基、置換されてよいフェノキシ基（当該置換基は、水酸基又は、ハロゲン原子及びＣ₁〜Ｃ₆アルコキシ基から選ばれる置換基により置換されたピリダジニルオキシ基である。）、置換されてよい５〜６員複素環オキシ基（当該複素環は、環中に、１個の、窒素原子、酸素原子又は硫黄原子を含有し、更に１〜２個の窒素原子を含有してよい。当該置換基は、下記置換基群Ｅから選ばれる置換基である。）、置換されてよいフェニルスルホニルオキシ基（当該置換基は、下記置換基群Ａから選ばれる置換基である。）、Ｃ₁〜Ｃ₆アルキルチオ基、Ｃ₁〜Ｃ₆アルキルスルフィニル基、Ｃ₁〜Ｃ₆アルキルスルホニル基又はトリ（Ｃ₁〜Ｃ₆アルキル）ケイ素基であり、又は、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、隣合う２個が、それぞれが結合する炭素原子と一緒になって、置換されてよい３〜６員環状炭化水素基（当該環状炭化水素は、窒素原子、酸素原子及び硫黄原子からなる群から選ばれる同一又は異なった１〜２個の複素原子により中断してよい。当該置換基は、ハロゲン原子、Ｃ₁〜Ｃ₆アルキル基、ヒドロキシＣ₁〜Ｃ₆アルキル基、Ｃ₁〜Ｃ₆アルコキシ基、オキソ基、ヒドロキシイミノ基又はＣ₁〜Ｃ₆アルコキシイミノ基であり、Ｃ₁〜Ｃ₆アルキル基が置換した場合、他のＣ₁〜Ｃ₆アルキル基又は環上の炭素原子と結合して新たな３員環を形成してよい。）を形成してよく、
ｍ及びｎは、互いに独立して、０又は１を表し、
置換基群Ａは、ハロゲン原子、Ｃ₁〜Ｃ₆アルキル基、Ｃ₁〜Ｃ₆ハロアルキル基、Ｃ₃〜Ｃ₆シクロアルキル基、シアノ基及びトリ（Ｃ₁〜Ｃ₆アルキル）ケイ素基からなる群であり、
置換基群Ｂは、ハロゲン原子、Ｃ₃〜Ｃ₆シクロアルキル基、シアノ基、Ｃ₂〜Ｃ₇アルキルカルボニル基、Ｃ₂〜Ｃ₇アルコキシカルボニル基、フェニル基、Ｃ₁〜Ｃ₆アルコキシ基、Ｃ₁〜Ｃ₆アルキルチオ基、Ｃ₁〜Ｃ₆アルキルスルフィニル基、Ｃ₁〜Ｃ₆アルキルスルホニル基、Ｃ₁〜Ｃ₄アルキレンジオキシ基、ヒドロキシイミノ基及びＣ₁〜Ｃ₆アルコキシイミノ基からなる群であり、
置換基群Ｃは、ハロゲン原子、置換されてよいＣ₁〜Ｃ₆アルキル基（当該置換基は、上記置換基群Ｂから選ばれる置換基である。）、Ｃ₃〜Ｃ₆シクロアルキル基、Ｃ₂〜Ｃ₆アルケニル基、シアノ基、Ｃ₂〜Ｃ₇アルキルカルボニル基、ベンゾイル基、カルボキシル基、Ｃ₂〜Ｃ₇アルコキシカルボニル基、カルバモイル基、ジ（Ｃ₁〜Ｃ₆アルキル）カルバモイル基、置換されてよいフェニル基（当該置換基は、上記置換基群Ａから選ばれる置換基である。）、５又は６員複素環基（当該複素環は、環中に、１個の、窒素原子、酸素原子又は硫黄原子を含有し、更に１〜２個の窒素原子を含有してよい。）、置換されてよいアミノ基（当該置換基は、下記置換基群Ｄから選ばれる置換基である。）、ニトロ基、水酸基、Ｃ₁〜Ｃ₆アルコキシ基、Ｃ₁〜Ｃ₆ハロアルコキシ基、フェノキシ基、Ｃ₁〜Ｃ₆アルキルチオ基、フェニルチオ基、Ｃ₁〜Ｃ₆アルキルスルフィニル基及びＣ₁〜Ｃ₆アルキルスルホニル基からなる群であり、
置換基群Ｄは、Ｃ₁〜Ｃ₆アルキル基、Ｃ₂〜Ｃ₇アルキルカルボニル基、Ｃ₂〜Ｃ₇アルコキシカルボニル基、ジ（Ｃ₁〜Ｃ₆アルキル）カルバモイル基及びＣ₁〜Ｃ₆アルキルスルホニル基からなる群であり、
置換基群Ｅは、ハロゲン原子、Ｃ₁〜Ｃ₆アルキル基、Ｃ₁〜Ｃ₆ハロアルキル基、水酸基、置換されてよいフェニルスルホニル基（当該置換基は、上記置換基群Ａから選ばれる置換基である。）及びジ（Ｃ₁〜Ｃ₆アルキル）スルファモイル基からなる群である。］で表される化合物、その塩及びそのエステル誘導体である3-フェノキシ-4-ピリダジノール誘導体〔以下、化合物（Ｉ）と略す〕は新規化合物である。

[Wherein, R ¹ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₃ -C ₆ cycloalkyl group, a C ₂ -C ₆ alkenyl group, a cyano group, C ₂ -C ₇ alkylcarbonyl group, a di (C ₁ -C ₆ alkyl) carbamoyl group, which may be substituted phenyl group (the substituent is a substituent selected from substituent group a.), 5 or 6-membered heterocyclic group (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 to 2 nitrogen atoms), C _1- . A C ₆ alkoxy group, an optionally substituted phenoxy group (the substituent is a substituent selected from the following substituent group A) or an optionally substituted 5- or 6-membered heterocyclic oxy group {the heterocyclic ring is Contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and one or two more Of nitrogen atoms. The substituent is a substituent selected from the group consisting of an optionally substituted benzoyl group (the substituent is a substituent selected from the following substituent group A) and a C _{1 to} C ₆ alkyl group. },
R ² is a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a (C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkyl group, a benzoyl group which may be substituted (the substituent is the following substituent group) A substituent selected from A.), a C ₂ -C ₇ alkoxycarbonyl group, an optionally substituted phenoxy group (the substituent is a substituent selected from the following substituent group A), substituted. A good phenylthio group (the substituent is a substituent selected from the following substituent group A) or a tri (C ₁ -C ₆ alkyl) silicon group;
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom or an optionally substituted C ₁ -C ₆ alkyl group (the substituent is selected from the following substituent group B) A C ₂ -C ₆ alkenyl group which may be substituted (the substituent is a cyano group or a nitro group), a C ₂ -C ₆ alkynyl group, a C ₃ which may be substituted. -C ₆ cycloalkyl group (said substituent is a substituent selected from substituent group C.), C ₄ ~C ₁₀ bicycloalkyl group, a cyano group, a formyl group, C ₂ -C ₇ alkylcarbonyl group , A benzoyl group which may be substituted (the substituent is a substituent selected from the following substituent group A), a carboxyl group, a C _{2 to} C ₇ alkoxycarbonyl group, a carbamoyl group, di (C _{1 to} C _6). Alkyl) carbamoyl group, optionally substituted phenyl A group (the substituent is a substituent selected from the following substituent group A), an optionally substituted 3- to 6-membered heterocyclic group (the heterocyclic ring includes one nitrogen atom, (It contains an oxygen atom or a sulfur atom, may further contain 1 to 2 nitrogen atoms, and may be condensed with a benzene ring. The substituent is a substituent selected from the following substituent group E.) , amino group which may be substituted (the substituent is a substituent selected from substituent group D.), a nitro group, a hydroxyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ haloalkoxy group, (C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkoxy group, optionally substituted phenoxy group (the substituent is substituted with a hydroxyl group or a substituent selected from a halogen atom and a C ₁ -C ₆ alkoxy group) A pyridazinyloxy group), which may be substituted; Ring oxy group (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 to 2 nitrogen atoms. is a substituent selected from group E.), which may be substituted phenylsulfonyloxy group (the substituent is a substituent selected from substituent group a.), C ₁ ~C ₆ alkylthio group, A C ₁ -C ₆ alkylsulfinyl group, a C ₁ -C ₆ alkylsulfonyl group or a tri (C ₁ -C ₆ alkyl) silicon group, or R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are Two adjacent groups may be substituted together with the carbon atom to which each is bonded. The 3- to 6-membered cyclic hydrocarbon group (the cyclic hydrocarbon is selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom) Interrupted by one or two identical or different heteroatoms There. The substituents are halogen atom, C ₁ -C ₆ alkyl group, a hydroxy C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, a oxo group, hydroxyimino group or a C ₁ -C ₆ alkoxyimino group If the C ₁ -C ₆ alkyl group is substituted, may form a new 3-membered ring with other C ₁ -C ₆ alkyl group or a carbon atom on the ring. )
m and n each independently represent 0 or 1,
Substituent Group A consists of halogen atoms, C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, C ₃ -C ₆ cycloalkyl group, a cyano group and a tri (C ₁ -C ₆ alkyl) silyl group A group,
Substituent group B, a halogen atom, C ₃ -C ₆ cycloalkyl group, a cyano group, C ₂ -C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group, a phenyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, consisting of C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, C ₁ -C ₄ alkylenedioxy group, hydroxyimino group and C ₁ -C ₆ alkoxyimino group A group,
Substituent group C includes a halogen atom, an optionally substituted C ₁ -C ₆ alkyl group (the substituent is a substituent selected from the above substituent group B), a C ₃ -C ₆ cycloalkyl group, C ₂ -C ₆ alkenyl group, cyano group, C ₂ -C ₇ alkylcarbonyl group, benzoyl group, carboxyl group, C ₂ -C ₇ alkoxycarbonyl group, carbamoyl group, di (C ₁ -C ₆ alkyl) carbamoyl group, A phenyl group which may be substituted (the substituent is a substituent selected from the above substituent group A), a 5- or 6-membered heterocyclic group (the heterocyclic ring has one nitrogen atom in the ring; , An oxygen atom or a sulfur atom, and further may contain 1 to 2 nitrogen atoms.), An amino group which may be substituted (the substituent is a substituent selected from the following substituent group D) .), a nitro group, a hydroxyl group, C ₁ -C ₆ alkoxy Group, a C ₁ -C ₆ haloalkoxy group, a phenoxy group, C ₁ -C ₆ alkylthio group, a phenylthio group, C ₁ -C ₆ alkylsulfinyl group consisting Le group and C ₁ -C ₆ alkylsulfonyl group,
Substituent group D is, C ₁ -C ₆ alkyl group, C ₂ -C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group, a di (C ₁ -C ₆ alkyl) carbamoyl group and C ₁ -C ₆ alkyl A group consisting of a sulfonyl group,
Substituent group E includes a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a hydroxyl group, an optionally substituted phenylsulfonyl group (the substituent is a substituent selected from substituent group A above) And di (C ₁ -C ₆ alkyl) sulfamoyl groups. ] The compound represented by these, its salt, and its ester derivative 3-phenoxy-4-pyridazinol derivative [Hereinafter abbreviated as compound (I)] is a novel compound.

  Another active ingredient, butyl (R) -2- [4- (4-cyano-2-fluorophenoxy) phenoxy] propionate [hereinafter abbreviated as compound (C). General name cihalohop butyl], 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-pyrazolyl-p-toluenesulfonate [hereinafter abbreviated as compound (P). General name pyrazolate], 2- [4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazol-5-yloxy] acetophenone [hereinafter abbreviated as compound (Q). General name pyrazoxifene], 2- [4- (2,4-dichloro-m-toluoyl) -1,3-dimethylpyrazol-5-yloxy] -4′-methylacetophenone [hereinafter abbreviated as compound (B). [Generic name benzophenap] is a known herbicidal compound and is described in The Pesticide Manual 12th Edition, pages 223-224, 793-794, 797-798, and 83, respectively.

  Compound (C) has a high effect on grass weeds, but the herbicidal effect on other weeds is not sufficient. Compounds (P), (Q), and (B) have a high effect on annual broadleaf weeds and some perennial weeds, but their effects on grass weeds and some perennial weeds are Not always enough.

The Pesticide Manual 12th Edition pp. 223-224, 793-794, 797-798, 83

  In order to improve the above-mentioned problems of conventional herbicides, the present inventors completely control various weeds with a single spray, and have a high level of safety against paddy rice. As a result of continuing to search for low safe herbicides, the herbicidal spectrum is expanded by combining the 3-phenoxy-4-pyridazinol derivative and the second herbicidal active compound with the third herbicidal active compound as an active ingredient. At the same time, the inventors have found that important weeds can be controlled with a smaller amount of active ingredients due to a synergistic action, thereby completing the present invention.

    The present invention is directed to general formula (I):

［式中、Ｒ¹は、水素原子、ハロゲン原子、Ｃ₁〜Ｃ₆アルキル基、Ｃ₁〜Ｃ₆ハロアルキル基、Ｃ₃〜Ｃ₆シクロアルキル基、Ｃ₂〜Ｃ₆アルケニル基、シアノ基、Ｃ₂〜Ｃ₇アルキルカルボニル基、ジ（Ｃ₁〜Ｃ₆アルキル）カルバモイル基、置換されてよいフェニル基（当該置換基は、下記置換基群Ａから選ばれる置換基である。）、５又は６員複素環基（当該複素環は、環中に、１個の、窒素原子、酸素原子又は硫黄原子を含有し、更に１〜２個の窒素原子を含有してよい。）、Ｃ₁〜Ｃ₆アルコキシ基、置換されてよいフェノキシ基（当該置換基は、下記置換基群Ａから選ばれる置換基である。）又は置換されてよい５又は６員複素環オキシ基｛当該複素環は、環中に、１個の、窒素原子、酸素原子又は硫黄原子を含有し、更に１〜２個の窒素原子を含有してよい。当該置換基は、置換されてよいベンゾイル基（当該置換基は、下記置換基群Ａから選ばれる置換基である。）及びＣ₁〜Ｃ₆アルキル基からなる群から選ばれる置換基である。｝であり、
Ｒ²は、水素原子、ハロゲン原子、Ｃ₁〜Ｃ₆アルキル基、（Ｃ₁〜Ｃ₆アルコキシ）Ｃ₁〜Ｃ₆アルキル基、置換されてよいベンゾイル基（当該置換基は、下記置換基群Ａから選ばれる置換基である。）、Ｃ₂〜Ｃ₇アルコキシカルボニル基、置換されてよいフェノキシ基（当該置換基は、下記置換基群Ａから選ばれる置換基である。）、置換されてよいフェニルチオ基（当該置換基は、下記置換基群Ａから選ばれる置換基である。）又はトリ（Ｃ₁〜Ｃ₆アルキル）ケイ素基であり、
Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、互いに独立して、水素原子、ハロゲン原子、置換されてよいＣ₁〜Ｃ₆アルキル基（当該置換基は、下記置換基群Ｂから選ばれる置換基である。）、置換されてよいＣ₂〜Ｃ₆アルケニル基（当該置換基は、シアノ基又はニトロ基である。）、Ｃ₂〜Ｃ₆アルキニル基、置換されてよいＣ₃〜Ｃ₆シクロアルキル基（当該置換基は、下記置換基群Ｃから選ばれる置換基である。）、Ｃ₄〜Ｃ₁₀ビシクロアルキル基、シアノ基、ホルミル基、Ｃ₂〜Ｃ₇アルキルカルボニル基、置換されてよいベンゾイル基（当該置換基は、下記置換基群Ａから選ばれる置換基である。）、カルボキシル基、Ｃ₂〜Ｃ₇アルコキシカルボニル基、カルバモイル基、ジ（Ｃ₁〜Ｃ₆アルキル）カルバモイル基、置換されてよいフェニル基（当該置換基は、下記置換基群Ａから選ばれる置換基である。）、置換されてよい３〜６員複素環基（当該複素環は、環中に、１個の、窒素原子、酸素原子又は硫黄原子を含有し、更に１〜２個の窒素原子を含有してよく、ベンゼン環と縮合してよい。当該置換基は、下記置換基群Ｅから選ばれる置換基である。）、置換されてよいアミノ基（当該置換基は、下記置換基群Ｄから選ばれる置換基である。）、ニトロ基、水酸基、Ｃ₁〜Ｃ₆アルコキシ基、Ｃ₁〜Ｃ₆ハロアルコキシ基、（Ｃ₁〜Ｃ₆アルコキシ）Ｃ₁〜Ｃ₆アルコキシ基、置換されてよいフェノキシ基（当該置換基は、水酸基又は、ハロゲン原子及びＣ₁〜Ｃ₆アルコキシ基から選ばれる置換基により置換されたピリダジニルオキシ基である。）、置換されてよい５〜６員複素環オキシ基（当該複素環は、環中に、１個の、窒素原子、酸素原子又は硫黄原子を含有し、更に１〜２個の窒素原子を含有してよい。当該置換基は、下記置換基群Ｅから選ばれる置換基である。）、置換されてよいフェニルスルホニルオキシ基（当該置換基は、下記置換基群Ａから選ばれる置換基である。）、Ｃ₁〜Ｃ₆アルキルチオ基、Ｃ₁〜Ｃ₆アルキルスルフィニル基、Ｃ₁〜Ｃ₆アルキルスルホニル基又はトリ（Ｃ₁〜Ｃ₆アルキル）ケイ素基であり、又は、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、隣合う２個が、それぞれが結合する炭素原子と一緒になって、置換されてよい３〜６員環状炭化水素基（当該環状炭化水素は、窒素原子、酸素原子及び硫黄原子からなる群から選ばれる同一又は異なった１〜２個の複素原子により中断してよい。当該置換基は、ハロゲン原子、Ｃ₁〜Ｃ₆アルキル基、ヒドロキシＣ₁〜Ｃ₆アルキル基、Ｃ₁〜Ｃ₆アルコキシ基、オキソ基、ヒドロキシイミノ基又はＣ₁〜Ｃ₆アルコキシイミノ基であり、Ｃ₁〜Ｃ₆アルキル基が置換した場合、他のＣ₁〜Ｃ₆アルキル基又は環上の炭素原子と結合して新たな３員環を形成してよい。）を形成してよく、
ｍ及びｎは、互いに独立して、０又は１を表し、
置換基群Ａは、ハロゲン原子、Ｃ₁〜Ｃ₆アルキル基、Ｃ₁〜Ｃ₆ハロアルキル基、Ｃ₃〜Ｃ₆シクロアルキル基、シアノ基及びトリ（Ｃ₁〜Ｃ₆アルキル）ケイ素基からなる群であり、
置換基群Ｂは、ハロゲン原子、Ｃ₃〜Ｃ₆シクロアルキル基、シアノ基、Ｃ₂〜Ｃ₇アルキルカルボニル基、Ｃ₂〜Ｃ₇アルコキシカルボニル基、フェニル基、Ｃ₁〜Ｃ₆アルコキシ基、Ｃ₁〜Ｃ₆アルキルチオ基、Ｃ₁〜Ｃ₆アルキルスルフィニル基、Ｃ₁〜Ｃ₆アルキルスルホニル基、Ｃ₁〜Ｃ₄アルキレンジオキシ基、ヒドロキシイミノ基及びＣ₁〜Ｃ₆アルコキシイミノ基からなる群であり、
置換基群Ｃは、ハロゲン原子、置換されてよいＣ₁〜Ｃ₆アルキル基（当該置換基は、上記置換基群Ｂから選ばれる置換基である。）、Ｃ₃〜Ｃ₆シクロアルキル基、Ｃ₂〜Ｃ₆アルケニル基、シアノ基、Ｃ₂〜Ｃ₇アルキルカルボニル基、ベンゾイル基、カルボキシル基、Ｃ₂〜Ｃ₇アルコキシカルボニル基、カルバモイル基、ジ（Ｃ₁〜Ｃ₆アルキル）カルバモイル基、置換されてよいフェニル基（当該置換基は、上記置換基群Ａから選ばれる置換基である。）、５又は６員複素環基（当該複素環は、環中に、１個の、窒素原子、酸素原子又は硫黄原子を含有し、更に１〜２個の窒素原子を含有してよい。）、置換されてよいアミノ基（当該置換基は、下記置換基群Ｄから選ばれる置換基である。）、ニトロ基、水酸基、Ｃ₁〜Ｃ₆アルコキシ基、Ｃ₁〜Ｃ₆ハロアルコキシ基、フェノキシ基、Ｃ₁〜Ｃ₆アルキルチオ基、フェニルチオ基、Ｃ₁〜Ｃ₆アルキルスルフィニル基及びＣ₁〜Ｃ₆アルキルスルホニル基からなる群であり、
置換基群Ｄは、Ｃ₁〜Ｃ₆アルキル基、Ｃ₂〜Ｃ₇アルキルカルボニル基、Ｃ₂〜Ｃ₇アルコキシカルボニル基、ジ（Ｃ₁〜Ｃ₆アルキル）カルバモイル基及びＣ₁〜Ｃ₆アルキルスルホニル基からなる群であり、
置換基群Ｅは、ハロゲン原子、Ｃ₁〜Ｃ₆アルキル基、Ｃ₁〜Ｃ₆ハロアルキル基、水酸基、置換されてよいフェニルスルホニル基（当該置換基は、上記置換基群Ａから選ばれる置換基である。）及びジ（Ｃ₁〜Ｃ₆アルキル）スルファモイル基からなる群である。］
で表される化合物、その塩又はそのエステル誘導体からなる群から選ばれる１種又は２種以上の3-フェノキシ-4-ピリダジノール誘導体とブチル （R）-2-［4-（4-シアノ-2-フルオロフェノキシ）フェノキシ］プロピオナートを有効成分として配合した除草性組成物、又は更に4-(2,4-ジクロロベンゾイル)-1,3-ジメチル-5-ピラゾリル-p-トルエンスルホネート、2-[4-(2,4-ジクロロベンゾイル)-1,3-ジメチルピラゾール-5-イルオキシ]アセトフェノン、2-[4-(2,4-ジクロロ-m-トルオイル)-1,3-ジメチルピラゾール-5-イルオキシ]-4'-メチルアセトフェノンからなる群から選ばれる１種又は2種以上の第三除草活性化合物を有効成分として含有する除草性組成物である。

[Wherein, R ¹ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₃ -C ₆ cycloalkyl group, a C ₂ -C ₆ alkenyl group, a cyano group, C ₂ -C ₇ alkylcarbonyl group, a di (C ₁ -C ₆ alkyl) carbamoyl group, which may be substituted phenyl group (the substituent is a substituent selected from substituent group a.), 5 or 6-membered heterocyclic group (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 to 2 nitrogen atoms), C _1- . A C ₆ alkoxy group, an optionally substituted phenoxy group (the substituent is a substituent selected from the following substituent group A) or an optionally substituted 5- or 6-membered heterocyclic oxy group {the heterocyclic ring is Contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and one or two more Of nitrogen atoms. The substituent is a substituent selected from the group consisting of an optionally substituted benzoyl group (the substituent is a substituent selected from the following substituent group A) and a C _{1 to} C ₆ alkyl group. },
R ² is a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a (C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkyl group, a benzoyl group which may be substituted (the substituent is the following substituent group) A substituent selected from A.), a C ₂ -C ₇ alkoxycarbonyl group, an optionally substituted phenoxy group (the substituent is a substituent selected from the following substituent group A), substituted. A good phenylthio group (the substituent is a substituent selected from the following substituent group A) or a tri (C ₁ -C ₆ alkyl) silicon group;
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom or an optionally substituted C ₁ -C ₆ alkyl group (the substituent is selected from the following substituent group B) A C ₂ -C ₆ alkenyl group which may be substituted (the substituent is a cyano group or a nitro group), a C ₂ -C ₆ alkynyl group, a C ₃ which may be substituted. -C ₆ cycloalkyl group (said substituent is a substituent selected from substituent group C.), C ₄ ~C ₁₀ bicycloalkyl group, a cyano group, a formyl group, C ₂ -C ₇ alkylcarbonyl group , A benzoyl group which may be substituted (the substituent is a substituent selected from the following substituent group A), a carboxyl group, a C _{2 to} C ₇ alkoxycarbonyl group, a carbamoyl group, di (C _{1 to} C _6). Alkyl) carbamoyl group, optionally substituted phenyl A group (the substituent is a substituent selected from the following substituent group A), an optionally substituted 3- to 6-membered heterocyclic group (the heterocyclic ring includes one nitrogen atom, (It contains an oxygen atom or a sulfur atom, may further contain 1 to 2 nitrogen atoms, and may be condensed with a benzene ring. The substituent is a substituent selected from the following substituent group E.) , amino group which may be substituted (the substituent is a substituent selected from substituent group D.), a nitro group, a hydroxyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ haloalkoxy group, (C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkoxy group, optionally substituted phenoxy group (the substituent is substituted with a hydroxyl group or a substituent selected from a halogen atom and a C ₁ -C ₆ alkoxy group) A pyridazinyloxy group), which may be substituted; Ring oxy group (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 to 2 nitrogen atoms. is a substituent selected from group E.), which may be substituted phenylsulfonyloxy group (the substituent is a substituent selected from substituent group a.), C ₁ ~C ₆ alkylthio group, A C ₁ -C ₆ alkylsulfinyl group, a C ₁ -C ₆ alkylsulfonyl group or a tri (C ₁ -C ₆ alkyl) silicon group, or R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are Two adjacent groups may be substituted together with the carbon atom to which each is bonded. The 3- to 6-membered cyclic hydrocarbon group (the cyclic hydrocarbon is selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom) Interrupted by one or two identical or different heteroatoms There. The substituents are halogen atom, C ₁ -C ₆ alkyl group, a hydroxy C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, a oxo group, hydroxyimino group or a C ₁ -C ₆ alkoxyimino group If the C ₁ -C ₆ alkyl group is substituted, may form a new 3-membered ring with other C ₁ -C ₆ alkyl group or a carbon atom on the ring. )
m and n each independently represent 0 or 1,
Substituent Group A consists of halogen atoms, C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, C ₃ -C ₆ cycloalkyl group, a cyano group and a tri (C ₁ -C ₆ alkyl) silyl group A group,
Substituent group B, a halogen atom, C ₃ -C ₆ cycloalkyl group, a cyano group, C ₂ -C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group, a phenyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, consisting of C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, C ₁ -C ₄ alkylenedioxy group, hydroxyimino group and C ₁ -C ₆ alkoxyimino group A group,
Substituent group C includes a halogen atom, an optionally substituted C ₁ -C ₆ alkyl group (the substituent is a substituent selected from the above substituent group B), a C ₃ -C ₆ cycloalkyl group, C ₂ -C ₆ alkenyl group, cyano group, C ₂ -C ₇ alkylcarbonyl group, benzoyl group, carboxyl group, C ₂ -C ₇ alkoxycarbonyl group, carbamoyl group, di (C ₁ -C ₆ alkyl) carbamoyl group, A phenyl group which may be substituted (the substituent is a substituent selected from the above substituent group A), a 5- or 6-membered heterocyclic group (the heterocyclic ring has one nitrogen atom in the ring; , An oxygen atom or a sulfur atom, and further may contain 1 to 2 nitrogen atoms.), An amino group which may be substituted (the substituent is a substituent selected from the following substituent group D) .), a nitro group, a hydroxyl group, C ₁ -C ₆ alkoxy Group, a C ₁ -C ₆ haloalkoxy group, a phenoxy group, C ₁ -C ₆ alkylthio group, a phenylthio group, C ₁ -C ₆ alkylsulfinyl group consisting Le group and C ₁ -C ₆ alkylsulfonyl group,
Substituent group D is, C ₁ -C ₆ alkyl group, C ₂ -C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group, a di (C ₁ -C ₆ alkyl) carbamoyl group and C ₁ -C ₆ alkyl A group consisting of a sulfonyl group,
Substituent group E includes a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a hydroxyl group, an optionally substituted phenylsulfonyl group (the substituent is a substituent selected from substituent group A above) And di (C ₁ -C ₆ alkyl) sulfamoyl groups. ]
Or one or two or more 3-phenoxy-4-pyridazinol derivatives selected from the group consisting of a compound represented by the formula: salt or ester derivative thereof; and butyl (R) -2- [4- (4-cyano-2 Herbicidal composition containing -fluorophenoxy) phenoxy] propionate as an active ingredient, or 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-pyrazolyl-p-toluenesulfonate, 2- [4 -(2,4-Dichlorobenzoyl) -1,3-dimethylpyrazol-5-yloxy] acetophenone, 2- [4- (2,4-dichloro-m-toluoyl) -1,3-dimethylpyrazol-5-yloxy ] A herbicidal composition containing, as an active ingredient, one or more third herbicidal active compounds selected from the group consisting of 4'-methylacetophenone.

  The herbicidal composition of the present invention is obtained as a single agent by applying the 3-phenoxy-4-pyridazinol derivative, the second herbicidal active compound, and further the third herbicidally active compound, which are the active ingredients. The range of slaughtering is expanded beyond the applicable range. The herbicidal width of the composition of the present invention extends to general perennial weeds such as Gramineae, annual broad-leaved weeds, Omodakaceae and Cyperaceae. Furthermore, the composition of the present invention is highly safe for paddy rice and has a wide application period. In addition, the composition of the present invention exhibits a synergistic effect on the herbicidal effect, and exhibits its effect sufficiently when the active ingredients are mixed at a dose much lower than the dose when each active ingredient is used alone. As a result, the composition of the present invention increases the herbicidal efficacy enough to be a single treatment, and the efficacy lasts for a long time. Further, the composition of the present invention has no phytotoxicity to paddy rice and can be treated before transplantation and immediately after transplanting.

  In the present invention, the “halogen atom” is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a chlorine atom or a bromine atom. And even more preferred is a chlorine atom.

In the present invention, the “C ₁ -C ₆ alkyl group” is a linear or branched alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl. , T-butyl, pentyl, isopentyl, 2-methylbutyl, neopentyl, 1-ethylpropyl, hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2 , 2-dimethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl or 2-ethylbutyl group, It is four straight or branched chain alkyl group (C ₁ -C ₄ alkyl group), more preferably 1 to 3 carbon atoms straight or branched chain alkyl group (C ₁ -C ₃ alkyl Group), and even more preferably, 1 to 2 carbon atoms. An alkyl group (C ₁ -C ₂ alkyl group), particularly preferably a methyl group.

In the present invention, the “C ₁ -C ₆ haloalkyl group” is the “C ₁ -C ₆ alkyl group” substituted with 1 to 5 of the same or different “halogen atoms”, such as chloromethyl, Dichloromethyl, trichloromethyl, 1-chloroethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 1-chloropropyl, 3-chloropropyl, 1-chlorobutyl, 4-chlorobutyl, fluoromethyl, difluoromethyl, trifluoromethyl 1-fluoroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, fluorochloromethyl, bromomethyl, 1-bromoethyl, 2-bromoethyl or iodomethyl groups, preferably fluorine atom, C ₁ -C ₃ alkyl group one to three substituents the same or different selected from the group consisting of chlorine atom and bromine atom is substituted There, more preferably, the same one to three, fluorine atoms C ₁ -C ₂ alkyl radical or a chlorine atom is substituted, further preferably more, fluoromethyl, difluoromethyl, trifluoromethyl or 2 2,2-trichloroethyl group, particularly preferably a trifluoromethyl group.

In the present invention, the “C ₃ -C ₆ cycloalkyl group” is a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl group, preferably a cyclopropyl or cyclobutyl group, and more preferably a cyclopropyl group. .

In the present invention, the “C ₂ -C ₆ alkenyl group” is a linear or branched alkenyl group having 2 to 6 carbon atoms, and examples thereof include vinyl, 1-methylvinyl, allyl, 1-propenyl, 1-propenyl, Methyl-1-propenyl, 2-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-ethyl-2-propenyl, 2-butenyl, 1-methyl-2-butenyl, 2-methyl- 2-butenyl, 1-ethyl-2-butenyl, 3-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 1-ethyl-3-butenyl, 2-pentenyl, 1-methyl-2- Pentenyl, 2-methyl-2-pentenyl, 3-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 4-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, It may be a 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl group, preferably a straight or branched chain alkyl having 2 to 4 carbon atoms. An alkenyl group (C ₂ -C ₄ alkenyl group), more preferably, vinyl, allyl, 1-methylvinyl, 2-propenyl or 1-methyl-2-propenyl group.

In the present invention, the “C ₂ -C ₇ alkylcarbonyl group” is a carbonyl group to which the “C ₁ -C ₆ alkyl group” is bonded, and examples thereof include acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, It can be a hexanoyl or heptanoyl group, and is preferably a carbonyl group (C ₂ -C ₅ alkylcarbonyl group) to which a linear or branched alkyl group having 1 to 4 carbon atoms is bonded, and even more preferably , A carbonyl group to which a linear or branched alkyl group having 1 to 3 carbon atoms is bonded (C _{2 to} C ₄ alkylcarbonyl group), particularly preferably an acetyl, propionyl, valeryl or pivaloyl group, Most preferred is an acetyl group.

In the present invention, the “di (C ₁ -C ₆ alkyl) carbamoyl group” is a carbamoyl group in which two identical or different “C ₁ -C ₆ alkyl groups” are bonded to a nitrogen atom. , Methylethylcarbamoyl, diethylcarbamoyl, dipropylcarbamoyl, dibutylcarbamoyl or dihexylcarbamoyl group, preferably a carbamoyl group in which the same two linear or branched alkyl groups having 1 to 3 carbon atoms are bonded {Di (C ₁ -C ₃ alkyl) carbamoyl group}, more preferably a dimethylcarbamoyl group or diethylcarbamoyl group, and even more preferably a dimethylcarbamoyl group.

In the present invention, the “tri (C ₁ -C ₆ alkyl) silicon group” is a silicon atom to which three identical or different “C ₁ -C ₆ alkyl groups” are bonded, and examples thereof include trimethylsilyl, triethylsilyl, It may be a triisopropylsilyl, dimethylisopropylsilyl, t-butyldimethylsilyl or trihexylsilyl group, preferably having the same or different 3 to 1 C 1-3 straight or branched alkyl groups attached thereto. A silicon atom {tri (C ₁ -C ₃ alkyl) silicon group}, more preferably a trimethylsilyl or dimethylisopropylsilyl group, and even more preferably a trimethylsilyl group.

In the present invention, “optionally substituted phenyl group (the substituent is a substituent selected from Substituent Group A)” means the “halogen atom”, the “C ₁ -C ₆ alkyl group”, The same or different selected from the group consisting of the “C ₁ -C ₆ haloalkyl group”, the “C ₃ -C ₆ cycloalkyl group”, the cyano group, and the “tri (C ₁ -C ₆ alkyl) silicon group”. 1 to 5 substituents may be substituted phenyl groups, such as phenyl, fluorophenyl, difluorophenyl, trifluorophenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, fluorochlorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, Tetramethylphenyl, pentamethylphenyl, ethylphenyl, fluoro (methyl) phenyl, chloro (me ) Phenyl, bromo (methyl) phenyl, cyclopropylphenyl, cyclopropyl (fluoro) phenyl, chloro (cyclopropyl) phenyl, cyclopropyl (methyl) phenyl, (trifluoromethyl) phenyl or fluoro (trifluoromethyl) phenyl groups in and obtained, preferably a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, the same or different 1-3 selected from the group consisting of chlorine and bromine C ₁ -C ₃ alkyl group "substituted group is substituted, C ₃ -C ₄ cycloalkyl group, the same or different 1 to 3 selected from cyano group and a tri (C ₁ -C ₃ alkyl) group consisting of silicon group Is an optionally substituted phenyl group, more preferably phenyl, chlorophenyl, methylphenyl, trifluorophenyl or cyanophenyl. A phenyl group.

  In the present invention, “5- or 6-membered heterocyclic group (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further contains 1 to 2 nitrogen atoms. Is a 5- to 6-membered heterocyclic group which contains one nitrogen atom, oxygen atom or sulfur atom as a hetero atom, and may further contain 1 to 2 nitrogen atoms, For example, it may be a furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, triazolyl, pyranyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl or triazinyl group, preferably a 5-membered heterocyclic group The ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring.), More preferably a furyl or thienyl group.

In the present invention, the “C ₁ -C ₆ alkoxy group” is a linear or branched alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s- Butoxy, t-butoxy, pentoxy, isopentoxy, 2-methylbutoxy, neopentoxy, 1-ethylpropoxy, hexyloxy, 4-methylpentoxy, 3-methylpentoxy, 2-methylpentoxy, 1-methylpentoxy, 3 , 3-dimethylbutoxy, 2,2-dimethylbutoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,3-dimethylbutoxy or 2-ethylbutoxy group, Preferred is a straight or branched alkoxy group having 1 to 3 carbon atoms (C ₁ -C ₃ alkoxy group), more preferred is a methoxy or ethoxy group, and even more preferred. Is a methoxy group.

In the present invention, “optionally substituted phenoxy group (the substituent is a substituent selected from Substituent Group A)” means the “halogen atom”, the “C ₁ -C ₆ alkyl group”, The same or different selected from the group consisting of the “C ₁ -C ₆ haloalkyl group”, the “C ₃ -C ₆ cycloalkyl group”, the cyano group and the “tri (C ₁ -C ₆ alkyl) silicon group”. 1 to 5 substituents may be substituted phenoxy groups, such as phenoxy, fluorophenoxy, difluorophenoxy, trifluorophenoxy, chlorophenoxy, dichlorophenoxy, trichlorophenoxy, fluorochlorophenoxy, methylphenoxy, dimethylphenoxy, Trimethylphenoxy, tetramethylphenoxy, pentamethylphenoxy, ethylphenoxy, Oro (methyl) phenoxy, chloro (methyl) phenoxy, bromo (methyl) phenoxy, cyclopropylphenoxy, cyclopropyl (fluoro) phenoxy, chloro (cyclopropyl) phenoxy, cyclopropyl (methyl) phenoxy, (trifluoromethyl) phenoxy or fluoro be a (trifluoromethyl) phenoxy group, preferably a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, the same selected from the group consisting of chlorine and bromine Or a C ₁ -C ₃ alkyl group substituted with 1 to 3 different substituents ”, a C ₃ -C ₄ cycloalkyl group, a cyano group, and a tri (C ₁ -C ₃ alkyl) silicon group. Are the same or different 1 to 3 substituents which may be substituted, more preferably phenoxy, chlorophene Noxy, methylphenoxy, trifluorophenoxy or cyanophenoxy groups.

In the present invention, “optionally substituted benzoyl group (the substituent is a substituent selected from Substituent Group A)” means the “halogen atom”, the “C ₁ -C ₆ alkyl group”, The same or different selected from the group consisting of the “C ₁ -C ₆ haloalkyl group”, the “C ₃ -C ₆ cycloalkyl group”, the cyano group, and the “tri (C ₁ -C ₆ alkyl) silicon group”. 1 to 5 substituents are optionally substituted benzoyl groups such as benzoyl, fluorobenzoyl, difluorobenzoyl, trifluorobenzoyl, chlorobenzoyl, dichlorobenzoyl, trichlorobenzoyl, fluorochlorobenzoyl, methylbenzoyl, dimethylbenzoyl, Trimethylbenzoyl, tetramethylbenzoyl, pentamethylbenzoyl, ethylbenzoyl, Oro (methyl) benzoyl, chloro (methyl) benzoyl, bromo (methyl) benzoyl, cyclopropylbenzoyl, cyclopropyl (fluoro) benzoyl, chloro (cyclopropyl) benzoyl, cyclopropyl (methyl) benzoyl, (trifluoromethyl) benzoyl or fluoro be a (trifluoromethyl) benzoyl group, preferably a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, the same selected from the group consisting of chlorine and bromine Or a C ₁ -C ₃ alkyl group substituted with 1 to 3 different substituents ”, a C ₃ -C ₄ cycloalkyl group, a cyano group, and a tri (C ₁ -C ₃ alkyl) silicon group. The same or different 1 to 3 substituents are optionally substituted benzoyl groups, more preferably benzoyl, chloroben A zoyl, dichlorobenzoyl, methylbenzoyl, trifluorobenzoyl or cyanobenzoyl group.

In the present invention, “optionally substituted 5- or 6-membered heterocyclic oxy group {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 nitrogen atoms The substituent may be a benzoyl group (the substituent is a substituent selected from Substituent Group A) and a C ₁ -C ₆ alkyl group which may be substituted. Is a substituent selected from the above-mentioned “benzoyl group which may be substituted (the substituent is a substituent selected from substituent group A)” and “C ₁ -C ₆ alkyl group”. May be substituted by the same or different 1 to 3 substituents selected from the group consisting of “as a hetero atom, containing one nitrogen atom, oxygen atom or sulfur atom, and further 1 to 2 nitrogen atoms A 5- to 6-membered heterocyclic oxy group which may contain Fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, C ₁ ~ in which one to three substituents the same or different selected from the group consisting of chlorine atom and bromine atom is substituted The same or different 1 to 3 substituents selected from the group consisting of “C ₃ alkyl group”, C ₃ -C ₄ cycloalkyl group, cyano group and tri (C ₁ -C ₃ alkyl) silicon group are substituted. Substituted with a good benzoyl group, as well as the same two C ₁ -C ₃ alkyl groups, “contains one nitrogen atom, oxygen atom or sulfur atom as a hetero atom, and one more nitrogen atom A 5-membered heterocyclic oxy group "which may contain, more preferably a benzoyl group substituted by two chlorine atoms and two C ₁ -C ₂ alkyl groups A pyrazolyloxy group;

In the present invention, the “(C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkyl group” is the “C ₁ -C ₆ alkyl group” substituted by _{one of the} “C ₁ -C ₆ alkoxy groups”. Yes, for example, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, s-butoxymethyl, t-butoxymethyl, pentyloxymethyl, hexyloxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, methoxypropyl, methoxy butyl, be a methoxy pentyl or methoxy hexyl, preferably, a single C ₁ of -C ₃ C ₁ -C ₆ alkyl group which alkoxy group is substituted, more preferably, methoxyethyl, ethoxyethyl or An ethoxymethyl group.

In the present invention, the “C ₂ -C ₇ alkoxycarbonyl group” is a carbonyl group to which the “C ₁ -C ₆ alkoxy group” is bonded, and examples thereof include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxy Carbonyl, isobutoxycarbonyl, s-butoxycarbonyl, t-butoxycarbonyl, pentoxycarbonyl, isopentoxycarbonyl, 2-methylbutoxycarbonyl, neopentoxycarbonyl, 1-ethylpropoxycarbonyl, hexyloxycarbonyl, 4-methylpen Toxylcarbonyl, 3-methylpentoxycarbonyl, 2-methylpentoxycarbonyl, 1-methylpentoxycarbonyl, 3,3-dimethylbutoxycarbonyl, 2,2-dimethylbutoxycarbonyl, 1,1-dimethylbutoxycarbonyl, 1, 2- Methyl-butoxycarbonyl, 1,3-dimethyl-butoxycarbonyl, 2,3-dimethylbutoxy be a carbonyl or 2-ethyl-butoxycarbonyl group, preferably, C ₁ -C ₃ carbonyl groups alkoxy group is bonded (C ₂ ~ a C ₄ alkoxycarbonyl group), more preferably a methoxycarbonyl or ethoxycarbonyl group, even more preferably more, a methoxycarbonyl group.

In the present invention, the “optionally substituted phenylthio group (the substituent is a substituent selected from Substituent Group A)” means the “halogen atom”, the “C ₁ -C ₆ alkyl group”, The same or different selected from the group consisting of the “C ₁ -C ₆ haloalkyl group”, the “C ₃ -C ₆ cycloalkyl group”, the cyano group and the “tri (C ₁ -C ₆ alkyl) silicon group”. 1 to 5 substituents may be substituted phenylthio groups such as phenylthio, fluorophenylthio, difluorophenylthio, trifluorophenylthio, chlorophenylthio, dichlorophenylthio, trichlorophenylthio, fluorochlorophenylthio, methylphenyl Thio, dimethylphenylthio, trimethylphenylthio, tetramethylphenylthio, pentamethylphenol Ruthio, ethylphenylthio, fluoro (methyl) phenylthio, chloro (methyl) phenylthio, bromo (methyl) phenylthio, cyclopropylphenylthio, cyclopropyl (fluoro) phenylthio, chloro (cyclopropyl) phenylthio, cyclopropyl (methyl) phenylthio, It is a (trifluoromethyl) phenylthio or fluoro (trifluoromethyl) phenylthio group, preferably, a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, chlorine atom and bromine atom C ₁ -C ₃ alkyl group "1-3 substituents selected same or different from the group is substituted composed, C ₃ -C ₄ cycloalkyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) Feni which may be substituted with 1 to 3 identical or different substituents selected from the group consisting of silicon groups More preferably a phenylthio group, a chlorophenylthio group, a methylphenylthio group, a trifluorophenylthio group, or a cyanophenylthio group.

In the present invention, the “C ₁ -C ₆ alkylthio group” is a linear or branched alkylthio group having 1 to 6 carbon atoms, such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, s -Butylthio, t-butylthio, pentylthio, isopentylthio, 2-methylbutylthio, neopentylthio, 1-ethylpropylthio, hexylthio, 4-methylpentylthio, 3-methylpentylthio, 2-methylpentylthio, 1 -Methylpentylthio, 3,3-dimethylbutylthio, 2,2-dimethylbutylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,3-dimethyl be a butylthio or 2-ethylbutylthio group, preferably a straight-chain or branched alkylthio group having 1 to 3 carbon atoms (C ₁ -C ₃ alkylthio group), More preferred is a methylthio or ethylthio group, and even more preferred is a methylthio group.

In the present invention, the “C ₁ -C ₆ alkylsulfinyl group” is a linear or branched alkylsulfinyl group having 1 to 6 carbon atoms, such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butyl Sulfinyl, isobutylsulfinyl, s-butylsulfinyl, t-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, 2-methylbutylsulfinyl, neopentylsulfinyl, 1-ethylpropylsulfinyl, hexylsulfinyl, 4-methylpentylsulfinyl, 3-methyl Pentylsulfinyl, 2-methylpentylsulfinyl, 1-methylpentylsulfinyl, 3,3-dimethylbutylsulfinyl, 2,2-dimethylbutylsulfinyl, 1,1-dimethylbutylsulfinyl, 1,2-dimethyl It can be a butylbutylsulfinyl, 1,3-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl or 2-ethylbutylsulfinyl group, preferably a linear or branched alkylsulfinyl group having 1 to 3 carbon atoms (C ₁ -C ₃ alkylsulfinyl group), more preferably a methylsulfinyl or ethylsulfinyl group, and even more preferably a methylsulfinyl group.

In the present invention, the “C ₁ -C ₆ alkylsulfonyl group” is a linear or branched alkylsulfonyl group having 1 to 6 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butyl Sulfonyl, isobutylsulfonyl, s-butylsulfonyl, t-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, 2-methylbutylsulfonyl, neopentylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl, 4-methylpentylsulfonyl, 3-methyl Pentylsulfonyl, 2-methylpentylsulfonyl, 1-methylpentylsulfonyl, 3,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 1,1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3 -Dimethylbutylsulfo Le, be a 2,3-dimethyl-butylsulfonyl or 2-ethyl-butylsulfonyl group, preferably a linear or branched alkylsulfonyl group (C ₁ -C ₃ alkylsulfonyl group) having 1 to 3 carbon atoms And more preferably a methylsulfonyl or ethylsulfonyl group, and even more preferably a methylsulfonyl group.

In the present invention, the “C ₁ -C ₄ alkylenedioxy group” is a linear or branched alkylenedioxy group having 1 to 4 carbon atoms, such as methylenedioxy, ethylenedioxy, propylenedioxy. , Trimethylenedioxy or tetramethylenedioxy group, preferably an alkylenedioxy group having 1 to 2 carbon atoms, and more preferably a 1,2-ethylenedioxy group.

In the present invention, the “C ₁ -C ₆ alkoxyimino group” is a linear or branched alkoxyimino group having 1 to 6 carbon atoms, and examples thereof include methoxyimino, ethoxyimino, propoxyimino, isopropoxyimino, Butoxyimino, isobutoxyimino, s-butoxyimino, t-butoxyimino, pentoxyimino, isopentoxyimino, 2-methylbutoxyimino, neopentoxyimino, 1-ethylpropoxyimino, hexyloxyimino, 4-methylpentoxy Imino, 3-methylpentoxyimino, 2-methylpentoxyimino, 1-methylpentoxyimino, 3,3-dimethylbutoxyimino, 2,2-dimethylbutoxyimino, 1,1-dimethylbutoxyimino, 1,2 -Dimethylbutoxyimino, 1,3-dimethylbutoxyimino, 2,3-dimethylbutoxyimino or 2-ethylbut It is a Shiimino group, preferably a straight or branched alkoxyimino group having 1 to 3 carbon atoms (C ₁ -C ₃ alkoxyimino group), more preferably, methoxyimino or ethoxyimino group And even more preferred is a methoxyimino group.

In the present invention, the “substituted C ₁ -C ₆ alkyl group (the substituent is a substituent selected from Substituent Group B)” means the “halogen atom” or the “C ₃ -C ₆ cycloalkyl group ", a cyano group, wherein" C ₂ -C ₇ alkylcarbonyl group ", the" C ₂ -C ₇ alkoxycarbonyl group ", phenyl group, wherein" C ₁ -C ₆ alkoxy group ", the "C ₁ -C ₆ alkylthio group", the "C ₁ -C ₆ alkylsulfinyl group", the "C ₁ -C ₆ alkylsulfonyl group", the "C ₁ -C ₄ alkylenedioxy group", hydroxyimino group or wherein a "C ₁ -C ₆ alkoxyimino group" optionally substituted the may "C ₁ -C ₆ alkyl group", for example, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trichloroethyl , Siku Ropropylmethyl, cyanomethyl, acetylmethyl, acetylethyl, methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, benzyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, methylthioethyl, ethylthio It may be methyl, ethylthioethyl, methylsulfinylmethyl, methylsulfonylmethyl, 2- (1,3-dioxolanyl), hydroxyiminomethyl or methoxyiminomethyl group, preferably consisting of a fluorine atom, a chlorine atom and a bromine atom C ₁ -C ₃ alkyl group one to three substituents the same or different from selected from the group is substituted, or, C ₃ -C ₄ cycloalkyl group, a cyano group, C ₂ -C ₄ alkylcarbonyl group, C ₂ ~C ₄ an alkoxycarbonyl Carbonyl group, a phenyl group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ alkylthio group, C ₁ -C ₃ alkylsulfinyl group, C ₁ -C ₃ alkylsulfonyl groups, C ₁ -C ₂ alkylenedioxy group, A hydroxyimino group or a C ₁ -C ₃ alkyl group that may be substituted by a C ₁ -C ₃ alkoxyimino group, and more preferably the same 1 to 3 C ₁ substituted with fluorine atoms or chlorine atoms. -C ₂ alkyl group, or a cyclopropyl group, a cyano group, C ₂ -C ₃ alkylcarbonyl group, C ₂ -C ₃ alkoxycarbonyl group, a phenyl group, C ₁ -C ₂ alkoxy group, C ₁ -C ₂ alkylthio group, C ₁ -C ₂ alkylsulfinyl group, C ₁ -C ₂ alkylsulfonyl group, an ethylenedioxy group, hydroxyimino group or C ₁ -C ₂ alkoxyimino group may C ₁ ~ to be substituted It is a _2-alkyl group.

In the present invention, the “substituted C ₂ -C ₆ alkenyl group (the substituent is a cyano group or a nitro group)” refers to the “C ₂ -C ₆ alkenyl group substituted by a cyano group or a nitro group”. a ", preferably a C ₂ -C ₃ alkenyl group cyano group or a nitro group is substituted, more preferably a cyanovinyl or nitrovinyl group.

In the present invention, the “C ₂ -C ₆ alkynyl group” is a linear or branched alkynyl group having 2 to 6 carbon atoms, and examples thereof include ethynyl, 2-propynyl, 1-methyl-2-propynyl, 1 -Ethyl-2-propynyl, 2-butynyl, 1-methyl-2-butynyl, 1-ethyl-2-butynyl, 3-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-ethyl -3-butynyl, 2-pentynyl, 1-methyl-2-pentynyl, 1-ethyl-2-pentynyl, 3-pentynyl, 1-methyl-3-pentynyl, 2-methyl-3-pentynyl, 4-pentynyl, 1 -Methyl-4-pentynyl, 2-methyl-4-pentynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl or 5-hexynyl, preferably a straight or branched chain having 3 to 4 carbon atoms a-chain alkynyl groups (C ₃ -C ₄ alkynyl group), more preferably ethynyl, 1-propynyl or 2-propynyl.

In the present invention, “an amino group which may be substituted (the substituent is a substituent selected from Substituent Group D)” refers to the “C ₁ -C ₆ alkyl group” and the “C ₂ -C”. Selected from the group consisting of “ ₇ alkylcarbonyl group”, “C ₂ -C ₇ alkoxycarbonyl group”, “di (C ₁ -C ₆ alkyl) carbamoyl group” and “C ₁ -C ₆ alkylsulfonyl group”. An amino group which may be substituted by one or two identical or different substituents, for example, amino, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, s-butylamino, t- Butylamino, pentylamino, isopentylamino, (2-methylbutyl) amino, neopentylamino, (1-ethylpropyl) amino, hexylamino, (4-methylpentyl) Mino, (3-methylpentyl) amino, (2-methylpentyl) amino, (1-methylpentyl) amino, (3,3-dimethylbutyl) amino, (2,2-dimethylbutyl) amino, (1,1 -Dimethylbutyl) amino, (1,2-dimethylbutyl) amino, (1,3-dimethylbutyl) amino, (2,3-dimethylbutyl) amino, (2-ethylbutyl) amino, dimethylamino, (methyl) ( Ethyl) amino, diethylamino, dipropylamino, (methyl) (isopropyl) amino, diisopropylamino, dibutylamino, diisobutylamino, dis-butylamino, di-t-butylamino, dipentylamino, diisopentylamino, di (2 -Methylbutyl) amino, dineopentylamino, di (1-ethylpropyl) amino, dihexylamino, di (4-methylpentyl) amino, di (3-methylpentyl) amino, di (2-methylpentyl) amino, di (1-methylpentyl) amino, di (3,3-dimethylbutyl) amino, di (2,2-dimethylbutyl) amino, di (1,1-dimethylbutyl) amino, di (1,2-dimethylbutyl) Amino, di (1,3-dimethylbutyl) amino, di (2,3-dimethylbutyl) amino, di (2-ethylbutyl) amino, acetylamino, propionylamino, butanoylamino, (2-methylpropanoyl) amino , Pentanoylamino, (2,2-dimethylpropanoyl) amino, (2,2-dimethylpentanoyl) amino, (2-methylbutanoyl) amino, (3-methylbutanoyl) amino, hexanoylamino, hepta Noylamino, (3,3-dimethylbutanoyl) amino, methoxycarbonylamino, ethoxycarbonylamino, propoxycarbonylamino, isopropoxycarbonylamino, butoxycarbonylamino, isobutoxycarbonyl Amino, s-butoxycarbonylamino, t-butoxycarbonylamino, pentoxycarbonylamino, isopentoxycarbonylamino, (2-methylbutoxycarbonyl) amino, neopentoxycarbonylamino, (1-ethylpropoxycarbonyl) amino, hexyl Oxycarbonylamino, (4-methylpentoxycarbonyl) amino, (3-methylpentoxycarbonyl) amino, (2-methylpentoxycarbonyl) amino, (1-methylpentoxycarbonyl) amino, (3,3-dimethyl) (Butoxycarbonyl) amino, (2,2-dimethylbutoxycarbonyl) amino, (1,1-dimethylbutoxycarbonyl) amino, (1,2-dimethylbutoxycarbonyl) amino, (1,3-dimethylbutoxycarbonyl) amino, ( 2,3-Dimethylbutoxycarbonyl) amino, (2-ethylbutoxycarbonyl) amino Dimethylcarbamoylamino, (methylethylcarbamoyl) amino, diethylcarbamoylamino, dipropylcarbamoylamino, dibutylcarbamoylamino, dihexylcarbamoylamino, methylsulfonylamino, ethylsulfonylamino, propylsulfonylamino, isopropylsulfonylamino, butylsulfonylamino, t- It is a butyl sulfonylamino, or hexyl sulfonylamino, preferably, identical or different one to two C ₁ -C ₃ alkyl group, or, C ₂ -C ₄ alkylcarbonyl group, C ₂ -C ₄ alkoxycarbonyl An amino group which may be substituted by a group, a di (C ₁ -C ₃ alkyl) carbamoyl group or a C ₁ -C ₃ alkylsulfonyl group, more preferably methylamino, ethylamino, dimethylamino, di Ethylamino, acetylamino, propionylamino, (2-methylpropanoyl) amino, (2,2-dimethylpropanoyl) amino, methoxycarbonylamino, ethoxycarbonylamino, dimethylcarbamoylamino, diethylcarbamoylamino, methylsulfonylamino or ethyl A sulfonylamino group.

In the present invention, the “C ₁ -C ₆ haloalkoxy group” is the above-mentioned “C ₁ -C ₆ alkoxy group” substituted with 1 to 5 of the above “halogen atoms”, for example, chloromethoxy , Dichloromethoxy, trichloromethoxy, 1-chloroethoxy, 2-chloroethoxy, 2,2,2-trichloroethoxy, 1-chloropropoxy, 3-chloropropoxy, 1-chlorobutoxy, 4-chlorobutoxy, fluoromethoxy, difluoro Methoxy, trifluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, fluorochloromethoxy, bromomethoxy, 1-bromoethoxy, 2-bromoethoxy or iodomethoxy groups Preferably, the same or different selected from the group consisting of fluorine atom, chlorine atom and bromine atom A 1-3 C ₁ substituent is substituted -C ₃ alkoxy group, and more preferably, the same one to three, fluorine atom or a chlorine atom is located at C ₁ -C ₂ alkoxy group substituted Even more preferred is a fluoromethoxy, difluoromethoxy, trifluoromethoxy or 2,2,2-trichloroethoxy group, and particularly preferred is a trifluoromethoxy group.

In the present invention, the “substituted C ₃ -C ₆ cycloalkyl group (the substituent is a substituent selected from the substituent group C)” is the above-mentioned “halogen atom” and the above “substituted”. C ₁ -C ₆ alkyl group (the substituent is a substituent selected from Substituent Group B) ”, the“ C ₃ -C ₆ cycloalkyl group ”, and the“ C ₂ -C ₆ alkenyl group ”. , A cyano group, the “C ₂ -C ₇ alkylcarbonyl group”, a benzoyl group, a carboxyl group, the “C ₂ -C ₇ alkoxycarbonyl group”, a carbamoyl group, and the “di (C ₁ -C ₆ alkyl) carbamoyl group” ", Said" optionally substituted phenyl group (the substituent is a substituent selected from substituent group A) "," the 5- or 6-membered heterocyclic group (the heterocyclic ring is in the ring, Contains one nitrogen, oxygen or sulfur atom Furthermore, it may contain 1 to 2 nitrogen atoms.) ”,“ The amino group which may be substituted (the substituent is a substituent selected from substituent group D) ”, nitro group, hydroxyl group The “C ₁ -C ₆ alkoxy group”, the “C ₁ -C ₆ haloalkoxy group”, the phenoxy group, the “C ₁ -C ₆ alkylthio group”, the phenylthio group, the “C ₁ -C ₆ alkylsulfinyl” The “C ₃ -C ₆ cycloalkyl group” substituted by the same or different 1 to 5 substituents selected from the group consisting of “group” and the “C ₁ -C ₆ alkylsulfonyl group”, for example, , Fluorocyclopropyl, difluorocyclopropyl, chlorocyclopropyl, dichlorocyclopropyl, bromocyclopropyl, dibromocyclopropyl, iodocyclopropyl, methylcyclopropyl, Tylcyclopropyl, propylcyclopropyl, isopropylcyclopropyl, butylcyclopropyl, t-butylcyclopropyl, hexylcyclopropyl, cyclopropylcyclopropyl, cyclobutylcyclopropyl, cyclopentylcyclopropyl, (fluoromethyl) cyclopropyl, (chloromethyl) ) Cyclopropyl, (bromomethyl) cyclopropyl, (difluoromethyl) cyclopropyl, (trifluoromethyl) cyclopropyl, (trichloromethyl) cyclopropyl, (2,2,2-trifluoroethyl) cyclopropyl, (2,2 , 2-trichloroethyl) cyclopropyl, vinylcyclopropyl, (methoxymethyl) cyclopropyl, (ethoxymethyl) cyclopropyl, (isopropoxymethyl) cyclopropyl, (methylthiomethyl) cyclopropyl, (ethylthiomethyl) ) Cyclopropyl, (isopropylthiomethyl) cyclopropyl, (methylsulfinylmethyl) cyclopropyl, (ethylsulfinylmethyl) cyclopropyl, (methylsulfonylmethyl) cyclopropyl, (ethylsulfonylmethyl) cyclopropyl, cyanocyclopropyl, 1-methoxyiminoethyl) cyclopropyl, acetylcyclopropyl, propionylcyclopropyl, benzoylcyclopropyl, carboxylcyclopropyl, methoxycarbonylcyclopropyl, ethoxycarbonylcyclopropyl, carbamoylcyclopropyl, (dimethylcarbamoyl) cyclopropyl, (diethylcarbamoyl) Cyclopropyl, phenylcyclopropyl, (fluorophenyl) cyclopropyl, (chlorophenyl) cyclopropyl, tolylcyclopropyl , Furylcyclopropyl, thienylcyclopropyl, pyridylcyclopropyl, aminocyclopropyl, (methylamino) cyclopropyl, (dimethylamino) cyclopropyl, (acetylamino) cyclopropyl, (methoxycarbonylamino) cyclopropyl, (3,3 -Dimethylureido) cyclopropyl, (methylsulfonylamino) cyclopropyl, nitrocyclopropyl, hydroxycyclopropyl, methoxycyclopropyl, ethoxycyclopropyl, (trifluoromethoxy) cyclopropyl, phenoxycyclopropyl, methylthiocyclopropyl, ethylthiocyclo Propyl, phenylthiocyclopropyl, methylsulfinylcyclopropyl, ethylsulfinylcyclopropyl, methylsulfonylcyclopropyl, ethylsulfonylcyclopropyl Pill, dimethylcyclopropyl, methyl (ethyl) cyclopropyl, diethylcyclopropyl, biscyanocyclopropyl, trimethylcyclopropyl, tetramethylcyclopropyl, pentamethylcyclopropyl, methylcyclobutyl, vinylcyclobutyl, cyanocyclobutyl, carboxylcyclo butyl, acetyl cyclobutyl, be a methoxycarbonyl cyclobutyl or aminocyclobutyl group, preferably a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₃ -C ₄ cycloalkyl group and cyano The same or different 1 to 5 substituents selected from the group consisting of a group, or “the same or different 1 to 3 substituents selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom are substituted; C ₁ -C ₃ alkyl group and, or, C ₃ -C ₄ consequent Alkyl group, cyano group, C ₂ -C ₄ alkylcarbonyl group, C ₂ -C ₄ alkoxycarbonyl group, a phenyl group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ alkylthio group, C ₁ -C ₃ alkylsulfinyl group, C ₁ -C ₃ alkylsulfonyl groups, C ₁ -C ₂ alkylenedioxy group, C ₁ -C ₃ alkyl group imino group or a C ₁ -C ₃ alkoxyimino group is substituted ", C ₂ -C ₄ alkenyl group, C ₂ -C ₄ alkylcarbonyl group, a benzoyl group, a carboxyl group, C ₂ -C ₄ alkoxycarbonyl group, a carbamoyl group, a di (C ₁ -C ₃ alkyl) carbamoyl group, "a fluorine atom, a chlorine atom, a bromine atom , C ₁ -C ₃ alkyl group, "a fluorine atom, C ₁ -C ₃ alkyl 1-3 substituents the same or different selected from the group consisting of chlorine atom and bromine atom is substituted ", C ₃ -C ₄ cycloalkyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) same or different 1 to 3 substituents may phenyl group substituted selected from the group consisting of silicon group" 5-membered heterocyclic group (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring). ), “One or two identical or different C ₁ -C ₃ alkyl groups, or C ₂ -C ₄ alkylcarbonyl groups, C ₂ -C ₄ alkoxycarbonyl groups, di (C ₁ -C ₃ alkyl) carbamoyl group or C ₁ -C ₃ alkylsulfonyl amino group which may be substituted by a group ", a nitro group, a hydroxyl group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ haloalkoxy group, a phenoxy group, C ₁ -C ₃ alkylthio group, a phenylthio group, C ₁ -C ₃ alkyl sulfinyl group or a C ₁ -C ₃ alkylsulfonyl group C ₃ -C ₄ cycloalkyl group substituted by, more preferably, a chlorine atom, a bromine atom, C ₁ -C ₂ alkyl group, the same or different 1 to 3 substituents selected from the group consisting of cyclopropyl group and cyano group, or the same selected from the group consisting of "a chlorine atom and a bromine atom 1-3 substituents is substituted with C ₁ -C ₂ alkyl group, or a cyclopropyl group, a cyano group, C ₂ -C ₃ alkylcarbonyl group, C ₂ -C ₃ alkoxycarbonyl group, a phenyl group, C ₁ -C ₂ alkoxy group, C ₁ -C ₂ alkylthio group, C ₁ -C ₂ alkylsulfinyl group, C ₁ -C ₂ alkylsulfonyl group, 1,2-ethylenedioxy group, an imino group or a C ₁ -C ₂ alkoxy C ₁ -C ₂ alkyl group "imino group is substituted, C ₂ -C ₃ alkenyl group, C ₂ -C ₃ alkylcarbonyl group, a benzoyl group, a carboxyl group, C ₂ -C ₃ alkoxycarbonyl group, a carbamoyl group, a di (C ₁ -C ₂ alkyl) carbamoyl group, “chlorine atom, bromine atom, C ₁ -C ₂ alkyl group,“ the same 1 to 3 C ₁ -C ₂ alkyl group substituted by fluorine atom or chlorine atom " Ropuropiru group, a cyano group and a tri (C ₁ -C ₂ alkyl) same or different 1 to 2 substituents may phenyl group substituted selected from the group consisting of silicon group ", a furyl group, a thienyl group," identical 1-2 C ₁ -C ₂ alkyl group, or, C ₂ -C ₃ alkylcarbonyl group, C ₂ -C ₃ alkoxycarbonyl group, a di (C ₁ -C ₂ alkyl) carbamoyl group or a C ₁ ~ C ₂ alkylsulfonyl amino group which may be substituted by a group ", a nitro group, a hydroxyl group, C ₁ -C ₂ alkoxy group, C ₁ -C ₂ haloalkoxy group, a phenoxy group, C ₁ -C ₂ alkylthio group, a phenylthio group, It is a cyclopropyl group substituted by a C ₁ -C ₂ alkylsulfinyl group or a C ₁ -C ₂ alkylsulfonyl group.

In the present invention, the “C ₄ -C ₁₀ bicycloalkyl group” is a bicyclic hydrocarbon having 4 to 10 carbon atoms, such as bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl. Or a bicyclodecyl group, preferably a bicyclohexyl or bicycloheptyl group, more preferably a bicyclo [3.1.0] hexyl or bicyclo [4.1.0] heptyl group, and even more preferably. , A bicyclo [3.1.0] hexane-6-yl group.

In the present invention, “optionally substituted phenylsulfonyl group (the substituent is a substituent selected from Substituent Group A)” means the “halogen atom” and the “C ₁ -C ₆ alkyl group”. , The same or different selected from the group consisting of the “C ₁ -C ₆ haloalkyl group”, the “C ₃ -C ₆ cycloalkyl group”, the cyano group and the “tri (C ₁ -C ₆ alkyl) silicon group” 1 to 5 substituents which may be substituted, such as phenylsulfonyl, fluorophenylsulfonyl, difluorophenylsulfonyl, trifluorophenylsulfonyl, chlorophenylsulfonyl, dichlorophenylsulfonyl, trichlorophenylsulfonyl, fluorochlorophenylsulfonyl , Methylphenylsulfonyl, dimethylphenylsulfo , Trimethylphenylsulfonyl, tetramethylphenylsulfonyl, pentamethylphenylsulfonyl, ethylphenylsulfonyl, fluoro (methyl) phenylsulfonyl, chloro (methyl) phenylsulfonyl, bromo (methyl) phenylsulfonyl, cyclopropylphenylsulfonyl, cyclopropyl (fluoro ) Phenylsulfonyl, chloro (cyclopropyl) phenylsulfonyl, cyclopropyl (methyl) phenylsulfonyl, (trifluoromethyl) phenylsulfonyl or fluoro (trifluoromethyl) phenylsulfonyl group, preferably fluorine atom, chlorine atom , bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, C ₁ -C ₃ alkyl group one to three substituents the same or different selected from the group consisting of chlorine atom and bromine atom is substituted In C ₃ -C ₄ cycloalkyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) identical are selected from the group consisting of silicon group or different 1 to 3 substituents are substituted to it phenylsulfonyl group And more preferably a phenylsulfonyl, chlorophenylsulfonyl, methylphenylsulfonyl, trifluorophenylsulfonyl or cyanophenylsulfonyl group.

In the present invention, the “di (C ₁ -C ₆ alkyl) sulfamoyl group” is a sulfamoyl group in which two identical or different “C ₁ -C ₆ alkyl groups” are bonded to a nitrogen atom. It may be sulfamoyl, methylethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, dibutylsulfamoyl or dihexylsulfamoyl, preferably two identical or different C ₁ -C ₃ alkyls A sulfamoyl group to which a group is bonded, more preferably a dimethylsulfamoyl group or a diethylsulfamoyl group, and even more preferably a dimethylsulfamoyl group.

In the present invention, “a 3- to 6-membered heterocyclic group which may be substituted (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 nitrogen atoms And may be condensed with a benzene ring. The substituent is a substituent selected from Substituent Group E.) ”is the“ halogen atom ”and the“ C ₁ -C ₆ alkyl group ”. And ₁ to 3 identical or different substituents selected from the group consisting of “C ₁ -C ₆ haloalkyl group”, or a hydroxyl group, the above “optionally substituted phenylsulfonyl group (the substituent is substituted Is a substituent selected from the group A.) ”or“ the di (C ₁ -C ₆ alkyl) sulfamoyl group ”, and may be condensed with a benzene ring, Contains nitrogen, oxygen or sulfur atoms, and It may contain ~ 2 nitrogen atoms, a 3- to 6-membered heterocyclic group ", preferably a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group and" a fluorine atom, a chlorine atom And the same or different 1 to 2 substituents selected from the group consisting of a C ₁ -C ₃ alkyl group substituted with 1 to 3 same or different substituents selected from the group consisting of bromine atoms, Or, a hydroxyl group, “a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group,“ the same or different 1 to 3 substituents selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom. ₁ to ₃ identical or different substitutions selected from the group consisting of “substituted C ₁ -C ₃ alkyl group”, C ₃ -C ₄ cycloalkyl group, cyano group and tri (C ₁ -C ₃ alkyl) silicon group A phenylsulfonyl group which may be substituted ”or Or different well two C ₁ -C ₃ sulfamoyl group which the alkyl group is attached "of substituted benzene ring fused may, as" heteroatom, one nitrogen atom, an oxygen atom or a sulfur atom A 3- to 6-membered heterocyclic group which may further contain one nitrogen atom, and more preferably a chlorine atom, a bromine atom, a methyl group, an ethyl group, and a trifluoromethyl group. The same 1 to 2 substituents selected from the group, or a hydroxyl group, phenylsulfonyl group, tolylsulfonyl group or dimethylsulfamoyl group, which may be substituted, aziridine, oxiranyl, oxetanyl, pyrrolyl, furyl, thienyl, pyrazolyl , Thiazolyl, pyridyl, benzimidazolyl or benzothiazolyl, and even more preferably from a chlorine atom, a methyl group and a trifluoromethyl group That the same or different 1 to 2 substituents may be substituted, thienyl, pyrazolyl, thiazolyl group.

In the present invention, “(C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkoxy group” is an alkoxy group having 1 to 6 carbon atoms to which an alkoxy group having 1 to 6 carbon atoms is bonded. Methoxy, ethoxymethoxy, propoxymethoxy, butoxymethoxy, s-butoxymethoxy, t-butoxymethoxy, pentyloxymethoxy, hexyloxymethoxy, methoxyethoxy, ethoxyethoxy, propoxyethoxy, butoxyethoxy, methoxypropoxy, methoxybutoxy, methoxypentyloxy Or a methoxyhexyloxy group, preferably an alkoxy group having 1 to 3 carbon atoms substituted by an alkoxy group having 1 to 3 carbon atoms, more preferably methoxyethoxy, ethoxyethoxy or ethoxymethoxy. It is a group.

In the present invention, “an optionally substituted phenoxy group (the substituent is a pyridazinyloxy group substituted by a hydroxyl group or a substituent selected from a halogen atom and a C ₁ -C ₆ alkoxy group)” Is a phenoxy group that may be substituted by one hydroxyl group, or ₁ to 3 identical or different substituents selected from the group consisting of the “halogen atom” and the “C ₁ -C ₆ alkoxy group”. phenoxy group substituted pyridazinyloxy group is substituted, preferably, hydroxy phenoxy group, or a fluorine atom, a chlorine atom, the same are selected from the group consisting of bromine and C ₁ -C ₃ alkoxy or It is a phenoxy group substituted by a pyridazinyloxy group substituted with 1 to 2 different substituents, and more preferably one chlorine atom and one methoxy or ethoxy group. Substituted pyridazinyloxy group is a phenoxy group substituted.

In the present invention, “a 5- to 6-membered heterocyclic oxy group which may be substituted (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and 1 to 2 nitrogen atoms). The substituent may be a substituent selected from Substituent Group E. The above-mentioned “halogen atom”, “C ₁ -C ₆ alkyl group”, and “C ₁ -C” ₆ haloalkyl group ”, hydroxyl group, the above“ optionally substituted phenylsulfonyl group (the substituent is a substituent selected from substituent group A) ”and the“ di (C ₁ -C ₆ alkyl) sulfamoyl group ”. May be substituted by the same or different 1 to 2 substituents selected from the group consisting of “a hetero atom containing one nitrogen atom, oxygen atom or sulfur atom, and further 1 to 2 A 5-6 membered heterocyclic oxy group which may contain a nitrogen atom. Preferably, fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, one to three substituents the same or different from selected from the group consisting of chlorine and bromine substituted C ₁ -C ₃ alkyl group ", a hydroxyl group," a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, the same or different selected from the group consisting of chlorine and bromine identical to 1 to 3 substituents are selected from the group consisting of C ₁ -C ₃ alkyl group ", C ₃ -C ₄ cycloalkyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) silyl group substituted with Or the same or different selected from the group consisting of “phenylsulfonyl group which may be substituted by 1 to 3 different substituents” and “sulfamoyl group to which two same or different C _{1 to} C ₃ alkyl groups are bonded”. 1 to 2 substituents A 5- to 6-membered heterocyclic oxy group which contains one nitrogen atom, oxygen atom or sulfur atom and may further contain one nitrogen atom as a hetero atom, which may be substituted; More preferably, 1 to 2 different groups selected from the group consisting of a chlorine atom, a bromine atom, a methyl group, an ethyl group, a trifluoromethyl group, a hydroxyl group, a phenylsulfonyl group, a tolylsulfonyl group, and a dimethylsulfamoyl group. The substituent may be a pyridyloxy, pyrrolyloxy, furyloxy, thienyloxy, pyrazolyloxy, thiazolyloxy, pyrimidyloxy, pyrazinyloxy or pyridazinyloxy group, and more preferably a chlorine atom and a hydroxyl group are substituted. A good pyridazinyloxy group.

In the present invention, “an optionally substituted phenylsulfonyloxy group (the substituent is a substituent selected from Substituent Group A)” refers to the “halogen atom” and the “C ₁ -C ₆ alkyl group”. ”, The“ C ₁ -C ₆ haloalkyl group ”, the“ C ₃ -C ₆ cycloalkyl group ”, the cyano group, and the“ tri (C ₁ -C ₆ alkyl) silicon group ” 1 to 5 different substituents are phenylsulfonyloxy groups which may be substituted, such as phenylsulfonyloxy, fluorophenylsulfonyloxy, difluorophenylsulfonyloxy, trifluorophenylsulfonyloxy, chlorophenylsulfonyloxy, dichlorophenylsulfonyloxy , Trichlorophenylsulfonyloxy, fluorochlorophenylsulfo Ruoxy, methylphenylsulfonyloxy, dimethylphenylsulfonyloxy, trimethylphenylsulfonyloxy, tetramethylphenylsulfonyloxy, pentamethylphenylsulfonyloxy, ethylphenylsulfonyloxy, fluoro (methyl) phenylsulfonyloxy, chloro (methyl) phenylsulfonyloxy, Bromo (methyl) phenylsulfonyloxy, cyclopropylphenylsulfonyloxy, cyclopropyl (fluoro) phenylsulfonyloxy, chloro (cyclopropyl) phenylsulfonyloxy, cyclopropyl (methyl) phenylsulfonyloxy, (trifluoromethyl) phenylsulfonyloxy or It may be a fluoro (trifluoromethyl) phenylsulfonyloxy group, preferably a fluorine atom, a chlorine atom Bromine, C ₁ -C ₃ alkyl group, "a fluorine atom, C ₁ -C ₃ alkyl group one to three substituents the same or different selected from the group consisting of a chlorine atom and a bromine atom-substituted" in C ₃ -C ₄ cycloalkyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) identical are selected from the group consisting of silicon group or different 1 to 3 substituents are substituted to be phenyl sulfonyloxy group And more preferably a phenylsulfonyloxy, chlorophenylsulfonyloxy, methylphenylsulfonyloxy, trifluorophenylsulfonyloxy or cyanophenylsulfonyloxy group.

In R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ of the present invention, “the two adjacent groups may be formed together with the carbon atom to which each is bonded, which may be substituted 3 to 6 members. A cyclic hydrocarbon group (the cyclic hydrocarbon may be interrupted by one or two different heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. The substituent is a halogen atom, C ₁ -C ₆ alkyl group, a hydroxy C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, an oxo group, a hydroxyimino group or a C ₁ -C ₆ alkoxyimino group, C ₁ -C ₆ alkyl group Is substituted with another C ₁ -C ₆ alkyl group or a carbon atom on the ring to form a new three-membered ring.) ”Means“ halogen atom ”,“ C _1- “C ₆ alkyl group”, “C ₆ alkyl group” substituted with 1 to 2 hydroxyl groups ₁ -C ₆ alkyl group ", the" C ₁ -C ₆ alkoxy group ", an oxo group, hydroxyimino group, and the" C ₁ -C ₆ alkoxyimino same or different 1 to 4 selected from the group consisting of group " Saturated or unsaturated 3- to 6-membered rings which may be substituted by one or two heteroatoms which may be substituted and may be substituted by the same or different heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur atoms It is a hydrocarbon group and may form a cyclopropane ring on the ring, and is preferably --CH _2- , --CH ₂ CH _2- , --CH ₂ CH ₂ CH _2- , --CH (CH ₃ ). CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH _2- , -C (CH ₃ ) ₂ CH ₂ CH _2- , -CH ₂ C (CH ₃ ) ₂ CH _2- , -CH (OCH ₃ ) CH ₂ CH _2- , -C (OCH ₃ ) ₂ CH ₂ CH _2- , -CH ₂ C (OCH ₃ ) ₂ CH _2- , -C (= O) CH ₂ CH _2- , -CH ₂ C (= O) CH _2- , -C (= NOCH ₃ ) CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ CH _2- , -CH (CH ₃ ) CH ₂ CH ₂ CH _2- , -C (CH ₃ ) ₂ CH ₂ CH ₂ CH _2- , -CH (OCH ₃ ) CH ₂ CH ₂ CH _2- , -C H = CH-CH = CH-, -OCH ₂ CH _2- , -OCH (CH ₃ ) CH _2- , -OCH ₂ CH (CH ₃ )-, -OC (CH ₃ ) ₂ CH _2- , -OCH = CH-, -OC (CH ₃ ) = CH-, -OCH = C (CH ₃ )-, -SCH = CH-, -N = CH-CH = CH-, -OCH ₂ O-, -OCH (CH ₃ ) O-, -OC (CH ₃ ) ₂ O-, -OCF ₂ O-, -OCH ₂ CH ₂ O-, -OCH = N-, -OC (CH ₃ ) = N-,

で表される基であり、より好適には、-CH₂CH₂-、-CH₂CH₂CH₂-、-CH(CH₃)CH₂CH₂-、-CH₂CH₂CH₂CH₂-、-CH=CH-CH=CH-、-OCH₂CH₂-、-OCH=CH-、-OCH=C(CH₃)-、-SCH=CH-、-N=CH-CH=CH-、-OCH₂O-、-OCH₂CH₂O-、

In a group represented by, more _{preferably, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, -CH = CH-CH = CH-, -OCH ₂ CH _2- , -OCH = CH-, -OCH = C (CH ₃ )-, -SCH = CH-, -N = CH-CH = CH- , -OCH ₂ O-, -OCH ₂ CH ₂ O-,

で表される基であり、更により好適には、-CH₂CH₂CH₂-、-CH(CH₃)CH₂CH₂-、-OCH₂CH₂-、-OCH=CH-又は

And more preferably, —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ CH ₂ —, —OCH ₂ CH ₂ —, —OCH═CH— or

で表される基である。

It is group represented by these.

  The compound (I) of the present invention can be converted into a salt used in ordinary agricultural chemicals, for example, an alkali metal salt, an alkaline earth metal salt or an ammonium salt, and a basic moiety in the molecule. If there is, for example, a salt such as sulfate, hydrochloride, nitrate, phosphate can be formed. As long as they can be used as herbicides for agriculture and horticulture, they are included in the present invention.

  In the present invention, the “alkali metal salt” can be, for example, a sodium salt, a potassium salt or a lithium salt, and is preferably a sodium salt or a potassium salt.

  In the present invention, the “alkaline earth metal salt” can be, for example, a calcium salt or a magnesium salt, and is preferably a calcium salt.

  Solvates of the compounds of the present invention are also encompassed by the present invention.

  Some compounds of the present invention have an asymmetric carbon, and in this case, the present invention also includes a mixture of one kind of optically active substance and several kinds of optically active substances in an arbitrary ratio.

In the present invention, the “ester derivative” is a compound in which an acyl group or the like is bonded to the oxygen atom of the hydroxyl group bonded to the 4-position of the pyridazine ring. For example, the C _{2 to} C ₁₅ alkylcarbonyl group [substituent group, halogen atom, C ₁ -C ₆ alkoxy group, C ₂ -C ₇ alkoxycarbonyl group, may be substituted C ₂ -C ₆ alkenyloxycarbonyl group {said substituent group is C ₃ -C ₆ cycloalkyl group , a cyano group and which may be substituted benzoyl group (the substituent is a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ ~ The same or different 1 to 3 substituents selected from the group consisting of C ₃ alkylsulfonyl groups.) The same or different 1 to 3 substituents selected from the group consisting of . }, An optionally substituted C ₃ -C ₆ cycloalkenyloxycarbonyl group {the substituent is an oxo group and an optionally substituted benzoyl group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ A group consisting of ₁ to ₃ identical or different substituents selected from the group consisting of a -C ₃ haloalkyl group, a C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group. 1 to 2 substituents selected from the same or different. }, A 5- or 6-membered heterocyclic oxycarbonyl group which may be substituted {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 nitrogen atoms May be included. The substituent is a halogen atom, a C ₁ -C ₆ alkyl group, an optionally substituted phenoxy group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₃ haloalkyl group, a C _3- The same or different 1 to 3 substituents selected from the group consisting of a C ₆ cycloalkyl group and a C ₂ -C ₇ alkoxycarbonyl group.), 2,3-dihydro-1H-indenyloxy group and substitution which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1 to 3 substituents selected from the group consisting of: }, Which may be substituted phenyl group (said substituent is a halogen atom, C ₁ -C ₆ alkyl group, a C ₁ -C ₃ haloalkyl group, C ₁ -C ₆ alkoxy group and C ₂ -C ₇ alkoxycarbonyl group Or the same or different 1 to 3 substituents selected from the group consisting of phenoxy group and C _{1 to} C ₆ alkylthio group. . ], C ₄ -C ₇ cycloalkylcarbonyl group, adamantyl group may be substituted C ₃ -C ₇ alkenylcarbonyl group (the substituent has the same or different selected from the group consisting of a halogen atom and a phenyl group 1 ˜2 substituents), a C ₃ -C ₇ alkynylcarbonyl group, an optionally substituted benzoyl group [the substituent is a halogen atom, an optionally substituted C ₁ -C ₆ alkyl group (the substituent Are the same or different 1 to 3 substituents selected from the group consisting of a halogen atom and a phenyl group.), A cyano group, a C ₂ -C ₇ alkylcarbonyl group, a C ₂ -C ₇ alkoxycarbonyl group, An optionally substituted C ₃ -C ₇ alkenyloxycarbonyl group {the substituent is a C ₃ -C ₆ cycloalkyl group, a cyano group and an optionally substituted benzoyl group (the Same substituent is selected from halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ group consisting of an alkylsulfonyl group Or 1 to 3 different substituents selected from the group consisting of 1 to 3 different substituents. }, An optionally substituted C ₄ -C ₇ cycloalkenyloxycarbonyl group {the substituent is an oxo group and an optionally substituted benzoyl group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ A group consisting of ₁ to ₃ identical or different substituents selected from the group consisting of a -C ₃ haloalkyl group, a C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group. 1 to 2 substituents selected from the same or different. }, A phenyl group, a nitro group, an optionally substituted C ₁ -C ₆ alkoxy group (the substituent is the same or different 1 to 3 substituents selected from the group consisting of a halogen atom and a phenyl group. ), A phenoxy group, an optionally substituted 5- or 6-membered heterocyclic oxycarbonyl group {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring; It may contain nitrogen atoms. The substituent is a halogen atom, a C ₁ -C ₆ alkyl group, an optionally substituted phenoxy group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₃ haloalkyl group, a C _3- The same or different 1 to 3 substituents selected from the group consisting of a C ₆ cycloalkyl group and a C ₂ -C ₇ alkoxycarbonyl group.), 2,3-dihydro-1H-indenyloxy group and substitution which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1 to 3 substituents selected from the group consisting of: } And a 5- or 6-membered heterocyclic oxysulfonyl group which may be substituted {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 nitrogen atoms May be included. The substituent is a halogen atom, a C ₁ -C ₆ alkyl group, an optionally substituted phenoxy group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₃ haloalkyl group, a C _3- The same or different 1 to 3 substituents selected from the group consisting of a C ₆ cycloalkyl group and a C ₂ -C ₇ alkoxycarbonyl group.), 2,3-dihydro-1H-indenyloxy group and substitution which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1 to 3 substituents selected from the group consisting of: } Are the same or different 1 to 3 substituents selected from the group consisting of: ], A naphthoyl group, an optionally substituted 3- to 8-membered heterocyclic carbonyl group [the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 nitrogen atoms It may contain atoms and may form a 5- to 6-membered spiro ring containing 1-2 oxygen atoms on any carbon atom in the heterocycle. The substituent is a halogen atom and an optionally substituted C ₁ -C ₆ alkyl group (the substituent is the same or different 1 to 3 substituents selected from the group consisting of a halogen atom and a phenyl group. ), A cyano group, a C ₂ -C ₇ alkylcarbonyl group, a C ₂ -C ₇ alkoxycarbonyl group, an optionally substituted phenyl group (the substituent is the same or different 1 to 3 halogen atoms). A 5- or 6-membered heterocyclic group which may be substituted (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom, and further contains 1 to 2 nitrogen atoms in the ring) The substituent is the same or different 1 to 3 substituents selected from the group consisting of a halogen atom and a C ₁ -C ₆ alkyl group.), Nitro group, hydroxyl group, C ₁ -C ₆ alkoxy Group, phenoxy group, oxo group, hydroxy Imino group, C ₁ -C ₆ alkoxyimino group, C ₁ -C ₆ alkylthio group, C ₂ -C ₆ alkenylthio group, a phenylthio group, which may be substituted 5 or 6-membered heterocyclic carbonyl group (said heterocyclic is in the ring, the one, nitrogen atom, contains an oxygen atom or a sulfur atom, may further contain one or two nitrogen atoms. the substituent is a halogen atom and a C ₁ -C ₆ alkyl group The same or different 1 to 3 substituents selected from the group consisting of: and a 5- or 6-membered heterocyclic oxycarbonyl group which may be substituted {the heterocyclic ring is one nitrogen atom in the ring; It contains atoms, oxygen atoms or sulfur atoms, and may contain 1 to 2 nitrogen atoms. The substituent is a halogen atom, a C ₁ -C ₆ alkyl group, an optionally substituted phenoxy group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₃ haloalkyl group, a C _3- The same or different 1 to 3 substituents selected from the group consisting of a C ₆ cycloalkyl group and a C ₂ -C ₇ alkoxycarbonyl group.), 2,3-dihydro-1H-indenyloxy group and substitution which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1 to 3 substituents selected from the group consisting of: } Are the same or different 1 to 3 substituents selected from the group consisting of: An optionally substituted 7 to 14-membered fused bi- or tricyclic heterocyclic carbonyl group (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring; may contain two nitrogen atoms or oxygen atoms. the substituents are the same or different 1 to 3 substituents selected from the group consisting of halogen atom and C ₁ -C ₆ alkyl group.) 5- or 6-membered heterocyclic carbonylcarbonyl group (the heterocyclic ring may contain one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 to 2 nitrogen atoms). ) may be substituted C ₂ -C ₇ alkoxycarbonyl group (said substituent is a halogen atom, C ₁ -C ₆ same or different 1 to 3 substituents selected from the alkoxy group and the group consisting of phenyl group in a.), C ₃ ~C ₇ alkenyloxycarbonyl , Which may be substituted phenoxycarbonyl group (said substituent is a halogen atom, C ₁ -C ₆ alkyl group, a cyano group, C ₂ -C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C identical or selected from the group consisting of ₁ -C ₆ alkoxy group



1 to 3 different substituents. ), A condensed polycyclic hydrocarbon oxycarbonyl group, an optionally substituted 5- or 6-membered heterocyclic oxycarbonyl group {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring. Further, it may contain 1 to 2 nitrogen atoms. The substituent is a halogen atom, a C ₁ -C ₆ alkyl group, an optionally substituted phenoxy group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₃ haloalkyl group, a C _3- The same or different 1 to 3 substituents selected from the group consisting of a C ₆ cycloalkyl group and a C ₂ -C ₇ alkoxycarbonyl group.), 2,3-dihydro-1H-indenyloxy group and substitution which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1 to 3 substituents selected from the group consisting of: }, Which may be substituted carbamoyl group {said substituents may be substituted C ₁ -C ₆ alkyl group (said substituent is a halogen atom, C ₂ -C ₇ alkoxycarbonyl group, a cyano group, a phenyl group, and C ₁ to 3 substituents selected from the group consisting of _{1 to} C ₆ alkoxy groups), C _{3 to} C ₆ alkenyl groups, phenyl groups, optionally substituted 5 or 6 membered heterocyclic groups. (The heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 to 2 nitrogen atoms. The substituent includes a halogen atom and C _1. -C ₆ identical or different 1 to 3 substituents selected from the group consisting of alkyl group.), C ₂ ~C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group and C ₁ -C ₆ The same or selected from the group consisting of alkoxy groups 1 to 3 different substituents. }, (C ₁ -C ₆ alkylthio) carbonyl group, (C ₃ -C ₆ cycloalkylthio) carbonyl group, (phenylthio) carbonyl group, optionally substituted C ₁ -C ₈ alkylsulfonyl group (the substituents are the same) or different 1 to 3 halogen atoms.), which may be substituted phenylsulfonyl group [the substituent is a halogen atom, C ₁ -C ₆ alkyl group, a cyano group, C ₂ -C ₇ alkylcarbonyl group , C ₂ -C ₇ alkoxycarbonyl group, nitro group, C ₁ -C ₆ alkoxy group, may be substituted C ₂ -C ₆ alkenyloxy sulfonyl group {said substituents, C ₃ -C ₆ cycloalkyl group, a cyano group and which may be substituted benzoyl group (the substituent is a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, two B are the same or different 1 to 3 substituents selected from the group, and C ₁ -C ₃ group consisting of an alkylsulfonyl group.) The same or selected from the group consisting of different with 1-3 substituents is there. }, An optionally substituted C ₃ -C ₆ cycloalkenyloxysulfonyl group {the substituent is an oxo group and an optionally substituted benzoyl group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ A group consisting of ₁ to ₃ identical or different substituents selected from the group consisting of a -C ₃ haloalkyl group, a C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group. 1 to 2 substituents selected from the same or different. } And a 5- or 6-membered heterocyclic oxysulfonyl group which may be substituted {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 nitrogen atoms May be included. The substituent is a halogen atom, a C ₁ -C ₆ alkyl group, an optionally substituted phenoxy group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₃ haloalkyl group, a C _3- The same or different 1 to 3 substituents selected from the group consisting of a C ₆ cycloalkyl group and a C ₂ -C ₇ alkoxycarbonyl group.), 2,3-dihydro-1H-indenyloxy group and substitution which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1 to 3 substituents selected from the group consisting of: } Are the same or different 1 to 3 substituents selected from the group consisting of: An optionally substituted 5- or 6-membered heterocyclic sulfonyl group (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further contains 1 to 2 nitrogen atoms) The substituent is the same or different 1 to 3 substituents selected from the group consisting of a halogen atom and a C _{1 to} C ₆ alkyl group. Ring oxysulfonyl group {The heterocyclic ring may contain one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 to 2 nitrogen atoms. The substituent is a halogen atom, a C ₁ -C ₆ alkyl group, an optionally substituted phenoxy group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₃ haloalkyl group, a C _3- The same or different 1 to 3 substituents selected from the group consisting of a C ₆ cycloalkyl group and a C ₂ -C ₇ alkoxycarbonyl group.), 2,3-dihydro-1H-indenyloxy group and substitution which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1 to 3 substituents selected from the group consisting of: }, Di (C ₁ -C ₆ alkyl) sulfamoyl group, C ₁ -C ₆ alkoxysulfonyl group, di (C ₁ -C ₆ alkyl) phosphoryl group, tri (C ₁ -C ₆ alkyl) silicon group or triphenyl silicon give a compound group is bonded, preferably, C ₂ -C ₁₀ alkylcarbonyl group, which may be substituted benzoyl group (the substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group ₁ to 2 identical or different groups selected from the group consisting of a C ₁ -C ₃ alkoxy group or a 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yloxycarbonyl group is a substituent.), pyrrolidinylcarbonyl group, azetidinyloxyimino carbonyl group, morpholine group, may be substituted C ₂ -C ₅ alkoxycarbonyl group (the substituent is off Atom are the same or different 1 to 3 substituents selected from the group consisting of chlorine atom and bromine atom.), Di (C ₁ -C ₃ alkyl) carbamoyl group, (C ₁ -C ₃ alkyl) (C ₁ -C ₃ alkoxy) carbamoyl group, optionally substituted C ₁ -C ₃ alkylsulfonyl group (the substituent is the same or different 1 to 3 selected from the group consisting of fluorine atom, chlorine atom and bromine atom) . a number of substituents) or substituted or a phenylsulfonyl group (the substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, 4- (2,4-dichlorobenzoyl) - 1,3-dimethyl-1H-pyrazol-5-yloxysulfonyl group and the same or different 1-2 substituents selected from the group consisting of nitro groups), and more preferably. , C ₂ -C ₄ alkylcarbonyl group, which may be substituted benzoyl group (the substituent is methyl or 4- (2,4-dichlorobenzoyl) -1,3-dimethyl--1H- pyrazol-5-yloxy is a carbonyl group.), 1-azetidinyloxyimino group, 4-morpholinylcarbonyl group, may be substituted C ₂ -C ₃ alkoxycarbonyl group (the substituent is a 1-3 chlorine atoms ), A dimethylcarbamoyl group, a methoxy (methyl) carbamoyl group, an optionally substituted C ₁ -C ₃ alkylsulfonyl group (the substituent is 1 to 3 fluorine atoms), or an optionally substituted phenylsulfonyl Group (the substituent is a chlorine atom, a methyl group, 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yloxysulfonyl) Group or nitro group. ) Is a bonded compound.

(A) In the present invention, R ¹ is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group (the halogen atom is 1 to 3 fluorine atoms)), cyclopropyl group, C ₂ -C ₃ alkenyl group, cyano group, C ₂ -C ₄ alkylcarbonyl group, di (C ₁ -C ₃ alkyl) carbamoyl group, may be substituted Phenyl group {the substituent is a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group (the halogen atom is a group consisting of a fluorine atom, a chlorine atom and a bromine atom) The same or different 1 to 3 halogen atoms selected), the same or different 1 to 2 selected from the group consisting of a cyclopropyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) silicon group. Substituents The }, A furyl group, a thienyl group, C ₁ -C ₃ alkoxy group, which may be substituted phenoxy group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ A haloalkyl group (the halogen atom is 1 to 3 fluorine atoms), a cyclopropyl group, a cyano group, and a tri (C ₁ -C ₃ alkyl) silicon group selected from the same or different 1 Two substituents. } Or a substituted pyrazolyloxy group (the substituent is one benzoyl group and two C ₁ -C ₃ alkyl groups substituted by two chlorine atoms),
More preferably, a chlorine atom, a bromine atom, a trifluoromethyl group or a cyano group,
Even more preferably, a chlorine atom or a bromine atom,
Particularly preferred is a chlorine atom.

(B) In the present invention, R ² is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a C ₁ -C ₃ alkyl group, or (C ₁ -C ₃ alkoxy) C ₁ -C. ₃ alkyl group, which may be substituted benzoyl group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is fluorine atom, chlorine selected from the group consisting of and bromine are the same or different 1 to 3 halogen atoms.), selected from the group consisting of cyclopropyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) silyl group Or the same or different 1 to 2 substituents. }, C ₂ -C ₄ alkoxycarbonyl group, may be substituted phenoxy group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen The atoms are the same or different 1 to 3 halogen atoms selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom.), Cyclopropyl group, cyano group and tri (C ₁ -C ₃ alkyl) It is the same or different 1-2 substituents selected from the group consisting of silicon groups. }, Which may be substituted phenylthio group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, a chlorine atom and The same or different one to three halogen atoms selected from the group consisting of bromine atoms), the same selected from the group consisting of cyclopropyl groups, cyano groups and tri (C ₁ -C ₃ alkyl) silicon groups. Or it is 1 to 2 different substituents. } Or a tri (C ₁ -C ₃ alkyl) silicon group,
More preferably, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethoxycarbonyl group or a trimethylsilyl group,
Even more preferred is a hydrogen atom.

(C) In the present invention, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are preferably independently of each other a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted atom. A good C ₁ -C ₄ alkyl group (the substituent is the same or different 1 to 3 substituents selected from the group consisting of fluorine atom, chlorine atom and bromine atom, or C ₃ -C ₄ cycloalkyl group) A C ₁ -C ₃ alkylthio group or a C ₁ -C ₃ alkoxyimino group), a C ₂ -C ₃ alkenyl group, a C ₂ -C ₃ alkynyl group, an optionally substituted C ₃ -C ₅ cycloalkyl group. (the substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₃ -C ₄ cycloalkyl group, a cyano group, C ₁ -C ₃ alkoxy groups and C ₁ -C ₃ alkylthio group 1 to 3 identical or different selected from the group consisting of Is a substituent.), C ₆ ~C ₇ bicycloalkyl group, a cyano group, C ₂ -C ₄ alkylcarbonyl group, C ₂ -C ₄ alkoxycarbonyl groups, which may be substituted phenyl group {said substituent is fluorine atoms 1, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl or C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, the same or different selected from the group consisting of chlorine and bromine 3 halogen atoms). }, A 5- to 6-membered heterocyclic group which may be substituted {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further contains 1 to 2 nitrogen atoms. You can. The substituents are fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl and C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, selected from the group consisting of chlorine and bromine 1 to 3 halogen atoms which are the same or different. }, Nitro group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ haloalkoxy group (said halogen atom is a fluorine atom, 1-3 was selected same or different from the group consisting of chlorine and bromine of a halogen atom.), which may be substituted phenoxy group (the substituent is a fluorine atom, a chlorine atom, pyridazinium substituted with a substituent selected from bromine atom, and C ₁ -C ₃ alkoxy group Gini oxy Or a C ₁ -C ₃ alkylthio group, or R ³ , R ⁴ , R ⁵ , R ^6, and R ⁷ are the two adjacent groups together with the carbon atom to which they are attached. _{Te, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH = CH-CH = CH- , -OCH ₂ CH _2- , -OCH = CH-, -OCH = C (CH ₃ )-, -SCH = CH-, -N = CH-CH = CH-, -OCH ₂ O-, -OCH ₂ CH ₂ O-,

で表される基であり、
より好適には、互いに独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、置換されてよいＣ₁〜Ｃ₄アルキル基（当該置換基は、１〜３個のフッ素原子、又は、１個のシクロプロピル基である。）、Ｃ₂〜Ｃ₃アルケニル基、置換されてよいＣ₃〜Ｃ₄シクロアルキル基（当該置換基は、フッ素原子、塩素原子、臭素原子、Ｃ₁〜Ｃ₂アルキル基、シクロプロピル基及びＣ₁〜Ｃ₂アルコキシ基からなる群から選ばれる同一の１〜２個の置換基である。）、シアノ基、Ｃ₂〜Ｃ₃アルコキシカルボニル基、ニトロ基、Ｃ₁〜Ｃ₃アルコキシ基又はトリフルオロメトキシ基であり、又は、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、隣合う２個が、それぞれが結合する炭素原子と一緒になって、-CH₂CH₂CH₂-、-CH(CH₃)CH₂CH₂-、-OCH₂CH₂-、-OCH=CH-又は

A group represented by
More preferably, independently of each other, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an optionally substituted C ₁ -C ₄ alkyl group (the substituent is 1 to 3 fluorine atoms, or a one cyclopropyl group.), C ₂ ~C ₃ alkenyl group, optionally substituted C ₃ to -C ₄ cycloalkyl group (said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₂ alkyl group, the same one to two substituents selected from the group consisting of cyclopropyl group, and C ₁ -C ₂ alkoxy group.), a cyano group, C ₂ -C ₃ alkoxycarbonyl group, a nitro A group, a C ₁ -C ₃ alkoxy group or a trifluoromethoxy group, or R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ , together with the carbon atoms to which two adjacent ones are attached to each other It is _{to, -CH 2 CH 2 CH 2 -} , - CH (CH 3) CH 2 CH 2 -, - OCH 2 CH 2 - -OCH = CH- or

で表される基であり、但し、Ｒ³は水素原子ではなく、
更により好適には、互いに独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、Ｃ₁〜Ｃ₃アルキル基、Ｃ₂〜Ｃ₃アルケニル基、置換されてよいＣ₃〜Ｃ₄シクロアルキル基（当該置換基は、塩素原子及びＣ₁〜Ｃ₂アルキル基からなる群から選ばれる同一の１〜２個の置換基である。）、シアノ基又はＣ₁〜Ｃ₂アルコキシ基であり、又は、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、隣合う２個が、それぞれが結合する炭素原子と一緒になって、-CH₂CH₂CH₂-又は-OCH=CH-で表される基であり、但し、Ｒ³は水素原子ではなく、
特に好適には、互いに独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メチル基、エチル基、アリル基、イソプロピル基、置換されてよいシクロプロピル基（当該置換基は、２個の塩素原子である。）又はメトキシ基であり、又は、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、隣合う２個が、それぞれが結合する炭素原子と一緒になって、-CH₂CH₂CH₂-又は-OCH=CH-で表される基であり、但し、Ｒ³は水素原子ではなく、
最も好適には、Ｒ³が、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メチル基、エチル基、イソプロピル基、シクロプロピル基又はメトキシ基であり、かつ、Ｒ⁷が、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メチル基、エチル基、イソプロピル基、シクロプロピル基又はメトキシ基であり、かつ、Ｒ⁴、Ｒ⁵及びＲ⁶が、互いに独立して、水素原子又はメチル基である。

Wherein R ³ is not a hydrogen atom,
Even more preferably, independently of each other, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a C ₁ -C ₃ alkyl group, a C ₂ -C ₃ alkenyl group, an optionally substituted C ₃ -C ₄ cycloalkyl group (said substituent is the same 1 to 2 substituents selected from the group consisting of a chlorine atom and C ₁ -C ₂ alkyl group.), a cyano group or a C ₁ -C ₂ alkoxy group Or R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ , together with the carbon atom to which each of the two adjacent groups is bonded, —CH ₂ CH ₂ CH ₂ — or —OCH = CH-, provided that R ³ is not a hydrogen atom,
Particularly preferably, independently of each other, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an allyl group, an isopropyl group, an optionally substituted cyclopropyl group (the substituent is 2 chlorine atoms) or a methoxy group, or R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ , together with the carbon atom to which two adjacent ones are bonded to each other. , -CH ₂ CH ₂ CH ₂ - is a or a group represented by -OCH = CH-, provided that, R ³ is not a hydrogen atom,
Most preferably, R ³ is a fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, isopropyl group, cyclopropyl group or methoxy group, and R ⁷ is a hydrogen atom, fluorine atom , A chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an isopropyl group, a cyclopropyl group or a methoxy group, and R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group It is.

  (D) In the present invention, m and n are preferably both 0.

The compound (I) of the present invention is preferably
(1a) R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group (the halogen atom is 1 to 3 fluorine atoms). ), cyclopropyl, C ₂ -C ₃ alkenyl group, a cyano group, C ₂ -C ₄ alkylcarbonyl group, a di (C ₁ -C ₃ alkyl) carbamoyl group, which may be substituted phenyl group {said substituent, fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, and the same or different selected from the group consisting of chlorine and bromine 1 ˜3 halogen atoms), a cyclopropyl group, a cyano group, and a tri (C ₁ -C ₃ alkyl) silicon group are the same or different 1-2 substituents selected from the group consisting of. }, A furyl group, a thienyl group, C ₁ -C ₃ alkoxy group, which may be substituted phenoxy group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ A haloalkyl group (the halogen atom is 1 to 3 fluorine atoms), a cyclopropyl group, a cyano group, and a tri (C ₁ -C ₃ alkyl) silicon group selected from the same or different 1 Two substituents. } Or a substituted pyrazolyloxy group (the substituent is one benzoyl group and two C ₁ -C ₃ alkyl groups substituted by two chlorine atoms),
(1b) R ² may be substituted with a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a C ₁ -C ₃ alkyl group, a (C ₁ -C ₃ alkoxy) C ₁ -C ₃ alkyl group, Benzoyl group {the substituent is a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group (the halogen atom is a group consisting of a fluorine atom, a chlorine atom and a bromine atom) The same or different 1 to 3 halogen atoms selected), the same or different 1 to 2 selected from the group consisting of a cyclopropyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) silicon group. Substituents. }, C ₂ -C ₄ alkoxycarbonyl group, may be substituted phenoxy group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen The atoms are the same or different 1 to 3 halogen atoms selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom.), Cyclopropyl group, cyano group and tri (C ₁ -C ₃ alkyl) It is the same or different 1-2 substituents selected from the group consisting of silicon groups. }, Which may be substituted phenylthio group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, a chlorine atom and The same or different one to three halogen atoms selected from the group consisting of bromine atoms), the same selected from the group consisting of cyclopropyl groups, cyano groups and tri (C ₁ -C ₃ alkyl) silicon groups. Or it is 1 to 2 different substituents. } Or a tri (C ₁ -C ₃ alkyl) silicon group,
(1c) R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a C ₁ -C ₄ alkyl group which may be substituted. (The substituent is the same or different 1 to 3 substituents selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom, or a C _{3 to} C ₄ cycloalkyl group, a C _{1 to} C ₃ alkylthio group. Or a C ₁ -C ₃ alkoxyimino group.), A C ₂ -C ₃ alkenyl group, a C ₂ -C ₃ alkynyl group, an optionally substituted C ₃ -C ₅ cycloalkyl group (the substituent is a fluorine atom) , a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₃ -C ₄ cycloalkyl group, a cyano group, the same or are selected from C ₁ -C ₃ alkoxy groups and C ₁ -C ₃ alkylthio group different from 1 to 3 substituents.), C ₆ ~C _7-bi Black alkyl group, a cyano group, C ₂ -C ₄ alkylcarbonyl group, C ₂ -C ₄ alkoxycarbonyl group, which may be substituted phenyl group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group or C ₁ -C ₃ haloalkyl group (the halogen atom is the same or different 1 to 3 halogen atoms selected from the group consisting of fluorine atom, chlorine atom and bromine atom). }, A 5- to 6-membered heterocyclic group which may be substituted {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further contains 1 to 2 nitrogen atoms. You can. The substituents are fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl and C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, selected from the group consisting of chlorine and bromine 1 to 3 halogen atoms which are the same or different. }, Nitro group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ haloalkoxy group (said halogen atom is a fluorine atom, 1-3 was selected same or different from the group consisting of chlorine and bromine of a halogen atom.), which may be substituted phenoxy group (the substituent is a fluorine atom, a chlorine atom, pyridazinyl substituted with a substituent selected from bromine atom, and C ₁ -C ₃ alkoxy groups An oxy group) or a C ₁ -C ₃ alkylthio group, or R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ , together with the carbon atom to which two adjacent ones are bonded to each other. is _{to, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH = CH-CH = CH -, -OCH ₂ CH _2- , -OCH = CH-, -OCH = C (CH ₃ )-, -SCH = CH-, -N = CH-CH = CH-, -OCH ₂ O-, -OCH ₂ CH ₂ O-,

で表される基であり、
(1d) ｍ及びｎが、共に０である化合物であり、
より好適には、
(2a) Ｒ¹が、塩素原子、臭素原子、トリフルオロメチル基又はシアノ基であり、
(2b) Ｒ²が、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メチル基、エトキシカルボニル基又はトリメチルシリル基であり、
(2c) Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷が、互いに独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、置換されてよいＣ₁〜Ｃ₄アルキル基（当該置換基は、１〜３個のフッ素原子、又は、１個のシクロプロピル基である。）、Ｃ₂〜Ｃ₃アルケニル基、置換されてよいＣ₃〜Ｃ₄シクロアルキル基（当該置換基は、フッ素原子、塩素原子、臭素原子、Ｃ₁〜Ｃ₂アルキル基、シクロプロピル基及びＣ₁〜Ｃ₂アルコキシ基からなる群から選ばれる同一の１〜２個の置換基である。）、シアノ基、Ｃ₂〜Ｃ₃アルコキシカルボニル基、ニトロ基、Ｃ₁〜Ｃ₃アルコキシ基又はトリフルオロメトキシ基であり、又は、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷が、隣合う２個が、それぞれが結合する炭素原子と一緒になって、-CH₂CH₂CH₂-、-CH(CH₃)CH₂CH₂-、-OCH₂CH₂-、-OCH=CH-又は

A group represented by
(1d) a compound in which m and n are both 0;
More preferably,
(2a) R ¹ is a chlorine atom, a bromine atom, a trifluoromethyl group or a cyano group,
(2b) R ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethoxycarbonyl group or a trimethylsilyl group,
^{(2c) R 3, R 4} , R 5, R 6 and R ^7, independently of one another, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, may be substituted C ₁ -C ₄ alkyl group (The substituent is 1 to 3 fluorine atoms or one cyclopropyl group), a C _{2 to} C ₃ alkenyl group, an optionally substituted C _{3 to} C ₄ cycloalkyl group (the substituent group, a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₂ alkyl group, the same one or two substituents selected from the group consisting of cyclopropyl group, and C ₁ -C ₂ alkoxy group.) , A cyano group, a C ₂ -C ₃ alkoxycarbonyl group, a nitro group, a C ₁ -C ₃ alkoxy group or a trifluoromethoxy group, or R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are adjacent to each other. Two of them, together with the carbon atom to which each is attached, are —CH ₂ CH ₂ CH ₂ —, —CH (C H ₃ ) CH ₂ CH _2- , -OCH ₂ CH _2- , -OCH = CH- or

で表される基であり、但し、Ｒ³は水素原子ではなく、
(2d) ｍ及びｎが、共に０である化合物であり、
更により好適には、
(3a) Ｒ¹が、塩素原子又は臭素原子であり、
(3b) Ｒ²が、水素原子であり、
(3c) Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷が、互いに独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、Ｃ₁〜Ｃ₃アルキル基、Ｃ₂〜Ｃ₃アルケニル基、置換されてよいＣ₃〜Ｃ₄シクロアルキル基（当該置換基は、塩素原子及びＣ₁〜Ｃ₂アルキル基からなる群から選ばれる同一の１〜２個の置換基である。）、シアノ基又はＣ₁〜Ｃ₂アルコキシ基であり、又は、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷が、隣合う２個が、それぞれが結合する炭素原子と一緒になって、-CH₂CH₂CH₂-又は-OCH=CH-で表される基であり、但し、Ｒ³は水素原子ではなく、
(3d) ｍ及びｎが、共に０である化合物であり、
特に好適には、
(4a) Ｒ¹が、塩素原子であり、
(4b) Ｒ²が、水素原子であり、
(4c) Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷が、互いに独立して、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メチル基、エチル基、アリル基、イソプロピル基、置換されてよいシクロプロピル基（当該置換基は、２個の塩素原子である。）又はメトキシ基であり、又は、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷が、隣合う２個が、それぞれが結合する炭素原子と一緒になって、-CH₂CH₂CH₂-又は-OCH=CH-で表される基であり、但し、Ｒ³は水素原子ではなく、
(4d) ｍ及びｎが、共に０である化合物であり、
最も好適には、6-クロロ-3-(2-ヨードフェノキシ)-4-ピリダジノール、6-クロロ-3-(2-メチルフェノキシ)-4-ピリダジノール、6-クロロ-3-(2-イソプロピルフェノキシ)-4-ピリダジノール、6-クロロ-3-(2-シクロプロピルフェノキシ)-4-ピリダジノール、6-クロロ-3-(2,3-ジヒドロ-1H-インデン-4-イルオキシ)-4-ピリダジノール、3-(1-ベンゾフラン-7-イルオキシ)-6-クロロ-4-ピリダジノール、6-クロロ-3-(2,5-ジメチルフェノキシ)-4-ピリダジノール、6-クロロ-3-(2-メトキシ-5-メチルフェノキシ)-4-ピリダジノール、6-クロロ-3-(2-クロロ-6-メチルフェノキシ)-4-ピリダジノール、6-クロロ-3-(2-クロロ-6-シクロプロピルフェノキシ)-4-ピリダジノール、3-(2-ブロモ-6-メチルフェノキシ)-6-クロロ-4-ピリダジノール、6-クロロ-3-(2-エチル-6-メチルフェノキシ)-4-ピリダジノール、6-クロロ-3-(2-シクロプロピル-6-メチルフェノキシ)-4-ピリダジノール、3-（2-アリル-6-メチルフェノキシ）-6-クロロ-4-ピリダジノール、6-クロロ-3-(2-シクロプロピル-3,5-ジメチルフェノキシ)-4-ピリダジノール、6-クロロ-3-[(5-メチル-2,3-ジヒドロ-1H-インデン-4-イル)オキシ]-4-ピリダジノール又は6-クロロ-3-(2,3,5,6-テトラメチルフェノキシ)-4-ピリダジノールである。

Wherein R ³ is not a hydrogen atom,
(2d) a compound in which m and n are both 0;
Even more preferably,
(3a) R ¹ is a chlorine atom or a bromine atom,
(3b) R ² is a hydrogen atom,
(3c) R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, C ₁ -C ₃ alkyl group, C _2- C ₃ alkenyl group, may be substituted C ₃ -C ₄ cycloalkyl group (the substituent is the same 1 to 2 substituents selected from the group consisting of a chlorine atom and C ₁ -C ₂ alkyl group ), A cyano group or a C ₁ -C ₂ alkoxy group, or R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ , together with two adjacent carbon atoms to which each is bonded. A group represented by —CH ₂ CH ₂ CH ₂ — or —OCH═CH—, wherein R ³ is not a hydrogen atom,
(3d) a compound in which m and n are both 0;
Particularly preferably,
(4a) R ¹ is a chlorine atom,
(4b) R ² is a hydrogen atom,
(4c) R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, allyl group, isopropyl group , An optionally substituted cyclopropyl group (the substituent is two chlorine atoms) or a methoxy group, or R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are adjacent to each other. Are groups represented by —CH ₂ CH ₂ CH ₂ — or —OCH═CH—, together with the carbon atoms to which each is bonded, provided that R ³ is not a hydrogen atom,
(4d) a compound in which m and n are both 0;
Most preferably, 6-chloro-3- (2-iodophenoxy) -4-pyridazinol, 6-chloro-3- (2-methylphenoxy) -4-pyridazinol, 6-chloro-3- (2-isopropylphenoxy) ) -4-pyridazinol, 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinol, 6-chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinol, 3- (1-benzofuran-7-yloxy) -6-chloro-4-pyridazinol, 6-chloro-3- (2,5-dimethylphenoxy) -4-pyridazinol, 6-chloro-3- (2-methoxy- 5-methylphenoxy) -4-pyridazinol, 6-chloro-3- (2-chloro-6-methylphenoxy) -4-pyridazinol, 6-chloro-3- (2-chloro-6-cyclopropylphenoxy) -4 -Pyridazinol, 3- (2-bromo-6-methylphenoxy) -6-chloro-4-pyridazinol, 6-chloro-3- (2-ethyl-6-methylphenoxy) -4-pyridazinol, 6-chloro-3 - (2-Cyclopropyl-6-methylphenoxy) -4-pyridazinol, 3- (2-allyl-6-methylphenoxy) -6-chloro-4-pyridazinol, 6-chloro-3- (2-cyclopropyl-3 , 5-dimethylphenoxy) -4-pyridazinol, 6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinol or 6-chloro-3- (2,3,5,6-tetramethylphenoxy) -4-pyridazinol.

  Representative compounds of the present invention are illustrated in Table 1 below, but the present invention is not limited to these compounds.

Hereinafter, in R ^{3 to} R ⁷ , “2-Cl” means that R ³ is a chlorine atom, “Me” means a methyl group, “Et” means an ethyl group, “iPr” means an isopropyl group, “cPr” Is a cyclopropyl group, “cPr-2,2-Cl ₂ ” is a 2,2-dichlorocyclopropyl group, “iBu” is an isobutyl group, “tBu” is a tert-butyl group, R ³ to In R ⁷ , “2-CH ₂ CH ₂ CH ₂ -3” means that R ³ and R ⁴ are trimethylene groups and together with the carbon atoms to which they are bonded form a 5-membered ring. "Represents a morpholinyl group," Azet "represents an azetidinyl group, and" Q ¹ "represents a 1,3-oxazolidin-3-yl group.

  The 3-phenoxy-4-pyridazinol compound and its ester derivative of the present invention can be produced by the methods of Steps A to Q described below.

  (Process A)

上記式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、前記と同意義を示し、
Ｌは、脱離基を示し、例えば、ハロゲン原子、Ｃ₁〜Ｃ₆アルキルスルホニルオキシ基又はフェニルスルホニルオキシ基（当該フェニルスルホニルオキシ基は、同一又は異なった１〜５個のハロゲン原子又はＣ₁〜Ｃ₆アルキル基により置換されていてよい。）であり得、
Ｘは、水素原子又はアシル基を示し、
Ｙは、Ｘの他、水酸基のその他の保護基であり、例えば、メチル基、メトキシメチル基、メトキシエトキシメチル基又はベンジル基であり得る。

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above,
L represents a leaving group, for example, a halogen atom, a C _{1 to} C ₆ alkylsulfonyloxy group or a phenylsulfonyloxy group (the phenylsulfonyloxy group is the same or different 1 to 5 halogen atoms or C ₁ the -C ₆ alkyl group may be substituted.), and obtained,
X represents a hydrogen atom or an acyl group,
Y is other protective group of hydroxyl group besides X, and may be, for example, methyl group, methoxymethyl group, methoxyethoxymethyl group or benzyl group.

  In step A, the pyridazine compound represented by the general formula (II) is reacted with the phenol compound represented by the general formula (III), then chlorinated, and further reacted with an oxygen nucleophile to thereby produce the compound of the present invention. It is a step of producing a compound in which the hydroxyl group represented by (Ia) or general formula (VII) is protected, and further, a step of producing the compound (Ib) of the present invention by removing the protecting group of compound (VII). .

(Process A-1)
In step A-1, compound (II) is reacted with compound (III) in the presence or absence of a solvent, and optionally in the presence of a base, to convert a phenoxypyridazine compound represented by the general formula (IV). It is a manufacturing process.

  The base to be used is not particularly limited as long as it usually has a pH of 8 or more. For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkalis such as sodium carbonate, potassium carbonate and cesium carbonate Metal carbonates; metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; alkali metals such as sodium and potassium; triethylamine and tributylamine Aliphatic tertiary amines such as diisopropylethylamine; 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) Aliphatic cyclic tertiary amines such as: pyridine, collidine Pyridines such as 4- (N, N-dimethylamino) pyridine; organometallic bases such as n-butyllithium, s-butyllithium, lithium diisopropylamide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide And is preferably an alkali metal hydroxide, alkali metal carbonate, metal alkoxide, alkali metal hydride or alkali metal, more preferably potassium carbonate, potassium t-butoxide, sodium hydride or Sodium.

  The amount of the base used is usually 0.5 to 5 mol and preferably 1 to 3 mol with respect to 1 mol of compound (II).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butanol; acetone, methyl isobutyl ketone Ketones such as acetonitrile; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons such as: amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; or a mixed solvent thereof, preferably nitriles, halogenated hydrocarbons , Ethers, aromatic hydrocarbons An amide or a sulfoxide, and more preferably dioxane, toluene, dimethylformamide or dimethyl sulfoxide.

  The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent and the like, but is usually -90 ° C to 200 ° C, and preferably 0 ° C to 100 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is generally 5 minutes to 48 hours, preferably 15 minutes to 12 hours.

(Process A-2)
In step A-2, compound (IV) is chlorinated with a chlorinating agent in the presence or absence of a solvent to produce a compound in which a chlorine atom is introduced at the 4-position of the pyridazine ring represented by general formula (V). It is a process to do.

  The chlorinating agent to be used is not particularly limited as long as it chlorinates an aromatic ring, and examples thereof include chlorine, chlorine-iron chloride, sulfuryl chloride, copper chloride, N-chlorosuccinimide, and phosphorus pentachloride. Preferably, it is chlorine.

  The amount of the chlorinating agent to be used is usually 0.5 to 10 mol, preferably 1 to 2 mol, relative to 1 mol of compound (IV).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. Examples thereof include phosphorus oxychloride; water; alcohols such as methanol, ethanol and t-butanol; Halogenated hydrocarbons such as methylene, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene; amides such as dimethylformamide and dimethylacetamide; dimethyl sulfoxide Such sulfoxides; aliphatic hydrocarbons such as hexane, cyclohexane, heptane; or a mixed solvent thereof, preferably phosphorus oxychloride, water, halogenated hydrocarbons or ethers; More preferred is phosphorus oxychloride.

  The reaction temperature varies depending on the raw material compound, the reaction reagent, and the type of solvent used, but is usually −90 ° C. to 200 ° C., and preferably 0 ° C. to 50 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is usually 5 minutes to 24 hours, and preferably 15 minutes to 6 hours.

(Process A-3)
In step A-3, compound (V) is reacted with an oxygen nucleophile represented by general formula (VI) in the presence or absence of a solvent, and optionally in the presence of a base, to give compound (Ia) of the present invention. Or it is the process of manufacturing the compound by which the hydroxyl group represented by general formula (VII) was protected.

  The base used is not particularly limited as long as it is a base exhibiting a pH of 8 or higher. For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; sodium carbonate, potassium carbonate and cesium carbonate are used. Alkali metal carbonates; metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide; alkali metal salts of organic acids such as sodium acetate, potassium acetate, sodium formate, potassium formate; sodium hydride, hydrogenation Alkali metal hydrides such as potassium; alkali metals such as sodium and potassium; aliphatic tertiary amines such as triethylamine, tributylamine and diisopropylethylamine; 1,4-diazabicyclo [2.2.2] octane (DABCO ), 1,8-diazabicyclo 5.4.0] Aliphatic cyclic tertiary amines such as undec-7-ene (DBU); pyridines such as pyridine, collidine, 4- (N, N-dimethylamino) pyridine; butyllithium, s -Organic bases such as butyl lithium, lithium diisopropylamide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, preferably alkali metal hydroxides, alkali metal carbonates, metal alkoxides, Alkali metal salt of organic acid, alkali metal hydride or alkali metal, more preferably sodium hydroxide, potassium hydroxide, potassium carbonate, potassium t-butoxide, sodium acetate, sodium formate, sodium hydride or sodium is there.

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butanol; acetone, methyl isobutyl Ketones such as ketones; Nitriles such as acetonitrile; Esters such as ethyl acetate; Halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; Ethers such as diethyl ether, tetrahydrofuran and dioxane; Toluene Aromatic hydrocarbons such as: amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; or a mixed solvent thereof, preferably water, alcohols, nitriles, Ethers, amides or sulfoxides By weight, more preferably, water, methanol, acetonitrile, tetrahydrofuran, dioxane, dimethylformamide or dimethyl sulfoxide.

  The reaction temperature varies depending on the raw material compound, the reaction reagent, and the type of solvent used, but is usually −90 ° C. to 200 ° C., and preferably 0 ° C. to 100 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is usually 5 minutes to 24 hours, and preferably 15 minutes to 6 hours.

  In this step, compound (VI) can also be used in this step after previously reacting with a base to form a salt.

(Process A-4)
Step A-4 is a step for producing the compound (Ib) of the present invention by removing the protecting group for the hydroxyl group of the compound (VII).

  The protecting group used in this step is not particularly limited as long as it can be selectively removed from compound (VII) to give compound (Ib). For example, methyl, methoxymethyl, benzyloxymethyl, methoxy Ethoxymethyl group, 2- (trimethylsilyl) ethoxymethyl group, methylthiomethyl group, phenylthiomethyl group, 2,2-dichloro-1,1-difluoroethyl group, tetrahydropyranyl group, phenacyl group, p-bromophenacyl group, cyclo Propylmethyl group, allyl group, isopropyl group, cyclohexyl group, t-butyl group, benzyl group, 2,6-dimethylbenzyl group, 4-methoxybenzyl group, 2-nitrobenzyl group, 2,6-dichlorobenzyl group, 4 -(Dimethylaminocarbonyl) benzyl group, 9-anthrylmethyl group, 4- It can be a cholyl group, a heptafluoro-p-tolyl group or a tetrafluoro-4-pyridyl group, preferably a methyl group, a methoxymethyl group, a methoxyethoxymethyl group, a methylthiomethyl group, a tetrahydropyranyl group, a phenacyl group, It is an allyl group or a benzyl group, and more preferably a methyl group.

  The method for removing the protecting group used in this step is not particularly limited as long as it can selectively remove the protecting group of the hydroxyl group, and a known method (for example, Protective Groups In -Organic Synthesis (Protective Groups in Organic Synthesis), 13th edition, Theodora W. Greene and Peter GM Wuts, the method described in JOHN WILEY & SONS, INC) or according to these methods. For example, when the protecting group is a methyl group, the removal of the methyl group can be accomplished, for example, by the potassium or sodium salt of 2-hydroxypyridine in dimethyl sulfoxide, the sodium salt of ethanethiol in dimethylformamide, or 3 in methylene chloride. It can be performed by the action of boron bromide. For example, when the protecting group is a methoxymethyl group, the removal of the methoxymethyl group can be performed, for example, by the action of trifluoroacetic acid. For example, when the protecting group is a methoxyethoxymethyl group, the removal of the methoxyethoxymethyl group can be performed by, for example, acting trifluoroacetic acid. For example, when the protecting group is a benzyl group, the benzyl group can be removed by catalytic hydrogenation.

  (Process B)

上記式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｌ、Ｘ及びＹは、前記と同意義を示す。

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , L, X and Y are as defined above.

  In step B, the pyridazine compound represented by the general formula (II) is oxidized, reacted with the phenol compound represented by the general formula (III), then chlorinated, and further reacted with an oxygen nucleophile. A step of producing a compound (Ia) or a compound in which the hydroxyl group represented by the general formula (VII) is protected, and further, a step of producing the compound (Ib) of the present invention by removing the protecting group of the compound (VII). It is.

(Process B-1)
Step B-1 is a step of producing pyridazine N-oxide represented by general formula (VIII) by oxidizing compound (II) with an oxidizing agent in the presence or absence of a solvent.

  The oxidizing agent used is not particularly limited as long as it converts amines to N-oxide. For example, m-chloroperbenzoic acid (mcpba), peracetic acid, pertrifluoroacetic acid, trifluoroacetic anhydride- Hydrogen peroxide, peroxydichloromaleic acid, dichloromaleic acid-hydrogen peroxide, peroxymaleic acid, maleic acid-hydrogen peroxide, t-butyl hydroperoxide, t-butyl hydroperoxide-vanadium oxyacetylacetonate, t-butyl hydroperoxide-peroxide such as molybdenum chloride, hydrogen peroxide; ozone; or oxygen, preferably m-chloroperbenzoic acid (mcpba), trifluoroacetic anhydride-hydrogen peroxide Or dichloromaleic acid-hydrogen peroxide.

  The amount of the oxidizing agent used for the reaction is usually 0.5 to 100 mol, preferably 1 to 2 mol, relative to 1 mol of compound (II).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butanol; acetone, methyl isobutyl ketone Ketones such as acetonitrile; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; or a mixed solvent thereof, preferably halogenated hydrocarbons, more preferably Is methylene chloride.

  While the reaction temperature varies depending on the raw material compound, reaction reagent, solvent and the like, it is generally -90 ° C to 200 ° C, preferably 0 ° C to 100 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is generally 5 minutes to 24 hours, preferably 15 minutes to 6 hours.

  By this process, isomers in which other nitrogen atoms are oxidized may be by-produced.However, by purifying after completion of this process or by performing subsequent processes while mixing, purifying after completion of the process, The target pyridazine N-oxide can be obtained.

(Process B-2)
In step B-2, compound (VIII) is reacted with compound (III) in the presence or absence of a solvent, and optionally in the presence of a base, to produce a phenoxypyridazine compound represented by general formula (IX). It is a process to do.

  This step can be performed according to step A-1.

(Process B-3)
Step B-3 is a step of producing compound (V) by reacting compound (IX) with phosphorus oxychloride in the presence or absence of a solvent.

  The amount of phosphorus oxychloride used in this step is usually 0.5 to 100 mol, preferably 1 to 5 mol, relative to 1 mol of compound (IX).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, ketones such as acetone and methyl isobutyl ketone; nitriles such as acetonitrile; ethyl acetate Esters such as; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene; dimethylformamide and dimethylacetamide Amides; Sulfoxides such as dimethyl sulfoxide; Aliphatic hydrocarbons such as hexane and cyclohexane; or a mixed solvent thereof, preferably halogenated hydrocarbons, and more preferably Methylene chloride or chloroform.

  While the reaction temperature varies depending on the raw material compound, reaction reagent, solvent and the like, it is generally -90 ° C to 200 ° C, preferably 0 ° C to 100 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is generally 5 minutes to 72 hours, and preferably 30 minutes to 24 hours.

(Process B-4)
In Step B-4, the compound (V) is reacted with an oxygen nucleophile represented by the general formula (VI) in the presence or absence of a solvent, and optionally in the presence of a base, to give the compound of the present invention (Ia ) Or a compound in which the hydroxyl group represented by formula (VII) is protected.

  This step is the same as step A-3.

(Process B-5)
Step B-5 is a step for producing the compound (Ib) of the present invention by removing the protecting group for the hydroxyl group of the compound (VII).

  This step is the same as step A-4.

  (Process C)

上記式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｘ及びＹは、前記と同意義を示す。

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X and Y are as defined above.

  Step C is a step of producing a compound in which the hydroxyl group represented by the present compound (Ia) or general formula (VII) is protected by oxidizing and chlorinating compound (IV) and then reacting with an oxygen nucleophile. Furthermore, this is a step for producing the compound (Ib) of the present invention by removing the protecting group of the compound (VII).

(Process C-1)
Step C-1 is a step of producing pyridazine N-oxide represented by general formula (IX) by oxidizing compound (IV) with an oxidizing agent in the presence or absence of a solvent.

  This process can be performed according to process B-1.

(Process C-2)
Step C-2 is a step of producing compound (V) by reacting compound (IX) with phosphorus oxychloride in the presence or absence of a solvent.

  This step is the same as step B-3.

(Process C-3)
In Step C-3, the compound (V) is reacted with an oxygen nucleophile represented by the general formula (VI) in the presence or absence of a solvent, and optionally in the presence of a base, to give a compound of the present invention ( This is a step of producing a compound in which the hydroxyl group represented by Ia) or general formula (VII) is protected.

  This step is the same as step A-3 or B-4.

(Process C-4)
Step C-4 is a step for producing the compound (Ib) of the present invention by removing the protecting group for the hydroxyl group of the compound (VII).

  This step is the same as step A-4 or B-5.

  (Process D)

上記式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｌ、Ｘ及びＹは、前記と同意義を示す。

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , L, X and Y are as defined above.

  In the step D, the compound represented by the present invention (Ia) or the general formula (I) is reacted with a phenol represented by the general formula (III) by reacting the pyridazine compound represented by the general formula (X) with the oxygen functional group previously substituted. VII) is a step of producing a compound in which the hydroxyl group is protected, and further is a step of producing the compound (Ib) of the present invention by removing the protecting group of compound (VII).

(Process D-1)
In step D-1, compound (X) is reacted with compound (III) in the presence or absence of a solvent, optionally in the presence of a base, to give compound (Ia) or general formula (VII) of the present invention. This is a process for producing a compound in which the hydroxyl group represented is protected.

  This process can be performed according to process A-1 or B-2.

(Process D-2)
Step D-2 is a step for producing the compound (Ib) of the present invention by removing the protecting group for the hydroxyl group of the compound (VII).

  This step is the same as step A-4, B-5 or C-4.

  (Process E)

上記式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｌ、Ｘ及びＹは、前記と同意義を示し、
ｍ'及びｎ'は、０又は１を示し、但し、ｍ'とｎ'は同時に０ではない。

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , L, X and Y are as defined above,
m ′ and n ′ represent 0 or 1, provided that m ′ and n ′ are not 0 at the same time.

  In step E, the pyridazine compound previously substituted with an oxygen functional group represented by the general formula (X) is oxidized and then reacted with the phenol represented by the general formula (III) to thereby react the compound (Ic) of the present invention or This is a step of producing a compound in which the hydroxyl group represented by the general formula (XII) is protected, and further, a step of producing the compound (Id) of the present invention by removing the protecting group of the compound (XII).

(Process E-1)
Step E-1 is a step of producing pyridazine N-oxide represented by general formula (XI) by oxidizing compound (X) with an oxidizing agent in the presence or absence of a solvent.

  This step can be performed according to Step B-1 or C-1 when m ′ = 0 or n ′ = 0, and when m ′ = n ′ = 1, the amount of oxidizing agent is excessive. Or by using more severe conditions such as oxidizing with a more reactive oxidizing agent.

(Process E-2)
In step E-2, compound (XI) is reacted with compound (III) in the presence or absence of a solvent, and optionally in the presence of a base, to give a compound of the present invention (Ic) or general formula (XII). This is a step of producing a compound in which the hydroxyl group represented is protected.

  This process can be performed according to process A-1, B-2, or D-1.

(Process E-3)
Step E-3 is a step of producing the compound (Id) of the present invention by removing the protecting group for the hydroxyl group of the compound (XII).

  This step is the same as step A-4, B-5, C-4 or D-2.

  (Process F)

上記式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｘ、Ｙ、ｍ'及びｎ'は、前記と同意義を示す。

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X, Y, m ′ and n ′ are as defined above.

  In Step F, the hydroxyl group represented by the compound (Ic) or the general formula (XII) is protected by oxidizing the compound represented by the compound (Ia) or the general formula (VII). And a step of producing the compound (Id) of the present invention by removing the protecting group of the compound (XII).

(Process F-1)
In Step F-1, the compound (Ia) or compound (VII) of the present invention is oxidized with an oxidizing agent in the presence or absence of a solvent, and is represented by the compound (Ic) or general formula (XII) of the present invention. This is a production process for producing a compound in which a hydroxyl group is protected.

  This step can be performed according to step E-1.

(Process F-2)
Step F-2 is a step of producing the compound (Id) of the present invention by removing the hydroxyl-protecting group of the compound (XII).

  This step is the same as Step A-4, B-5, C-4, D-2 or E-3.

  (Process G)

上記式中、Ｒ¹、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｘ及びＹは、前記と同意義を示し、
Ｒ^2aは、水素原子を除く他、Ｒ²と同意義を示す。

In the above formula, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X and Y are as defined above,
R ^2a has the same meaning as R ² except for a hydrogen atom.

  In Step G, the 5-position of the pyridazine ring of the compound (Ie) or the compound represented by the general formula (XIII) in which the hydroxyl group is protected is metalated and then reacted with an electrophile, If) is a step of producing a compound in which the hydroxyl group represented by formula (XIV) is protected, and further is a step of producing the compound (Ig) of the present invention by removing the protecting group of compound (XIV). .

(Process G-1)
In Step G-1, the compound of the present invention (Ie) or the compound represented by formula (XIII) in which the hydroxyl group is protected is reacted with a metallizing agent in the presence or absence of a solvent, This is a step of producing a compound in which the hydroxyl group represented by the present compound (If) or general formula (XIV) is protected by reacting.

  The metallizing agent to be used is not particularly limited as long as it can metallate an aromatic ring. For example, an organolithium compound such as methyl lithium, butyl lithium, sec-butyl lithium, t-butyl lithium, or phenyl lithium; Organomagnesium compounds such as magnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, phenylmagnesium bromide; Organometallic amides such as lithium diisopropylamide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide; sodium methoxide, sodium Metal alkoxides such as ethoxide and potassium t-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; lithium, sodium and potassium Alkali metals such as beam; obtained an alkali earth metal such as magnesium, preferably an organolithium compound, more preferably a butyl lithium.

  The amount of the metallizing agent used in the reaction is usually 0.5 to 10 mol, preferably 1 to 2 mol, relative to 1 mol of compound (Ie) or compound (XIII).

  The electrophile used in the reaction is not particularly limited as long as it reacts with an organometallic compound. For example, silylating agents such as trimethylsilyl chloride, triethylsilyl chloride, t-butyldimethylsilyl chloride, trimethylsilyl trifluoromethanesulfonate, etc. Acylating agents such as acetyl chloride, benzoyl chloride, ethyl chlorocarbonate, methyl chlorocarbonate, N, N-dimethylformamide, methyl formate; carbonyl compounds such as acetaldehyde, benzaldehyde, acetone, cyclohexanone; methyl iodide, bromide Alkylating agents such as methyl and benzyl bromide; fluorine, chlorine, bromine, iodine, N-fluorobenzenesulfonamide, 1-fluoro-2,6-dichloropyridinium triflate, N-chlorosuccinimide (NCS) ), A halogenating agent such as N-bromosuccinimide (NBS); or carbon dioxide, preferably a silylating agent, acylating agent, alkylating agent or halogenating agent, more preferably Is trimethylsilyl chloride, benzoyl chloride, ethyl chlorocarbonate or methyl iodide.

  The amount of the electrophile used for the reaction is usually 0.5 to 10 mol, preferably 1 to 3 mol, relative to 1 mol of compound (Ie) or compound (XIII).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting materials to some extent. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane; diethyl ether, tetrahydrofuran, dioxane Ethers such as toluene; aromatic hydrocarbons such as toluene; aliphatic hydrocarbons such as hexane and cyclohexane; or a mixed solvent thereof, preferably ethers, more preferably Is tetrahydrofuran.

  While the reaction temperature varies depending on the raw material compound, the reaction reagent, and the type of solvent used, it is generally −90 ° C. to 100 ° C., and preferably −70 ° C. to 30 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is generally 5 minutes to 24 hours, preferably 30 minutes to 12 hours.

(Process G-2)
Step G-2 is a step for producing the compound (Ig) of the present invention by removing the protecting group for the hydroxyl group of the compound (XIV).

  This step is the same as Step A-4, B-5, C-4, D-2, E-3 or F-2.

  (Process H)

上記式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、前記と同意義を示し、
Ｘ^aは、水素原子を除く他、Ｘと同意義を示す。

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above,
X ^a has the same meaning as X except for a hydrogen atom.

  Step H is a step of converting the ester derivative of the present invention represented by the general formula (Ih) into the hydroxy form of the present invention represented by the general formula (Ib).

(Process H-1)
Step H-1 is a step of producing the present compound (Ib) by reacting the present compound (Ih) with a nucleophile in the presence or absence of a solvent.

  The nucleophile used is not particularly limited as long as it can nucleophilically attack an ester derivative and cleave the ester bond into an acid moiety and an alcohol moiety. For example, water; lithium hydroxide, sodium hydroxide Alkali metal hydroxides such as potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; sodium methoxide, sodium ethoxide, 2-hydroxypyridine potassium salt, 2- Metal alkoxides such as hydroxypyridine sodium salt; alkali metal salts of organic acids such as sodium acetate, potassium acetate, sodium formate and potassium formate; fluorides such as tetrabutylammonium fluoride and potassium fluoride; lithium chloride and chloride Chlorides such as sodium; lithium bromide, sodium bromide Bromides; iodides such as sodium iodide and potassium iodide; or metal salts of sulfur compounds such as methanethiol sodium salt and ethanethiol sodium salt, preferably water, alkali metal hydroxides , Metal alkoxides or alkali metal salts of organic acids, more preferably water, sodium hydroxide, potassium hydroxide or sodium acetate.

  The amount of the nucleophile to be used is usually 1 to 10 mol, preferably 1 to 5 mol, relative to 1 mol of compound (Ih).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butanol; acetone, methyl isobutyl ketone Ketones such as acetonitrile; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethylsulfoxide; or a mixed solvent thereof, preferably water, alcohols, nitriles, ethers Amides or sulfoxides , More preferably, water, methanol, ethanol, tetrahydrofuran, dioxane, dimethylformamide or dimethyl sulfoxide.

  While the reaction temperature varies depending on the raw material compound, reaction reagent, solvent and the like, it is generally -90 ° C to 200 ° C, preferably 0 ° C to 100 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is usually 5 minutes to 48 hours, preferably 15 minutes to 12 hours.

  In addition, this process can also use a well-known method as normal deprotection of a hydroxyl group.

  (Process I)

上記式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷及びＸ^aは、前記と同意義を示す。

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and X ^a are as defined above.

  Step I is a step of converting the hydroxy compound of the present invention represented by the general formula (Ib) into the ester derivative of the present invention represented by the general formula (Ih).

(Step I-1)
Step I-1 is a step of producing the present compound (Ih) by reacting the present compound (Ib) with an esterifying agent in the presence or absence of a solvent.

  The esterifying agent used is not particularly limited as long as it esterifies a hydroxyl group. For example, acetyl chloride, acetyl bromide, acetic anhydride, trifluoroacetic anhydride, benzoyl chloride, toluoyl chloride, methyl chlorocarbonate, Acylating agents such as ethyl chlorocarbonate, N, N-dimethylcarbamoyl chloride, 4-morpholine carbonyl chloride, methyl chlorothioformate; or methanesulfonyl chloride, propanesulfonyl chloride, p-toluenesulfonyl chloride, anhydrous trifluoromethanesulfone Acid, may be a sulfonylating agent such as N, N-dimethylsulfamoyl chloride, and preferably acetyl chloride, acetic anhydride, trifluoroacetic anhydride, benzoyl chloride, toluoyl chloride, methyl chlorocarbonate, chlorocarbonic acid Ethyl, N, N-dimethylcarbamoyl chloride, 4-morpholine carbonyl chloride, methanesulfonyl chloride, propanesulfonyl chloride, p-toluenesulfonyl chloride or trifluoromethanesulfonic anhydride, more preferably benzoyl chloride, toluoyl chloride, N, N-dimethylcarbamoyl chloride, 4-morpholine carbonyl chloride, p-toluenesulfonyl chloride or trifluoromethanesulfonic anhydride.

  The amount of the esterifying agent used in the reaction is usually 0.5 to 10 mol, preferably 1 to 3 mol, relative to 1 mol of compound (Ib).

  The reaction is preferably carried out in the presence of a base.

  The base used is not particularly limited as long as it usually shows a pH of 8 or more. For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkalis such as sodium carbonate, potassium carbonate and cesium carbonate Metal carbonates; metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; aliphatic triions such as triethylamine, tributylamine and diisopropylethylamine Tertiary amines; aliphatic cyclic tertiary amines such as 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) Of pyridine, collidine, 4- (N, N-dimethylamino) pyridine Or pyridines; or organometallic bases such as n-butyllithium, sec-butyllithium, lithium diisopropylamide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, and preferably aliphatic Tertiary amines, aliphatic cyclic tertiary amines or pyridines, more preferably triethylamine, 1,4-diazabicyclo [2.2.2] octane (DABCO), pyridine or 4- (N, N -Dimethylamino) pyridine.

  The amount of the base used for the reaction is usually 0.5 to 20 mol, preferably 1 to 5 mol, relative to 1 mol of compound (Ib).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, ketones such as acetone and methyl isobutyl ketone; nitriles such as acetonitrile; ethyl acetate Esters such as; Halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; Ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons such as toluene; Aliphatics such as hexane and cyclohexane Hydrocarbons; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; or a mixed solvent thereof, preferably nitriles, halogenated hydrocarbons or ethers, More preferably, acetonitrile or salt It is methylene.

  The reaction temperature mainly varies depending on the raw material compound, the reaction reagent, and the type of solvent used, but is usually −90 ° C. to 200 ° C., and preferably 0 ° C. to 100 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is usually 5 minutes to 48 hours, preferably 15 minutes to 12 hours.

  In addition, this process can also use a well-known method as protection of a normal hydroxyl group.

  (Process J)

上記式中、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｘ及びＹは、前記と同意義を示し、
Ｒ^1aは、水素原子を除く他、Ｒ¹と同意義を示す。

In the above formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X and Y are as defined above,
R ^1a has the same meaning as R ¹ except for a hydrogen atom.

  In Step J, the 6-chloropyridazine derivative represented by the general formula (IVa) is reduced, oxidized, metalated, and reacted with an electrophile to introduce a substituent at the 6-position of the pyridazine ring. Further, it is a step of producing a compound in which the hydroxyl group represented by the compound (Ii) or general formula (XVIII) of the present invention is protected by chlorination and substitution reaction with an oxygen nucleophile. In this step, the protecting group is removed to produce the compound (Ij) of the present invention.

(Process J-1)
Step J-1 is a compound wherein R ¹ is a chlorine atom in the compound (IV) and (IVa), the presence of a solvent or absence, by reacting with a reducing agent, wherein R ¹ is hydrogen in the compound (IV) In this step, compound (IVb), which is an atom, is produced.

  The reducing agent used in the reaction is not particularly limited as long as it can reduce the chlorine atom on the aromatic ring. For example, it can be a reducing agent used in a normal hydrogenation reaction, preferably a hydrogen-palladium catalyst. It is.

  In the case of hydrogenation reaction in this step, the hydrogen pressure is usually 1 atm to 100 atm, preferably 1 to 3 atm.

  The amount of palladium used for the hydrogenation reaction is usually 0.001 to 10 mol, preferably 0.01 to 1 mol, relative to 1 mol of compound (IVa).

  The hydrogenation reaction is preferably performed in the presence of a base.

  The base used is not particularly limited as long as it usually shows a pH of 8 or more. For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkalis such as sodium carbonate, potassium carbonate and cesium carbonate Metal carbonates; metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; aqueous ammonia; triethylamine, tri-n-butylamine, diisopropylethylamine Fatty tertiary amines such as: 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) Group cyclic tertiary amines; pyridine, collidine, 4- (N, N-dimethyl) Pyridine) such as mino) pyridine; or organometallic bases such as butyllithium, sec-butyllithium, lithium diisopropylamide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, etc. Is ammonia water or aliphatic tertiary amines, more preferably ammonia water or triethylamine.

  The amount of the base used in the reaction is usually 0.1 to 100 mol, preferably 1 to 3 mol, relative to 1 mol of compound (IVa).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butanol; acetone, methyl isobutyl ketone Ketones such as acetonitrile; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; aliphatic hydrocarbons such as hexane and cyclohexane; or a mixed solvent thereof, preferably Is alcohol, yo Preferably methanol or ethanol.

  The reaction temperature mainly varies depending on the raw material compound, the reaction reagent, and the type of solvent used, but is usually −90 ° C. to 200 ° C., and preferably 0 ° C. to 100 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is usually 5 minutes to 48 hours, preferably 15 minutes to 12 hours.

(Process J-2)
Step J-2 is a step of producing pyridazine N-oxide represented by general formula (XV) by oxidizing compound (IVb) with an oxidizing agent in the presence or absence of a solvent.

  This process can be performed according to process B-1 or C-1.

(Process J-3)
Step J-3 is a step of producing the compound (XVI) of the present invention by reacting the compound (XV) with a metallating agent in the presence or absence of a solvent and then reacting with an electrophile. is there.

  This process can be performed according to the process G-1.

(Process J-4)
Step J-4 is a step of producing compound (XVII) by reacting compound (XVI) with phosphorus oxychloride in the presence or absence of a solvent.

  This step is the same as step B-3 or C-2.

(Process J-5)
In Step J-5, compound (XVII) is reacted with an oxygen nucleophile represented by the general formula (VI) in the presence or absence of a solvent, and optionally in the presence of a base, to give a compound of the present invention ( This is a step of producing a compound in which the hydroxyl group represented by Ii) or general formula (XVIII) is protected.

  This step is the same as step A-3, B-4 or C-3.

(Process J-6)
Step J-6 is a step for producing the compound (Ij) of the present invention by removing the protecting group for the hydroxyl group of the compound (XVIII).

  This step is the same as Step A-4, B-5, C-4, D-2, E-3, F-2 or G-2.

  (Process K)

上記式中、Ｒ^1a、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｘ及びＹは、前記と同意義を示す。

In the above formula, R ^1a , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X and Y are as defined above.

  In step K, the 6-chloropyridazine derivative of the present invention represented by the general formula (Ik) or the 6-chloropyridazine derivative protected by the hydroxyl group represented by the general formula (XIX) is oxidized, dechlorinated, and then It is a step of producing a compound in which the hydroxyl group represented by the compound (Ii) of the present invention or the general formula (XVIII) is protected by introducing an electrophile after metalation and finally reducing the compound. XVIII) is a process for producing the compound (Ij) of the present invention by removing the protecting group.

(Process K-1)
In step K-1, compound (Ik) or compound (XIX) is oxidized with an oxidizing agent in the presence or absence of a solvent to give an N-oxypyridazine compound represented by general formula (Il) or (XX) Is a process of manufacturing.

  This process can be performed according to process B-1, C-1, or J-2.

(Process K-2)
In Step K-2, N-oxide compound (Il) or (XX) in which the pyridazine ring 6-position is a chlorine atom is reacted with a reducing agent in the presence or absence of a solvent, whereby the pyridazine ring 6-position is This is a step for producing an N-oxide compound (Im) or (XXI) which is a hydrogen atom.

  This step can be performed according to step J-1.

(Process K-3)
In Step K-3, the compound (Im) or (XXI) is reacted with a metallizing agent in the presence or absence of a solvent and then reacted with an electrophile, whereby the compound (In) of the present invention or In this step, the hydroxyl group represented by the general formula (XXII) is protected.

  This process can be performed according to the process G-1 or J-3.

(Process K-4)
Step K-4 is performed by reacting the N-oxide derivative represented by the general formula (In) or (XXII) with phosphorus trichloride or phosphorus tribromide in the presence or absence of a solvent. This is a step for producing a compound in which the hydroxyl group represented by compound (Ii) or general formula (XVIII) is protected.

  The amount of phosphorus trichloride or phosphorus tribromide used is usually 0.5 to 100 mol, preferably 1 to 20 mol, relative to 1 mol of compound (In) or (XXII).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting materials to some extent. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane; diethyl ether, tetrahydrofuran, dioxane Ethers such as toluene; aromatic hydrocarbons such as toluene; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; aliphatic hydrocarbons such as hexane, cyclohexane and heptane; or These may be mixed solvents, preferably halogenated hydrocarbons, and more preferably chloroform.

  The reaction temperature mainly varies depending on the raw material compound, the reaction reagent, and the type of solvent used, but is usually −90 ° C. to 200 ° C., and preferably 0 ° C. to 100 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is generally 5 minutes to 24 hours, preferably 15 minutes to 6 hours.

(Process K-5)
Step K-5 is a step for producing the compound (Ij) of the present invention by removing the protecting group for the hydroxyl group of the compound (XVIII).

  This step is the same as step A-4, B-5, C-4, D-2, E-3, F-2, G-2 or J-6.

  (Process L)

上記式中、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｘ及びＹは、前記と同意義を示し、
Ｒ^1bは、水素原子及びハロゲン原子を除く他、Ｒ¹と同意義を示す。

In the above formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X and Y are as defined above,
R ^1b has the same meaning as R ¹ except for a hydrogen atom and a halogen atom.

  In step L, a 6-chloropyridazine derivative represented by the general formula (Ik) or (XIX) is reacted with an organometallic compound to thereby produce a hydroxyl group represented by the present compound (Io) or the general formula (XXIII). Is a step for producing a protected compound, and further is a step for producing the compound (Ip) of the present invention by removing the protecting group of compound (XXIII).

(Process L-1)
In Step L-1, compound (Ik) or (XIX) is reacted with an organometallic compound in the presence or absence of a solvent and in the presence of a metal catalyst to give a compound of the present invention (Io) or general formula ( XXIII) is a step of producing a compound in which the hydroxyl group is protected.

The organometallic compound used is not particularly limited as long as it is used for the cross-coupling reaction in which the R ^1b group is substituted with a chlorine atom. For example, organic compounds such as methyl magnesium chloride, ethyl magnesium bromide, and phenyl magnesium chloride are used. Magnesium compounds; organozinc compounds such as phenylzinc chloride; organoaluminum compounds such as (diisobutyl) (1-hexenyl) aluminum; (vinyl) trimethyltin, (1-ethoxyvinyl) tributyltin, (2-furyl) tributyltin, Organotin compounds such as (2-thienyl) tributyltin; organoboron compounds such as phenylboronic acid; organosilicate compounds such as trimethylvinylsilicon-tris (dimethylamino) sulfonium difluorotrimethylsilicate; It can be potassium cyanide, and acetylene compounds such as trimethylsilylacetylene and phenylacetylene can also be used in the reaction in the presence of amines such as triethylamine in the same manner as the above organometallic compounds, and are preferably organotin compounds or organoboron compounds. .

  The amount of the organometallic compound used in the reaction is usually 0.5 to 10 mol, preferably 1 to 2 mol, relative to 1 mol of compound (Ik) or (XIX).

  The metal catalyst used in this step is not particularly limited as long as it is used for the cross coupling reaction, and is, for example, a nickel catalyst or a palladium catalyst.

  The amount of the metal catalyst used in the reaction is usually 0.0001 to 10 mol, preferably 0.01 to 0.5 mol, relative to 1 mol of compound (Ik) or (XIX).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butanol; acetone, methyl isobutyl ketone Ketones such as acetonitrile; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; aliphatic hydrocarbons such as hexane and cyclohexane; organic amines such as triethylamine and pyridine; or these Mixing Agents and are obtained, preferably ethers, aromatic hydrocarbons or amides, more preferably ether, tetrahydrofuran, toluene or dimethylformamide.

  The reaction temperature mainly varies depending on the raw material compound, the reaction reagent, and the type of solvent used, but is usually −90 ° C. to 200 ° C., and preferably 0 ° C. to 130 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is generally 5 minutes to 48 hours, preferably 15 minutes to 24 hours.

(Process L-2)
Step L-2 is a step of producing the compound (Ip) of the present invention by removing the protecting group for the hydroxyl group of the compound (XXIII).

  This step is the same as step A-4, B-5, C-4, D-2, E-3, F-2, G-2, J-6 or K-5.

  (Process M)

上記式中、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｘ及びＹは、前記と同意義を示す。

In the above formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X and Y are as defined above.

  Step M is represented by the present compound (Iq) or general formula (XXIV) by cyanating a 6-position unsubstituted pyridazine N-oxide derivative represented by general formula (Im) or (XXI). This is a step of producing a compound in which the hydroxyl group is protected, and further, a step of producing the compound (Ir) of the present invention by removing the protecting group of the compound (XXIV).

(Process M-1)
Step M-1 is represented by the present compound (Iq) or general formula (XXIV) by reacting compound (Im) or (XXI) with a cyanating agent in the presence or absence of a solvent. This is a process for producing a compound in which a hydroxyl group is protected.

  This step can be performed according to a known Reissert-Henze reaction (JOC, 48, 1983, 1375 to 1377; Heterocycles, 15, 1981, 981 to 984; Synthesis, 1983, 316 to 319, etc.).

(Process M-2)
Step M-2 is a step of producing the compound (Ir) of the present invention by removing the protecting group for the hydroxyl group of the compound (XXIV).

  This step is the same as steps A-4, B-5, C-4, D-2, E-3, F-2, G-2, J-6, K-5 or L-2.

  (Process N)

上記式中、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｘ及びＹは、前記と同意義を示す。

In the above formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X and Y are as defined above.

  In Step N, the 6-chloropyridazine derivative represented by the general formula (Ik) or (XIX) is dechlorinated to protect the hydroxyl group represented by the present compound (Is) or the general formula (XXV). This is a step for producing the compound (It) of the present invention by removing the protecting group of the compound (XXV).

(Process N-1)
In Step N-1, the compound (Ik) or (XIX) is reacted with a reducing agent in the presence or absence of a solvent to give a hydroxyl group represented by the present compound (Is) or the general formula (XXV). Is a process for producing a protected compound.

  This process can be performed according to process J-1 or K-2.

(Process N-2)
Step N-2 is a step of producing the compound (It) of the present invention by removing the protecting group for the hydroxyl group of the compound (XXV).

  This step is the same as step A-4, B-5, C-4, D-2, E-3, F-2, G-2, J-6, K-5, L-2 or M-2. It is.

  (Process O)

上記式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、前記と同意義を示す。

In the above formula, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above.

  In Step O, the 3,4-dichloropyridazine derivative represented by the general formula (XXVI) is reacted with the catechol derivative represented by the general formula (XXVII), and then hydrolyzed to give the compound (Iu) of the present invention. It is a manufacturing process.

(Step O-1)
In Step O-1, compound (XXVI) is reacted with compound (XXVII) in the presence or absence of a solvent, and optionally in the presence of a base, to produce a condensed compound represented by general formula (XXVIII). It is a process.

  This step can be performed according to step A-1, B-2, D-1 or E-2, and the amount of the base used is usually 1 to 10 mol per 1 mol of compound (XXVI). Yes, preferably 2 to 6 mol.

(Process O-2)
Step O-2 is a step of producing the compound (Iu) of the present invention by hydrolyzing the compound (XXVIII).

  This step can be performed according to the case where Y is a hydrogen atom in Step A-3, B-4 or C-3, and the reaction temperature is preferably 80 ° C to 100 ° C.

  (Process P)

上記式中、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｘ及びＹは、前記と同意義を示す。

In the above formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X and Y are as defined above.

  In Step P, the 6-position of the 4,6-dichloropyridazine derivative represented by the general formula (Va) is selectively hydrolyzed to form a compound (XXIX), and then brominated at 4 and 6 positions with phosphorus oxybromide. Then, a process for producing a compound in which the hydroxyl group represented by the compound (Iv) or the general formula (XXXI) of the present invention is protected by selectively reacting an oxygen nucleophile at the 4-position, XXXI) is a process for producing the compound (Iw) of the present invention by removing the protecting group.

(Process P-1)
In Step P-1, the compound (Va) is hydrolyzed in the presence or absence of a solvent in the presence of an acid to selectively convert the 6-position chlorine atom to a hydroxyl group, and is represented by the general formula (XXIX). This is a process for producing a compound to be produced.

  The acid used is not particularly limited as long as it is an acid having a pH of 6 or less. For example, organic acids such as formic acid, acetic acid, succinic acid, propionic acid, succinic acid, maleic acid, fumaric acid, benzoic acid; hydrogen fluoride; Mineral acids such as acids, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid; or Lewis acids such as aluminum chloride, iron chloride, titanium chloride, boron trifluoride, etc. Preferred are organic acids, and more preferred are formic acid or acetic acid.

  This step is preferably performed in the presence of an acid metal salt.

  The metal salt of the acid used is, for example, an alkali metal salt of an organic acid such as sodium formate, potassium formate, lithium acetate, sodium acetate, potassium acetate, cesium acetate, sodium benzoate; magnesium formate, calcium formate, magnesium acetate, Alkaline earth metal salts of organic acids such as calcium acetate and magnesium benzoate; Alkali metal salts or alkaline earth metal salts of carbonic acid such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; Sodium fluoride, potassium fluoride, sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide, sodium sulfate, sodium hydrogen sulfate, potassium sulfate, potassium hydrogen sulfate, magnesium sulfate, sodium phosphate, Binatto hydrogen phosphate Or alkali metal salts of mineral acids such as sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, etc., preferably alkali metals of organic acids A salt, more preferably sodium formate, potassium formate, sodium acetate or potassium acetate.

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butanol; acetone, methyl isobutyl ketone Ketones such as acetonitrile; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethylsulfoxide; organic acids such as formic acid, acetic acid and propionic acid; or a mixed solvent thereof, preferably , Water, nitriles, ethers, amino S, a sulfoxide or an organic acid, more preferably water, acetonitrile, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, formic acid or acetic acid.

  The reaction temperature varies depending on the raw material compound, the reaction reagent, and the type of solvent used, but is usually -90 ° C to 200 ° C, and preferably 0 ° C to 150 ° C.

  The reaction time mainly varies depending on the reaction temperature, the raw material compound, the reaction reagent, and the type of solvent used, but is usually 5 minutes to 24 hours, and preferably 15 minutes to 12 hours.

(Process P-2)
Step P-2 is a step of producing compound (XXX) by reacting compound (XXIX) with phosphorus oxybromide in the presence or absence of a solvent.

  The amount of phosphorus oxybromide used in this step is usually 0.5 to 100 mol, preferably 1 to 10 mol, relative to 1 mol of compound (XXIX).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, ketones such as acetone and methyl isobutyl ketone; nitriles such as acetonitrile; ethyl acetate Esters such as; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene; dimethylformamide and dimethylacetamide Amides; Sulfoxides such as dimethyl sulfoxide; Aliphatic hydrocarbons such as hexane and cyclohexane; or a mixed solvent thereof, preferably halogenated hydrocarbons, and more preferably Methylene chloride and chloroform.

  While the reaction temperature varies depending on the raw material compound, reaction reagent, solvent and the like, it is generally -90 ° C to 200 ° C, preferably 0 ° C to 100 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the kind of solvent used, it is generally 5 minutes to 72 hours, preferably 30 minutes to 24 hours.

(Process P-3)
In Step P-3, the compound (XXX) is reacted with an oxygen nucleophile represented by the general formula (VI) in the presence or absence of a solvent, and optionally in the presence of a base, to give a compound of the present invention ( Iv) or a process for producing a compound in which a hydroxyl group represented by formula (XXXI) is protected.

  This step is the same as step A-3, B-4, C-3 or J-5.

(Process P-4)
Step P-4 is a step of producing the compound (Iw) of the present invention by removing the protecting group for the hydroxyl group of the compound (XXXI).

  This step is a step A-4, B-5, C-4, D-2, E-3, F-2, G-2, J-6, K-5, L-2, M-2 or N -2.

  (Process Q)

上記式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、前記と同意義を示す。一般式（ＸＸＸＩＩ）で表される化合物は酸素求核剤、硫黄求核剤、窒素求核剤を示す。Ｚは酸素求核剤、硫黄求核剤または窒素求核剤からプロトンを除いた置換基であり、例えば、アルコキシ基、チオアルコキシ基、ジアルキルアミノ基等であり得る。

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above. The compound represented by the general formula (XXXII) represents an oxygen nucleophile, a sulfur nucleophile, and a nitrogen nucleophile. Z is a substituent obtained by removing a proton from an oxygen nucleophile, sulfur nucleophile or nitrogen nucleophile, and may be, for example, an alkoxy group, a thioalkoxy group, a dialkylamino group, or the like.

  Step Q is a step of converting the hydroxy compound of the present invention represented by the general formula (Ib) into the ester derivative of the present invention represented by the general formula (Iy).

(Process Q-1)
Step Q-1 is a step of producing the compound (Ix) of the present invention by reacting the compound (Ib) of the present invention with phosgene in the presence or absence of a solvent.

  The amount of phosgene used in the reaction is usually 0.5 to 10 mol, preferably 1 to 3 mol, relative to 1 mol of compound (Ib).

  The reaction is preferably carried out in the presence of a base.

  The base used is not particularly limited as long as it usually shows a pH of 8 or more. For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkalis such as sodium carbonate, potassium carbonate and cesium carbonate Metal carbonates; metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; aliphatic triions such as triethylamine, tributylamine and diisopropylethylamine Tertiary amines; aliphatic cyclic tertiary amines such as 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) Of pyridine, collidine, 4- (N, N-dimethylamino) pyridine Or an organometallic base such as n-butyllithium, sec-butyllithium, lithium diisopropylamide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, and preferably an alkali metal Hydroxides, alkali metal carbonates, aliphatic tertiary amines, aliphatic cyclic tertiary amines or pyridines, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate , Triethylamine, 1,4-diazabicyclo [2.2.2] octane (DABCO), pyridine or 4- (N, N-dimethylamino) pyridine.

  The amount of the base used for the reaction is usually 0.5 to 20 mol, preferably 1 to 5 mol, relative to 1 mol of compound (Ib).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water, acetone, ketones such as methyl isobutyl ketone; nitriles such as acetonitrile; acetic acid Esters such as ethyl; Halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; Ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons such as toluene; Hexane and cyclohexane Aliphatic hydrocarbons; Amides such as dimethylformamide and dimethylacetamide; Sulfoxides such as dimethylsulfoxide; or a mixed solvent thereof, preferably nitriles, halogenated hydrocarbons, ethers, Water-ester mixed solvent, water-halogenated Hydrogenated mixed solvent, water-ether mixed solvent, water-aromatic hydrocarbon mixed solvent or water-aliphatic hydrocarbon mixed solvent, more preferably acetonitrile, methylene chloride or water-toluene mixed solvent It is.

  The reaction temperature mainly varies depending on the raw material compound, the reaction reagent, and the type of solvent used, but is usually −90 ° C. to 200 ° C., and preferably 0 ° C. to 100 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is usually 5 minutes to 48 hours, preferably 15 minutes to 12 hours.

(Process Q-2)
Step Q-2 comprises reacting the compound (Ix) of the present invention with a nucleophile represented by the general formula (XXXII) in the presence or absence of a solvent, and optionally in the presence of a base. This is a process for producing the inventive compound (Iy).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water, acetone, ketones such as methyl isobutyl ketone; nitriles such as acetonitrile; acetic acid Esters such as ethyl; Halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; Ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons such as toluene; Hexane and cyclohexane Aliphatic hydrocarbons; Amides such as dimethylformamide and dimethylacetamide; Sulfoxides such as dimethylsulfoxide; or a mixed solvent thereof, preferably nitriles, halogenated hydrocarbons, ethers, Water-ester mixed solvent, water-halogenated Hydrogenated mixed solvent, water-ether mixed solvent, water-aromatic hydrocarbon mixed solvent or water-aliphatic hydrocarbon mixed solvent, more preferably acetonitrile, methylene chloride or water-toluene mixed solvent It is.

  The base used is not particularly limited as long as it usually shows a pH of 8 or more. For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkalis such as sodium carbonate, potassium carbonate and cesium carbonate Metal carbonates; metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; aliphatic triions such as triethylamine, tributylamine and diisopropylethylamine Tertiary amines; aliphatic cyclic tertiary amines such as 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) Of pyridine, collidine, 4- (N, N-dimethylamino) pyridine Or an organometallic base such as n-butyllithium, sec-butyllithium, lithium diisopropylamide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, and preferably an alkali metal Hydroxides, alkali metal carbonates, aliphatic tertiary amines, aliphatic cyclic tertiary amines or pyridines, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate , Triethylamine, 1,4-diazabicyclo [2.2.2] octane (DABCO), pyridine or 4- (N, N-dimethylamino) pyridine.

  The amount of the base used for the reaction is usually 0.5 to 20 mol, and preferably 1 to 5 mol with respect to 1 mol of compound (Ix).

  The nucleophile (XXXII) used in the reaction is not particularly limited as long as it replaces the chlorine atom of the chlorocarbonate (Ix), but examples of the oxygen nucleophile include methanol, ethanol and propanol. Or alcohols such as phenol and 4-chlorophenol, and examples of sulfur nucleophiles include thiols such as methanethiol, ethanethiol and propanethiol; The nitrogen nucleophile can be, for example, methylamine, dimethylamine, diethylamine, methyl (t-butyl) amine, methyl (cyanomethyl) amine, methyl (ethoxycarbonylmethyl). Amine, bis (cyanomethyl) amine, bis (2-cyanoethyl) a Aliphatic chain such as bis (ethoxycarbonylmethyl) amine, bis (2-methoxyethyl) amine, bis (2-ethoxyethyl) amine, bis (2-chloroethyl) amine, N, O-dimethylhydroxylamine Amines; aromatic amines such as methyl (phenyl) amine, methyl (pyridyl) amine; aziridine, azetidine, pyrrolidine, piperidine, morpholine, thiomorpholine, N-methylpiperazine, N-phenylpiperazine, 2-methoxycarbonylpyrrolidine 3-hydroxypyrrolidine, 4-bromopiperidine, 4-methylpiperidine, 2,2,6,6-tetramethylpiperidine, 2-ethoxycarbonylpiperidine, 4-ethoxycarbonylpiperidine, 2,6-dimethylmorpholine, 1,2 , 3,4-Tetra Aliphatic cyclic amines such as droisoquinoline and 1,3-oxazolidine; aromatic cyclic amines such as carbazole and 2,5-dimethylpyrrole, preferably methanol, ethanol, methanethiol, ethanethiol, Methylamine, dimethylamine, methyl (cyanomethyl) amine, methyl (ethoxycarbonylmethyl) amine, bis (cyanomethyl) amine, bis (2-cyanoethyl) amine, bis (ethoxycarbonylmethyl) amine, bis (2-methoxyethyl) amine Bis (2-ethoxyethyl) amine, bis (2-chloroethyl) amine, N, O-dimethylhydroxylamine, methyl (pyridyl) amine, azetidine, pyrrolidine, piperidine, morpholine, thiomorpholine, N-methylpiperazine, 2- Metoki Cicarbonylpyrrolidine, 3-hydroxypyrrolidine, 2-ethoxycarbonylpiperidine, 4-ethoxycarbonylpiperidine, 2,6-dimethylmorpholine, 1,3-oxazolidine, 2,5-dimethylpyrrole, more preferably dimethylamine , Methyl (cyanomethyl) amine, methyl (ethoxycarbonylmethyl) amine, bis (cyanomethyl) amine, bis (ethoxycarbonylmethyl) amine, bis (2-methoxyethyl) amine, bis (2-ethoxyethyl) amine, N, O -Dimethylhydroxylamine, azetidine, morpholine, thiomorpholine, N-methylpiperazine, 2-methoxycarbonylpyrrolidine, 3-hydroxypyrrolidine, 2-ethoxycarbonylpiperidine, 4-ethoxycarbonylpiperidine, , 6-dimethyl-morpholine.

  The amount of the nucleophile used for the reaction is usually 0.5 to 20 mol, preferably 1 to 5 mol, relative to 1 mol of compound (Ix).

  The reaction temperature mainly varies depending on the raw material compound, the reaction reagent, and the type of solvent used, but is usually −90 ° C. to 200 ° C., and preferably 0 ° C. to 100 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is usually 5 minutes to 48 hours, preferably 15 minutes to 12 hours.

Note that after the completion of each reaction step, prior to the subsequent step, functional groups in R ¹ to R ⁷ of the target compound of each step, as long as it is within the scope of the definition of R ¹ to R ^7, according to a conventional method Functional group conversion is possible.

In Steps A-1, B-2, D-1 and E-2, when at least one of R ¹ and R ² is a chlorine atom, depending on the reaction conditions, R ¹ or R ² Of chlorine atom

によって置換されることがあり、更に、工程Ａ−３、Ｂ−４、Ｃ−３及びＪ−５において、Ｒ¹及びＲ²の少なくともいずれか１つが塩素原子の場合、反応条件によっては、当該工程において、Ｒ¹又はＲ²の塩素原子が基OYによって置換されることがあり、更にまた、工程Ｐ−３において、ピリダジン環６位の臭素原子が、又は、Ｒ²が塩素原子の場合は、Ｒ²の塩素原子が、基OYによって置換されることがある。

Further, in Steps A-3, B-4, C-3 and J-5, when at least one of R ¹ and R ² is a chlorine atom, depending on the reaction conditions, In the process, the chlorine atom of R ¹ or R ² may be substituted by the group OY. Furthermore, in process P-3, when the bromine atom at the 6-position of the pyridazine ring or R ² is a chlorine atom, , R ² chlorine atom may be replaced by the group OY.

  The starting compounds (II) of steps A and B are either commercially available or, for example, Industrial Chemical Journal, 1971, 74, 7, 1490-1491; Tetrahedron, 1999 55, 52, 15067-15070; The Journal of Organic Chemistry, 1963, 28, 218-221, or according to these methods.

  Starting compounds (X) of steps D and E are, for example, Helvetica Chimica Acta, 1956, 39, 1755-1664; Monatshefte fur Chemie, 1968, 99, 15 -81 (in this description the letter u in Monatshefte fur Chemie represents u-umlaut); German Patent 1,912,472, filed November 12, 1970 (filed April 12, 1969) (Ger.Offen. 1,912,472 , 12 Nov 1970, Appl. 12 Mar 1969).

  As the phenol compound (III) used in Steps A, B, D and E, a commercially available product can be used, or it can be produced using a known method or according to a known method.

  2-cyclopropylphenol can be produced, for example, by the method described in Bioorganic & Medicinal Chemistry, 1997, Vol. 5, No. 10, pp. 1959-1968.

  2- (2,2-dichlorocyclopropyl) phenol is described, for example, in Heterocycles, 1998, Vol. 48, No. 7, pages 1373-1394 From 2- (methoxymethoxy) benzaldehyde, which can be produced by the method of The Journal of Organic Chemistry, 1963, 28, 1128 or Synthetic Communications 1985, 15, 10, 855-864 (conversion of carbonyl group to olefin, Wittig reaction) and Synthetic Communications, 1999, 29, 23, 4101 -4112 (conversion of olefins to dichlorocyclopropane) and tetrahedron, 1998, 54, 15861-15869 Conversion to phenol of methoxy methyl ether, can be prepared analogously to demethoxylation methylation reaction).

  4-indanol is, for example, a method described in Organic Reactions, 1941, Vol. 1, page 155 from commercially available 4-hydroxy-1-indanone. It can be produced according to (Clemmensen reduction).

  1-benzofuran-7-ol, for example, is commercially available from 7-methoxy-1-benzofuran from Bioscience, Biotechnology and Biochemistry (Bioscience, Biotechnology, and Biochemistry), 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-Fluoro-6-isopropylphenol is, for example, from commercially available 2-isopropyl-6-nitrophenol, Organic Synthesis, Collective Volume Vol. 4, 836-838 (conversion of phenol to phenyl methyl ether, methylation reaction), Liebigs Annalen der Chemie, 1975, 608, 128 (method of nitro group) (Reduction reaction to amino group), Synthesis, 1989, method described on page 905 (conversion reaction of amino group to fluorine atom), and bioscience, biotechnology and biochemistry (Bioscience, Biotechnolory, and Biochemistry) 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (phenone of phenyl methyl ether) In accordance with the conversion to desulfurization, demethylation reaction).

  2-chloro-6-cyclopropylphenol is, for example, from commercially available 2-chlorophenol, Tetrahedron Letters, 1998, Vol. 39, 2947 page (bromination reaction of phenol) and Helvetica Chimica Acta, 1992, vol. 75, page 457 (conversion of phenol to phenylmethoxymethyl ether, methoxymethylation) Reaction) and the method described in Tetrahedron Letters, 2000, 41, 4251-4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction), and tetrahedron (Tetrahedron) 1998, 54, 15861-15869 (conversion to phenylmethoxymethyl ether phenol, demethoxymethylation reaction).

  2-Bromo-6-methylphenol can be produced, for example, by the method described in Tetrahedron Letters, 1998, Vol. 39, page 2947.

  2-cyclopropyl-6-methylphenol is, for example, from commercially available 2-hydroxy-3-methylbenzaldehyde, organic synthesis, Collective Volume, Volume 4, pages 836-838 (conversion of phenol to phenyl methyl ether, methylation reaction) and The Journal of Organic Chemistry, 1963 28, 1128 or Synthetic Communications, 1985, 15, 10, 855-864 (conversion of carbonyl group to olefin, Wittg reaction) and Organic Reactions ( Organic Reactions), 1973, 20, pp. 1-131, or Journal of the American Chemical Society (J ournal of the American Chemical Society), 1975, 97, 3428 or Tetrahedron Letters, 1998, 39, 8621-8624 (construction of cyclopropyl groups, Simmons-Smith reaction) ), And the method described in Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or JP 11-322755 (to the phenol of phenyl methyl ether) Conversion, demethylation reaction).

  2- (2,2-dichlorocyclopropyl) -6-methylphenol (2- (2,2-dichlorocyclopropyl) -6-methylphenol) is, for example, commercially available 2-hydroxy-3-methylbenzaldehyde (2-hydroxy- 3-methylbenzaldehyde), organic synthesis, collective volume, volume 4, pages 836-838 (conversion of phenol to phenyl methyl ether, methylation reaction), and the The method described in The Journal of Organic Chemistry, 1963, 28, 1128 or Synthetic Communications, 1985, 15, 10, 855-864 (olefins of carbonyl group) Conversion, Wittig reaction) and the method described in Synthetic Communications, 1999, 29, 23, pages 4101-4112 (Conversion of olefin to dichlorocyclopropane) and organic synthesis, collective volume, Vol. 5, pages 412-414 (conversion of phenylmethyl ether to phenol, demethylation) Can be produced according to the following reaction.

  2-cyclopropyl-3,5-dimethylphenol, for example, is commercially available from Tetrahedron Letters than 3,5-dimethylphenol. ), 1998, 39, page 2947 (phenol bromination reaction), and organic synthesis, collective volume, volume 4, pages 836-838 ( (Phenol to phenylmethyl ether, methylation reaction) and the method described in Tetrahedron Letters, 1979, 20, 4159-4162 or Tetrahedron, 1997, 53 Vol. 43, pages 14599-14614 or Bulletin of the Chemical Society of Japan, 1971, vol. 44, pages 2237-2248 (aromatic Conversion reaction of bromide to aromatic aldehyde) and The Journal of Organic Chemistry, 1963, 28, 1128 or Synthetic Communications, 1985, 15, 10 855-864 (conversion of carbonyl group to olefin, Wittg reaction) and Organic Reactions, 1973, 20, pp. 1-131 or Journal of the American Chemical Society (Journal of the American Chemical Society), 1975, 97, 3428 or Tetrahedron Letters, 1998, 39, 8621-8624 (construction of cyclopropyl groups, Simmons-Smith reaction) Bioscience, Biotechnology, and Biochemistry ), 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  5-Methyl-4-indanol is, for example, from the commercially available 4-hydroxy-1-indanone, Journal of the American Chemical Society (Journal of the American Chemical Society), 1946, vol. 68, page 2487 (reduction of carbonyl group, Wolff-Kishner reduction) and Tetrahedron Letters, 1998, vol. 39, page 2947. The method (bromination reaction of phenol) and the method described in Helvetica Chimica Acta, 1992, 75, 457 (conversion of phenol to phenylmethoxymethyl ether, methoxymethylation reaction), and Helvetica Chimica Acta, 1990, Vol. 73, pages 417-425 (conversion reaction of bromo group to methyl group), and tetrahedron, 1998, vol. 54 , 15861- It can be produced according to the method described on page 15869 (conversion of phenylmethoxymethyl ether to phenol, demethoxymethylation reaction).

  2,3,5,6-tetramethylphenol (2,3,5,6-tetramethylphenol) is, for example, a tetrahedron from commercially available 2,3,5-trimethylphenol (2,3,5-trimethylphenol). It can be produced by the method described in Letters (Tetrahedron Letters), 1989, volume 30, page 5215.

  After completion of each reaction step, the target compound in each step can be collected from the reaction mixture according to a conventional method. For example, it can be obtained by neutralizing the reaction mixture as appropriate, or by removing insoluble matters by filtration, adding an organic solvent immiscible with water, washing with water, and distilling off the solvent. If necessary, the obtained target compound can be further purified by a conventional method such as recrystallization, reprecipitation or chromatography.

  The compound (I) of the present invention can be converted into a salt. These salts are included in the present invention as long as they can be used as herbicides for agriculture and horticulture.

  Salts of the compound (I) of the present invention include, for example, alkali metal salts such as lithium, sodium and potassium; alkaline earth metal salts such as magnesium and calcium; aluminum salts; transition metal salts such as iron and copper; ammonium and trimethylammonium Amine salts such as triethylammonium, tetramethylammonium and pyridinium; inorganic mineral salts such as hydrochloride, sulfate and phosphate; or organic acid salts such as formate, acetate, toluenesulfonate and oxalate It can be.

  When the pyridazine derivative becomes the acid component of the salt, the salt can be produced, for example, by mixing the pyridazine derivative and a base in the presence or absence of a solvent and distilling off the solvent.

  The base used is not particularly limited as long as it is a base exhibiting a pH of 8 or higher. For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; sodium carbonate, potassium carbonate and cesium carbonate are used. Alkali metal carbonates; metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide; alkali metal salts of organic acids such as sodium acetate, potassium acetate, sodium formate, potassium formate; sodium hydride, hydrogenation Alkali metal hydrides such as potassium; alkali metals such as sodium and potassium; aliphatic tertiary amines such as triethylamine, tributylamine and diisopropylethylamine; 1,4-diazabicyclo [2.2.2] octane (DABCO ), 1,8-diazabicyclo 5.4.0] Aliphatic cyclic tertiary amines such as undec-7-ene (DBU); pyridines such as pyridine, collidine, 4- (N, N-dimethylamino) pyridine; lithium amide, sodium Metal amides such as amides; or organometallic bases such as butyl lithium, s-butyl lithium, lithium diisopropylamide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide.

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butanol; acetone, methyl isobutyl ketone Ketones such as acetonitrile; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons such as; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; or a mixed solvent thereof.

  When the pyridazine derivative becomes the base component of the salt, the salt can be produced, for example, by mixing the pyridazine derivative and an acid in the presence or absence of a solvent and distilling off the solvent.

  The acid to be used is not particularly limited as long as it is an acid having a pH of 6 or less, for example, inorganic mineral acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid; or formic acid, acetic acid, toluene It can be an organic acid such as sulfonic acid, succinic acid, benzoic acid.

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butanol; acetone, methyl isobutyl ketone Ketones such as acetonitrile; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons such as; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; or a mixed solvent thereof.

  The composition of the present invention includes various weeds that are problematic in paddy fields, for example, grasses such as Tainubie, broadleaf weeds such as Azena, azetope, kakashigusa, Mizo-Hakobe, Abnome, Himehisohagi, Konagi; It shows herbicidal activity against cyprinid weeds such as Spodoptera litura and Shizui; and weeping weeds such as Urikawa, Omodaka and Heramodaka, and does not show any phytotoxicity to rice.

  The synergistic effect of the present invention is recognized in a wide range of mixing ratios, and the ratio of compound (C) is usually 0.01 to 50 parts by mass, compound (P), (Q), 1 part by mass of compound (I), A useful herbicide can be prepared by mixing (B) at a ratio of 0.1 to 50 parts by mass, and the mixing ratio is preferably 0.05 to 10 parts by mass of compound (C) and compound (P). , (Q), (B) is 0.2 to 20 parts by mass, and more preferably, compound (C) is 0.1 to 5 parts by mass, and compounds (P), (Q), and (B) are 0.5 to 10 parts by mass. Part. The herbicide of the present invention thus completed can obtain a high herbicidal effect by soil treatment or foliage treatment before and after germination of weeds.

  In the present invention, a 3-phenoxy-4-pyridazinol derivative and a second herbicidal active compound, or a third herbicidal active compound may be mixed and sprayed as one preparation, and the above active ingredients are not mixed and sprayed simultaneously. Alternatively, one active ingredient may be sprayed first and the other active ingredient may be sprinkled later. Moreover, the order of spreading is arbitrary.

  The composition of the present invention may be sprayed with the active ingredient itself, or mixed with a carrier and other auxiliary agents as necessary, and is usually used as a herbicide, for example, a powder, a coarse powder, a fine granule, It is prepared and used in granules, wettable powders, emulsions, aqueous suspensions, granular wettable powders, oil suspensions, paddy throwers and the like. As used herein, a carrier refers to a synthetic or natural inorganic or organic substance mixed in a herbicide to help reach the plant of an active ingredient compound or to facilitate storage, transportation or handling of the active ingredient. means.

  Suitable solid carriers include, for example, clays represented by the kaolinite group, montmorillonite group, attapulgite group, etc .; talc, mica, phyllite, pumice, vermiculite, gypsum, dolomite, diatomaceous earth, magnesium lime, phosphorus lime , Zeolite, anhydrous silicic acid, synthetic calcium silicate, kaolin, bentonite, calcium carbonate and other inorganic substances; soy flour, tobacco powder, walnut powder, wheat flour, wood flour, starch, crystalline cellulose, and other plant organic substances; coumarone resin , Petroleum resins, alkyd resins, polyvinyl chloride, polyalkylene glycols, ketone resins, ester gums, copal gums, dammar gums, and other synthetic or natural polymer compounds; waxes such as carnauba wax, paraffin wax, beeswax; or urea possible.

  Suitable liquid carriers are, for example, paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, white oil; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, methylnaphthalene; carbon tetrachloride, Chlorinated hydrocarbons such as chloroform, trichloroethylene, monochlorobenzene, chlorotoluene; ethers such as dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone; ethyl acetate, amyl acetate, ethylene glycol acetate , Esters such as diethylene glycol acetate, dibutyl maleate and diethyl succinate; methanol, hexanol, ethylene glycol, diethylene glycol, Rohekisanoru, alcohols such as benzyl alcohol, ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether, ether alcohols such as diethylene glycol butyl ether; dimethylformamide, polar solvents such as dimethyl sulfoxide; or, may be water.

  Surfactants used for emulsification, dispersion, wetting, spreading, bonding, disintegration control, active ingredient stabilization, fluidity improvement, rust prevention, plant absorption promotion, etc. are ionic or nonionic But you can.

  Suitable nonionic surfactants include, for example, fatty acid sucrose esters, lauryl alcohol, stearyl alcohol, ethylene oxide polymerization adducts of higher aliphatic alcohols such as oleyl alcohol, and ethylene oxide polymerization of alkylphenols such as isooctylphenol and nonylphenol. Oxidized ethylene polymerized adducts of adducts, alkyl naphthols such as butyl naphthol and octyl naphthol, oxidized ethylene polymerized adducts of higher fatty acids such as palmitic acid, stearic acid and oleic acid, and oxidation of mono- or dialkyl phosphoric acids such as stearyl phosphate dilauryl phosphate Ethylene polymerized adducts, ethylene oxide polymerized adducts of higher aliphatic amines such as dodecylamine and stearamide, higher fatty acid esters of polyhydric alcohols such as sorbitan and ethylene oxide polymerized adducts thereof And it can be exemplified copolymers of ethylene oxide and propylene oxide.

  Suitable anionic surfactants include, for example, alkyl sulfate salts such as sodium lauryl sulfate and oleyl alcohol sulfate amine salt, fatty acid salts such as sodium dioctyl sulfosuccinate, sodium oleate and sodium stearate, isopropyl naphthalene, and the like. Examples thereof include alkylaryl sulfonates such as sodium sulfonate, sodium methylenebisnaphthalene sulfonate, sodium lignin sulfonate, and sodium dodecylbenzene sulfonate.

  Examples of suitable cationic surfactants include higher aliphatic amines, quaternary ammonium salts, alkylpyridinium salts, and the like.

  Furthermore, the herbicide of the present invention has other components such as gelatin, gum arabic, casein, albumin, glue, sodium alginate, polyvinyl alcohol, carboxymethylcellulose, for the purpose of improving the properties of the preparation and enhancing the biological effect. Polymer compounds such as methylcellulose and hydroxymethylcellulose, thixotropic agents such as sodium polyphosphate and bentonite, and other auxiliary agents can also be contained.

  For example, powders and coarse powders usually contain 0.1 to 25 parts by mass of an active ingredient, and the balance is a solid carrier.

  The wettable powder and the granular wettable powder, for example, usually contain 1 to 90 parts by mass of the active ingredient, and the balance is a solid carrier and a dispersion wetting agent. If necessary, a protective colloid, a thixotropic agent and an antifoaming agent. Is added. These preparations are suspended and dispersed in water when stirred in water.

  Granules and fine granules contain, for example, usually 0.1 to 35 parts by mass of an active ingredient, and the remainder is mostly a solid carrier. The active ingredient compound is uniformly mixed with the solid carrier, or is fixed or adsorbed uniformly on the surface of the solid carrier, and the particle diameter is usually 0.2 to 1.5 mm.

  Emulsions usually contain, for example, 1 to 70 parts by weight of an active ingredient compound, which contains 5 to 20 parts by weight of an emulsifier, the balance being a liquid carrier, and other components such as rust inhibitors as required. Of supplements are added.

  An aqueous suspension or oil suspension is a suspension or emulsification dispersion of an active ingredient in water or an organic solvent with a high boiling point using an appropriate surfactant. To maintain stability over time.

  The paddy throwing agent is an active ingredient formulated into an appropriate dosage form such as powder, granule, tablet, emulsion, bulk tablet, etc., and if necessary, these are packaged in a water-soluble film or container. In use, several to several hundreds of these are used as they are in the paddy field.

  When the composition of the present invention thus prepared in various dosage forms is treated with soil before or after germination of weeds in paddy fields, for example, 1 g to 1000 g, preferably 10 g to 300 g as an active ingredient per 10a. By treating the weeds, weeds can be effectively controlled.

  As a method for treating the composition of the present invention, it can be usually formulated and treated with soil, foliage or flooding before germination of weeds or within about one month after emergence. Soil treatment includes soil surface treatment, soil admixing treatment, etc., and foliage treatment includes treatment from the top of the plant body, extreme treatment that treats only weeds so as not to adhere to crops, The flooding treatment includes spraying of granules and flowables and irrigation treatment on the water surface.

  Other herbicides can be blended with the herbicide of the present invention in order to broaden the herbicidal spectrum.

  The herbicide of the present invention can be used by mixing with, for example, plant growth regulators, fungicides, insecticides, acaricides, nematicides or fertilizers.

  Examples, preparation examples and test examples of the present invention will be described below in detail, but the present invention is not limited to these. In the following formulation examples, “%” indicates mass%.

Example 1
6-Chloro-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 2)
(1) 3-Chloro-6- (2-methylphenoxy) pyridazine (Step A-1)
A mixture of 278.7 g (1.87 mol) of 3,6-dichloropyridazine, 202.3 g (1.87 mol) of 2-methylphenol and 259 g (1.87 mol) of potassium carbonate was heated and stirred at 160 ° C. for 6 hours. The reaction mixture was cooled to 70 ° C. and 2 L of ethyl acetate was added. The mixture was washed successively with 1 mol / L aqueous sodium hydroxide solution (4 × 500 mL), water (4 × 500 mL) and saturated brine (50 mL), and dried over anhydrous magnesium sulfate. The solvent was distilled off, and isopropyl ether was added to the residue for crystallization. Crystals were collected by filtration to obtain 234.2 g (1.06 mol, yield 56.7%) of 3-chloro-6- (2-methylphenoxy) pyridazine.
(2) 4,6-Dichloro-3- (2-methylphenoxy) pyridazine (Step A-2)
3-Chloro-6- (2-methylphenoxy) pyridazine (234.2 g, 1.06 mol) obtained in (1) was dissolved in phosphorus oxychloride (1.85 L), and 76.7 g (1.08 mol) of chlorine gas was added to this solution. Was blown in over 4 hours. Nitrogen gas was blown into the reaction mixture to remove excess chlorine gas, and then phosphorus oxychloride was distilled off. The residue was dissolved in ethyl acetate (1.5 L), washed successively with water (4 × 500 mL) and saturated brine (200 mL), and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was washed with 500 mL of hexane to obtain 193.1 g of a crude product. This crude product was recrystallized from a mixed solvent of hexane-ethyl acetate (400 mL-240 mL) to obtain 114.4 g (0.448 mol, yield 42.3%) of 4,6-dichloro-3- (2-methylphenoxy) pyridazine. It was.
(3) 6-chloro-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 2, step A-3)
100.0 g (0.392 mol) of 4,6-dichloro-3- (2-methylphenoxy) pyridazine obtained by (2) was dissolved in 1,4-dioxane (1 L), and sodium hydroxide (purity 96 %, 19.6 g, 0.470 mol) aqueous solution (water 400 mL) and tetrabutylammonium chloride 1.09 g (4.78 mmol) were added and heated to reflux for 4 hours. The reaction mixture was concentrated under reduced pressure to a total volume of about 100 mL. To this residue was added an aqueous sodium hydroxide solution (dissolved in 13.1 g of sodium hydroxide in 1.4 L of water) and 500 mL of ethyl acetate. The aqueous layer was washed with ethyl acetate (3 × 200 mL), and adjusted to pH 5 by adding concentrated hydrochloric acid under ice cooling. The precipitated solid was collected by suction filtration, washed with 1 L of water, and air-dried. The obtained solid was recrystallized from acetonitrile to obtain 34.4 g (0.145 mol, yield 37.0%) of 6-chloro-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 2). The organic layer was dried over magnesium sulfate and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (YMC GEL, SIL60, 350 / 250mesh, hexane-ethyl acetate, gradient), and 13.5 g of 6-chloro-3,4-bis (2-methylphenoxy) pyridazine was obtained. (0.0414 mol, yield 10.5%).
¹ H-NMR (200 MHz, DMSO-d ₆ ) δ ppm: 7.35-7.08 (4H, m), 6.84 (1H, br.s), 2.11 (3H, s).
Melting point (° C): 211-213.

(Example 2)
6-Chloro-3- (2-cyclopropylphenoxy) -4-pyridazinol (Compound No. 4)
(1) Mixture of 6-chloro-3- (2-cyclopropylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-cyclopropylphenoxy) pyridazine 1-oxide (step B-2)
25.3 g (189 mmol) of 2-cyclopropylphenol, 1,4-dioxane (120 mL) and dimethyl sulfoxide (120 mL) were mixed, and 23.2 g (207 mmol) of potassium tert-butoxide was added to this mixture under ice cooling. Stir for 10 minutes. To this mixture, 32.0 g (194 mmol) of 3,6-dichloropyridazine 1-oxide, which is a known compound, was added and left at room temperature for 5 days. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient) to give 6-chloro-3- (2-cyclopropylphenoxy) pyridazine 1-oxide and 3-chloro-6- ( 43.3 g (165 mmol, yield 87.3%) of a mixture of 2-cyclopropylphenoxy) pyridazine 1-oxide was obtained.
(2) 4,6-Dichloro-3- (2-cyclopropylphenoxy) pyridazine (Step B-3)
43.3 g (165 mmol) of a mixture of 6-chloro-3- (2-cyclopropylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-cyclopropylphenoxy) pyridazine 1-oxide obtained by (1) , Chloroform (30 mL) and phosphorus oxychloride 18.0 mL (194 mmol) were mixed and the mixture was heated to 60 ° C. to dissolve. This was stirred at room temperature overnight and concentrated. The residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient) to obtain 32.5 g (116 mmol, yield 70.3%) of 4,6-dichloro-3- (2-cyclopropylphenoxy) pyridazine.
(3) 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinol (Compound No. 4, step B-4)
Dissolve 3,2.5 g (116 mmol) of 4,6-dichloro-3- (2-cyclopropylphenoxy) pyridazine obtained in (2) in dimethyl sulfoxide (500 mL) and add 84 mL of 10% (W / V) aqueous sodium hydroxide solution. (210 mmol) was added and stirred at room temperature overnight. The reaction mixture was poured into ice-cold 1 mol / L aqueous sodium hydroxide and washed with ether. The aqueous layer was acidified with hydrochloric acid, and the precipitated solid was collected by filtration and washed with water. Acetonitrile was added to the resulting solid and heated. Allowed to cool overnight and the crystals were collected by filtration (14.04 g). The filtrate was concentrated and the residue was recrystallized from ethanol to obtain 2.64 g of crystals. These crystals were combined to obtain 16.7 g (63.5 mmol, yield 54.7%) of 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinol (Compound No. 4).
¹ H-NMR (200 MHz, DMSO-d ₆ ) δppm: 7.28-6.97 (4H, m), 6.82 (1H, s), 1.89-1.77 (1H, m), 0.87-0.73 (2H, m), 0.73- 0.58 (2H, m).
Melting point (° C): 229-231.

(Example 3)
6-Chloro-3- [2- (2,2-dichlorocyclopropyl) phenoxy] -4-pyridazinol (Compound No. 5)
(1) 2- (Methoxymethoxy) benzaldehyde Commercial salicylaldehyde (5.01 g, 41.1 mmol) was dissolved in N, N-dimethylformamide (20 mL), and this solution was dissolved in ice-cooled 60% sodium hydride (1.80 g, 45.0 mmol). After stirring for 10 minutes under ice cooling, 3.43 mL (45.2 mmol) of chloro (methoxy) methane was slowly added dropwise and stirred for 1 hour under ice cooling. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 6.54 g (39.4 mmol, yield 95.9) of 2- (methoxymethoxy) benzaldehyde. %)Obtained.
(2) 1- (methoxymethoxy) -2-vinylbenzene In a nitrogen atmosphere, 877 mg (21.9 mmol) of 60% sodium hydride washed with hexane was suspended in dry dimethyl sulfoxide (10 mL). After stirring with heating at 85 ° C. for 30 minutes, the solution was returned to room temperature and further a solution of 7.83 g (21.9 mmol) of methyl (triphenyl) phosphonium bromide in dry dimethyl sulfoxide (20 mL) was slowly added dropwise under ice cooling. After stirring at room temperature for 15 minutes, a solution of 3.02 g (18.2 mmol) of 2- (methoxymethoxy) benzaldehyde obtained in (1) in dry dimethyl sulfoxide (9 mL) was added dropwise and stirred at room temperature for 15 minutes. The reaction mixture was poured into water and extracted with diethyl ether. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 2.54 g (15.5 mmol) of 1- (methoxymethoxy) -2-vinylbenzene. Yield 85.2%).
(3) 1- (2,2-Dichlorocyclopropyl) -2- (methoxymethoxy) benzene 305 mg (1.86 mmol) of 1- (methoxymethoxy) -2-vinylbenzene obtained from (2) was added to chloroform (12 mL) To this solution, 5 mL (63 mmol) of 50% aqueous sodium hydroxide solution was added dropwise, followed by 54.1 mg (0.237 mmol) of benzyl (triethyl) ammonium chloride and stirred overnight at room temperature. The reaction mixture was poured into water and extracted with chloroform. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, using 3 plates, developed with ethyl acetate: hexane = 1: 2), and 1- (2, 387 mg (1.57 mmol, yield 84.4%) of 2-dichlorocyclopropyl) -2- (methoxymethoxy) benzene was obtained.
(4) 2- (2,2-dichlorocyclopropyl) phenol 203 mg (0.822 mmol) of 1- (2,2-dichlorocyclopropyl) -2- (methoxymethoxy) benzene obtained from (3) was added to methanol (5 mL In this solution, 0.1 mL of concentrated hydrochloric acid was added and stirred at 60 ° C. for 2 hours. After confirming the disappearance of the raw materials by thin layer chromatography, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 194 mg of a crude product of 2- (2,2-dichlorocyclopropyl) phenol.
(5) 6-chloro-3- [2- (2,2-dichlorocyclopropyl) phenoxy] pyridazine 1-oxide (step B-2)
The crude product of 2- (2,2-dichlorocyclopropyl) phenol obtained in (4), 194 mg, 1,4-dioxane (3 mL) and dimethyl sulfoxide (3 mL) were mixed, and this mixture was cooled with ice. 118 mg (1.05 mmol) of potassium tert-butoxide was added, and the mixture was stirred for 10 minutes. Thereto was added 157 mg (0.952 mmol) of 3,6-dichloropyridazine 1-oxide, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin layer chromatography (MERCK, 1.05744, 3 plates used, developed with ethyl acetate: hexane = 1: 2), and 6-chloro-3- [2 268 mg of a crude product of-(2,2-dichlorocyclopropyl) phenoxy] pyridazine 1-oxide was obtained.
(6) 4,6-dichloro-3- [2- (2,2-dichlorocyclopropyl) phenoxy] pyridazine (Step B-3)
268 mg of the crude product of 6-chloro-3- [2- (2,2-dichlorocyclopropyl) phenoxy] pyridazine 1-oxide obtained by (5) and 3 mL of phosphorus oxychloride were mixed, and this mixture was mixed at room temperature. Stir overnight. Water and dichloromethane were added to the reaction mixture and stirred for 30 minutes. The mixture was separated, and the organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed with ethyl acetate: hexane = 1: 2), and 4,6-dichloro-3- 162 mg (0.463 mmol, 3-step yield from 1- (2,2-dichlorocyclopropyl) -2- (methoxymethoxy) benzene, 56.3%) [2- (2,2-dichlorocyclopropyl) phenoxy] pyridazine Obtained.
(7) 6-Chloro-3- [2- (2,2-dichlorocyclopropyl) phenoxy] -4-pyridazinol (Compound No. 5, Step B-4)
4,6-dichloro-3- [2- (2,2-dichlorocyclopropyl) phenoxy] pyridazine obtained by (6) 162 mg (0.463 mmol), 1,4-dioxane (3 mL) and dimethyl sulfoxide (3 mL) To this mixture, 1.15 mL (2.30 mmol) of 2 mol / L aqueous sodium hydroxide solution was added and stirred overnight at room temperature. The reaction mixture was poured into water and acidified with dilute hydrochloric acid. This mixture was extracted with dichloromethane. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed with ethyl acetate) to give 6-chloro-3- [2- (2,2- 50.0 mg (0.151 mmol, yield 32.6%) of dichlorocyclopropyl) phenoxy] -4-pyridazinol (Compound No. 5) was obtained.
¹ H-NMR (200 MHz, CD ₃ OD) δppm: 7.55-7.15 (4H, m), 6.69 (1H, s), 2.90 (1H, dd, J = 10.6, 8.8Hz), 2.07-1.89 (2H, m ).
Melting point (° C): 158-163.

Example 4
6-Chloro-3- (2-methoxy-5-methylphenoxy) -4-pyridazinol (Compound No. 9)
(1) 6-chloro-3- (2-methoxy-5-methylphenoxy) pyridazine 1-oxide (step B-2)
167.5 mg (1.21 mmol) of commercially available 2-methoxy-5-methylphenol was dissolved in a mixed solvent of 1,4-dioxane (3 mL) and dimethyl sulfoxide (3 mL), and 142.8 mg (1.27 mmol) of potassium tert-butoxide was added to this solution. Then, 202.9 mg (1.23 mmol) of 3,6-dichloropyridazine 1-oxide was added and stirred overnight at room temperature. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed with ethyl acetate: hexane = 2: 1), and 6-chloro-3 226.5 mg (0.849 mmol, yield 70.2%) of-(2-methoxy-5-methylphenoxy) pyridazine 1-oxide was obtained.
(2) 4,6-Dichloro-3- (2-methoxy-5-methylphenoxy) pyridazine (Step B-3)
Dissolve 226.5 mg (0.849 mmol) of 6-chloro-3- (2-methoxy-5-methylphenoxy) pyridazine 1-oxide obtained in (1) in phosphorus oxychloride (1 mL) and stir this solution at room temperature overnight. did. Water and methylene chloride were added to the reaction solution, and the mixture was stirred for 30 minutes and extracted with methylene chloride. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed with ethyl acetate: hexane = 2: 1), and 4,6-dichloro 205.3 mg (0.720 mmol, yield 84.8%) of -3- (2-methoxy-5-methylphenoxy) pyridazine was obtained.
(3) 6-chloro-3- (2-methoxy-5-methylphenoxy) -4-pyridazinol (Compound No. 9, step B-4)
205.3 mg (0.720 mmol) of 4,6-dichloro-3- (2-methoxy-5-methylphenoxy) pyridazine obtained by (2) was mixed with 1,4-dioxane (5 mL) and dimethyl sulfoxide (5 mL) mixed solvent. Then, 1.8 mL (3.6 mmol) of a 2 mol / L aqueous sodium hydroxide solution was added to the solution, and the mixture was stirred overnight at room temperature. Water was added to the reaction mixture, diluted hydrochloric acid was added to adjust to pH 2, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (MERCK, 1.05744, 3 plates used, developed with ethyl acetate), and 6-chloro-3- (2-methoxy- 148.1 mg (0.555 mmol, yield 77.1%) of 5-methylphenoxy) -4-pyridazinol (Compound No. 9) was obtained.
¹ H-NMR (200 MHz, CD ₃ OD) δ ppm: 7.04-6.91 (3H, m), 6.66 (1H, s), 3.70 (3H, s), 2.27 (3H, s).
Melting point (° C): 126-134.

(Example 5)
6-Chloro-3- (2,6-dimethylphenoxy) -4-pyridazinol (Compound No. 14)
(1) 6-chloro-3- (2,6-dimethylphenoxy) pyridazine 1-oxide (step B-2)
268 mg (2.20 mmol) of 2,6-dimethylphenol, 1,4-dioxane (3 mL) and dimethyl sulfoxide (3 mL) were mixed, and 270 mg (2.41 mmol) of potassium tert-butoxide was added to the mixture under ice cooling. Stir for minutes. Thereto was added 370 mg (2.24 mmol) of 3,6-dichloropyridazine 1-oxide, and the mixture was stirred at room temperature for 10 hours and allowed to stand for 2 days. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, the residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient), and 350 mg (1.39 mmol, 6-chloro-3- (2,6-dimethylphenoxy) pyridazine 1-oxide was collected. Rate 63.1%).
(2) 4,6-Dichloro-3- (2,6-dimethylphenoxy) pyridazine (Step B-3)
6-chloro-3- (2,6-dimethylphenoxy) pyridazine 1-oxide 330 mg (1.31 mmol) obtained by (1) was mixed with dichloromethane (0.6 mL) and phosphorus oxychloride 0.60 mL (6.5 mmol), The mixture was stirred for 1 hour and left for another 5 days. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, the residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient), and 322 mg (1.20 mmol, yield) of 4,6-dichloro-3- (2,6-dimethylphenoxy) pyridazine 91.6%).
(3) 6-chloro-3- (2,6-dimethylphenoxy) -4-pyridazinol (Compound No. 14, step B-4)
300 mg (1.12 mmol) of 4,6-dichloro-3- (2,6-dimethylphenoxy) pyridazine obtained in (2) was dissolved in dimethyl sulfoxide (8 mL), and 10% (W / V) water was added to this solution. Sodium oxide aqueous solution 0.80mL (2.0 mmol) was added, and it stirred at room temperature overnight. Further, 0.80 mL (2.0 mmol) of 10% (W / V) aqueous sodium hydroxide solution was added, and after the disappearance of the raw materials, the reaction mixture was poured into ice-cold water. The mixture was acidified with hydrochloric acid and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient) and preparative thin layer chromatography (Merck, 1.05744, developed in dichloromethane: methanol = 9: 1), 128 mg (0.510 mmol, yield 45.5%) of 6-chloro-3- (2,6-dimethylphenoxy) -4-pyridazinol (Compound No. 14) was obtained.
¹ H-NMR (200 MHz, DMSO-d ₆ ) δ ppm: 7.18-7.05 (3H, m), 6.83 (1H, s), 2.05 (6H, s).
Melting point (° C): 214-215.

(Example 6)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol (Compound No. 16)
(1) 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-cyclopropyl-6-methylphenoxy) pyridazine 1-oxide (Step B- 2)
2-Cyclopropyl-6-methylphenol 221 mg (1.49 mmol) was mixed with 1,4-dioxane (2 mL) and dimethyl sulfoxide (2 mL). Under ice cooling, 184 mg (1.64 mmol) of potassium tert-butoxide was added to the mixture. Added and stirred for 10 minutes. Thereto was added 258 mg (1.56 mmol) of 3,6-dichloropyridazine 1-oxide, and the mixture was stirred at room temperature for 10 hours and allowed to stand for 3 days. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient) to give 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine 1-oxide and 3-chloro 222 mg (0.801 mmol, yield 53.8%) of a mixture of -6- (2-cyclopropyl-6-methylphenoxy) pyridazine 1-oxide was obtained.
(2) 4,6-Dichloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine (Step B-3)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-cyclopropyl-6-methylphenoxy) pyridazine 1-oxide obtained by (1) 210 mg (0.758 mmol) of the above mixture was dissolved in chloroform (1 mL). To this solution was added 0.106 mL (1.14 mmol) of phosphorus oxychloride, and most of the chloroform was distilled off with a nitrogen stream, followed by stirring at room temperature for 2 days. . Further, chloroform (2 mL) and 0.150 mL (1.62 mmol) of phosphorus oxychloride were added, and most of chloroform was distilled off with a nitrogen stream, followed by stirring for 3 hours. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, the residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient), and 167 mg (0.566 mmol) of 4,6-dichloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine was obtained. Yield 74.7%).
(3) 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol (Compound No. 16, step B-4)
150 mg (0.508 mmol) of 4,6-dichloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine obtained in (2) was dissolved in dimethyl sulfoxide (3 mL), and 10% (W / V ) A sodium hydroxide aqueous solution (0.37 mL, 0.925 mmol) was added, and the mixture was stirred at room temperature for 4 days. The reaction mixture was poured into ice-cold 5% aqueous sodium hydroxide and extracted with ether. The aqueous layer was acidified with hydrochloric acid and extracted with ether. The organic layer was dried and concentrated. The residue was purified by preparative thin layer chromatography (Merck, 1.05744, developed with dichloromethane: methanol = 20: 1), and 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4 114 mg (0.412 mmol, yield 81.1%) of pyridazinol (Compound No. 16) were obtained.
¹ H-NMR (200 MHz, DMSO-d ₆ ) δppm: 7.13-7.03 (2H, m), 6.84-6.79 (2H, m), 2.06 (3H, s), 1.83-1.68 (1H, m), 0.82- 0.72 (2H, m), 0.64-0.51 (2H, m).
Melting point (° C): 201-202.

(Example 7)
6-Chloro-3- [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] -4-pyridazinol (Compound No. 17)
(1) 1- (2,2-dichlorocyclopropyl) -2-methoxy-3-methylbenzene
2-Methoxy-1-methyl-3-vinylbenzene (304 mg, 2.05 mmol) was dissolved in chloroform (12 mL), and 50 mL of 50% aqueous sodium hydroxide solution (63 mmol) was added dropwise to this solution, followed by benzyl (triethyl) ammonium. 59.9 mg (0.263 mmol) of chloride was added and stirred at room temperature overnight. The reaction mixture was poured into water and extracted with chloroform. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed with hexane: ethyl acetate = 4: 1), and 1- (2, 390 mg (1.69 mmol, yield 82.4%) of 2-dichlorocyclopropyl) -2-methoxy-3-methylbenzene was obtained.
(2) 2- (2,2-dichlorocyclopropyl) -6-methylphenol 102 mg (0.442 mmol) of 1- (2,2-dichlorocyclopropyl) -2-methoxy-3-methylbenzene obtained from (1) ) Was dissolved in dichloromethane (5 mL), the solution was ice-cooled, and 0.045 mL (0.47 mmol) of boron tribromide was added dropwise with stirring. The reaction mixture was stirred for 2 hours under ice-cooling, poured into water, and extracted with dichloromethane. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 2 plates used, developed with hexane: ethyl acetate = 2: 1), and 2- (2, 76.9 mg (0.354 mmol, yield 80.1%) of 2-dichlorocyclopropyl) -6-methylphenol was obtained.
(3) 6-chloro-3- [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] pyridazine 1-oxide (step B-2)
198 mg (0.912 mmol) of 2- (2,2-dichlorocyclopropyl) -6-methylphenol obtained by (2) was mixed with 1,4-dioxane (3 mL) and dimethyl sulfoxide (3 mL). Under ice cooling, 113 mg (1.01 mmol) of potassium tert-butoxide was added and stirred for 10 minutes. Thereto was added 151 mg (0.915 mmol) of 3,6-dichloropyridazine 1-oxide, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed 3 times with hexane: ethyl acetate = 2: 1), and 6-chloro-3- 257 mg of a crude product of [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] pyridazine 1-oxide was obtained.
(4) 4,6-Dichloro-3- [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] pyridazine (Step B-3)
The crude product of 6-chloro-3- [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] pyridazine 1-oxide obtained in (3) was mixed with phosphorus oxychloride (3 mL). The mixture was stirred overnight at room temperature. Water and dichloromethane were added to the reaction mixture and stirred for 30 minutes. The mixture was separated, and the organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin layer chromatography (MERCK, 1.05744, 3 plates used, developed with hexane: ethyl acetate = 2: 1), and 4,6-dichloro-3- [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] pyridazine 209 mg (0.574 mmol, 2-step yield from 2- (2,2-dichlorocyclopropyl) -6-methylphenol, 62.9% )Obtained.
(5) 6-chloro-3- [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] -4-pyridazinol (Compound No. 17, Step B-4)
209 mg (0.574 mmol) of 4,6-dichloro-3- [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] pyridazine obtained by (4) was added to 1,4-dioxane (3 mL) and dimethyl The mixture was mixed with sulfoxide (3 mL), and 1.43 mL (2.86 mmol) of a 2 mol / L aqueous sodium hydroxide solution was added to the mixture and stirred overnight at room temperature. The reaction mixture was poured into water and acidified with dilute hydrochloric acid. This mixture was extracted with dichloromethane. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed with ethyl acetate) to give 6-chloro-3- [2- (2,2- 120 mg (0.349 mmol, yield 60.8%) of dichlorocyclopropyl) -6-methylphenoxy] -4-pyridazinol (Compound No. 17) was obtained.
¹ H-NMR (200MHz, CD ₃ OD) δppm: 7.25 (1H, br.d, J = 6.3Hz), 7.16 (1H, t, J = 7.7Hz), 6.98 (1H, d, J = 7.7Hz) , 6.72 (1H, s), 2.85 (1H, dd, J = 10.6, 8.8Hz), 2.22 (3H, s), 2.05-1.86 (2H, m).
Melting point (° C): 213-215.

(Example 8)
6-Chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 52, Step I-1)
53.4 mg (0.203 mmol) of 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinol (Compound No. 4) obtained according to Example 2 was dissolved in acetonitrile (3 mL). -Diazabicyclo [2.2.2] octane (23.1 mg, 0.206 mmol) was added, then 4-methylbenzenesulfonyl chloride (39.2 mg, 0.205 mmol) was added, and the mixture was stirred at room temperature for 1 hour and 30 minutes. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by preparative thin layer chromatography (MERCK, 1.05744, developed with ethyl acetate: hexane = 2: 1) to give 6-chloro-3- (2- 68.8 mg (0.165 mmol, 81.3% yield) of cyclopropylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 52) was obtained.
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.87 (2H, d, J = 8.1Hz), 7.58 (1H, s), 7.36 (2H, d, J = 8.1Hz), 7.26-7.11 (2H, m ), 6.97-6.93 (1H, m), 6.74-6.70 (1H, m), 2.45 (3H, s), 1.67-1.59 (1H, m), 0.71-0.56 (4H, m).
Physical property: Oily substance.

Example 9
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl ethoxy (methyl) carbamate (Compound No. 55, Step Q)
200 mg (0.722 mmol) of 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol was mixed with toluene (2 mL). While stirring under a nitrogen atmosphere, 150 μL (1.86 mmol) of pyridine and then 0.68 mL (0.734 mmol) of a 1.08 mol / L phosgenetoluene solution were added and stirred at room temperature for 20 minutes. This mixture was mixed with 150 μL of pyridine (1.86 mmol), O-ethyl-N-methylhydroxylamine hydrochloride 80.0 mg {0.717 mmol, Bioorganic & Medicinal Chemistry Letters, 2001, Vol. 11, No. 13. In the mixture of toluene (2 mL), and stirred at room temperature for 1 hour. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (using MERCK 1.05744 4 plates, developed with hexane: ethyl acetate = 2: 1), and 6-chloro-3- (2 96.0 mg (0.254 mmol, yield 35.4%) of -cyclopropyl-6-methylphenoxy) -4-pyridazinyl ethoxy (methyl) carbamate (Compound No. 55) was obtained.
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.54 (1H, s), 7.15-7.05 (2H, m), 6.90-6.80 (1H, m), 4.08 (2H, q, J = 7.0Hz), 3.35 (3H, s), 2.15 (3H, s), 1.84-1.65 (1H, m), 1.30 (3H, t, J = 7.0Hz), 0.80-0.55 (4H, m).
Melting point (° C): 82-83.

(Example 10)
6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 56, Step I)
70.0 mg (0.266 mmol) of 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinol was mixed with acetonitrile (2 mL), where 40.4 mg (0.360 mmol) of 1,4-diazabicyclo [2.2.2] octane was mixed. ) Was added and stirred. The mixture was ice-cooled, 51.3 mg (0.343 mmol) of 4-morpholinecarbonyl chloride was added, and the mixture was stirred for 1 hour under ice-cooling. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (MERCK, 1.05744, developed with ethyl acetate: hexane = 2: 1) to give 6-chloro-3- (2- 97.4 mg (0.259 mmol, 97.4% yield) of cyclopropylphenoxy) -4-pyridazinyl 4-morpholine carboxylate (Compound No. 56) was obtained.
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.58 (1H, s), 7.26-7.13 (2H, m), 7.13-7.05 (1H, m), 7.05-6.98 (1H, m), 3.79-3.63 ( 6H, m), 3.63-3.52 (2H, m), 1.92-1.81 (1H, m), 0.84-0.74 (2H, m), 0.72-0.61 (2H, m).
Physical properties: Pasty.

(Example 11)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1,3-oxazolidine-3-carboxylate (Compound No. 64, Step Q)
100 mg (0.361 mmol) of 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol was mixed with toluene (0.4 mL). While stirring, 0.20 mL (0.40 mmol) of 2 mol / L sodium hydroxide aqueous solution was added and stirred for 1 hour. Next, 0.35 mL (0.38 mmol) of a 1.08 mol / L phosgene toluene solution was added, and the mixture was stirred at room temperature for 1 hour. Further, 1,3-oxazolidine 50.0 mg {0.684 mmol, Agricultural and Biological Chemistry, 1991, 55, No. 1, can be produced by the method described on pages 37-43}, Stir at room temperature for 1 hour. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (using MERCK 1.05744, 2 hexanes: ethyl acetate = 2: 1), and 6-chloro-3- (2 52.7 mg (0.140 mmol, yield 38.8%) of -cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1,3-oxazolidine-3-carboxylate (Compound No. 64) was obtained.
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.15-7.08 (2H, m), 6.90-6.83 (1H, m), 5.07 (1H, s), 4.99 (1H, s) , 4.18-4.10 (2H, m), 3.77-3.72 (1H, m), 3.66-3.61 (1H, m), 2.14 (3H, s), 1.81-1.70 (1H, m), 0.78-0.68 (2H, m), 0.65-0.55 (2H, m).
Melting point (° C): 97-98.

In addition, the following compounds were produced by or according to the methods of Examples 1 to 11 above.

(Example 12)
6-Chloro-3- (2-iodophenoxy) -4-pyridazinol (Compound No. 1)
¹ H-NMR (200 MHz, CD ₃ OD) δ ppm: 7.89 (1H, dd, J = 7.7, 1.5 Hz), 7.45 (1H, td, J = 7.7, 1.5 Hz), 7.22 (1H, dd, J = 7.7 , 1.5Hz), 7.04 (1H, td, J = 7.7, 1.5Hz), 6.74 (1H, s).
Melting point (° C): 216-217.

(Example 13)
6-Chloro-3- (2-isopropylphenoxy) -4-pyridazinol (Compound No. 3)
¹ H-NMR (60MHz, DMF-d ₇ ) δppm: 7.60-7.00 (4H, m), 6.92 (1H, s), 3.11 (1H, septet, J = 7.0Hz), 1.18 (6H, d, J = 7.0Hz).
Melting point (° C): 183.

(Example 14)
6-Chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinol (Compound No. 6)
¹ H-NMR (200 MHz, DMSO-d ₆ ) δppm: 7.20 (1H, t, J = 7.3 Hz), 7.14 (1H, d, J = 7.3 Hz), 6.92 (1H, d, J = 7.3 Hz), 6.83 (1H, br.s), 2.92 (2H, t, J = 7.3Hz), 2.64 (2H, t, J = 7.3Hz), 2.00 (2H, quintet, J = 7.3Hz).
Melting point (° C): 230-232.

(Example 15)
3- (1-Benzofuran-7-yloxy) -6-chloro-4-pyridazinol (Compound No. 7)
¹ H-NMR (200 MHz, CD ₃ OD) δ ppm: 7.73 (1H, d, J = 2.2 Hz), 7.53 (1H, dd, J = 7.7, 1.4 Hz), 7.26 (1H, t, J = 7.7 Hz) , 7.15 (1H, dd, J = 7.7, 1.4 Hz), 6.90 (1H, d, J = 2.2 Hz), 6.76 (1H, s).
Melting point (° C): 201-202.

(Example 16)
6-Chloro-3- (2,5-dimethylphenoxy) -4-pyridazinol (Compound No. 8)
¹ H-NMR (90 MHz, CD ₃ OD) δ ppm: 7.16 (1H, d, J = 9.0 Hz), 7.08 (1H, d, J = 9.0 Hz), 6.90 (1H, s), 6.70 (1H, s) , 2.30 (3H, s), 2.10 (3H, s).
Melting point (° C): 80-83.

(Example 17)
6-Chloro-3- (2-fluoro-6-isopropylphenoxy) -4-pyridazinol (Compound No. 10)
¹ H-NMR (200MHz, DMSO-d ₆ ) δppm: 7.35-7.15 (3H, m), 6.89 (1H, br.s), 3.02 (1H, septet, J = 7.0Hz), 1.14 (6H, J = 7.0Hz).
Melting point (° C): 215-220.

(Example 18)
6-Chloro-3- (2-chloro-6-methylphenoxy) -4-pyridazinol (Compound No. 11)
¹ H-NMR (90 MHz, CD ₃ OD) δ ppm: 7.50-7.00 (3H, m), 6.75 (1H, s), 2.22 (3H, s).
Melting point (° C): 235.

(Example 19)
6-Chloro-3- (2-chloro-6-cyclopropylphenoxy) -4-pyridazinol (Compound No. 12)
¹ H-NMR (200 MHz, CD ₃ OD) δ ppm: 7.30 (1H, dd, J = 8.1, 1.5 Hz), 7.17 (1H, dd, J = 8.1, 7.7 Hz), 6.96 (1H, dd, J = 7.7 1.5Hz), 6.76 (1H, s), 2.00-1.84 (1H, m), 0.95-0.80 (2H, m), 0.70-0.60 (2H, m).
Melting point (° C): 224-225.

(Example 20)
3- (2-Bromo-6-methylphenoxy) -6-chloro-4-pyridazinol (Compound No. 13)
¹ H-NMR (200 MHz, DMSO-d ₆ ) δppm: 7.56 (1H, br.d, J = 7.7 Hz), 7.36 (1H, br.d, J = 7.7 Hz), 7.16 (1H, t, J = 7.7Hz), 6.92 (1H, br.s), 2.14 (3H, s).
Melting point (° C): 242-243.

(Example 21)
6-Chloro-3- (2-ethyl-6-methylphenoxy) -4-pyridazinol (Compound No. 15)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.12-6.97 (3H, m), 6.52 (1H, s), 2.37 (2H, q, J = 7.6Hz), 1.95 (3H, s), 1.04 (3H , t, J = 7.6Hz).
Physical properties: amorphous.

(Example 22)
3- (2-Allyl-6-methylphenoxy) -6-chloro-4-pyridazinol (Compound No. 18)
¹ H-NMR (270 MHz, CD ₃ OD) δppm: 7.17-7.10 (3H, m), 6.71 (1H, s), 5.95-5.73 (1H, m), 5.00-4.90 (2H, m), 3.26 (1H , d, J = 7.0Hz), 2.12 (3H, s).
Melting point (° C): 126-128.

(Example 23)
6-Chloro-3- (2-cyclopropyl-3,5-dimethylphenoxy) -4-pyridazinol (Compound No. 19)
¹ H-NMR (200 MHz, CD ₃ OD) δ ppm: 6.89 (1H, s), 6.73 (1H, s), 6.69 (1H, s), 2.39 (3H, s), 2.26 (3H, s), 1.45- 1.28 (1H, m), 0.78-0.67 (2H, m), 0.65-0.51 (2H, m).
Melting point (° C): 200-203.

(Example 24)
6-Chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinol (Compound No. 20)
^{1 H-NMR (200MHz, DMSO} -d 6) δppm: 7.11-7.01 (2H, m), 6.83 (1H, br.s), 2.88 (2H, t, J = 7.3Hz), 2.59 (2H, t, J = 7.3Hz), 2.06 (3H, s), 2.06-1.91 (2H, m).
Melting point (° C): 222-225.

(Example 25)
6-Chloro-3- (2,3,5,6-tetramethylphenoxy) -4-pyridazinol (Compound No. 21)
¹ H-NMR (200 MHz, CD ₃ OD) δ ppm: 6.88 (1H, s), 6.69 (1H, s), 2.22 (6H, s), 1.98 (6H, s).
Melting point (° C): 278-283.

(Example 26)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl acetate (Compound No. 22)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.39 (1H, s), 7.15-7.00 (2H, m), 6.90-6.75 (1H, m), 2.42 (3H, s), 2.12 (3H, s) , 1.90-1.67 (1H, m), 0.85-0.50 (4H, m).
Melting point (° C): 98-101.

(Example 27)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl pivalate (Compound No. 23)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.38 (1H, s), 7.15-7.05 (2H, m), 6.90-6.84 (1H, m), 2.13 (3H, s), 1.81-1.65 (1H, m), 1.41 (9H, s), 0.90-0.50 (4H, m).
Melting point (° C): 84-87.

(Example 28)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl ethyl succinate (Compound No. 24)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.08-6.92 (2H, m), 6.85-6.68 (1H, m), 6.55 (1H, s), 4.14 (2H, br.q, J = 7.1Hz) , 3.00 (1H, t, J = 7.0Hz), 2.76 (1H, t, J = 7.0Hz), 2.61 (2H, br.s), 1.98 (3H, s), 1.78-1.60 (1H, m), 1.25 (3H, t, J = 7.1Hz), 0.75-0.40 (4H, m).
Physical properties: amorphous.

(Example 29)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl benzoate (Compound No. 25)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.23-8.18 (2H, m), 7.75-7.50 (3H, m), 7.60 (1H, s), 7.30-7.08 (4H, m), 2.18 (3H, s).
Physical property: Oily substance.

(Example 30)
6-Chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl benzoate (Compound No. 26)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 8.20 (2H, d, J = 7.3Hz), 7.74-7.50 (4H, m), 7.26-7.01 (3H, m), 6.98-6.97 (1H, m) , 1.91-1.80 (1H, m), 0.83-0.57 (4H, m).
Physical properties: amorphous.

(Example 31)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl benzoate (Compound No. 27)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.24-8.20 (2H, m), 7.75-7.68 (1H, m), 7.67-7.52 (3H, m), 7.09-7.07 (2H, m), 6.87- 6.82 (1H, m), 2.16 (3H, s), 1.82-1.71 (1H, m), 0.75-0.71 (2H, m), 0.62-0.53 (2H, m).
Physical properties: amorphous.

(Example 32)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-bromobenzoate (Compound No. 28)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.20-8.05 (1H, m), 7.85-7.70 (1H, m), 7.59 (1H, s), 7.55-7.38 (2H, m), 7.15-7.00 ( 2H, m), 6.90-6.80 (1H, m), 2.17 (3H, s), 1.88-1.70 (1H, m), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 33)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl 2-methylbenzoate (Compound No. 29)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 8.35-8.08 (2H, m), 7.59 (1H, s), 7.68-7.00 (6H, m), 2.70 (3H, s), 2.21 (3H, s) .
Melting point (° C): 91-93.

(Example 34)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-methylbenzoate (Compound No. 30)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 8.20 (1H, d, J = 7.0Hz), 7.56 (1H, s), 7.52 (1H, d, J = 7.7Hz), 7.40-7.28 (2H, m ), 7.10-7.00 (2H, m), 6.90-6.88 (1H, m), 2.69 (3H, s), 2.16 (3H, s), 1.90-1.70 (1H, m), 0.82-0.65 (2H, m ), 0.65-0.50 (2H, m).
Physical property: Oily substance.

(Example 35)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-methoxybenzoate (Compound No. 31)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.09 (1H, dd, J = 7.9, 2.0Hz), 7.68-7.57 (1H, m), 7.59 (1H, s), 7.15-7.03 (4H, m) , 6.90-6.82 (1H, m), 3.96 (3H, s), 2.17 (3H, s), 1.96-1.72 (1H, m), 0.78-0.65 (2H, m), 0.65-0.51 (2H, m) .
Physical properties: Gummy.

(Example 36)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-methylbenzoate (Compound No. 32)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.05-8.00 (2H, m), 7.58 (1H, s), 7.55-7.38 (2H, m), 7.10-7.05 (2H, m), 6.88-6.80 ( 1H, m), 2.46 (3H, s), 2.16 (3H, s), 1.90-1.68 (1H, m), 0.80-0.50 (4H, m).
Physical property: Oily substance.

(Example 37)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-bromobenzoate (Compound No. 33)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.07 (2H, d, J = 8.6Hz), 7.70 (2H, d, J = 8.6Hz), 7.59 (1H, s), 7.12-7.03 (2H, m ), 6.89-6.82 (1H, m), 2.15 (3H, s), 1.83-1.67 (1H, m), 0.78-0.50 (4H, m).
Physical properties: amorphous.

(Example 38)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl 4-methylbenzoate (Compound No. 34)
^{1 H-NMR (60MHz, CDCl} 3) δppm: 8.07 (2H, d, J = 8.0Hz), 7.58 (1H, s), 7.40-7.03 (4H, m), 7.36 (2H, d, J = 8.0Hz ), 2.51 (3H, s), 2.23 (3H, s).
Melting point (° C): 105-108.

(Example 39)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methylbenzoate (Compound No. 35)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.10 (2H, d, J = 8.1Hz), 7.60 (1H, s), 7.34 (2H, d, J = 8.1Hz), 7.12-7.03 (2H, m ), 6.88-6.81 (1H, m), 2.46 (3H, s), 2.15 (3H, s), 1.85-1.71 (1H, m), 0.78-0.65 (2H, m), 0.62-0.52 (2H, m ).
Melting point (° C): 77.5-78.

(Example 40)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,5-dimethylbenzoate (Compound No. 36)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.99 (1H, s), 7.54 (1H, s), 7.37-7.30 (1H, m), 7.25-7.21 (1H, m), 7.13-7.05 (2H, m), 6.89-6.82 (1H, m), 2.63 (3H, s), 2.40 (3H, s), 2.16 (3H, s), 1.86-1.72 (1H, m), 0.80-0.70 (2H, m) , 0.62-0.54 (2H, m).
Physical property: Oily substance.

(Example 41)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3,5-dimethylbenzoate (Compound No. 37)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.82 (2H, s), 7.56 (1H, s), 7.32 (1H, s,), 7.13-7.04 (2H, m), 6.89-6.82 (1H, m ), 2.41 (6H, s), 2.16 (3H, s), 1.85-1.72 (1H, m), 0.80-0.70 (2H, m), 0.63-0.53 (2H, m).
Melting point (° C): 117-119.

(Example 42)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl isobutyl carbonate (Compound No. 38)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.49 (1H, s), 7.15-7.05 (2H, m), 6.89-6.82 (1H, m), 4.13 (2H, d, J = 6.6Hz), 2.14 (3H, s), 2.09 (1H, br. Septet, J = 7.0Hz), 1.88-1.68 (1H, m), 1.01 (6H, d, J = 7.0Hz), 0.78-0.52 (4H, m).
Melting point (° C): 72-74.

(Example 43)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl dimethyl carbamate (Compound No. 39)
¹ H-NMR (60 MHz, CDCl ₃ ) δ ppm: 7.55 (1H, s), 7.40-6.92 (4H, m), 3.10 (3H, s), 3.01 (3H, s), 2.19 (3H, s).
Melting point (° C): 107-109.

(Example 44)
6-Chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl dimethyl carbamate (Compound No. 40)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.22-6.98 (4H, m), 3.13 (3H, s), 3.04 (3H, s), 1.97-1.80 (1H, m) , 0.85-0.63 (4H, m).
Melting point (° C): 137-138.

(Example 45)
6-Chloro-3- (2,6-dimethylphenoxy) -4-pyridazinyl dimethyl carbamate (Compound No. 41)
¹ H-NMR (500 MHz, CDCl ₃ ) δ ppm: 7.56 (1H, s), 7.09 (3H, s), 3.15 (3H, s), 3.05 (3H, s), 2.13 (6H, s).
Melting point (° C): 149-150.

(Example 46)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl dimethyl carbamate (Compound No. 42)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.56 (1H, s), 7.13-7.05 (2H, m), 6.89-6.82 (1H, m), 3.16 (3H, s), 3.05 (3H, s) , 2.15 (3H, s), 1.85-1.71 (1H, m), 0.78-0.54 (4H, m).
Melting point (° C): 136-138.

(Example 47)
6-Chloro-3- (2,3,5,6-tetramethylphenoxy) -4-pyridazinyl dimethyl carbamate (Compound No. 43)
¹ H-NMR (500MHz, CDCl ₃ ) δppm: 7.55 (1H, s), 6.90 (1H, s), 3.15 (3H, s), 3.05 (3H, s), 2.23 (6H, s), 2.04 (6H , s).
Melting point (° C): 200 (sublimation).

(Example 48)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl 1-propanesulfonate (Compound No. 44)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.34-7.05 (4H, m), 3.48 (2H, t, J = 7.7Hz), 2.20 (3H, s), 2.10 (2H , sixtet, J = 7.7Hz), 1.14 (3H, t, J = 7.7Hz).
Melting point (° C): 72-73.

(Example 49)
6-Chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl 1-propanesulfonate (Compound No. 45)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.28-7.15 (2H, m), 7.12-6.99 (2H, m), 3.52-3.45 (2H, m), 2.17-1.98 ( 2H, m), 1.92-1.78 (1H, m), 1.11 (3H, t, J = 7.3Hz), 0.85-0.73 (2H, m), 0.69-0.60 (2H, m).
Physical properties: Pasty.

(Example 50)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-propanesulfonate (Compound No. 46)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.58 (1H, s), 7.18-7.05 (2H, m), 6.94-6.83 (1H, m), 3.53 (2H, t, J = 7.7Hz), 2.20 -2.00 (2H, m), 2.15 (3H, s), 1.82-1.67 (1H, m), 1.15 (3H, t, J = 7.7Hz), 0.80-0.50 (4H, m).
Melting point (° C): 70.5-71.5.

(Example 51)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl benzenesulfonate (Compound No. 47)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 8.10-7.83 (2H, m), 7.80-7.40 (3H, m), 7.59 (1H, s), 7.30-7.00 (3H, m), 6.90-6.60 ( 1H, m).
Melting point (° C): 91.5-92.

(Example 52)
6-Chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl benzenesulfonate (Compound No. 48)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.02-7.98 (2H, m), 7.78-7.70 (1H, m), 7.62-7.54 (2H, m), 7.58 (1H, s), 7.26-7.09 ( 2H, m), 6.98-6.93 (1H, m), 6.78-6.69 (1H, m), 1.68-1.54 (1H, m), 0.74-0.52 (4H, m).
Physical property: Oily substance.

(Example 53)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl benzenesulfonate (Compound No. 49)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.07-8.01 (2H, m), 7.80-7.71 (1H, m), 7.65-7.56 (2H, m), 7.60 (1H, s), 7.11-6.99 ( 2H, m), 6.80 (1H, dd, J = 4.4, 2.4Hz), 1.93 (3H, s), 1.61-1.45 (1H, m), 0.65-0.45 (4H, m).
Melting point (° C): 105-106.

(Example 54)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-chlorobenzenesulfonate (Compound No. 50)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.01-7.92 (2H, m), 7.62-7.53 (3H, m), 7.13-7.00 (2H, m), 6.85-6.77 (1H, m), 2.04 ( 3H, s), 1.58-1.45 (1H, m), 0.70-0.45 (4H, m).
Physical properties: Gummy.

(Example 55)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 51)
¹ H-NMR (60MHz, CDCl ₃ ) δppm: 7.83 (2H, d, J = 8.4Hz), 7.47 (2H, d, J = 8.4Hz), 7.32-6.95 (4H, m), 6.85-6.55 (1H m), 2.43 (3H, s), 1.98 (3H, s).
Melting point (° C): 102-104.

(Example 56)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 53)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.90 (2H, d, J = 8.1Hz), 7.60 (1H, s), 7.38 (2H, d, J = 8.1Hz), 7.11-7.01 (2H, m ), 6.80 (1H, dd, J = 6.6, 2.6Hz), 2.47 (3H, s), 1.93 (3H, s), 1.59-1.46 (1H, m), 0.64-0.45 (4H, m).
Melting point (° C): 85-87.

(Example 57)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methoxybenzenesulfonate (Compound No. 54)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.99-7.91 (2H, m), 7.61 (1H, s), 7.11-6.98 (4H, m), 6.80 (1H, dd, J = 2.6Hz, 6.6Hz ), 3.90 (3H, s), 1.95 (3H, s), 1.60-1.45 (1H, m), 0.70-0.45 (4H, m).
Physical properties: candy-like.

(Example 58)
6-Chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 57)
¹ H-NMR (500MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.19 (1H, t, J = 7.6Hz), 7.13 (1H, d, J = 7.6Hz), 6.94 (1H, d, J = 7.6Hz), 3.77-3.70 (4H, m), 3.70-3.66 (2H, m), 3.62-3.57 (2H, m), 2.97 (2H, t, J = 7.6Hz), 2.74 (2H, t, J = 7.6Hz), 2.06 (2H, quintet, J = 7.6Hz).
Melting point (° C): 136.

(Example 59)
6-Chloro-3- (2-chloro-6-methylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 58)
¹ H-NMR (270MHz, CDCl ₃ ) δppm: 7.65 (1H, s), 7.30-7.10 (3H, m), 3.75 (6H, s), 3.62 (2H, br.d, J = 4.6Hz), 2.23 (3H, s).
Melting point (° C): 90-92.

(Example 60)
3- (2-Bromo-6-methylphenoxy) -6-chloro-4-pyridazinyl 4-morpholinecarboxylate (Compound No. 59)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.67 (1H, s), 7.45 (1H, d, J = 7.6 Hz), 7.23 (1H, d, J = 7.6 Hz), 7.07 (1H, t, J = 7.6Hz), 3.80-3.73 (6H, m), 3.64-3.60 (2H, m), 2.24 (3H, s).
Physical properties: Pasty.

(Example 61)
6-Chloro-3- (2,6-dimethylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 60)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.10 (3H, s), 3.80-3.70 (6H, m), 3.62-3.58 (2H, m), 2.12 (6H, s) .
Melting point (° C): 86-87.

(Example 62)
6-Chloro-3- (2-ethyl-6-methylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 61)
¹ H-NMR (270MHz, CDCl ₃ ) δppm: 7.56 (1H, s), 7.20-7.07 (3H, m), 3.85-3.56 (8H, m), 2.47 (2H, q, J = 7.6Hz), 2.10 (3H, s), 1.14 (3H, t, J = 7.6Hz).
Melting point (° C): 110-115.

(Example 63)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 62)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.13-7.06 (2H, m), 6.90-6.83 (1H, m), 3.70-3.55 (8H, m), 2.14 (3H, s), 1.83-1.68 (1H, m), 0.80-0.65 (2H, m), 0.65-0.53 (2H, m).
Melting point (° C): 102.5-103.5.

(Example 64)
6-Chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 63)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.56 (1H, s), 7.05 (2H, s), 3.79-3.73 (4H, m), 3.73-3.67 (2H, m), 3.63-3.65 (2H, m), 2.92 (2H, t, J = 7.6 Hz), 2.67 (2H, t, J = 7.6 Hz), 2.14 (3H, s), 2.05 (2H, quintet, J = 7.6 Hz).
Physical properties: amorphous.

(Example 65)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-azetidine carboxylate (Compound No. 65)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.53 (1H, s), 7.13-7.02 (2H, m), 6.90-6.78 (1H, m), 4.38-4.05 (4H, m), 2.45-2.29 ( 2H, m), 2.15 (3H, s), 1.85-1.67 (1H, m), 0.80-0.50 (4H, m).
Melting point (° C): 134-136.

  Compound Nos. 1, 3, 6-8, 10-13, 15, and 18-20 and 21 are the compounds of Example 1, Example 2, Example 3, Example 4, Example 5, Example 6. Alternatively, it can be produced according to the method described in Example 7.

  Compounds Nos. 22 to 37, 44 to 53, and 54 can be produced according to the method described in Example 8 or Example 10.

Compounds Nos. 38 to 43, 57 to 63 and 65 can be produced according to the method described in Example 8, Example 9, Example 10 or Example 11.
(Formulation example 1)
Compound (10 parts by mass) of wettable powder compound number 16, Compound C (5 parts by mass), Carplex # 80D (manufactured by Shionogi & Co., Ltd., 10 parts by mass), Gohsenol GL05-S (manufactured by Nippon Synthetic Chemical Co., Ltd.) , 2 parts by mass), New Coal 291PG (dioctylsulfosuccinate sodium salt, manufactured by Nippon Emulsifier Co., Ltd., 0.5 parts by mass), Neogen Powder (Daiichi Kogyo Seiyaku Co., Ltd., 5 parts by mass), Radiolite # 200 ( Showa Chemical Industries, Ltd., 10 parts by mass) and H derivative (Keiwa Furnace Co., Ltd., 57.5 parts by mass) were thoroughly mixed. The mixture was pulverized with an air mill (SK-JET O MIZER model 0101, manufactured by Seishin Enterprise Co., Ltd.) to obtain a mixed wettable powder of Compound No. 16 (10%) and Compound B (5%).
(Formulation example 2)
Compound (10 parts by mass) of wettable powder compound number 35, Compound C (5 parts by mass), Compound P (10 parts by mass) Carplex # 80D (manufactured by Shionogi & Co., Ltd., 10 parts by mass), Gohsenol GL05-S (Nippon Synthetic Chemical Co., Ltd., 2 parts by mass), New Coal 291PG (Dioctylsulfosuccinate sodium salt, Nippon Emulsifier Co., Ltd., 0.5 parts by mass), Neogen Powder (Daiichi Kogyo Seiyaku Co., Ltd., 5 parts by mass) ), Radiolite # 200 (manufactured by Showa Chemical Industry Co., Ltd., 10 parts by mass) and H derivative (manufactured by Keiwa Furnace Co., Ltd., 47.5 parts by mass) were thoroughly mixed. Crush the mixture with an air mill (SK-JET O MIZER model 0101, manufactured by Seishin Enterprise Co., Ltd.) and mix and hydrate compound (35%), compound C (5%) and compound P (10%) An agent was obtained.
(Test Example 1)
Test of herbicidal effect and phytotoxicity to transplanted rice
After paddy soil was filled in 1 / 5000a Wagner pots, the seeds of Tainubie, firefly, and annual broad-leaved weeds (Azena and Kikashigusa) awakened to dormancy were mixed in 1 cm of the surface layer. In addition, a tuber of Mizugayatsuri and Urikawa, which had been awakened from dormancy, was planted, and a 2.2-leaf stage rice seedling was transplanted, submerged, and grown in a greenhouse. Three days after transplantation, the prescribed amount of wettable powder prepared according to Formulation Example 1 was diluted in water and treated with flooded soil, and 25 days later, herbicidal effects and phytotoxicity to transplanted rice were determined according to the following criteria. The results are shown in Table 2. In the table, “-” represents a composition not containing the active ingredient.

Criterion 0: Growth inhibition rate 0-15%
1: Growth inhibition rate 16-35%
2: Growth suppression rate 36-55%
3: Growth inhibition rate 56-75%
4: Growth inhibition rate 76-95%
5: Growth suppression rate 96-100%.

(Table 2) Herbicidal effect and phytotoxicity test for transplanted rice

（試験例2）
除草効果及び移植水稲に対する薬害の試験
1/5000aのワグネルポットに水田土壌を充填し、代掻きした後、休眠覚醒したタイヌビエ、ホタルイ及び一年生広葉雑草(アゼナ及びキカシグサ)の種子を表層1cmに混和した。また休眠覚醒したミズガヤツリ及びウリカワの塊茎を植え、さらに2.2葉期の水稲の苗を移植して、湛水状態とし、温室内で生育させた。タイヌビエが2.5葉期まで生育した時期に、製剤例1に準じて調製した水和剤の所定薬量を水に希釈して、湛水土壌処理し、14日後に試験例1に記載の判定基準に従って除草効果及び移植水稲に対する薬害を判定し、その結果を表３に示した。なお、表中「-」は、当該有効成分を含有しない組成物を表す。

（表３） 除草効果及び移植水稲に対する薬害の試験（ヒエ2.5葉期）

(Test Example 2)
Test of herbicidal effect and phytotoxicity to transplanted rice
After paddy soil was filled in 1 / 5000a Wagner pots, the seeds of Tainubie, firefly, and annual broad-leaved weeds (Azena and Kikashigusa) awakened to dormancy were mixed in 1 cm of the surface layer. In addition, a tuber of Mizugayatsuri and Urikawa, which had been awakened from dormancy, was planted, and a 2.2-leaf stage rice seedling was transplanted, submerged, and grown in a greenhouse. At the time when Tainubier grew to 2.5 leaf stage, the prescribed dosage of wettable powder prepared according to Formulation Example 1 was diluted with water and treated with flooded soil, and the criteria described in Test Example 1 after 14 days The herbicidal effect and phytotoxicity to transplanted rice were determined according to the results, and the results are shown in Table 3. In the table, “-” represents a composition not containing the active ingredient.

(Table 3) Test of herbicidal effect and phytotoxicity on transplanted rice (Hie 2.5 leaf stage)

Claims (19)

Formula (I):

[Wherein, R ¹ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₃ -C ₆ cycloalkyl group, a C ₂ -C ₆ alkenyl group, a cyano group, C ₂ -C ₇ alkylcarbonyl group, a di (C ₁ -C ₆ alkyl) carbamoyl group, which may be substituted phenyl group (the substituent is a substituent selected from substituent group a.), 5 or 6-membered heterocyclic group (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 to 2 nitrogen atoms), C _1- . A C ₆ alkoxy group, an optionally substituted phenoxy group (the substituent is a substituent selected from the following substituent group A) or an optionally substituted 5- or 6-membered heterocyclic oxy group {the heterocyclic ring is Contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and one or two more Of nitrogen atoms. The substituent is a substituent selected from the group consisting of an optionally substituted benzoyl group (the substituent is a substituent selected from the following substituent group A) and a C _{1 to} C ₆ alkyl group. },
R ² is a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a (C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkyl group, a benzoyl group which may be substituted (the substituent is the following substituent group) A substituent selected from A.), a C ₂ -C ₇ alkoxycarbonyl group, an optionally substituted phenoxy group (the substituent is a substituent selected from the following substituent group A), substituted. A good phenylthio group (the substituent is a substituent selected from the following substituent group A) or a tri (C ₁ -C ₆ alkyl) silicon group;
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom or an optionally substituted C ₁ -C ₆ alkyl group (the substituent is selected from the following substituent group B) A C ₂ -C ₆ alkenyl group which may be substituted (the substituent is a cyano group or a nitro group), a C ₂ -C ₆ alkynyl group, a C ₃ which may be substituted. -C ₆ cycloalkyl group (said substituent is a substituent selected from substituent group C.), C ₄ ~C ₁₀ bicycloalkyl group, a cyano group, a formyl group, C ₂ -C ₇ alkylcarbonyl group , A benzoyl group which may be substituted (the substituent is a substituent selected from the following substituent group A), a carboxyl group, a C _{2 to} C ₇ alkoxycarbonyl group, a carbamoyl group, di (C _{1 to} C _6). Alkyl) carbamoyl group, optionally substituted phenyl A group (the substituent is a substituent selected from the following substituent group A), an optionally substituted 3- to 6-membered heterocyclic group (the heterocyclic ring includes one nitrogen atom, (It contains an oxygen atom or a sulfur atom, may further contain 1 to 2 nitrogen atoms, and may be condensed with a benzene ring. The substituent is a substituent selected from the following substituent group E.) , amino group which may be substituted (the substituent is a substituent selected from substituent group D.), a nitro group, a hydroxyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ haloalkoxy group, (C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkoxy group, optionally substituted phenoxy group (the substituent is selected from the group consisting of _one hydroxyl group or a halogen atom and C ₁ -C ₆ alkoxy group Pyridazinyl substituted by 1 to 3 identical or different substituents A 5- to 6-membered heterocyclic oxy group which may be substituted (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 The substituent is a substituent selected from the following substituent group E.), a phenylsulfonyloxy group which may be substituted (the substituent is selected from the following substituent group A) A C ₁ -C ₆ alkylthio group, a C ₁ -C ₆ alkylsulfinyl group, a C ₁ -C ₆ alkylsulfonyl group or a tri (C ₁ -C ₆ alkyl) silicon group, or Each of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is a 3- to 6-membered cyclic hydrocarbon group which may be substituted together with the carbon atom to which each of the adjacent two is bonded (the cyclic carbon Hydrogen is the same or selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. It may be interrupted by a different one or two hetero atoms. The substituents are halogen atom, C ₁ -C ₆ alkyl group, a hydroxy C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, a oxo group, hydroxyimino group or a C ₁ -C ₆ alkoxyimino group If the C ₁ -C ₆ alkyl group is substituted, may form a new 3-membered ring with other C ₁ -C ₆ alkyl group or a carbon atom on the ring. )
m and n each independently represent 0 or 1,
Substituent Group A consists of halogen atoms, C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, C ₃ -C ₆ cycloalkyl group, a cyano group and a tri (C ₁ -C ₆ alkyl) silyl group A group,
Substituent group B, a halogen atom, C ₃ -C ₆ cycloalkyl group, a cyano group, C ₂ -C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group, a phenyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, consisting of C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, C ₁ -C ₄ alkylenedioxy group, hydroxyimino group and C ₁ -C ₆ alkoxyimino group A group,
Substituent group C includes a halogen atom, an optionally substituted C ₁ -C ₆ alkyl group (the substituent is a substituent selected from the above substituent group B), a C ₃ -C ₆ cycloalkyl group, C ₂ -C ₆ alkenyl group, cyano group, C ₂ -C ₇ alkylcarbonyl group, benzoyl group, carboxyl group, C ₂ -C ₇ alkoxycarbonyl group, carbamoyl group, di (C ₁ -C ₆ alkyl) carbamoyl group, A phenyl group which may be substituted (the substituent is a substituent selected from the above substituent group A), a 5- or 6-membered heterocyclic group (the heterocyclic ring has one nitrogen atom in the ring; , An oxygen atom or a sulfur atom, and further may contain 1 to 2 nitrogen atoms.), An amino group which may be substituted (the substituent is a substituent selected from the following substituent group D) .), a nitro group, a hydroxyl group, C ₁ -C ₆ alkoxy Group, a C ₁ -C ₆ haloalkoxy group, a phenoxy group, C ₁ -C ₆ alkylthio group, a phenylthio group, C ₁ -C ₆ alkylsulfinyl group consisting Le group and C ₁ -C ₆ alkylsulfonyl group,
Substituent group D is, C ₁ -C ₆ alkyl group, C ₂ -C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group, a di (C ₁ -C ₆ alkyl) carbamoyl group and C ₁ -C ₆ alkyl A group consisting of a sulfonyl group,
Substituent group E includes a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a hydroxyl group, an optionally substituted phenylsulfonyl group (the substituent is a substituent selected from substituent group A above) And di (C ₁ -C ₆ alkyl) sulfamoyl groups. ]
The compound represented by these, its salt, and its ester derivative
[Here, ester derivative, an oxygen atom of hydroxyl group bonded to the 4-position of the pyridazine ring, may be substituted C ₂ -C ₁₅ alkylcarbonyl group [the substituent is a halogen atom, C ₁ -C ₆ alkoxy group , C ₂ -C ₇ alkoxycarbonyl group, may be substituted C ₂ -C ₆ alkenyloxycarbonyl group {said substituents, C ₃ -C ₆ cycloalkyl group, a cyano group and which may be substituted benzoyl group (the substituent group, halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, the same is selected from the group consisting of nitro and C ₁ -C ₃ alkylsulfonyl group, or 1 to 3 substituents selected from the group consisting of 1 to 3 different substituents. }, An optionally substituted C ₃ -C ₆ cycloalkenyloxycarbonyl group {the substituent is an oxo group and an optionally substituted benzoyl group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ A group consisting of ₁ to ₃ identical or different substituents selected from the group consisting of a -C ₃ haloalkyl group, a C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group. 1 to 2 substituents selected from the same or different. }, A 5- or 6-membered heterocyclic oxycarbonyl group which may be substituted {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 nitrogen atoms May be included. The substituents are halogen atom, C ₁ -C ₆ alkyl group, which may be substituted phenoxy group (the substituent is halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₃ ~ The same or different 1 to 3 substituents selected from the group consisting of a C ₆ cycloalkyl group and a C ₂ -C ₇ alkoxycarbonyl group.), 2,3-dihydro-1H-indenyloxy group and substitution which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1 to 3 substituents selected from the group consisting of: }, Which may be substituted phenyl group (said substituent is a halogen atom, C ₁ -C ₆ alkyl group, a C ₁ -C ₃ haloalkyl group, C ₁ -C ₆ alkoxy group and C ₂ -C ₇ alkoxycarbonyl group Or the same or different 1 to 3 substituents selected from the group consisting of phenoxy group and C _{1 to} C ₆ alkylthio group. . ],
C ₄ -C ₇ cycloalkylcarbonyl group, adamantyl group may be substituted C ₃ -C ₇ alkenylcarbonyl group (said substituents may be the same or different 1 to 2 selected from the group consisting of a halogen atom and a phenyl group A C ₃ -C ₇ alkynylcarbonyl group, an optionally substituted benzoyl group [the substituent is a halogen atom, an optionally substituted C ₁ -C ₆ alkyl group (the substituent is are the same or different 1 to 3 substituents selected from the group consisting of a halogen atom and a phenyl group.), a cyano group, C ₂ -C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group, substituted C ₃ -C ₇ alkenyloxycarbonyl group {the substituent is a C ₃ -C ₆ cycloalkyl group, a cyano group and an optionally substituted benzoyl group (the substituent Is halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, the same or different selected from the group consisting of nitro and C ₁ -C ₃ alkylsulfonyl group 1 to 3 substituents selected from the group consisting of 1 to 3 substituents. }, An optionally substituted C ₄ -C ₇ cycloalkenyloxycarbonyl group {the substituent is an oxo group and an optionally substituted benzoyl group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ A group consisting of ₁ to ₃ identical or different substituents selected from the group consisting of a -C ₃ haloalkyl group, a C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group. 1 to 2 substituents selected from the same or different. }, A phenyl group, a nitro group, an optionally substituted C ₁ -C ₆ alkoxy group (the substituent is the same or different 1 to 3 substituents selected from the group consisting of a halogen atom and a phenyl group. ), A phenoxy group, an optionally substituted 5- or 6-membered heterocyclic oxycarbonyl group {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring; It may contain nitrogen atoms. The substituents are halogen atom, C ₁ -C ₆ alkyl group, which may be substituted phenoxy group (the substituent is halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₃ ~ The same or different 1 to 3 substituents selected from the group consisting of a C ₆ cycloalkyl group and a C ₂ -C ₇ alkoxycarbonyl group.), 2,3-dihydro-1H-indenyloxy group and substitution which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1 to 3 substituents selected from the group consisting of: } And a 5- or 6-membered heterocyclic oxysulfonyl group which may be substituted {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 nitrogen atoms May be included. The substituents are halogen atom, C ₁ -C ₆ alkyl group, which may be substituted phenoxy group (the substituent is halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₃ ~ The same or different 1 to 3 substituents selected from the group consisting of a C ₆ cycloalkyl group and a C ₂ -C ₇ alkoxycarbonyl group.), 2,3-dihydro-1H-indenyloxy group and substitution which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1 to 3 substituents selected from the group consisting of: } Are the same or different 1 to 3 substituents selected from the group consisting of: ], A naphthoyl group, an optionally substituted 3- to 8-membered heterocyclic carbonyl group [the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 nitrogen atoms It may contain atoms and may form a 5- to 6-membered spiro ring containing 1-2 oxygen atoms on any carbon atom in the heterocycle. The substituent is a halogen atom and an optionally substituted C ₁ -C ₆ alkyl group (the substituent is the same or different 1 to 3 substituents selected from the group consisting of a halogen atom and a phenyl group. ), A cyano group, a C ₂ -C ₇ alkylcarbonyl group, a C ₂ -C ₇ alkoxycarbonyl group, an optionally substituted phenyl group (the substituent is the same or different 1 to 3 halogen atoms). A 5- or 6-membered heterocyclic group which may be substituted (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom, and further contains 1 to 2 nitrogen atoms in the ring) The substituent is the same or different 1 to 3 substituents selected from the group consisting of a halogen atom and a C ₁ -C ₆ alkyl group.), Nitro group, hydroxyl group, C ₁ -C ₆ alkoxy Group, phenoxy group, oxo group, hydroxy Imino group, C ₁ -C ₆ alkoxyimino group, C ₁ -C ₆ alkylthio group, C ₂ -C ₆ alkenylthio group, a phenylthio group, which may be substituted 5 or 6-membered heterocyclic carbonyl group (said heterocyclic is in the ring, the one, nitrogen atom, contains an oxygen atom or a sulfur atom, may further contain one or two nitrogen atoms. the substituent is a halogen atom and a C ₁ -C ₆ alkyl group The same or different 1 to 3 substituents selected from the group consisting of: and a 5- or 6-membered heterocyclic oxycarbonyl group which may be substituted {the heterocyclic ring is one nitrogen atom in the ring; It contains atoms, oxygen atoms or sulfur atoms, and may contain 1 to 2 nitrogen atoms. The substituents are halogen atom, C ₁ -C ₆ alkyl group, which may be substituted phenoxy group (the substituent is halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₃ ~ The same or different 1 to 3 substituents selected from the group consisting of a C ₆ cycloalkyl group and a C ₂ -C ₇ alkoxycarbonyl group.), 2,3-dihydro-1H-indenyloxy group and substitution which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1 to 3 substituents selected from the group consisting of: } Are the same or different 1 to 3 substituents selected from the group consisting of: ],
A 7 to 14-membered fused bi- or tricyclic heterocyclic carbonyl group which may be substituted (the heterocycle contains one nitrogen atom, oxygen atom or sulfur atom in the ring; nitrogen atom or oxygen atom of the may contain. the substituents are the same or different 1 to 3 substituents selected from the group consisting of halogen atom and C ₁ -C ₆ alkyl group.), 5 Or a 6-membered heterocyclic carbonylcarbonyl group (the heterocyclic ring may contain one nitrogen atom, oxygen atom or sulfur atom, and may further contain 1 to 2 nitrogen atoms). An optionally substituted C ₂ -C ₇ alkoxycarbonyl group (the substituent is the same or different 1 to 3 substituents selected from the group consisting of a halogen atom, a C ₁ -C ₆ alkoxy group and a phenyl group) .), C ₃ ~C ₇ alkenyloxycarbonyl group, Conversion has been or phenoxycarbonyl group (said substituent is a halogen atom, C ₁ -C ₆ alkyl group, a cyano group, C ₂ -C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₆ identical or different 1 to 3 substituents selected from the group consisting of an alkoxy group.), a condensed polycyclic hydrocarbon oxy carbonyl group, which may be substituted 5 or 6-membered heterocyclic oxycarbonyl group {The heterocyclic ring may contain one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 to 2 nitrogen atoms. The substituents are halogen atom, C ₁ -C ₆ alkyl group, which may be substituted phenoxy group (the substituent is halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₃ ~ The same or different 1 to 3 substituents selected from the group consisting of a C ₆ cycloalkyl group and a C ₂ -C ₇ alkoxycarbonyl group.), 2,3-dihydro-1H-indenyloxy group and substitution which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1 to 3 substituents selected from the group consisting of: }, A carbamoyl group that may be substituted {the substituent is a C ₁ -C ₆ alkyl group that may be substituted (the substituent is a halogen atom, a C ₂ -C ₇ alkoxycarbonyl group, a cyano group, a phenyl group, and C ₁ to 3 substituents selected from the group consisting of _{1 to} C ₆ alkoxy groups), C _{3 to} C ₆ alkenyl groups, phenyl groups, optionally substituted 5 or 6 membered heterocyclic groups. (The heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 to 2 nitrogen atoms. The substituent includes a halogen atom and C _1. -C ₆ identical or different 1 to 3 substituents selected from the group consisting of alkyl group.), C ₂ ~C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group and C ₁ -C ₆ The same or selected from the group consisting of alkoxy groups 1 to 3 different substituents. }, (C ₁ -C ₆ alkylthio) carbonyl group, (C ₃ -C ₆ cycloalkylthio) carbonyl group, (phenylthio) carbonyl group, optionally substituted C ₁ -C ₈ alkylsulfonyl group (the substituents are the same) or different 1 to 3 halogen atoms.), which may be substituted phenylsulfonyl group [the substituent is a halogen atom, C ₁ -C ₆ alkyl group, a cyano group, C ₂ -C ₇ alkylcarbonyl group , C ₂ -C ₇ alkoxycarbonyl group, nitro group, C ₁ -C ₆ alkoxy group, may be substituted C ₂ -C ₆ alkenyloxy sulfonyl group {said substituents, C ₃ -C ₆ cycloalkyl group, a cyano group and which may be substituted benzoyl group (the substituent is a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, two B are the same or different 1 to 3 substituents selected from the group, and C ₁ -C ₃ group consisting of an alkylsulfonyl group.) The same or selected from the group consisting of different with 1-3 substituents is there. }, An optionally substituted C ₃ -C ₆ cycloalkenyloxysulfonyl group {the substituent is an oxo group and an optionally substituted benzoyl group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ A group consisting of ₁ to ₃ identical or different substituents selected from the group consisting of a -C ₃ haloalkyl group, a C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group. 1 to 2 substituents selected from the same or different. } And a 5- or 6-membered heterocyclic oxysulfonyl group which may be substituted {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 nitrogen atoms May be included. The substituents are halogen atom, C ₁ -C ₆ alkyl group, which may be substituted phenoxy group (the substituent is halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₃ ~ The same or different 1 to 3 substituents selected from the group consisting of a C ₆ cycloalkyl group and a C ₂ -C ₇ alkoxycarbonyl group.), 2,3-dihydro-1H-indenyloxy group and substitution which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1 to 3 substituents selected from the group consisting of: } Are the same or different 1 to 3 substituents selected from the group consisting of: An optionally substituted 5- or 6-membered heterocyclic sulfonyl group (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further contains 1 to 2 nitrogen atoms) The substituent is the same or different 1 to 3 substituents selected from the group consisting of a halogen atom and a C _{1 to} C ₆ alkyl group. Ring oxysulfonyl group {The heterocyclic ring may contain one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 to 2 nitrogen atoms. The substituents are halogen atom, C ₁ -C ₆ alkyl group, which may be substituted phenoxy group (the substituent is halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₃ ~ The same or different 1 to 3 substituents selected from the group consisting of a C ₆ cycloalkyl group and a C ₂ -C ₇ alkoxycarbonyl group.), 2,3-dihydro-1H-indenyloxy group and substitution which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1 to 3 substituents selected from the group consisting of: }, Di (C ₁ -C ₆ alkyl) sulfamoyl group, C ₁ -C ₆ alkoxysulfonyl group, di (C ₁ -C ₆ alkyl) phosphoryl group, tri (C ₁ -C ₆ alkyl) silicon group or triphenyl silicon One or two or more 3-phenoxy-4-pyridazinol derivatives selected from the group consisting of a group to which a group is bonded , and butyl (R) -2- [4- (4 -Cyano-2-fluorophenoxy) phenoxy] propionate as an active ingredient. In the general formula (I), R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group (the halogen atom is represented by 1 to 3 fluorine atoms) an atom.), a cyclopropyl group, C ₂ -C ₃ alkenyl group, a cyano group, C ₂ -C ₄ alkylcarbonyl group, a di (C ₁ -C ₃ alkyl) carbamoyl group, which may be substituted phenyl group {said identical substituents are fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is selected from fluorine atom, the group consisting of chlorine and bromine Or ₁ to 2 different substituents selected from the group consisting of a cyclopropyl group, a cyano group, and a tri (C ₁ -C ₃ alkyl) silicon group. It is. }, A furyl group, a thienyl group, C ₁ -C ₃ alkoxy group, which may be substituted phenoxy group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ A haloalkyl group (the halogen atom is 1 to 3 fluorine atoms), a cyclopropyl group, a cyano group, and a tri (C ₁ -C ₃ alkyl) silicon group selected from the same or different 1 Two substituents. } Or substituted pyrazolyloxy group (the substituent is two one benzoyl group and two C ₁ -C ₃ alkyl group substituted by a chlorine atom.) Is, according to claim 1 Herbicidal composition. The herbicidal composition according to claim 1, wherein in the general formula (I), R ¹ is a chlorine atom, a bromine atom, a trifluoromethyl group or a cyano group. The herbicidal composition according to claim ¹ , wherein R ¹ in formula (I) is a chlorine atom or a bromine atom. The herbicidal composition according to claim ¹ , wherein R ¹ in formula (I) is a chlorine atom. In the general formula (I), R ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a C ₁ -C ₃ alkyl group, a (C ₁ -C ₃ alkoxy) C ₁ -C ₃ alkyl group, which may be substituted benzoyl group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, a chlorine atom and a bromine atom The same or different 1 to 3 halogen atoms selected from the group consisting of :), the same or different selected from the group consisting of cyclopropyl group, cyano group and tri (C ₁ -C ₃ alkyl) silicon group. 1 to 2 substituents. }, C ₂ -C ₄ alkoxycarbonyl group, may be substituted phenoxy group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen The atoms are the same or different 1 to 3 halogen atoms selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom.), Cyclopropyl group, cyano group and tri (C ₁ -C ₃ alkyl) It is the same or different 1-2 substituents selected from the group consisting of silicon groups. }, Which may be substituted phenylthio group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, a chlorine atom and The same or different one to three halogen atoms selected from the group consisting of bromine atoms), the same selected from the group consisting of cyclopropyl groups, cyano groups and tri (C ₁ -C ₃ alkyl) silicon groups. Or it is 1 to 2 different substituents. } Or tri (C ₁ -C ₃ alkyl) silyl group, herbicidal composition according to any one of claims 1 to 5. 6. The general formula (I), wherein R ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethoxycarbonyl group, or a trimethylsilyl group. Herbicidal composition. In general formula (I), R ² is a hydrogen atom, herbicidal composition according to any one of claims 1 to 5. In the general formula (I), R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an optionally substituted C _1- C ₄ alkyl group (the substituent is the same or different 1 to 3 substituents selected from the group consisting of fluorine atom, chlorine atom and bromine atom, or C _{3 to} C ₄ cycloalkyl group, C ₁ to A C ₃ alkylthio group or a C ₁ -C ₃ alkoxyimino group.), A C ₂ -C ₃ alkenyl group, a C ₂ -C ₃ alkynyl group, an optionally substituted C ₃ -C ₅ cycloalkyl group (the substituent) It is fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl group, C ₃ -C ₄ cycloalkyl group, a cyano group, a C ₁ -C ₃ alkoxy groups and C ₁ -C ₃ alkylthio group 1 to 3 identical or different substituents selected .), C ₆ ~C ₇ bicycloalkyl group, a cyano group, C ₂ -C ₄ alkylcarbonyl group, C ₂ -C ₄ alkoxycarbonyl group, which may be substituted phenyl group {said substituent is a fluorine atom, a chlorine atom , A bromine atom, a C ₁ -C ₃ alkyl group or a C ₁ -C ₃ haloalkyl group (the halogen atom is the same or different 1 to 3 halogens selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom) Is an atom.) }, A 5- to 6-membered heterocyclic group which may be substituted {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further contains 1 to 2 nitrogen atoms. You can. The substituents are fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl and C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, selected from the group consisting of chlorine and bromine 1 to 3 halogen atoms which are the same or different. }, Nitro group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ haloalkoxy group (said halogen atom is a fluorine atom, 1-3 was selected same or different from the group consisting of chlorine and bromine of a halogen atom.), which may be substituted phenoxy group (the substituent is a fluorine atom, a chlorine atom, the same or different 1 to 2 atoms selected from the group consisting of bromine and C ₁ -C ₃ alkoxy groups Or a C ₁ -C ₃ alkylthio group, or two of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ that are adjacent to each other. pieces _{together, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH = CH -CH = CH-, -OCH ₂ CH _2- , -OCH = CH-, -OCH = C (CH ₃ )-, -SCH = CH-, -N = CH-CH = CH-, -OCH ₂ O- , -OCH ₂ CH ₂ O-,

The herbicidal composition according to any one of claims 1 to 8, which forms a group represented by: In the general formula (I), R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an optionally substituted C _1- C ₄ alkyl group (the substituent is 1 to 3 fluorine atoms or 1 cyclopropyl group), C _{2 to} C ₃ alkenyl group, C _{3 to} C ₄ cycloalkyl which may be substituted group (said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₂ alkyl group, the same one or two substituents selected from the group consisting of cyclopropyl group, and C ₁ -C ₂ alkoxy group in a.), a cyano group, C ₂ -C ₃ alkoxycarbonyl group, a nitro group, a C ₁ -C ₃ alkoxy group or a trifluoromethoxy group, or, R ^3, R ^4, R ^5, R ⁶ and R Two of the ⁷ adjacent to each other are joined together to form —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ C H _2- , -OCH ₂ CH _2- , -OCH = CH- or

The herbicidal composition according to any one of claims 1 to 8, wherein R ³ is not a hydrogen atom. In the general formula (I), R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a C ₁ -C ₃ alkyl group. , C ₂ -C ₃ alkenyl group, may be substituted C ₃ -C ₄ cycloalkyl group (said substituents may be the same of one to two selected from the group consisting of a chlorine atom and C ₁ -C ₂ alkyl group A cyano group or a C ₁ -C ₂ alkoxy group, or two of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are combined together to form — CH ₂ CH ₂ CH ₂ - or forms a group represented by -OCH = CH-, provided that, R ³ is not a hydrogen atom, herbicidal composition according to any one of claims 1 to 8. In the general formula (I), R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, allyl group A group, an isopropyl group, an optionally substituted cyclopropyl group (the substituent is two chlorine atoms) or a methoxy group, or R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ . Among them, two adjacent groups together form a group represented by —CH ₂ CH ₂ CH ₂ — or —OCH═CH—, wherein R ³ is not a hydrogen atom. The herbicidal composition as described in any one of these.   The herbicidal composition according to any one of claims 1 to 12, wherein in the general formula (I), m and n are both 0. R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group (the halogen atom is 1 to 3 fluorine atoms), cyclo Propyl group, C ₂ -C ₃ alkenyl group, cyano group, C ₂ -C ₄ alkylcarbonyl group, di (C ₁ -C ₃ alkyl) carbamoyl group, optionally substituted phenyl group {the substituent is a fluorine atom, Chlorine atom, bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (the halogen atom is the same or different 1 to 3 selected from the group consisting of fluorine atom, chlorine atom and bromine atom) ₁ or 2 substituents selected from the group consisting of a cyclopropyl group, a cyano group, and a tri (C ₁ -C ₃ alkyl) silicon group. }, A furyl group, a thienyl group, C ₁ -C ₃ alkoxy group, which may be substituted phenoxy group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ A haloalkyl group (the halogen atom is 1 to 3 fluorine atoms), a cyclopropyl group, a cyano group, and a tri (C ₁ -C ₃ alkyl) silicon group selected from the same or different 1 Two substituents. } Or a substituted pyrazolyloxy group (the substituent is one benzoyl group and two C ₁ -C ₃ alkyl groups substituted by two chlorine atoms),
R ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a C ₁ -C ₃ alkyl group, a (C ₁ -C ₃ alkoxy) C ₁ -C ₃ alkyl group, an optionally substituted benzoyl group { The substituent is a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group (the halogen atom is selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom) 1 to 3 halogen atoms which are the same or different.), ₁ to 2 substituents which are the same or different and are selected from the group consisting of a cyclopropyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) silicon group. It is a group. }, C ₂ -C ₄ alkoxycarbonyl group, may be substituted phenoxy group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen The atoms are the same or different 1 to 3 halogen atoms selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom.), Cyclopropyl group, cyano group and tri (C ₁ -C ₃ alkyl) It is the same or different 1-2 substituents selected from the group consisting of silicon groups. }, Which may be substituted phenylthio group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, a chlorine atom and The same or different one to three halogen atoms selected from the group consisting of bromine atoms), the same selected from the group consisting of cyclopropyl groups, cyano groups and tri (C ₁ -C ₃ alkyl) silicon groups. Or it is 1 to 2 different substituents. } Or a tri (C ₁ -C ₃ alkyl) silicon group,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently of each other a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an optionally substituted C ₁ -C ₄ alkyl group The group is the same or different 1 to 3 substituents selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom, or a C _{3 to} C ₄ cycloalkyl group, a C _{1 to} C ₃ alkylthio group or C _1. -C is a ₃ alkoxyimino group.), C ₂ -C ₃ alkenyl group, C ₂ -C ₃ alkynyl group may be substituted C ₃ -C ₅ cycloalkyl group (said substituent is a fluorine atom, a chlorine atom , bromine atom, C ₁ -C ₃ alkyl group, C ₃ -C ₄ cycloalkyl group, the same or different 1 selected from the group consisting of cyano group, C ₁ -C ₃ alkoxy groups and C ₁ -C ₃ alkylthio group a to 3 substituents.), C ₆ ~C ₇ Bishiku Roarukiru group, cyano group, C ₂ -C ₄ alkylcarbonyl group, C ₂ -C ₄ alkoxycarbonyl group, which may be substituted phenyl group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group or a C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, a chlorine atom and one to three halogen atoms selected same or different from the group consisting of bromine atoms.) it is. }, A 5- to 6-membered heterocyclic group which may be substituted {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further contains 1 to 2 nitrogen atoms. You can. The substituents are fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl and C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, selected from the group consisting of chlorine and bromine 1 to 3 halogen atoms which are the same or different. }, Nitro group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ haloalkoxy group (said halogen atom is a fluorine atom, 1-3 was selected same or different from the group consisting of chlorine and bromine of a halogen atom.), which may be substituted phenoxy group (the substituent is a fluorine atom, a chlorine atom, the same or different 1 to 2 atoms selected from the group consisting of bromine and C ₁ -C ₃ alkoxy groups Or a C ₁ -C ₃ alkylthio group, or two of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ that are adjacent to each other. pieces _{together, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH = CH -CH = CH-, -OCH ₂ CH _2- , -OCH = CH-, -OCH = C (CH ₃ )-, -SCH = CH-, -N = CH-CH = CH-, -OCH ₂ O- , -OCH ₂ CH ₂ O-,

A group represented by
The herbicidal composition according to claim 1, wherein m and n are both 0 compounds. R ¹ is a chlorine atom, a bromine atom, a trifluoromethyl group or a cyano group,
R ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethoxycarbonyl group or a trimethylsilyl group,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently of each other a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an optionally substituted C ₁ -C ₄ alkyl group Group is 1 to 3 fluorine atoms, or 1 cyclopropyl group), a C _{2 to} C ₃ alkenyl group, an optionally substituted C _{3 to} C ₄ cycloalkyl group (the substituent is A fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₂ alkyl group, a cyclopropyl group, and a C ₁ -C ₂ alkoxy group, the same one or two substituents, and a cyano group. , A C ₂ -C ₃ alkoxycarbonyl group, a nitro group, a C ₁ -C ₃ alkoxy group or a trifluoromethoxy group, or two of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ that are adjacent to each other. Together, -CH ₂ CH ₂ CH _2- , -CH (CH ₃ ) CH ₂ CH _2- ,
-OCH ₂ CH _2- , -OCH = CH- or

In which R ³ is not a hydrogen atom,
The herbicidal composition according to claim 1, wherein m and n are both 0 compounds. R ¹ is a chlorine atom or a bromine atom,
R ² is a hydrogen atom,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, C ₁ -C ₃ alkyl group, C ₂ -C ₃ alkenyl. A C _{3 to} C ₄ cycloalkyl group which may be substituted (the substituent is the same 1 or 2 substituents selected from the group consisting of a chlorine atom and a C _{1 to} C ₂ alkyl group), A cyano group or a C ₁ -C ₂ alkoxy group, or two of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are combined together to form —CH ₂ CH ₂ CH ₂ —. Or a group represented by -OCH = CH-, provided that R ³ is not a hydrogen atom,
The herbicidal composition according to claim 1, wherein m and n are both 0 compounds. R ¹ is a chlorine atom,
R ² is a hydrogen atom,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently of each other hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, allyl group, isopropyl group, substituted A cyclopropyl group (the substituent is two chlorine atoms) or a methoxy group, or two of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are adjacent to each other. Together, a group represented by —CH ₂ CH ₂ CH ₂ — or —OCH═CH— is formed, provided that R ³ is not a hydrogen atom,
The herbicidal composition according to claim 1, wherein m and n are both 0 compounds.   The compound represented by the general formula (I) is 6-chloro-3- (2-iodophenoxy) -4-pyridazinol, 6-chloro-3- (2-methylphenoxy) -4-pyridazinol, 6-chloro- 3- (2-Isopropylphenoxy) -4-pyridazinol, 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinol, 6-chloro-3- (2,3-dihydro-1H-indene-4- Yloxy) -4-pyridazinol, 3- (1-benzofuran-7-yloxy) -6-chloro-4-pyridazinol, 6-chloro-3- (2,5-dimethylphenoxy) -4-pyridazinol, 6-chloro- 3- (2-methoxy-5-methylphenoxy) -4-pyridazinol, 6-chloro-3- (2-chloro-6-methylphenoxy) -4-pyridazinol, 6-chloro-3- (2-chloro-6 -Cyclopropylphenoxy) -4-pyridazinol, 3- (2-bromo-6-methylphenoxy) -6-chloro-4-pyridazinol, 6-chloro-3- (2-ethyl-6-methylphenoxy) -4- Pirida , 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol, 3- (2-allyl-6-methylphenoxy) -6-chloro-4-pyridazinol, 6-chloro-3 -(2-Cyclopropyl-3,5-dimethylphenoxy) -4-pyridazinol, 6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4- The herbicidal composition according to claim 1, which is pyridazinol or 6-chloro-3- (2,3,5,6-tetramethylphenoxy) -4-pyridazinol.   The herbicidal composition according to any one of claims 1 to 18, further comprising 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-pyrazolyl-p-toluenesulfonate, 2- [4 -(2,4-Dichlorobenzoyl) -1,3-dimethylpyrazol-5-yloxy] acetophenone, 2- [4- (2,4-dichloro-m-toluoyl) -1,3-dimethylpyrazol-5-yloxy ] A herbicidal composition comprising as an active ingredient one or more third herbicidal active compounds selected from the group consisting of 4'-methylacetophenone.