JP2008280344A - Hydrazide compound and harmful arthropod-controlling agent comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound having excellent controlling effect on harmful arthropod. <P>SOLUTION: The compound is a hydrazide compound represented by formula (1) [wherein, A<SP>1</SP>and A<SP>2</SP>are each independently an oxygen atom or the like; R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are each independently a hydrogen atom, a 1-6C alkyl group or the like which maybe substituted with a halogen atom: Q is -C(=A<SP>3</SP>)-R<SP>4</SP>or the like, wherein A<SP>3</SP>is an oxygen atom or the like, and R<SP>4</SP>is H, a 1-10C alkyl group or the like; and Z<SP>1</SP>, Z<SP>2</SP>, Z<SP>3</SP>and Z<SP>4</SP>are each independently a hydrogen atom, a halogen atom or the like]. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a hydrazide compound and a harmful arthropod control agent containing the same.

  Conventionally, many compounds have been developed and put into practical use for controlling harmful arthropods. Certain amide compounds are also known in the art.

JP-T 09-510471 Japanese Patent Laid-Open No. 48-60743 Journal fuer Praktische Chemie 1927, (116), 1-9

  An object of the present invention is to provide a hydrazide compound having an excellent control effect against harmful arthropods.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a hydrazide compound represented by the following formula (1) having an excellent control effect against harmful arthropods, and have reached the present invention.

〔式中、
Ａ¹およびＡ²は各々独立して、酸素原子または硫黄原子を表し、
Ｒ¹は水素原子、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキル基、Ｃ２−Ｃ６シアノアルキル基、Ｃ２−Ｃ６アルコキシアルキル基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルケニル基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルキニル基、または、下記の置換基Ａでベンゼン環部分が置換されていてもよいＣ７−Ｃ９フェニルアルキル基を表し、
Ｒ²は、水素原子、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキル基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルケニル基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルキニル基、Ｃ２−Ｃ６シアノアルキル基、下記の置換基Ｄで置換されていてもよいＣ３−Ｃ６シクロアルキル基、または、Ｃ４−Ｃ７（シクロアルキル）アルキル基を表し、
Ｒ³は、水素原子、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキル基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルケニル基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルキニル基、Ｃ２−Ｃ６シアノアルキル基、または、下記の置換基Ｄで置換されていてもよいＣ３−Ｃ６シクロアルキル基、Ｃ４−Ｃ７（シクロアルキル）アルキル基、ホルミル基、Ｃ２−Ｃ６アルキルカルボニル基、Ｃ２−Ｃ６アルコキシカルボニル基、Ｃ３−Ｃ７ジアルキルカルバモイル基、または、下記の置換基Ｂで置換されていてもよいフェニル基を表すか、或いは、
Ｒ^２とＲ^３とが一緒になって、下記のＵ１〜Ｕ３
Ｕ１：−（ＣＲ⁹Ｒ¹⁰）_ｍ−
Ｕ２：−ＣＲ¹¹Ｒ¹²−ＣＲ¹³＝ＣＲ¹⁴−ＣＲ^15７Ｒ¹⁶−
Ｕ３：−（ＣＲ¹⁷Ｒ¹⁸）_２−Ｙ−（ＣＲ¹⁹Ｒ²⁰）_２−
（ここで、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹およびＲ²⁰は各々独立して、水素原子またはＣ１−Ｃ４アルキル基を表し、
ｍは、３〜５の整数を表し、
Ｙは、酸素原子、−Ｓ（Ｏ）_ｎ−または−ＮＲ²¹−〈ここで、ｎは０〜２の整数を表し、Ｒ²¹はＣ１−Ｃ４アルキル基を表す。〉を表す。）を表し、
Ｑは、下記のＱ１〜Ｑ４
Ｑ１：−Ｃ（＝Ａ³）−Ｒ⁴
Ｑ２：−Ｃ（＝Ａ⁴）−ＯＲ⁵
Ｑ３：−Ｃ（＝Ａ⁵）−ＳＲ⁶
Ｑ４：−Ｃ（＝Ａ⁶）−ＮＲ⁷Ｒ⁸
（ここで、
Ａ³、Ａ⁴、Ａ⁵およびＡ⁶は酸素原子または硫黄原子を表し、
Ｒ⁴は水素原子、下記の置換基Ｃで置換されていてもよいＣ１−Ｃ１０アルキル基、ハロゲン原子で置換されていてもよいＣ２−Ｃ６アルケニル基、ハロゲン原子で置換されていてもよいＣ２−Ｃ６アルキニル基、下記の置換基Ｄで置換されていてもよいＣ３−Ｃ６シクロアルキル基、下記の置換基Ｅで置換されていてもよいフェニル基、下記の置換基Ａで置換されていてもよいナフチル基、下記の置換基Ｄで置換されていてもよい５−６員環ヘテロアリール基、下記の置換基Ｄで置換されていてもよい３−８員非芳香へテロ環基、下記の置換基Ｂでベンゼン環部分が置換されていてもよいＣ７−Ｃ９フェニルアルキル基、下記の置換基Ａで置換されていてもよいＣ８−Ｃ１０フェニルアルケニル基、または、下記の置換基Ａでベンゼン環部分が置換されていてもよいＣ７−Ｃ９フェノキシアルキル基を表し、
Ｒ⁵およびＲ⁶はハロゲン原子で置換されていてもよいＣ１−Ｃ１０アルキル基、Ｃ３−Ｃ６アルコキシアルキル基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルケニル基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルキニル基、下記の置換基Ｄで置換されていてもよいＣ３−Ｃ６シクロアルキル基、下記の置換基Ｅで置換されていてもよいフェニル基、下記の置換基Ａで置換されていてもよい置換されていてもよい５−６員環へテロアリール基、または、下記の置換基Ａでベンゼン環部分が置換されていてもよいＣ７−Ｃ９フェニルアルキル基を表し、
Ｒ⁷およびＲ⁸は各々独立して、水素原子、ハロゲン原子で置換されていてもよいＣ１−Ｃ１０アルキル基、Ｃ２−Ｃ６アルコキシアルキル基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルケニル基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルキニル基、下記の置換基Ｄで置換されていてもよいＣ３−Ｃ６シクロアルキル基、下記の置換基Ｅで置換されていてもよいフェニル基、下記の置換基Ａで置換されていてもよい５−６員環へテロアリール基、または、下記の置換基Ａでベンゼン環部分が置換されていてもよいＣ７−Ｃ９フェニルアルキル基を表す。）
を表し、
Ｚ^１、Ｚ^２、Ｚ^３及びＺ^４は各々独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキル基、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルコキシ基、ハロゲン原子で置換されていてもよいフェニル基、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキルチオ基、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキルスルフィニル基、または、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキルスルホニル基を表すか、或いは、
Ｚ^１とＺ^２、Ｚ^２とＺ^３、または、Ｚ^３とＺ^４とが一緒になって、下記の置換基Ｆで置換されていてもよい１，３−ブタジエン−１，４−ジイル基、下記の置換基Ｄで置換されていてもよいプロパン−１，３−ジイル基、下記の置換基Ｄで置換されていてもよいブタン−１，４−ジイル基、または、下記の置換基Ｄで置換されていてもよいメチレンジオキシ基を表す。 That is, the present invention
Formula (1)

[Where,
A ¹ and A ² each independently represents an oxygen atom or a sulfur atom,
R ¹ is a hydrogen atom, a C1-C6 alkyl group optionally substituted with a halogen atom, a C2-C6 cyanoalkyl group, a C2-C6 alkoxyalkyl group, a C3-C6 alkenyl group optionally substituted with a halogen atom, A C3-C6 alkynyl group optionally substituted with a halogen atom, or a C7-C9 phenylalkyl group in which the benzene ring moiety may be substituted with the following substituent A,
R ² represents a hydrogen atom, a C1-C6 alkyl group optionally substituted with a halogen atom, a C3-C6 alkenyl group optionally substituted with a halogen atom, or a C3-C6 alkynyl optionally substituted with a halogen atom. Group, a C2-C6 cyanoalkyl group, a C3-C6 cycloalkyl group optionally substituted with the following substituent D, or a C4-C7 (cycloalkyl) alkyl group,
R ³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted with a halogen atom, a C3-C6 alkenyl group optionally substituted with a halogen atom, or a C3-C6 alkynyl optionally substituted with a halogen atom. Group, C2-C6 cyanoalkyl group, or C3-C6 cycloalkyl group, C4-C7 (cycloalkyl) alkyl group, formyl group, C2-C6 alkylcarbonyl group optionally substituted by the following substituent D, Represents a C2-C6 alkoxycarbonyl group, a C3-C7 dialkylcarbamoyl group, or a phenyl group optionally substituted by the following substituent B, or
R ² and R ³ are combined to form the following U1 to U3
U1: − (CR ⁹ R ¹⁰ ) _m −
^{U2: -CR 11 R 12 -CR 13} = CR 14 -CR 157 R 16 -
_{^{U3 :-( CR 17 R 18) 2}} -Y- (CR 19 R 20) 2 -
(Here, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a hydrogen atom or C1- Represents a C4 alkyl group,
m represents an integer of 3 to 5,
Y represents an oxygen atom, -S _{(O) n} - or -NR ²¹ - <Here, n represents an integer of 0 to 2, R ²¹ represents a C1-C4 alkyl group. > )
Q is the following Q1-Q4
^{Q1: -C (= A 3)} -R 4
^{Q2: -C (= A 4)} -OR 5
^{Q3: -C (= A 5)} -SR 6
^{Q4: -C (= A 6)} -NR 7 R 8
(here,
A ³ , A ⁴ , A ⁵ and A ⁶ represent an oxygen atom or a sulfur atom,
R ⁴ represents a hydrogen atom, a C1-C10 alkyl group which may be substituted with the following substituent C, a C2-C6 alkenyl group which may be substituted with a halogen atom, or a C2- which is optionally substituted with a halogen atom. A C6-alkynyl group, a C3-C6 cycloalkyl group optionally substituted with the following substituent D, a phenyl group optionally substituted with the following substituent E, and optionally substituted with the following substituent A. A naphthyl group, a 5-6 membered heteroaryl group optionally substituted with the following substituent D, a 3-8 membered non-aromatic heterocyclic group optionally substituted with the following substituent D, the following substitution: C7-C9 phenylalkyl group optionally substituted with benzene ring moiety with group B, C8-C10 phenylalkenyl group optionally substituted with substituent A below, or benzene ring moiety with substituent A below There represents optionally substituted C7-C9 phenoxyalkyl group,
R ⁵ and R ⁶ are a C1-C10 alkyl group which may be substituted with a halogen atom, a C3-C6 alkoxyalkyl group, a C3-C6 alkenyl group which may be substituted with a halogen atom, or a halogen atom. C3-C6 alkynyl group, C3-C6 cycloalkyl group optionally substituted with the following substituent D, phenyl group optionally substituted with the following substituent E, substituted with the following substituent A An optionally substituted 5-6 membered heteroaryl group, or a C7-C9 phenylalkyl group in which the benzene ring moiety may be substituted with the following substituent A,
R ⁷ and R ⁸ are each independently a hydrogen atom, a C1-C10 alkyl group optionally substituted with a halogen atom, a C2-C6 alkoxyalkyl group, or a C3-C6 alkenyl group optionally substituted with a halogen atom. A C3-C6 alkynyl group which may be substituted with a halogen atom, a C3-C6 cycloalkyl group which may be substituted with the following substituent D, a phenyl group which may be substituted with the following substituent E, It represents a 5-6 membered heteroaryl group which may be substituted with the following substituent A, or a C7-C9 phenylalkyl group where the benzene ring moiety may be substituted with the following substituent A. )
Represents
Z ¹ , Z ² , Z ³ and Z ⁴ are each independently substituted with a hydrogen atom, a halogen atom, a cyano group, a nitro group, an optionally substituted C1-C6 alkyl group or a halogen atom. C1-C6 alkoxy group which may be substituted, phenyl group which may be substituted with halogen atom, C1-C6 alkylthio group which may be substituted with halogen atom, C1-C6 alkylsulfinyl which may be substituted with halogen atom Represents a group, or a C1-C6 alkylsulfonyl group which may be substituted with a halogen atom, or
Z ¹ and Z ² , Z ² and Z ³ , or Z ³ and Z ⁴ together, 1,3-butadiene-1,4-diyl group optionally substituted with the following substituent F The propane-1,3-diyl group optionally substituted with the following substituent D, the butane-1,4-diyl group optionally substituted with the following substituent D, or the following substituent D Represents a methylenedioxy group optionally substituted by

Substituent A: a substituent selected from the group consisting of a halogen atom, a cyano group, a nitro group, a C1-C6 alkyl group which may be substituted with a halogen atom, and a C1-C6 alkoxy group which may be substituted with a halogen atom .
Substituent B: A substituent selected from the group consisting of a halogen atom, a cyano group, a nitro group, a phenyl group, and a C1-C6 alkyl group optionally substituted with a halogen atom.
Substituent C: From halogen atom, C1-C6 alkoxy group, C1-C6 alkylthio group, C1-C6 alkylsulfinyl group, C1-C6 alkylsulfonyl group, C2-C6 dialkylamino group, C3-C6 cycloalkyl group and adamantyl group A substituent selected from the group consisting of
Substituent D: A substituent selected from the group consisting of a halogen atom and a C1-C6 alkyl group.
Substituent E: halogen atom, cyano group, nitro group, C1-C6 alkyl group which may be substituted with halogen atom, phenyl group which may be substituted with halogen atom, C1 which may be substituted with halogen atom -C6 alkoxy group, C1-C6 alkylthio group optionally substituted with a halogen atom, C1-C6 alkylsulfinyl group optionally substituted with a halogen atom, C1-C6 alkylsulfonyl optionally substituted with a halogen atom A substituent selected from the group consisting of a group, a C2-C6 dialkylamino group and a C2-C6 alkoxycarbonyl group.
Substituent F: halogen atom, cyano group, nitro group, C1-C6 alkyl group optionally substituted with a halogen atom, C1-C6 alkoxy group optionally substituted with a halogen atom, substituted with a halogen atom A substituent selected from the group consisting of a C1-C6 alkylthio group which may be substituted, a C1-C6 alkylsulfinyl group which may be substituted with a halogen atom, and a C1-C6 alkylsulfonyl group which may be substituted with a halogen atom. ]
A hydrazide compound represented by the following (hereinafter referred to as the present compound).

  Since the compound of the present invention has an excellent control effect against harmful arthropods, it is useful as an active ingredient of a harmful arthropod control agent.

  In the present invention, examples of the “halogen atom” include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

  Examples of the “C1-C6 alkyl group optionally substituted with a halogen atom” include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a pentyl group. Hexyl group, perfluoropropyl group, perfluorobutyl group and perfluorohexyl group.

  Examples of the “C2-C6 cyanoalkyl group” include a cyanomethyl group and a 2-cyanoethyl group.

  Examples of the “C2-C6 alkoxyalkyl group” include a 2-methoxyethyl group, a 2-ethoxyethyl group, and a 2-isopropyloxyethyl group.

  Examples of the “C3-C6 alkenyl group optionally substituted with a halogen atom” include 2-propenyl group, 3-chloro-2-propenyl group, 2-chloro-2-propenyl group, and 3,3-dichloro-2. -Propenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-2-propenyl group, 3-methyl-2-butenyl group, 2-pentenyl group and 2-hexenyl group are exemplified.

  Examples of the “C3-C6 alkynyl group optionally substituted with a halogen atom” include 2-propynyl group, 3-chloro-2-propynyl group, 3-bromo-2-propynyl group, 2-butynyl group and 3- A butynyl group is mentioned.

  Examples of the “C7-C9 phenylalkyl group in which the benzene ring moiety may be substituted with the substituent A” include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 2-chlorobenzyl group, 3-chloro Benzyl group, 4-chlorobenzyl group, 2-cyanobenzyl group, 3-cyanobenzyl group, 4-cyanobenzyl group, 2-nitrobenzyl group, 3-nitrobenzyl group, 4-nitrobenzyl group, 2-methylbenzyl group 3-methylbenzyl group, 4-methylbenzyl group, 2- (trifluoromethyl) benzyl group, 3- (trifluoromethyl) benzyl group, 4- (trifluoromethyl) benzyl group, 2-methoxybenzyl group, 3 -Methoxybenzyl group and 4-methoxybenzyl group are mentioned.

  Examples of the “C4-C7 (cycloalkyl) alkyl group” include a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, and a cyclohexylmethyl group.

  Examples of the “C2-C6 alkylcarbonyl group” include an acetyl group, an ethylcarbonyl group, an isopropylcarbonyl group, and a tert-butylcarbonyl group.

  Examples of the “C2-C6 alkoxycarbonyl group” include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, and a tert-butoxycarbonyl group.

  Examples of the “C3-C7 dialkylcarbamoyl group” include an N, N-dimethylcarbamoyl group and an N, N-diethylcarbamoyl group.

  Examples of the “phenyl group optionally substituted with the substituent B” include a phenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-cyanophenyl group, 3-cyanophenyl group, 4- Cyanophenyl group, 2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2- (trifluoromethyl) phenyl group, Examples include 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, and 4-biphenyl group.

  Examples of the “C1-C4 alkyl group” include methyl group, ethyl group, propyl group and butyl group, isopropyl group, isobutyl group, sec-butyl group and tert-butyl group.

  Examples of the “C1-C10 alkyl group optionally substituted with substituent C” include, for example, methyl group, trifluoromethyl group, trichloromethyl group, chloromethyl group, dichloromethyl group, fluoromethyl group, difluoromethyl group, methoxy Methyl group, ethoxymethyl group, methylthiomethyl group, ethylthiomethyl group, methylsulfinylmethyl group, methylsulfonylmethyl group, dimethylaminomethyl group, cyclopropylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, ethyl group, pentafluoroethyl Group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cyclopropylmethyl group, cyclohexylmethyl Group, 1- Daman chill methyl group, 2-bromoethyl group, and a 3-chloropropyl group and 5-bromopentyl groups.

  Examples of the “C2-C6 alkenyl group optionally substituted with a halogen atom” include a vinyl group, 1-propenyl group, 2-propenyl group, 1-methylvinyl group, 2-chlorovinyl group and 2-methyl-1 -A propenyl group is mentioned.

  Examples of the “C2-C6 alkynyl group optionally substituted with a halogen atom” include an ethynyl group, a 2-propynyl group, a 3-chloro-2-propynyl group, a 3-bromo-2-propynyl group, and a 2-butynyl group. And 3-butynyl group.

  Examples of the “C3-C6 cycloalkyl group optionally substituted with the substituent D” include a cyclopropyl group, a 2-methylcyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

  Examples of the “phenyl group optionally substituted with the substituent E” include a phenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 4-fluorophenyl group, 4-bromophenyl group, 4- Iodophenyl group, 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, 2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group, 2-methylphenyl group, 3-methylphenyl Group, 4-methylphenyl group, 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2-biphenyl group, 3-biphenyl group, 4- Biphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 4- (trifluoromethyl group) Xyl) phenyl group, 4- (methylthio) phenyl group, 4- (methylsulfinyl) phenyl group, 4- (methylsulfonyl) phenyl group, 2-dimethylaminophenyl group, 3-dimethylaminophenyl group, 4-dimethylaminophenyl Group, 2- (methoxycarbonyl) phenyl group, 3- (methoxycarbonyl) phenyl group and 4- (methoxycarbonyl) phenyl group.

  Examples of the “naphthyl group optionally substituted with the substituent A” include a 1-naphthyl group and a 2-naphthyl group.

  Examples of the “5-6-membered heteroaryl group optionally substituted by the substituent D” include 1-methyl-2-pyrrolyl group, 2-furyl group, 3-furyl group, 5-bromo-2-furyl. Group, 5-nitro-2-furyl group, 2-methyl-3-furyl group, 2,5-dimethyl-3-furyl group, 2,4-dimethyl-3-furyl group, 2-thienyl group, 3-thienyl Group, 5-methyl-2-thienyl group, 3-methyl-2-thienyl group, 1-methyl-3-trifluoromethyl-5-pyrazolyl group, 5-chloro-1,3-dimethyl-4-pyrazolyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 2-methyl-3-pyridinyl group, 6-methyl-3-pyridinyl group, 2-chloro-3-pyridinyl group, 6-chloro-3-pyridinyl group , Pyrazinyl group, 1-pyrrolyl group Preliminary 1-pyrazolyl group, and the like.

  Examples of the “C3-C8 membered non-aromatic heterocyclic group optionally substituted with substituent D” include, for example, tetrahydro-2-furyl group, tetrahydro-3-furyl group, 4-morpholino group, 4-thiomorpholino group 2,6-dimethyl-4-morpholino group, piperidino group, 1-imidazolidino group and 4-methylpiperazino group.

  Examples of the “C7-C9 phenylalkyl group in which the benzene ring moiety may be substituted with the substituent B” include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 2-chlorobenzyl group, 3-chloro Benzyl group, 4-chlorobenzyl group, 4-bromobenzyl group, 2-cyanobenzyl group, 3-cyanobenzyl group, 4-cyanobenzyl group, 2-nitrobenzyl group, 3-nitrobenzyl group, 4-nitrobenzyl group 2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, 2-methoxybenzyl group, 3-methoxybenzyl group, 4-methoxybenzyl group and 4-biphenyl group.

  Examples of the “C8-C10 phenylalkenyl group in which the benzene ring moiety may be substituted with the substituent A” include a cinnamyl group, a 2-chlorocinnamyl group, a 4-nitrocinnamyl group, and a 3-trifluoromethylcinnamyl group. Groups.

  Examples of the “C7-C9 phenoxyalkyl group in which the benzene ring moiety may be substituted with the substituent A” include a phenoxymethyl group, a 4-chlorophenoxymethyl group, a 2-phenoxyethyl group, and a 1-phenoxyethyl group. It is done.

  Examples of the “C1-C10 alkyl group optionally substituted with a halogen atom” include a methyl group, an ethyl group, a 2,2,2-trifluoroethyl group, a 2,2,2-trichloroethyl group, a propyl group, Examples include isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group.

  Examples of the “C3-C6 alkoxyalkyl group” include a 2-methoxyethyl group, a 2-ethoxyethyl group, and a 2-isopropyloxyethyl group.

  Examples of the “5-6-membered heteroaryl group optionally substituted with the substituent A” include a 2-pyridinyl group.

  Examples of the “C1-C6 alkoxy group optionally substituted with a halogen atom” include a methoxy group, a trifluoromethoxy group, an ethoxy group, a 2,2,2-trifluoroethoxy group, a propyloxy group, an isopropyloxy group, Examples include butoxy group, isobutyloxy group, sec-butoxy group, tert-butoxy group, pentyloxy group and hexyloxy group.

  Examples of the “phenyl group optionally substituted with a halogen atom” include a phenyl group, a 2-chlorophenyl group, a 3-chlorophenyl group, and a 4-chlorophenyl group.

  Examples of the “C1-C6 alkylthio group optionally substituted with a halogen atom” include a methylthio group, a trifluoromethylthio group, and an ethylthio group.

  Examples of the “C1-C6 alkylsulfinyl group optionally substituted with a halogen atom” include a methylsulfinyl group, a trifluoromethylsulfinyl group, and an ethylsulfinyl group.

  Examples of the “C1-C6 alkylsulfonyl group optionally substituted with a halogen atom” include a methylsulfonyl group, a trifluoromethylsulfonyl group, and an ethylsulfonyl group.

  Examples of the “1,3-butadiene-1,4-diyl group optionally substituted with the substituent F” include 1,3-butadiene-1,4-diyl group, 2-bromo-1,3-butadiene. -1,4-diyl group, 2-chloro-1,3-butadiene-1,4-diyl group, 2-cyano-1,3-butadiene-1,4-diyl group, 1-nitro-1,3- Examples include butadiene-1,4-diyl group and 1-methyl-1,3-butadiene-1,4-diyl group.

  Examples of the “propane-1,3-diyl group optionally substituted with the substituent D” include a propane-1,3-diyl group and a 1,1-dimethylpropane-1,3-diyl group.

  Examples of the “butane-1,4-diyl group optionally substituted with the substituent D” include a butane-1,3-diyl group.

  Examples of the “methylenedioxy group optionally substituted with the substituent D” include a methylenedioxy group and a difluoromethylenedioxy group.

  Examples of the “C1-C6 alkoxy group” include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutyloxy group, sec-butoxy group, tert-butoxy group, pentyloxy group and hexyloxy group. Can be mentioned.

  Examples of the “C1-C6 alkylthio group” include a methylthio group and an ethylthio group.

  Examples of the “C1-C6 alkylsulfinyl group” include a methylsulfinyl group and an ethylsulfinyl group.

  Examples of the “C1-C6 alkylsulfonyl group” include a methylsulfonyl group and an ethylsulfonyl group.

  Examples of the “C2-C6 dialkylamino group” include a dimethylamino group and a diethylamino group.

  Examples of the “C3-C6 cycloalkyl group” include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

  As an aspect of this invention compound, the following aspects are mentioned, for example.

“Aspect 1”
A hydrazide compound represented by formula (1), wherein Q is Q1.

“Aspect 2”
A hydrazide compound represented by the formula (1), wherein Q is Q2.

“Aspect 3”
A hydrazide compound represented by formula (1), wherein Q is Q3.

“Aspect 4”
A hydrazide compound represented by formula (1), wherein Q is Q4.

“Aspect 5”
A hydrazide compound represented by the formula (1), wherein A ¹ and A ² are oxygen atoms.

“Aspect 6”
A hydrazide compound represented by the formula (1), wherein Q is Q1, and A ¹ , A ² and A ³ are oxygen atoms.
“Aspect 7”
A hydrazide compound represented by the formula (1), wherein Q is Q2 and A ¹ , A ² and A ⁴ are oxygen atoms.
“Aspect 8”
A hydrazide compound represented by the formula (1), wherein Q is Q3, and A ¹ , A ² and A ⁵ are oxygen atoms.
“Aspect 9”
A hydrazide compound represented by the formula (1), wherein Q is Q4, and A ¹ , A ² and A ⁶ are oxygen atoms.

"Aspect 10"
A hydrazide compound represented by the formula (1), wherein Z ¹ , Z ² and Z ⁴ are hydrogen atoms, and Z ³ is a hydrogen atom, a halogen atom or a C1 to C6 alkyl group optionally substituted with a halogen atom.
“Aspect 11”
A hydrazide compound represented by the formula (1), wherein Z ¹ , Z ² and Z ⁴ are hydrogen atoms, and Z ³ is a hydrogen atom, a chlorine atom or a methyl group.
“Aspect 12”
A hydrazide compound represented by the formula (1), wherein Z ^{1 to} Z ⁴ are hydrogen atoms.

“Aspect 13”
In equation (1),
R ¹ is a hydrogen atom or a C1-C6 alkyl group optionally substituted with a halogen atom,
R ² is a hydrogen atom or a C1-C6 alkyl group optionally substituted with a halogen atom,
R ³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted with a halogen atom, or a C2-C6 alkoxycarbonyl group,
A ^{1 to} A ⁶ are oxygen atoms,
R ⁴ is a hydrogen atom, a C1-C10 alkyl group which may be substituted with the substituent C, a C2-C6 alkenyl group which may be substituted with a halogen atom, or a C2-C6 optionally substituted with a halogen atom. An alkynyl group, a C3-C6 cycloalkyl group optionally substituted with the substituent D, or a 3- to 8-membered non-aromatic heterocyclic group optionally substituted with the substituent D;
R ⁵ is a C1-C10 alkyl group optionally substituted with a halogen atom, a C3-C6 alkoxyalkyl group, a C2-C6 alkenyl group optionally substituted with a halogen atom, or the substituent D And may be a C3-C6 cycloalkyl group,
R ⁶ is a C1-C6 alkyl group optionally substituted with a halogen atom,
R ⁷ and R ⁸ are each independently a hydrogen atom, a C1-C10 alkyl group optionally substituted with a halogen atom, or a C2-C6 alkoxyalkyl group,
Z ¹ , Z ² , Z ³ and Z ⁴ are each independently substituted with a hydrogen atom, a halogen atom, a cyano group, a nitro group, a C1-C6 alkyl group which may be substituted with a halogen atom, or a halogen atom. Represents an optionally substituted C1-C6 alkoxy group, or
Z ¹ and Z ² , Z ² and Z ³ , or Z ³ and Z ⁴ together, 1,3-butadiene-1,4-diyl group optionally substituted with the substituent F, A hydrazide compound which is a propane-1,3-diyl group optionally substituted by the substituent D.

“Aspect 14”
In equation (1),
R ¹ and R ² represent a hydrogen atom or a C1-C6 alkyl group optionally substituted with a halogen atom,
R ³ represents a hydrogen atom, a C1-C6 alkyl group which may be substituted with a halogen atom, or a C2-C6 alkoxycarbonyl group,
A ^{1 to} A ⁶ are oxygen atoms,
Z ¹ , Z ² , Z ³ and Z ⁴ are each independently substituted with a hydrogen atom, a halogen atom, a cyano group, a nitro group, a C1-C6 alkyl group which may be substituted with a halogen atom, or a halogen atom. Represents an optionally substituted C1-C6 alkoxy group, or
Z ¹ and Z ² , Z ² and Z ³ , or Z ³ and Z ⁴ together, 1,3-butadiene-1,4-diyl group optionally substituted with the substituent F, Represents a propane-1,3-diyl group optionally substituted by the substituent D;
R ⁴ may be substituted with a hydrogen atom, a C1-C6 alkyl group that may be substituted with a halogen atom, a C3-C6 cycloalkyl group that may be substituted with a halogen atom, or the substituent D. Represents a 3-8 membered non-aromatic heterocyclic group,
R ⁵ may be a C1-C6 alkyl group optionally substituted with a halogen atom, a C2-C6 alkenyl group optionally substituted with a halogen atom, or a C3-C6 cycloalkyl group optionally substituted with a halogen atom Represents
R ⁶ represents a C1-C6 alkyl group which may be substituted with a halogen atom,
A hydrazide compound in which R ⁷ and R ⁸ are each independently a hydrogen atom or a C1-C6 alkyl group optionally substituted with a halogen atom.

“Aspect 15”
In equation (1),
R ¹ and R ² are hydrogen atoms,
R ³ is a hydrogen atom or a C1-C6 alkyl group optionally substituted with a halogen atom,
A ^{1 to} A ⁶ are oxygen atoms,
Z ¹ , Z ² and Z ⁴ are hydrogen atoms,
Z ³ is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a C1-C6 alkyl group optionally substituted with a halogen atom, or a C1-C6 alkoxy group optionally substituted with a halogen atom,
R ⁴ is a hydrogen atom, a C1-C6 alkyl group optionally substituted with a halogen atom, or a 3- to 8-membered non-aromatic heterocyclic group optionally substituted with the substituent D;
R ⁵ and R ⁶ are C1-C6 alkyl groups optionally substituted with a halogen atom,
A hydrazide compound in which R ⁷ and R ⁸ are each independently a C1-C6 alkyl group optionally substituted with a hydrogen atom or a halogen atom.

“Aspect 16”
In equation (1),
R ¹ , R ² and R ³ are hydrogen atoms;
A ^{1 to} A ⁶ are oxygen atoms,
Z ¹ , Z ² and Z ⁴ are hydrogen atoms;
Z ³ is a hydrogen atom or a C1-C6 alkyl group optionally substituted with a halogen atom,
R ⁴ is a C1-C6 alkyl group that may be substituted with a halogen atom, or a 3- to 8-membered non-aromatic heterocyclic group that may be substituted with the substituent D;
R ⁵ and R ⁶ are C1-C6 alkyl groups optionally substituted with a halogen atom,
R ⁷ and R ⁸ are each a hydrazide compound which is a C1-C6 alkyl group optionally substituted with a halogen atom.

"Aspect 17"
In equation (1),
R ¹ is a hydrogen atom, a methyl group or an ethyl group,
R ² is a hydrogen atom, a methyl group, or an ethyl group,
R ³ is a hydrogen atom, a methyl group or an ethyl group,
A ^{1 to} A ⁶ are oxygen atoms,
Z ¹ , Z ² and Z ⁴ are hydrogen atoms,
Z ³ is a hydrogen atom, a halogen atom, a methyl group, or an ethyl group,
R ⁴ is a hydrogen atom, a C1-C6 alkyl group optionally substituted with a halogen atom, a tetrahydro-2-furyl group, a tetrahydro-3-furyl group, a 4-morpholino group, a 4-thiomorpholino group, 2,6- A dimethyl-4-morpholino group, a piperidino group, or a 4-methylpiperazino group,
R ⁵ and R ⁶ are a methyl group, an ethyl group, or a propyl group,
A hydrazide compound in which R ⁷ and R ⁸ are each independently a methyl group, an ethyl group, or a propyl group.

〔式中、Ｒ^1aは水素原子、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキル基、Ｃ２−Ｃ６シアノアルキル基、Ｃ２−Ｃ６アルコキシアルキル基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルケニル基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルキニル基、または、下記の置換基Ａでベンゼン環部分が置換されていてもよいＣ７−Ｃ９フェニルアルキル基を表し、
Ｒ^2aは、水素原子、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキル基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルケニル基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルキニル基、Ｃ２−Ｃ６シアノアルキル基、下記の置換基Ｄで置換されていてもよいＣ３−Ｃ６シクロアルキル基、または、Ｃ４−Ｃ７（シクロアルキル）アルキル基を表し、
Ｒ^3aは、水素原子、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキル基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルケニル基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルキニル基、Ｃ２−Ｃ６シアノアルキル基、または、下記の置換基Ｄで置換されていてもよいＣ３−Ｃ６シクロアルキル基、Ｃ４−Ｃ７（シクロアルキル）アルキル基、ホルミル基、Ｃ２−Ｃ６アルキルカルボニル基、Ｃ２−Ｃ６アルコキシカルボニル基、Ｃ３−Ｃ７ジアルキルカルバモイル基、または、下記の置換基Ｂで置換されていてもよいフェニル基を表すか、或いは、
Ｒ^２aとＲ^３aとが一緒になって、−（ＣH₂）₃−、−（ＣH₂）₄−、−（ＣH₂）₅−、−ＣH₂−ＣH＝ＣH−ＣH₂−、−（ＣH₂）_２−Ｏ−（ＣH₂）_２−、−（ＣH₂）_２−Ｓ−（ＣH₂）_２−、−（ＣH₂）_２−Ｓ（Ｏ）−（ＣH₂）_２−、−（ＣH₂）_２−Ｓ（Ｏ_２）−（ＣH₂）_２−、−（ＣH₂）_２−ＮＨ−（ＣH₂）_２−又は−（ＣH₂）_２−ＮＲ^21a−（ＣH₂）_２−〈ここで、Ｒ²¹はＣ１−Ｃ４アルキル基を表す。〉を表し、
Ｒ^aは水素原子、下記の置換基Ｃで置換されていてもよいＣ１−Ｃ１０アルキル基、ハロゲン原子で置換されていてもよいＣ２−Ｃ６アルケニル基、ハロゲン原子で置換されていてもよいＣ２−Ｃ６アルキニル基、下記の置換基Ｄで置換されていてもよいＣ３−Ｃ６シクロアルキル基、下記の置換基Ｅで置換されていてもよいフェニル基、下記の置換基Ａで置換されていてもよいナフチル基、下記の置換基Ｄで置換されていてもよい５−６員環ヘテロアリール基、下記の置換基Ｄで置換されていてもよい３−８員非芳香へテロ環基、下記の置換基Ｂでベンゼン環部分が置換されていてもよいＣ７−Ｃ９フェニルアルキル基、下記の置換基Ａで置換されていてもよいＣ８−Ｃ１０フェニルアルケニル基、下記の置換基Ａでベンゼン環部分が置換されていてもよいＣ７−Ｃ９フェノキシアルキル基、
ハロゲン原子で置換されていてもよいＣ１−Ｃ１０アルコキシ基、Ｃ３−Ｃ６アルコキシアルコキシ基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルケニルオキシ基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルキニルオキシ基、下記の置換基Ｄで置換されていてもよいＣ３−Ｃ６シクロアルキルオキシ基、下記の置換基Ｅで置換されていてもよいフェニルオキシ基、下記の置換基Ａで置換されていてもよい置換されていてもよい５−６員環へテロアリールオキシ基、下記の置換基Ａでベンゼン環部分が置換されていてもよいＣ７−Ｃ９フェニルアルキルオキシ基、
ハロゲン原子で置換されていてもよいＣ１−Ｃ１０アルキルチオ基、Ｃ３−Ｃ６アルコキシアルキルチオ基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルケニルチオ基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルキニルチオ基、下記の置換基Ｄで置換されていてもよいＣ３−Ｃ６シクロアルキルチオ基、下記の置換基Ｅで置換されていてもよいフェニルチオ基、
アミノ基、ハロゲン原子で置換されていてもよいＣ１−Ｃ１０アルキルアミノ基、ハロゲン原子で置換されていてもよいジ（Ｃ１−Ｃ１０アルキル）アミノ基、Ｃ２−Ｃ６アルコキシアルキルアミノ基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルケニルアミノ基、ハロゲン原子で置換されていてもよいジ（Ｃ１−Ｃ１０アルケニル）アミノ基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルキニルアミノ基、下記の置換基Ｄで置換されていてもよいＣ３−Ｃ６シクロアルキルアミノ基、下記の置換基Ｅで置換されていてもよいフェニルアミノ基、下記の置換基Ａで置換されていてもよい５−６員環へテロアリールアミノ基、または、下記の置換基Ａでベンゼン環部分が置換されていてもよいＣ７−Ｃ９フェニルアルキルアミノ基を表す。
置換基Ａ：ハロゲン原子、シアノ基、ニトロ基、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキル基およびハロゲン原子で置換されていてもよいＣ１−Ｃ６アルコキシ基からなる群より選ばれる置換基。
置換基Ｂ：ハロゲン原子、シアノ基、ニトロ基、フェニル基およびハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキル基からなる群より選ばれる置換基。
置換基Ｃ：ハロゲン原子、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、Ｃ２−Ｃ６ジアルキルアミノ基、Ｃ３−Ｃ６シクロアルキル基およびアダマンチル基からなる群より選ばれる置換基。
置換基Ｄ：ハロゲン原子およびＣ１−Ｃ６アルキル基からなる群より選ばれる置換基。
置換基Ｅ：ハロゲン原子、シアノ基、ニトロ基、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキル基、ハロゲン原子で置換されていてもよいフェニル基、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルコキシ基、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキルチオ基、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキルスルフィニル基、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキルスルホニル基、Ｃ２−Ｃ６ジアルキルアミノ基およびＣ２−Ｃ６アルコキシカルボニル基からなる群より選ばれる置換基。
置換基Ｆ：ハロゲン原子、シアノ基、ニトロ基、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキル基、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルコキシ基、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキルチオ基、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキルスルフィニル基およびハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキルスルホニル基からなる群より選ばれる置換基。〕
で示されるヒドラジド化合物。 “Aspect 18”
Formula (1-1)

[Wherein, R ^1a is a hydrogen atom, a C1-C6 alkyl group optionally substituted with a halogen atom, a C2-C6 cyanoalkyl group, a C2-C6 alkoxyalkyl group, a C3-optionally substituted C3- A C6-alkenyl group, a C3-C6 alkynyl group optionally substituted with a halogen atom, or a C7-C9 phenylalkyl group in which the benzene ring moiety may be substituted with the following substituent A,
R ^2a represents a hydrogen atom, a C1-C6 alkyl group optionally substituted with a halogen atom, a C3-C6 alkenyl group optionally substituted with a halogen atom, or a C3-C6 alkynyl optionally substituted with a halogen atom. Group, a C2-C6 cyanoalkyl group, a C3-C6 cycloalkyl group optionally substituted with the following substituent D, or a C4-C7 (cycloalkyl) alkyl group,
R ^3a is a hydrogen atom, a C1-C6 alkyl group optionally substituted with a halogen atom, a C3-C6 alkenyl group optionally substituted with a halogen atom, or a C3-C6 alkynyl optionally substituted with a halogen atom. Group, C2-C6 cyanoalkyl group, or C3-C6 cycloalkyl group, C4-C7 (cycloalkyl) alkyl group, formyl group, C2-C6 alkylcarbonyl group optionally substituted by the following substituent D, Represents a C2-C6 alkoxycarbonyl group, a C3-C7 dialkylcarbamoyl group, or a phenyl group optionally substituted by the following substituent B, or
R ^2a and R ^3a are combined to form — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, —CH ₂ —CH═CH—CH ₂ —, — ( _{CH 2) 2 -O- (CH 2} ) 2 -, - (CH 2) 2 -S- (CH 2) 2 -, - (CH 2) 2 -S (O) - (CH 2) 2 -, - (CH ₂ ) ₂ —S (O ₂ ) — (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —NH— (CH ₂ ) ₂ — or — (CH ₂ ) ₂ —NR ^21a — (CH ₂ ) ₂ - <where, R ²¹ represents a C1-C4 alkyl group. >
R ^a is a hydrogen atom, ^a C1-C10 alkyl group that may be substituted with the following substituent C, a C2-C6 alkenyl group that may be substituted with a halogen atom, or C2- that is optionally substituted with a halogen atom. A C6-alkynyl group, a C3-C6 cycloalkyl group optionally substituted with the following substituent D, a phenyl group optionally substituted with the following substituent E, and optionally substituted with the following substituent A. A naphthyl group, a 5-6 membered heteroaryl group optionally substituted with the following substituent D, a 3-8 membered non-aromatic heterocyclic group optionally substituted with the following substituent D, the following substitution: C7-C9 phenylalkyl group optionally substituted with benzene ring moiety by group B, C8-C10 phenylalkenyl group optionally substituted with substituent A below, and benzene ring moiety substituted with substituent A below Which may also be C7-C9 phenoxyalkyl group,
C1-C10 alkoxy group optionally substituted with a halogen atom, C3-C6 alkoxyalkoxy group, C3-C6 alkenyloxy group optionally substituted with a halogen atom, C3-C6 optionally substituted with a halogen atom An alkynyloxy group, a C3-C6 cycloalkyloxy group which may be substituted with the following substituent D, a phenyloxy group which may be substituted with the following substituent E, and a substituent A described below. An optionally substituted 5-6 membered heteroaryloxy group, a C7-C9 phenylalkyloxy group in which the benzene ring moiety may be substituted with the following substituent A,
C1-C10 alkylthio group, C3-C6 alkoxyalkylthio group optionally substituted with a halogen atom, C3-C6 alkenylthio group optionally substituted with a halogen atom, C3-C6 optionally substituted with a halogen atom An alkynylthio group, a C3-C6 cycloalkylthio group optionally substituted with the following substituent D, a phenylthio group optionally substituted with the following substituent E,
Substituted with amino group, C1-C10 alkylamino group optionally substituted with halogen atom, di (C1-C10 alkyl) amino group optionally substituted with halogen atom, C2-C6 alkoxyalkylamino group, halogen atom An optionally substituted C3-C6 alkenylamino group, an optionally substituted di (C1-C10 alkenyl) amino group, an optionally substituted C3-C6 alkynylamino group, the following substitution: C3-C6 cycloalkylamino group optionally substituted with group D, phenylamino group optionally substituted with the following substituent E, 5-6 membered ring optionally substituted with the following substituent A Heteroarylamino group or C7-C9 phenylalkylamino in which the benzene ring moiety may be substituted with the following substituent A It represents a group.
Substituent A: a substituent selected from the group consisting of a halogen atom, a cyano group, a nitro group, a C1-C6 alkyl group which may be substituted with a halogen atom, and a C1-C6 alkoxy group which may be substituted with a halogen atom .
Substituent B: A substituent selected from the group consisting of a halogen atom, a cyano group, a nitro group, a phenyl group, and a C1-C6 alkyl group optionally substituted with a halogen atom.
Substituent C: From halogen atom, C1-C6 alkoxy group, C1-C6 alkylthio group, C1-C6 alkylsulfinyl group, C1-C6 alkylsulfonyl group, C2-C6 dialkylamino group, C3-C6 cycloalkyl group and adamantyl group A substituent selected from the group consisting of
Substituent D: A substituent selected from the group consisting of a halogen atom and a C1-C6 alkyl group.
Substituent E: halogen atom, cyano group, nitro group, C1-C6 alkyl group which may be substituted with halogen atom, phenyl group which may be substituted with halogen atom, C1 which may be substituted with halogen atom -C6 alkoxy group, C1-C6 alkylthio group optionally substituted with a halogen atom, C1-C6 alkylsulfinyl group optionally substituted with a halogen atom, C1-C6 alkylsulfonyl optionally substituted with a halogen atom A substituent selected from the group consisting of a group, a C2-C6 dialkylamino group and a C2-C6 alkoxycarbonyl group.
Substituent F: halogen atom, cyano group, nitro group, C1-C6 alkyl group optionally substituted with a halogen atom, C1-C6 alkoxy group optionally substituted with a halogen atom, substituted with a halogen atom A substituent selected from the group consisting of a C1-C6 alkylthio group which may be substituted, a C1-C6 alkylsulfinyl group which may be substituted with a halogen atom, and a C1-C6 alkylsulfonyl group which may be substituted with a halogen atom. ]
A hydrazide compound represented by:

"Aspect 19"
In formula (1-1),
R ^1a is a hydrogen atom or a C1-C6 alkyl group optionally substituted with a halogen atom,
R ^2a is a hydrogen atom or a C1-C6 alkyl group optionally substituted with a halogen atom,
R ^3a is a hydrogen atom, a C1-C6 alkyl group optionally substituted with a halogen atom, or a C2-C6 alkoxycarbonyl group,
R ^a is a hydrogen atom, ^a C1-C10 alkyl group that may be substituted with the substituent C, a C2-C6 alkenyl group that may be substituted with a halogen atom, or a C2-C6 that may be substituted with a halogen atom. An alkynyl group, a C3-C6 cycloalkyl group optionally substituted with the substituent D, a 3-8-membered non-aromatic heterocyclic group optionally substituted with the substituent D,
A C1-C10 alkoxy group optionally substituted with a halogen atom, a C3-C6 alkoxyalkyloxy group, a C2-C6 alkenyloxy group optionally substituted with a halogen atom, and optionally substituted with the substituent D. A C3-C6 cycloalkyloxy group,
A C1-C6 alkylthio group optionally substituted with a halogen atom,
Hydrazide which is an amino group, a C1-C10 alkylamino group optionally substituted with a halogen atom, a di (C1-C10 alkyl) amino group optionally substituted with a halogen atom, or a C2-C6 alkoxyalkylamino group Compound.

“Aspect 20”
In formula (1-1),
R ^1a and R ^2a are a hydrogen atom or a C1-C6 alkyl group optionally substituted by a halogen atom,
R ^3a is a hydrogen atom, a C1-C6 alkyl group optionally substituted with a halogen atom, or a C2-C6 alkoxycarbonyl group,
R ^a is a hydrogen atom, ^a C1-C6 alkyl group optionally substituted with a halogen atom, a C3-C6 cycloalkyl group optionally substituted with a halogen atom, or the substituent D 3- 8-membered non-aromatic heterocyclic group,
A C1-C6 alkoxy group optionally substituted with a halogen atom, a C2-C6 alkenyloxy group optionally substituted with a halogen atom, a C3-C6 cycloalkyloxy group optionally substituted with a halogen atom,
A C1-C6 alkylthio group optionally substituted with a halogen atom,
A hydrazide compound which is an amino group, a C1-C6 alkylamino group which may be substituted with a halogen atom, or a di (C1-C6 alkyl) amino group which may be substituted with a halogen atom.

“Aspect 21”
In formula (1-1),
R ^1a and R ^2a are hydrogen atoms,
R ^3a is a hydrogen atom or a C1-C6 alkyl group optionally substituted with a halogen atom,
R ^a is a hydrogen atom, ^a C1-C6 alkyl group that may be substituted with a halogen atom, ^{a 3-} to 8-membered non-aromatic heterocyclic group that may be substituted with the substituent D, or a halogen atom. C1-C6 alkoxy group which may be substituted, C1-C6 alkylthio group which may be substituted with halogen atom, amino group, C1-C6 alkylamino group which may be substituted with halogen atom, or substituted with halogen atom A hydrazide compound which may be a di (C1-C6 alkyl) amino group.

“Aspect 22”
In formula (1-1),
R ^1a , R ^2a and R ^3a are hydrogen atoms;
R ^a is ^a C1-C6 alkyl group optionally substituted with ^a halogen atom, ^{a 3-} to 8-membered non-aromatic heterocyclic group optionally substituted with the substituent D,
A C1-C6 alkoxy group optionally substituted with a halogen atom, a C1-C6 alkylthio group optionally substituted with a halogen atom,
A hydrazide compound which is a C1-C6 alkylamino group optionally substituted with a halogen atom or a di (C1-C6 alkyl) amino group optionally substituted with a halogen atom.

“Aspect 23”
In formula (1-1),
R ^1a is a hydrogen atom, a methyl group or an ethyl group,
R ^2a is a hydrogen atom, a methyl group or an ethyl group,
R ^3a is a hydrogen atom, a methyl group or an ethyl group,
R ^a is a hydrogen atom, ^a C1-C6 alkyl group optionally substituted with a halogen atom, a tetrahydro-2-furyl group, a tetrahydro-3-furyl group, a 4-morpholino group, a 4-thiomorpholino group, 2,6- Dimethyl-4-morpholino group, piperidino group, 4-methylpiperazino group,
Methoxy group, ethoxy group, propyloxy group,
Methylthio group, ethylthio group, propylthio group,
A hydrazide compound which is a methylamino group, an ethylamino group, a propylamino group, a dimethylamino group, a diethylamino group, or a dipropylamino group.

Next, the manufacturing method of this invention compound is shown.
The compound of the present invention can be produced, for example, by the following (Production Method A-1) to (Production Method C-1).

〔式中、Ｒ¹、Ｒ²、Ｒ³、Ａ¹、Ａ²、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、前記と同じ意味を表し、
Ｑ’は、前記Ｑ１〜Ｑ４からなる群より選ばれるいずれか（但し、Ｑ’がＱ４であり、Ｒ⁷およびＲ⁸の両者が水素原子である場合を除く）を表す。〕
で示される化合物（以下、化合物（１−ｉ）と記す。）は、
式（２）

〔式中、Ｒ¹、Ｒ²、Ｒ³、Ａ¹、Ａ²、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（２）と記す。）と、
式（３）

〔式中、Ｑ’は前記と同じ意味を表し、
Ｌ¹は、ハロゲン原子またはＱ’−Ｏ−基（但し、Ｑ’がＱ４であり、Ｒ⁸およびＲ⁹が水素原子である場合を除く。）を表す。）〕
で示される化合物（以下、化合物（３）と記す。）とを反応させることにより製造することができる。 (Production method A-1)
Among the compounds of the present invention,
Formula (1-i)

[Wherein R ¹ , R ² , R ³ , A ¹ , A ² , Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above,
Q ′ represents any one selected from the group consisting of Q1 to Q4 (except when Q ′ is Q4 and both R ⁷ and R ⁸ are hydrogen atoms). ]
(Hereinafter referred to as compound (1-i))
Formula (2)

[Wherein, R ¹ , R ² , R ³ , A ¹ , A ² , Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above. ]
A compound represented by the following (hereinafter referred to as compound (2));
Formula (3)

[Wherein Q ′ represents the same meaning as described above,
L ¹ represents a halogen atom or a Q′—O— group (except when Q ′ is Q4 and R ⁸ and R ⁹ are hydrogen atoms). )]
It can manufacture by making the compound shown below (it is hereafter described as a compound (3)) react.

  The reaction is performed in the presence or absence of a solvent. Examples of the solvent used in the reaction include 1,4-dioxane, diethyl ether, tetrahydrofuran, ethers such as methyl = tert-butyl ether, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene. Aprotic polarities such as hydrocarbons, hydrocarbons such as toluene, benzene, xylene, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide Examples include solvents and mixtures thereof.

  The amount of compound (3) used in the reaction is usually 1 to 2 moles relative to 1 mole of compound (2).

  The reaction is performed in the presence of a base, if necessary. Examples of the base used when carried out in the presence of a base include pyridine, picoline, 2,6-lutidine, 1,8-diazabicyclo [5,4,0] 7-undecene (DBU), 1,5-diazabicyclo. Examples thereof include nitrogen-containing heterocyclic compounds such as [4,3,0] 5-nonene (DBN), tertiary amines such as triethylamine and N, N-diisopropylethylamine, and inorganic bases such as potassium carbonate and sodium hydride. When performed in the presence of a base, the amount of the base used is usually 1 mol or more per 1 mol of the compound (2).

  The reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.

  After completion of the reaction, the compound (1-i) can be isolated by pouring the reaction mixture into water and extracting the mixture with an organic solvent, or collecting a deposited precipitate by filtration. The isolated compound (1-i) can be further purified by recrystallization, chromatography or the like.

〔式中、Ｒ¹、Ｒ²、Ｒ³、Ａ¹、Ａ²、Ａ⁶、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、前記と同じ意味を表し、
Ｒ^7aはハロゲン原子で置換されていてもよいＣ１−Ｃ１０アルキル基、Ｃ２−Ｃ６アルコキシアルキル基、ハロゲン原子で置換されていてもよいＣ２−Ｃ６アルケニル基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルキニル基、前記置換基Ｄで置換されていてもよいＣ３−Ｃ６シクロアルキル基、前記置換基Ｅで置換されていてもよいフェニル基、前記置換基Ａで置換されていてもよい５−６員環へテロアリール基、または、前記置換基Ａでベンゼン環部分が置換されていてもよいＣ７−Ｃ９フェニルアルキル基を表す。〕
で示される化合物（以下、化合物（１−ｉｉ）と記す。）は、化合物（２）と、
式（４）

〔式中、Ａ⁶およびＲ^7aは、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（４）と記す。）とを反応させることにより製造することができる。 (Production method A-2)
Among the compounds of the present invention,
Formula (1-ii)

[Wherein R ¹ , R ² , R ³ , A ¹ , A ² , A ⁶ , Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above,
R ^7a is a C1-C10 alkyl group which may be substituted with a halogen atom, a C2-C6 alkoxyalkyl group, a C2-C6 alkenyl group which may be substituted with a halogen atom, or a C3 which may be substituted with a halogen atom. -C6 alkynyl group, C3-C6 cycloalkyl group optionally substituted with the substituent D, phenyl group optionally substituted with the substituent E, and optionally substituted with the substituent A 5- It represents a 6-membered heteroaryl group or a C7-C9 phenylalkyl group in which the benzene ring moiety may be substituted with the substituent A. ]
The compound represented by (hereinafter referred to as compound (1-ii)) is compound (2),
Formula (4)

[Wherein, A ⁶ and R ^7a represent the same meaning as described above. ]
It can manufacture by making the compound shown below (it is hereafter described as a compound (4)) react.

  The reaction is performed in the presence or absence of a solvent. Examples of the solvent used in the reaction include 1,4-dioxane, diethyl ether, tetrahydrofuran, ethers such as methyl = tert-butyl ether, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene. Aprotic polarities such as hydrocarbons, hydrocarbons such as toluene, benzene, xylene, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide Examples include solvents and mixtures thereof.

  The amount of compound (4) used in the reaction is usually 1 mol or more per 1 mol of compound (2).

  The reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.

  After completion of the reaction, the compound (1-ii) can be isolated by pouring the reaction mixture into water and extracting the mixture with an organic solvent, or collecting a deposited precipitate by filtration. The isolated compound (1-ii) can be further purified by recrystallization, chromatography or the like.

〔式中、Ｒ¹、Ｒ²、Ｒ³、Ａ¹、Ａ²、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（１−iii）と記す。）は、化合物（２）と、シアン酸塩またはチオシアン酸塩とを反応させることにより製造することができる。 (Production method A-3)
Among the compounds of the present invention,
Formula (1-iii)

[Wherein, R ¹ , R ² , R ³ , A ¹ , A ² , Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above. ]
(Hereinafter referred to as compound (1-iii)) can be produced by reacting compound (2) with cyanate or thiocyanate.

  The reaction is performed in the presence of a solvent. Examples of the solvent used in the reaction include organic acids such as acetic acid and mineral acids such as hydrochloric acid, and mixtures of these acids with water, chloroform and the like.

  The amount of cyanate or thiocyanate used in the reaction is usually 1 mol or more per 1 mol of compound (2).

  The reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.

  Examples of cyanate or thiocyanate include potassium cyanate, sodium cyanate, ammonium cyanate, potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate.

  After completion of the reaction, the compound (1-iii) can be isolated by pouring the reaction mixture into water and extracting the mixture with an organic solvent, or collecting a deposited precipitate by filtration. The isolated compound (1-iii) can be further purified by recrystallization, chromatography or the like.

〔式中、Ｒ¹、Ｒ²、Ｒ³、Ａ²、Ｚ¹、Ｚ²、Ｚ³、Ｚ⁴およびＱは、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（６）と記す。）と、
式（７）

〔式中、Ｌ²は、ハロゲン原子を表し、Ａ¹は、前記と同じ意味を表す。〕
で示される化合物、またはその塩酸塩（以下、化合物（７）と記す。）とを反応させることにより製造することができる。 (Production method B-1)
The compound of the present invention
Formula (6)

[Wherein, R ¹ , R ² , R ³ , A ² , Z ¹ , Z ² , Z ³ , Z ⁴ and Q represent the same meaning as described above. ]
A compound represented by formula (hereinafter referred to as compound (6)),
Formula (7)

[Wherein L ² represents a halogen atom, and A ¹ represents the same meaning as described above. ]
Or a hydrochloride thereof (hereinafter referred to as compound (7)).

  The reaction is performed in the presence or absence of a solvent. Examples of the solvent used in the reaction include 1,4-dioxane, diethyl ether, tetrahydrofuran, ethers such as methyl = tert-butyl ether, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene. Aprotic polarities such as hydrocarbons, hydrocarbons such as toluene, benzene, xylene, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide Examples include solvents and mixtures thereof.

  The amount of compound (7) used in the reaction is usually 1 mol or more per 1 mol of compound (6).

  The reaction is performed in the presence of a base, if necessary. Examples of the base used when carried out in the presence of a base include pyridine, picoline, 2,6-lutidine, 1,8-diazabicyclo [5,4,0] 7-undecene (DBU), 1,5-diazabicyclo. Examples thereof include nitrogen-containing heterocyclic compounds such as [4,3,0] 5-nonene (DBN), tertiary amines such as triethylamine and N, N-diisopropylethylamine, and inorganic bases such as potassium carbonate and sodium hydride. When performed in the presence of a base, the amount of the base used is usually 1 mol or more per 1 mol of the compound (6).

  The reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.

  After completion of the reaction, the compound of the present invention can be isolated by pouring the reaction mixture into water and extracting the mixture with an organic solvent, or collecting a deposited precipitate by filtration. The isolated compound of the present invention can be further purified by recrystallization, chromatography or the like.

〔式中、Ｒ¹、Ｒ²、Ｒ³、Ａ²、Ｚ¹、Ｚ²、Ｚ³、Ｚ⁴およびＱは、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（１−ｉｖ）と記す。）は、化合物（６）と、
式（８）

で示される化合物（以下、化合物（８）と記す。）とを脱水剤の存在下で反応させることにより製造することができる。 (Production method B-2)
Among the compounds of the present invention,
Formula (1-iv)

[Wherein, R ¹ , R ² , R ³ , A ² , Z ¹ , Z ² , Z ³ , Z ⁴ and Q represent the same meaning as described above. ]
The compound represented by (hereinafter referred to as compound (1-iv)) is compound (6),
Formula (8)

In the presence of a dehydrating agent (hereinafter, referred to as compound (8)).

  The reaction is performed in the presence or absence of a solvent. Examples of the solvent used in the reaction include 1,4-dioxane, diethyl ether, tetrahydrofuran, ethers such as methyl = tert-butyl ether, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene. Aprotic polarities such as hydrocarbons, hydrocarbons such as toluene, benzene, xylene, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide Examples include solvents and mixtures thereof.

  The amount of compound (8) used in the reaction is usually 1 mol or more per 1 mol of compound (6).

  Examples of the dehydrating agent used in the reaction include carbodiimides such as dicyclohexylcarbodiimide (DCC) and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC). The amount of the dehydrating agent used is usually 1 mol or more per 1 mol of the compound (6).

  The reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.

  After completion of the reaction, the compound (1-iv) can be isolated by pouring the reaction mixture into water and extracting the mixture with an organic solvent, or collecting a deposited precipitate by filtration. The isolated compound (1-iv) can be further purified by recrystallization, chromatography or the like.

〔式中、Ｒ²、Ｒ³、Ｚ¹、Ｚ²、Ｚ³、Ｚ⁴およびＱは、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（１−ｖ）と記す。）は、
式（９）

〔式中、Ｚ¹、Ｚ²、Ｚ³、Ｚ⁴は、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（９）と記す。）と、
式（１０）

〔式中、Ｒ²、Ｒ³およびＱは、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（１０）と記す。）
とを反応させることにより製造することができる。 (Production method C-1)
Among the compounds of the present invention,
Formula (1-v)

[Wherein R ² , R ³ , Z ¹ , Z ² , Z ³ , Z ⁴ and Q represent the same meaning as described above. ]
(Hereinafter referred to as the compound (1-v))
Formula (9)

[Wherein Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above. ]
A compound represented by formula (hereinafter referred to as compound (9)),
Formula (10)

[Wherein R ² , R ³ and Q represent the same meaning as described above. ]
(Hereinafter referred to as compound (10))
It can manufacture by making these react.

  The reaction is performed in the presence or absence of a solvent. Examples of the solvent used in the reaction include 1,4-dioxane, diethyl ether, tetrahydrofuran, ethers such as methyl = tert-butyl ether, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene. Aprotic polarities such as hydrocarbons, hydrocarbons such as toluene, benzene, xylene, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide Examples include solvents and mixtures thereof.

  The amount of compound (10) used in the reaction is usually 1 mol or more per 1 mol of compound (9).

  The reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 48 hours.

  After completion of the reaction, the compound (1-v) can be isolated by pouring the reaction mixture into water and extracting the mixture with an organic solvent, or collecting a deposited precipitate by filtration. The isolated compound (1-v) can be further purified by recrystallization, chromatography or the like.

〔式中、Ｒ²、Ｒ³、Ａ¹、Ｚ¹、Ｚ²、Ｚ³、Ｚ⁴およびＱは、前記と同じ意味を表し、
Ｒ^1aは、ハロゲン原子で置換されていてもよいＣ１−Ｃ６アルキル基、Ｃ２−Ｃ６シアノアルキル基、Ｃ２−Ｃ６アルコキシアルキル基、ハロゲン原子で置換されていてもよいＣ２−Ｃ６アルケニル基、ハロゲン原子で置換されていてもよいＣ３−Ｃ６アルキニル基、または、前記置換基Ａでベンゼン環部分が置換されていてもよいＣ７−Ｃ９フェニルアルキル基を表す。〕
で示される化合物（以下、化合物（１−ｖｉ）と記す。）は、
式（１１）

〔式中、Ｒ^1a、Ａ¹、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、前記と同じ意味を表し、
Ｌ³はハロゲン原子を表す。〕
で示される化合物（以下、化合物（１１）と記す。）と、化合物（１０）とを反応させることにより製造することができる。 (Production method C-2)
Among the compounds of the present invention,
Formula (1-vi)

[Wherein R ² , R ³ , A ¹ , Z ¹ , Z ² , Z ³ , Z ⁴ and Q represent the same meaning as described above,
R ^1a is a C1-C6 alkyl group optionally substituted with a halogen atom, a C2-C6 cyanoalkyl group, a C2-C6 alkoxyalkyl group, a C2-C6 alkenyl group optionally substituted with a halogen atom, a halogen atom Represents a C3-C6 alkynyl group which may be substituted with or a C7-C9 phenylalkyl group where the benzene ring moiety may be substituted with the substituent A. ]
(Hereinafter referred to as the compound (1-vi))
Formula (11)

[Wherein, R ^1a , A ¹ , Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above,
L ³ represents a halogen atom. ]
It can manufacture by making the compound (it is hereafter described as a compound (11)) shown by these, and a compound (10) react.

  The reaction is performed in the presence or absence of a solvent. Examples of the solvent used in the reaction include 1,4-dioxane, diethyl ether, tetrahydrofuran, ethers such as methyl = tert-butyl ether, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene. Aprotic polarities such as hydrocarbons, hydrocarbons such as toluene, benzene, xylene, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide Examples include solvents and mixtures thereof.

  The amount of compound (10) used in the reaction is usually 1 mol or more per 1 mol of compound (11).

  The reaction is performed in the presence of a base as necessary. Examples of the base used when carried out in the presence of a base include pyridine, picoline, 2,6-lutidine, 1,8-diazabicyclo [5,4,0] 7-undecene (DBU), 1,5-diazabicyclo. Examples thereof include nitrogen-containing heterocyclic compounds such as [4,3,0] 5-nonene (DBN), tertiary amines such as triethylamine and N, N-diisopropylethylamine, and inorganic bases such as potassium carbonate and sodium hydride. When performed in the presence of a base, the amount of the base used is usually 1 mol or more per 1 mol of the compound (6).

  The reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.

  After completion of the reaction, the compound (1-vi) can be isolated by pouring the reaction mixture into water and extracting the mixture with an organic solvent, or collecting a deposited precipitate by filtration. The isolated compound (1-vi) can be further purified by recrystallization, chromatography or the like.

〔式中、Ｒ^1a、Ａ¹、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（１２）と記す。）と、化合物（１０）とを脱水剤と存在下反応させることにより製造することもできる。 (Production method C-3)
Compound (1-vi) is
Formula (12)

[Wherein, R ^1a , A ¹ , Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above. ]
It can also be produced by reacting a compound represented by formula (hereinafter referred to as compound (12)) with compound (10) in the presence of a dehydrating agent.

  The reaction is performed in the presence or absence of a solvent. Examples of the solvent used in the reaction include 1,4-dioxane, diethyl ether, tetrahydrofuran, ethers such as methyl = tert-butyl ether, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene. Aprotic polarities such as hydrocarbons, hydrocarbons such as toluene, benzene, xylene, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide Examples include solvents and mixtures thereof.

  The amount of compound (10) used in the reaction is usually 1 mol or more per 1 mol of compound (12).

  Examples of the dehydrating agent used in the reaction include carbodiimides such as dicyclohexylcarbodiimide (DCC) and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC). The amount of the dehydrating agent used is usually 1 mol or more per 1 mol of the compound (12).

  The reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.

  After completion of the reaction, the compound (1-vi) can be isolated by pouring the reaction mixture into water and extracting the mixture with an organic solvent, or collecting a deposited precipitate by filtration. The isolated compound (1-vi) can be further purified by recrystallization, chromatography or the like.

  Next, the manufacturing method of the manufacturing intermediate of this invention compound is demonstrated.

〔式中、Ｒ²、Ｒ³、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（２−ｉ）と記す。）は、化合物（９）と、
式（１３）

〔式中、Ｒ²およびＲ³は、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（１３）と記す。）とを反応させることにより製造することができる。 (Reference production method 1)
Of the compounds (2)
Formula (2-i)

[Wherein R ² , R ³ , Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above. ]
(Hereinafter referred to as compound (2-i)) is a compound (9),
Formula (13)

[Wherein R ² and R ³ represent the same meaning as described above. ]
It can manufacture by making the compound shown below (it is hereafter described as a compound (13)) react.

  The reaction is performed in the presence or absence of a solvent. Examples of the solvent used in the reaction include 1,4-dioxane, diethyl ether, tetrahydrofuran, ethers such as methyl = tert-butyl ether, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene. Aprotic polarities such as hydrocarbons, hydrocarbons such as toluene, benzene, xylene, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide Examples include solvents, alcohols such as methanol, ethanol, 2-propanol, and mixtures thereof.

  The amount of compound (13) used in the reaction is usually 1 mol or more per 1 mol of compound (9).

  The reaction temperature of the reaction is usually in the range of −50 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.

  After completion of the reaction, the compound (2-i) can be isolated by pouring the reaction mixture into water and extracting the mixture with an organic solvent, or collecting a deposited precipitate by filtration. The isolated compound (2-i) can be further purified by recrystallization, chromatography or the like.

〔式中、Ｒ²、Ｒ³、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（２−ｉｉ）と記す。）は、
式（１４）

〔式中、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（１４）と記す。）と、化合物（１３）とを反応させることにより製造することができる。 (Reference production method 2)
Of the compounds (2)
Formula (2-ii)

[Wherein R ² , R ³ , Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above. ]
(Hereinafter referred to as the compound (2-ii))
Formula (14)

[Wherein, Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above. ]
It can manufacture by making the compound (henceforth a compound (14)) shown by these, and a compound (13) react.

  The reaction is performed in the presence or absence of a solvent. Examples of the solvent used in the reaction include 1,4-dioxane, diethyl ether, tetrahydrofuran, ethers such as methyl = tert-butyl ether, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene. Aprotic polarities such as hydrocarbons, hydrocarbons such as toluene, benzene, xylene, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide Examples include solvents, alcohols such as methanol, ethanol, 2-propanol, and mixtures thereof.

  The amount of compound (13) used in the reaction is usually 1 mol or more per 1 mol of compound (14).

  The reaction temperature of the reaction is usually in the range of −50 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.

  After completion of the reaction, the compound (2-ii) can be isolated by pouring the reaction mixture into water and extracting the mixture with an organic solvent, or collecting a deposited precipitate by filtration. The isolated compound (2-ii) can be further purified by recrystallization, chromatography or the like.

〔式中、Ｒ^1-a、Ｒ²、Ｒ³、Ａ¹、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（２−iii）と記す。）は、化合物（１１）と、化合物（１３）とを反応させることにより製造することができる。 (Reference production method 3)
Of the compounds (2)
Formula (2-iii)

[Wherein, R ^1-a , R ² , R ³ , A ¹ , Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above. ]
(Hereinafter referred to as compound (2-iii)) can be produced by reacting compound (11) with compound (13).

  The reaction is performed in the presence or absence of a solvent. Examples of the solvent used in the reaction include 1,4-dioxane, diethyl ether, tetrahydrofuran, ethers such as methyl = tert-butyl ether, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene. Aprotic polarities such as hydrocarbons, hydrocarbons such as toluene, benzene, xylene, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide Examples include solvents and mixtures thereof.

  The amount of compound (13) used in the reaction is usually 1 mol or more per 1 mol of compound (11).

  The reaction temperature of the reaction is usually in the range of −50 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.

  After completion of the reaction, the compound (2-iii) can be isolated by pouring the reaction mixture into water and extracting the mixture with an organic solvent, or collecting a deposited precipitate by filtration. The isolated compound (2-iii) can be further purified by recrystallization, chromatography or the like.

〔式中、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（１６）と記す。）と、
式（７’）

〔式中、Ｌ²は、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（７’）と記す。）とを反応させることにより製造することができる。 (Reference production method 4)
Compound (9) is
Formula (16)

[Wherein, Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above. ]
A compound represented by formula (hereinafter referred to as compound (16)),
Formula (7 ')

[Wherein L ² represents the same meaning as described above. ]
It can manufacture by making the compound (henceforth a compound (7 ')) react.

  The reaction is performed in the presence of a base, in the presence or absence of a solvent. Examples of the solvent used in the reaction include 1,4-dioxane, diethyl ether, tetrahydrofuran, ethers such as methyl = tert-butyl ether, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene. Aprotic polarities such as hydrocarbons, hydrocarbons such as toluene, benzene, xylene, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide Examples include solvents and mixtures thereof.

  The amount of the compound (7 ′) used in the reaction is usually 0.5 to 2 moles relative to the compound (16).

  Examples of the base used in the reaction include pyridine, picoline, 2,6-lutidine, 1,8-diazabicyclo [5,4,0] 7-undecene (DBU), 1,5-diazabicyclo [4,3,0. Nitrogen-containing heterocyclic compounds such as 5-nonene (DBN), tertiary amines such as triethylamine and N, N-diisopropylethylamine, and inorganic bases such as potassium carbonate and sodium hydride. When performed in the presence of a base, the amount of the base used is usually 1 mol or more per 1 mol of the compound (16).

  The reaction temperature of the reaction is usually in the range of 50 to 150 ° C., and the reaction time is usually in the range of 1 to 24 hours.

  After completion of the reaction, the compound (9) can be isolated by pouring the reaction mixture into water and extracting the mixture with an organic solvent, or collecting a deposited precipitate by filtration. The isolated compound (9) can be further purified by recrystallization, chromatography or the like.

〔式中、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（１７）と記す。）と、化合物（７’）とを反応させることにより製造することができる。 (Reference production method 5)
Compound (9) is
Formula (17)

[Wherein, Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above. ]
It can manufacture by making the compound (henceforth a compound (17)) shown by these and a compound (7 ') react.

  The reaction is performed in the presence or absence of a solvent. Examples of the solvent used in the reaction include 1,4-dioxane, diethyl ether, tetrahydrofuran, ethers such as methyl = tert-butyl ether, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene. Aprotic polarities such as hydrocarbons, hydrocarbons such as toluene, benzene, xylene, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide Examples include solvents and mixtures thereof.

  The production method comprises the following (Step 5-1) and (Step 5-2).

(Step 5-1)
This step is performed by reacting compound (17) with compound (7 ′) in the presence of a base.

  The amount of compound (7 ′) used in this step is usually 1 mol or more per 1 mol of compound (17). Examples of the base used in this step include pyridine, picoline, 2,6-lutidine, 1,8-diazabicyclo [5,4,0] 7-undecene (DBU), 1,5-diazabicyclo [4,3,0. Nitrogen-containing heterocyclic compounds such as 5-nonene (DBN), tertiary amines such as triethylamine and N, N-diisopropylethylamine, and inorganic bases such as potassium carbonate and sodium hydride. The amount of the base used is usually 1 mol or more per 1 mol of the compound (17).

  The reaction temperature in this step is usually in the range of 0 to 50 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.

  After completion of the step, the reaction mixture is usually used as it is in the next (step 5-2).

(Step 5-2)
This step is performed by reacting the reaction mixture in the above (Step 5-1) with a sulfonic acid halide in the presence of a base.

  Examples of the sulfonic acid halide used in the step include methanesulfonic acid chloride, p-toluenesulfonic acid chloride, and trifluoromethanesulfonic acid chloride. The amount of the sulfonic acid halide used in the step is usually 1 mol or more per 1 mol of the compound (17) used in (Step 5-1).

  Examples of the base used in this step include the same bases as described in (Step 5-1), and usually the same bases as those used in (Step 5-1). The amount of the base used is usually 1 mol or more per 1 mol of the compound (17) used in (Step 5-1).

  The reaction temperature in this step is usually in the range of 0 to 50 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.

  After completion of this step, the compound (9) can be isolated by pouring the reaction mixture into water and then extracting it with a normal organic solvent extraction or the like. The isolated compound (9) can be further purified by recrystallization, chromatography or the like.

(Reference production method 6)
Compound (14) can be produced by reacting compound (9) with a thiocarbonylating agent.

  The reaction is performed in the presence or absence of a solvent. Examples of the solvent used in the reaction include 1,4-dioxane, diethyl ether, tetrahydrofuran, ethers such as methyl = tert-butyl ether, diglyme, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and the like. Examples thereof include halogenated hydrocarbons, hydrocarbons such as toluene, benzene and xylene, nitriles such as acetonitrile, pyridines such as pyridine, picoline and lutidine, and mixtures thereof.

  Examples of the thiocarbonylating agent used in the reaction include niline pentasulfide, Lawesson's reagent (2,4-bis- (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane 2,4-disulfide), etc. Is mentioned.

  The amount of the thiocarbonylating agent used in the reaction is usually 1 mol or more per 1 mol of the compound (9).

  The reaction temperature of the reaction is usually in the range of 0 ° C. to 200 ° C., and the reaction time is usually in the range of 1 to 24 hours.

  After completion of the reaction, the precipitate precipitated in the reaction mixture can be collected by filtration, or the compound (14) can be isolated from the reaction mixture by organic solvent extraction or the like. The isolated compound (14) can be further purified by recrystallization, chromatography or the like.

(Reference production method 7)
Compound (11) can be produced by using compound (12) as a halogenating agent.

  The reaction is performed in the presence or absence of a solvent. Examples of the solvent used in the reaction include 1,4-dioxane, diethyl ether, tetrahydrofuran, ethers such as methyl = tert-butyl ether, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene. Aprotic polarities such as hydrocarbons, hydrocarbons such as toluene, benzene, xylene, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide Examples include solvents and mixtures thereof.

  Examples of the halogenating agent used in the reaction include thionyl chloride, thionyl bromide, phosphorus oxychloride, phosphorus oxybromide, phosphorus pentachloride, oxalyl chloride, and phosgene.

  The amount of the halogenating agent used in the reaction is usually 1 mol or more per 1 mol of the compound (12).

  The reaction temperature of the reaction is usually in the range of 0 ° C. to 150 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.

  After completion of the reaction, the compound (11) can be isolated by filtering the precipitate deposited in the reaction mixture or concentrating the reaction mixture. The isolated compound (11) is usually used in the next step as it is, but can be further purified by recrystallization or the like, if necessary.

〔式中、Ｒ^1-a、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（１８’）と記す。）と、化合物（７）とを反応させることにより製造することができる。 (Reference Production Example 8)
Compound (12) is
Formula (18 ')

[Wherein R ^1-a , Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above. ]
Can be produced by reacting the compound (hereinafter referred to as compound (18 ′)) with compound (7).

  The reaction is performed in the presence or absence of a solvent. Examples of the solvent used in the reaction include 1,4-dioxane, diethyl ether, tetrahydrofuran, ethers such as methyl = tert-butyl ether, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene. Aprotic polarities such as hydrocarbons, hydrocarbons such as toluene, benzene, xylene, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide Examples include solvents and mixtures thereof.

  The amount of compound (7) used in the reaction is usually 1 mol or more per 1 mol of compound (18 ').

  The reaction is performed in the presence of a base. Examples of the base used include pyridine, picoline, 2,6-lutidine, 1,8-diazabicyclo [5,4,0] 7-undecene (DBU), 1,5-diazabicyclo [4,3,0] 5- Examples thereof include nitrogen-containing heterocyclic compounds such as nonene (DBN), tertiary amines such as triethylamine and N, N-diisopropylethylamine, and inorganic bases such as potassium carbonate and sodium hydride. The amount of the base used is usually 1 mol or more per 1 mol of compound (18 ').

  The reaction temperature in this step is usually in the range of 0 to 50 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.

  After completion of the step, the compound (12) can be isolated by pouring the reaction mixture into water and extracting with a normal organic solvent, or collecting the precipitated precipitate by filtration. The isolated compound (12) can be further purified by recrystallization, chromatography or the like.

〔式中、Ｒ^1a、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、前記と同じ意味を表す。〕
で示される化合物（以下、化合物（２０）と記す。）と、化合物（１０）とを反応させることにより製造することができる。 (Reference production method 9)
Compound (6) is
Formula (20)

[Wherein, R ^1a , Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above. ]
It can manufacture by making the compound (henceforth a compound (20)) shown by these and a compound (10) react.

  The reaction is performed in the presence or absence of a solvent. Examples of the solvent used in the reaction include 1,4-dioxane, diethyl ether, tetrahydrofuran, ethers such as methyl = tert-butyl = ether, halogenation such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and the like. Aprotic polarities such as hydrocarbons, hydrocarbons such as toluene, benzene, xylene, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide Examples include solvents, alcohols such as methanol, ethanol, isopropyl alcohol, and mixtures thereof.

  The amount of compound (10) used in the reaction is usually 1 mol or more per 1 mol of compound (20).

  The reaction temperature of the reaction is usually in the range of −20 to 150 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.

  After completion of the reaction, the compound (20) can be isolated by pouring the reaction mixture into water and extracting the mixture with an organic solvent, or collecting a deposited precipitate by filtration. The isolated compound (20) can be further purified by recrystallization, chromatography or the like.

  Compounds (3), (4) and (13) are known compounds or known methods (for example, Organic Functional Group Preparations, 2nd edition, Vol.1, chapter 12, p.359-376 ( Stanley R. Sandler, Wolf Karo.) Or Organic Functional Group Preparations, 2nd edition, Vol.1, chapter 14, p.434-465 (see Stanley R. Sandler, Wolf Karo.)) It can manufacture from the compound of this.

  Compound (10) can be produced, for example, according to the following scheme (1).

〔スキーム中、Ａ⁶、Ｌ^１、Ｑ^’、Ｒ^２、Ｒ^３およびＲ^7aは、前記と同じ意味を表す。〕 Scheme (1)

[In the scheme, A ⁶ , L ¹ , Q ^′ , R ² , R ³ and R ^7a represent the same meaning as described above. ]

〔式中、Ｒ²、Ｒ³およびＲ⁵は、前記と同じ意味を表す。〕で示される化合物は、例えば、下記のスキーム（２）に従って製造することができる。 Of the compounds (10)
Formula (10-i)

[Wherein R ² , R ³ and R ⁵ represent the same meaning as described above. ] Can be manufactured according to the following scheme (2), for example.

〔スキーム中、Ｒ²、Ｒ³およびＲ⁵は、前記と同じ意味を表す。〕 Scheme (2)

[In the scheme, R ² , R ³ and R ⁵ represent the same meaning as described above. ]

  Compound (17) can be produced, for example, according to the following scheme (3).

〔スキーム中、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、前記と同じ意味を表す。〕 Scheme (3)

[In the scheme, Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above. ]

  Compounds (16), (18 ') and (20) can be produced, for example, according to the following scheme (4).

〔スキーム中、Ｒ^1-a、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、前記と同じ意味を表し、
Ｌ⁴は、脱離基（例えばハロゲン原子、メタンスルホニルオキシ基、ｐ−トルエンスルホニルオキシ基等）を表す。〕 Scheme (4)

[In the scheme, R ^1-a , Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above,
L ⁴ represents a leaving group (for example, a halogen atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, etc.). ]

  The compounds obtained by the above (Production Method A-1) to (Production Method C-1), Reference Production Methods 1 to 9, and Schemes (1) to (4) were pulverized, pulverized, recrystallized, and column chromatograms. It can be isolated and purified by conventional methods such as chromatography, high performance liquid column chromatography (HPLC), medium pressure preparative HPLC, desalting resin column chromatography, and reprecipitation.

  The compound of the present invention may be isolated in the form of a salt (a salt obtained by reacting the compound of the present invention with an acid or a base) or a solvate (for example, hydrate) depending on conditions. In the invention, these forms of compounds are also included in the present invention.

  The compound of the present invention may exist as a tautomer as shown below, for example, but the compound of the present invention also includes the tautomer.

〔式中、Ｒ¹、Ｒ⁴、Ａ¹、Ａ²、Ａ³、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は前記と同じ意味を表す。〕 In the compound of the present invention, when R ² and R ³ are hydrogen atoms and Q is Q1.

[Wherein, R ¹ , R ⁴ , A ¹ , A ² , A ³ , Z ¹ , Z ² , Z ³ and Z ⁴ represent the same meaning as described above. ]

Specific examples of the compound of the present invention are shown below. (Note that R ¹ , R ² , R ³ and R ^a are combinations of the following [Table 1].)

Compound represented by formula (1-A).

A compound represented by formula (1-B).

A compound represented by formula (1-C).

[Table 1]
R ¹ ; R ² ; R ³ ; R ^a
-----------------
H; H; H; H
H; H; H; CH ₃
H; H; H; CH ₂ CH ₃
H; H; H; (CH ₂ ) ₂ CH ₃
H; H; H; (CH ₂ ) ₃ CH ₃
H; H; H; (CH ₂ ) ₄ CH ₃
H; H; H; (CH ₂ ) ₅ CH ₃
H; H; H; (CH ₂ ) ₆ CH ₃
H; H; H; (CH ₂ ) ₇ CH ₃
H; H; H; (CH ₂ ) ₈ CH ₃
H; H; H; (CH ₂ ) ₉ CH ₃
H; H-iso-butyl H; H; H; iso-pentyl H; H; H; sec-butyl H; H; H; sec-pentyl H; H; H Tert-butyl H; H; H; cyclopropyl H; H; H; cyclobutyl H; H; H; cyclopentyl H; H; H; cyclohexyl H; H; H; cyclopropylmethyl H; H; H; H; Cyclohexylmethyl H; H; H; CH ₂ OCH ₃
H; H; H; CH ₂ CH ₂ OCH ₃
H; H; H; CH ₂ N (CH ₃ ) ₂

H; H; H; CH = CH ₂
H; H; H; CH = CH (CH ₃ )
H; H; H; CH = C (CH ₃ ) ₂
H; H; H; CH ₂ CH═CH ₃
H; H; H; CH ₂ CH═CHCH ₂ CH ₃
H; H; H; CCH
H; H; H; CCCH ₃
H; 2-pyridino H; H; 3-pyridino H; H; H; 4-pyridino H; H; H; 2-flufurino H; H; H; 3-flufurino H; H; H Piperidino H; H; H; tetrahydro-2-furyl H; H; H; tetrahydro-3-furyl H; H; H; 4-morpholino H; H; H; 4-thiomorpholino H; H; H; , 6-dimethyl-4-morpholino H; H; H; piperidino H; H; H; 4-methylpiperazino

H; H; H; OCH ₃
H; H; H; OCH ₂ CH ₃
H; H; H; O (CH ₂ ) ₂ CH ₃
H; H; H; O (CH ₂ ) ₃ CH ₃
H; H; H; O (CH ₂ ) 4 CH _{3
H; H; H; O (} CH 2) 5CH 3
H; H; H; O (CH ₂ ) 6 CH ₃
H; H; H; O (CH ₂ ) 7 CH _{3
H; H; H; O (} CH 2) 8CH 3
H; H; H; O (CH ₂ ) 9 CH ₃
H; H; H; OCH (CH ₃ ) ₂
H; H; H; OC (CH ₃ ) ₃
H; H; H; OCH ₂ CH (CH ₃ ) ₂
H; H; H; OCH ₂ CH ₂ OCH ₃
H; H; H; OCH ₂ CH═CH _{2
H; H; H; O (} CH 2) 2 CH = CH 2
H; H; H; OCH ₂ CCH
H; H; H; OCH ₂ CCCH ₃
H; H; H; SCH ₃
H; H; H; SCH ₂ CH ₃
H; H; H; SCH ₂ CH ₂ CH ₃
H; H; H; SCH ₂ CH (CH ₃ ) ₂
H; H; H; SCH (CH ₃ ) CH ₂ CH ₃

H; H; H; NH ₂
H; H; H; NHCH ₃
H; H; H; NHCH ₂ CH ₃
H; H; H; NH (CH ₂ ) ₂ CH ₃
H; H; H; NH (CH ₂ ) ₃ CH ₃
H; H; H; NH (CH ₂ ) ₄ CH ₃
H; H; H; NH (CH ₂ ) ₅ CH ₃
H; H; H; NH (CH ₂ ) ₆ CH ₃
H; H; H; NH (CH ₂ ) ₇ CH ₃
H; H; H; NH (CH ₂ ) ₈ CH ₃
H; H; H; NH (CH ₂ ) ₉ CH ₃
H; H; H; N (CH ₃ ) ₂
H; H; H; N (CH ₂ CH ₃ ) ₂
H; H; H; N (CH ₂ CH ₂ CH ₃ ) ₂
H; H; H; N (CH ₂ CH ₂ CH ₂ CH ₃ ) ₂
H; H; H; N [CH (CH ₃ ) ₂ ] ₂
H; H; H; N (CH ₂ CH ₂ Cl) ₂
H; H; H; N (CH ₂ CH═CH ₂ ) ₂

CH ₃ ; H; H; H
CH ₃ ; H; H; CH ₃
CH ₃ ; H; H; CH ₂ CH ₃
CH ₃ ; H; H; CH ₂ CH ₂ CH ₃
CH _3; H; H; iso- propyl _CH 3; H; H; iso- butyl _CH 3; H; H; cyclopropyl _{CH 3; H; H; OCH} 3
CH ₃ ; H; H; OCH ₂ CH ₃
CH ₃ ; H; H; OCH (CH ₃ ) ₂
CH ₃ ; H; H; OCH ₂ CH ₂ OCH ₃
CH ₃ ; H; H; N (CH ₃ ) ₂
CH ₃ ; H; H; N (CH ₂ CH ₃ ) ₂
CH ₃ ; H; H; 4-morpholino H; CH ₃ ; H; H
H; CH ₃ ; H; CH ₃
H; CH ₃ ; H; CH ₂ CH ₃
H; CH ₃ ; H; CH ₂ CH ₂ CH ₃
H; _CH 3; H; iso- propyl _H; CH _{3; H;} iso- butyl H; _CH 3; H; cyclopropyl _{H; CH 3; H; OCH} 3
H; CH ₃ ; H; OCH ₂ CH ₃
H; CH ₃ ; H; OCH (CH ₃ ) ₂
H; CH ₃ ; H; OCH ₂ CH ₂ OCH ₃
H; CH ₃ ; H; N (CH ₃ ) ₂
H; CH ₃ ; H; N (CH ₂ CH ₃ ) ₂
H; CH ₃ ; H; 4-morpholino

H; H; CH ₃ ; H
H; H; CH ₃ ; CH ₃
H; H; CH ₃ ; CH ₂ CH ₃
H; H; CH ₃ ; CH ₂ CH ₂ CH _3
H; H; CH 3; iso- propyl _H; H; CH 3; iso- butyl H; H; _CH 3; cyclopropyl _{H; H; CH 3; OCH} 3
H; H; CH ₃ ; OCH ₂ CH ₃
H; H; CH ₃ ; OCH (CH ₃ ) ₂
H; H; CH ₃ ; OCH ₂ CH ₂ OCH ₃
H; H; CH ₃ ; N (CH ₃ ) ₂
H; H; CH ₃ ; N (CH ₂ CH ₃ ) ₂
H; CH ₃ ; 4-morpholino H; CH ₃ ; CH ₃ ; H
H; CH ₃ ; CH ₃ ; CH ₃
H; CH ₃ ; CH ₃ ; CH ₂ CH _{3
H; CH 3; CH 3;} CH 2 CH 2 CH 3
_{H; CH 3; CH 3;} iso- propyl _{H; CH 3; CH 3;} iso- butyl _{H; CH 3;} CH _3; cyclopropyl _{H; CH 3; CH 3;} OCH 3
H; CH ₃ ; CH ₃ ; OCH ₂ CH ₃
H; CH ₃ ; CH ₃ ; OCH (CH ₃ ) _{2
H; CH 3; CH 3;} OCH 2 CH 2 OCH 3
H; CH ₃ ; CH ₃ ; N (CH ₃ ) ₂
H; CH ₃ ; CH ₃ ; N (CH ₂ CH ₃ ) _{2
H; CH 3; CH 3;} 4- morpholino

  Examples of harmful arthropods containing the compound of the present invention as an active ingredient include harmful insects and harmful mites, and specific examples thereof include the following.

  Hemiptera: Pepper (Laodelphax striatellus), brown planthopper (Nilaparvata lugens), leafhopper (Sogatella furcifera) and other species, Nephotettix cincticeps, Nephotettip Leafhoppers, cotton aphids (Aphis gossypii), peach aphids (Myzus persicae), radish aphids (Brevicoryne brassicae), snowy aphids (Aphis spiraecola), tulip mustard aphids (Macrosiphum euphorbiae), potato aphids Aphids such as aphids (Rhopalosiphum padi), citrus black aphids (Toxoptera citricidus), peach beetles (Hyalopterus pruni) Riptortus clavetus, Leptocorisa chinensis, Eysarcoris parvus, Halyomorpha mista, etc., Trialeurodes vaporariorum, Tribaleuros vaporariorum, Tobacco emisia Whitefly, such as Bemisia argentifolii, citrus whitefly (Dialeurodes citri), whitefly (Aleurocanthus spiniferus), red beetle (Aonidiella aurantii), safflower scale (Comstockaspis perniciosa), citrus snow scale (Unaspis tris) ), Icerya purchasi, Planococcus kraunhiae, Pseudococcus longispinis, Pseudaulacaspis pentagona, etc. Ramushi such, tingidae acids, psyllid, and the like.

  Lepidopterous insects: Chilo suppressalis, Tryporyza incertulas, Cnaphalocrocis medinalis, Notarcha derogata, Plodia interpunctella, Odaltrihis, Ostrinia furnacalis, Ostrinia furnacalis Common moths such as Pediasia teterrellus, Spodoptera litura, Spodoptera exigua, Pseudaletia separata, Mamestra brassicae, Agrotis ipsilon, Agrotis ipsilon, Heliotis genus, Helicoberpa genus moths, white butterflies (Pieris rapae), white butterflies, adoxofies genus, grapholita molesta, bean melon moth (Leguminivora glycinivorella), azoxa Mushiga (Matsumuraeses azukivora), Apple cockroach (Adoxophyes orana fasciata), Chanokokumonmonaki (Adoxophyes sp.), Chamonaki (Homona magnanima), Midarekamonmonki (Archips fuscocupreanus) Chanohosoga (Caloptilia theivora), Golden moth Hosoga (Phyllonorycter ringoneella) Hosogaga, Carposina niponensis, etc. Sugas, cotton moths (Pectinophora gossypiella) potato moths (Phthorimaea operculella), etc., tigers such as Hyphantria cunea, tigers (Tinea translucens), Hirosukoga such as Tineola bisselliella, etc.

  Thrips pests: Citrus thrips (Frankliniella occidentalis), Thrips parmi, Scirtothrips dorsalis, Thrips tabaci, ella thrips

  Diptera: Musca domestica, Culex popiens pallens, Cattle fly (Tabanus trigonus), Onion fly (Hylemya antiqua), Flyfly (Hylemya platura), Sycaenidae (Anopheles sinensis), Aye grouse flies Hydrellia griseola, Chlorops oryzae, Dacus cucurbitae, Ceratitis capitata, Bean-spotted fly (Liriomyza trifolii), Tomato-spotted leaf (Liriomyza trifolii)

  Coleopterous pests: Epilachna vigintioctopunctata, Aulacophora femoralis, Phyllotreta striolata, Oulema oryzth, Lyz (Echinocnemus squameus), Echinocnemus squameus, Echinocnemus squameus, Echinocnemus squameus Azuki beetle (Callosobruchus chinensis), Sphenophorus venatus, beetle (Popillia japonica), Anomala cuprea, corn rootworm mate (Diabrotica spp.), Colorado potato beetle (Leptinotarsa decemline squirrel) spp.), tobacco beetle (Lasioderma serricorne), Anthrenus verbasci, Tribolium castaneum, Lyctus brunneus, Anoplophora malasiaca), Toxus piniperda, etc.

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

  Hymenoptera: Athalia rosae, Achillyrmex spp., Fire ant (Solenopsis spp.), Etc.

  Cockroach eye pest: German cockroach (Blattella germanica), Black cockroach (Periplaneta fuliginosa), American cockroach (Periplaneta americana), Great cockroach (Periplaneta brunnea), Great cockroach (Blatta orientalis), etc.

  Acarid pests: Nite spider mite (Tetranychus urticae), Kanzawa spider mite (Tetranychus kanzawai), Scarlet spider mite (Panonychus citri) Apple spider mite (Panonychus ulmi), Oligonicus spp. Tomato rustic mites (Aculops lycopersici), Chinese radish mites (Calacarus carinatus), Chinese radish mites (Acaphylla theavagrans), red ticks (Eriophyes chibaensis) and other ticks (Polyphagotarsonemus latus) Scarlet ticks, mosquito spider mites (Haemaphysalis longicornis), Yamato tick (Haemaphysalis flava), Dermacentor taiwanicus, Yamato tick (Ixodes ovatus), Shulz tick (Ixodes p ersulcatus, tick such as Boophilus microplus, Rhipicephalus sanguineus, tick such as Tyrophagus putrescentiae, tyrophagogo mite, ides D Leopard ticks such as Leopard ticks (Cheyletus eruditus), Ticks ticks (Cheyletus malaccensis), Ticks ticks (Cheyletus moorei), etc.

  The harmful arthropod control agent of the present invention may be the compound of the present invention itself, but usually the compound of the present invention and an inert carrier such as a solid carrier, a liquid carrier, a gaseous carrier, etc. are mixed, if necessary, Add surfactants and other formulation adjuvants to prepare emulsions, oils, powders, granules, wettable powders, flowables, microcapsules, aerosols, smokers, poison baits, resin formulations, etc. It has become. These preparations usually contain 0.01 to 95% by weight of the compound of the present invention.

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

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

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

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

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

  The method for controlling harmful arthropods of the present invention usually involves the harmful arthropod control agent of the present invention directly on the harmful arthropods or the place where the harmful arthropods live (plants, soil, indoors, animals, etc.) It is done by applying to.

In addition, although the compound of the present invention can be used as it is in the method for controlling harmful arthropods of the present invention, the compound of the present invention is usually formulated in the form of the above-mentioned harmful arthropod control agent of the present invention, for example, Examples of the method include applying to a harmful arthropod or a place where the harmful arthropod is inhabited in the same manner as a conventional harmful arthropod controlling agent, and contacting or ingesting the above-mentioned harmful arthropod.
Examples of habitats for harmful arthropods in the present invention include paddy fields, fields, orchards, non-agricultural land, and houses.
Examples of such application methods include spraying treatment, soil treatment, seed treatment, and hydroponic liquid treatment.
Specifically, the spraying treatment in the present invention is directed to harmful arthropods by treating an active ingredient (the compound of the present invention) on the surface of the plant body such as foliage spraying, trunk spraying, etc. or harmful arthropods themselves. It is a treatment method that exhibits a control effect,
Soil treatment is, for example, by treating the active ingredient in soil or irrigation liquid in order to infiltrate and transfer from the root etc. into the plant body of the crop to be protected from damage such as feeding by harmful arthropods, This is a treatment method for protecting the crop from damage caused by harmful arthropods. Specifically, for example, planting treatment (planting hole spraying, planting hole treatment soil mixing), plant source processing (stock source spraying, plant source soil mixing) Irrigation, planting irrigation, seedling treatment in the latter half of the seedling season), grooving treatment (spreading grooving, mixing grooving soil), cropping treatment (spreading, sprinkling soil mixing, sprinkling in growing season), cropping at sowing Strip treatment (spreading at sowing, mixing with soil at the time of sowing), full treatment (spreading all over the soil, blending with all the soil), other soil spraying treatment (growth of leaves in the growing season, spraying under the crown or around the trunk, soil Surface spraying, soil surface mixing, sowing hole spraying, buttocks surface spraying, inter-strain spraying) Other irrigation treatments (soil irrigation, seedling irrigation, chemical injection, submerged irrigation, chemical drip irrigation, chemigation), seedling box treatment (nursery box spraying, seedling box irrigation), seedling tray processing (nursery tray spraying, seedling raising Tray irrigation), nursery treatment (seedbed spraying, nursery bed irrigation, water seedling surrogate seedling spraying, seedling immersion), bed soil admixture treatment (floor soil admixture, bed soil before sowing), and other treatments (culture soil admixing, plowing, topsoil admixture) , Raindrop part soil admixture, planting position treatment, granule inflorescence spraying, paste fertilizer admixture),
Seed treatment is, for example, the control effect on harmful arthropods by treating the active ingredients directly or in the vicinity of seeds, seed buds or bulbs of crops to be protected from damage such as feeding by harmful arthropods. Specifically, for example, spraying treatment, smearing treatment, dipping treatment, impregnation treatment, coating treatment, film coating treatment, pellet coating treatment can be mentioned,
Hydroponic liquid treatment is, for example, by treating active ingredients in hydroponic liquid etc. in order to infiltrate and transfer from the root etc. to the inside of the plant body of crops to be protected from damage such as feeding by harmful arthropods, This is a treatment method for protecting the crops from damage caused by harmful arthropods. Specific examples include hydroponic liquid mixing and hydroponic liquid mixing.

When the harmful arthropod control agent of the present invention is used for controlling harmful arthropods in the agricultural field, the application amount is the amount of the compound of the present invention per 10,000 m ² and is usually 1 to 10,000 g. When the harmful arthropod control agent of the present invention is formulated into an emulsion, a wettable powder, a flowable agent, etc., it is usually diluted with water so that the active ingredient concentration becomes 0.01 to 10,000 ppm. Granules, powders and the like are usually applied as they are.

  These preparations and water dilutions of these preparations may be applied directly to harmful arthropods or plants such as crops to be protected from harmful arthropods, and harmful arthropods that inhabit the soil of cultivated land. You may treat to this soil in order to control.

  Moreover, it can also process by the method of wrapping the resin formulation processed into the sheet form or the string form around the crop, stretching over the crop vicinity, and laying on the stock soil.

When the arthropod pest control agent of the present invention is used to control harmful arthropods (such as flies, mosquitoes, cockroaches) living in the house, the application rate is 1 m ² when treated on the surface. The amount of the compound of the present invention is usually 0.01 to 1000 mg, and when treating in space, the amount of the compound of the present invention per 1 m ³ of treatment space is usually 0.01 to 500 mg. When the harmful arthropod control agent of the present invention is formulated into an emulsion, a wettable powder, a flowable agent, etc., it is usually diluted with water so that the active ingredient concentration is 0.1 to 1000 ppm, and applied. Apply oils, aerosols, smoke, poison baits, etc. as they are.

  The compound of the present invention can be used as a harmful arthropod control agent for agricultural land such as fields, paddy fields, lawns, orchards or non-agricultural land.

  The harmful arthropod control agent of the present invention includes other harmful arthropod control agents, acaricides, nematicides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil improvers. It may contain animal feed or the like.

  The compounds of the present invention and pesticides such as other types of insecticides, acaricides, nematicides or fungicides, plant hormone agents, plant growth regulators, herbicides, etc. (isomers and salts thereof) Or a synergist, a safener, a pigment, a fertilizer, and the like, and a mixed preparation can be appropriately prepared and used for spraying treatment, soil treatment, and hydroponic liquid treatment.

  Examples of the active ingredients of the other harmful arthropod control agents, acaricides and / or nematicides include the following.

(1) Organophosphorous compounds Acephate, Aluminum phosphide, Butathiofos, Cadosafos, Chlorethoxyfos, Chlorfenvinphos, Chlorpyrifos, Chlorpyrifos, Chlorpyrifos-methyl, cyanophos (CYAP), diazinon, DCIP (dichlorodiisopropyl ether), dichlorfenthion (ECP), dichlorvos (DDVP), dimethoate, dimethylvinphos (dimethylvinphos) ), Disulfoton, EPN, ethion, ethoprophos, etrimfos, fenthion (MPP), fenitrothion (MEP), fosthiazate, formimothio (Formothion), hydrogen phosphide, isofenphos, isoxathion, malathion, mesulfenfos, methidathion (DMTP), monocrotophos, nared (BRP) ), Oxydeprofos (ESP), parathion, phosalone, phosmet (PMP), pyrimiphos-methy1, pyridafenthion, quinalphos, phenthoate: PAP ), Profenofos, propaphos, prothiofos, pyraclorfos, salithion, sulprofos, tebupirimfos, temephos, tetrachlorbinphos (tetrach1) orvinphos), terbufos, thiometon, trichlorphon (DEP), bamidothion,

(2) Carbamate compounds alaniccarb, bendiocarb, benfuracarb, BPMC, carbaryl, carbfuran, carbosulfan, cloethocarb, ethiofencarb ), Fenobucarb, fenothiocarb, fenoxycarb, furathiocarb, isoprocarb (MIPC), metolcarb, metomyl, methiocarb, NAC, oxamyl (amyl) ), Pirimicarb, propoxur (PHC), XMC, thiodicarb, xylylcarb, etc.

(3) Synthetic pyrethroid compounds acrinathrin, allethrin, benfluthrin, beta-cyfluthrin, bifenthrin, cycloprothrin, cyfluthrin, cyhalothrin (cyfluthrin) cyhalothrin), cypermethrin, deltamethrin, esfenvalerate, ethofenprox, fenpropathrin, fenvalerate, flucythrinate, flufenthrinate Prox (flufenoprox), flumethrin, fluvalinate, halfenprox (halfenprox), imiprothrin, permethrin, praretrin (pi) Threin (pyrethrins), resmethrin, sigma-cypermethrin, silafluofen, tefluthrin, tralomethrin, transfluthrin, 2,3,5,6-tetra Fluoro-4- (methoxymethyl) benzyl (EZ)-(1RS, 3RS; 1RS, 3SR) -2,2-dimethyl-3-prop-1-enylcyclopropanecarboxylate, 2,3,5,6-tetra Fluoro-4-methylbenzyl (EZ)-(1RS, 3RS; 1RS, 3SR) -2,2-dimethyl-3-prop-1-enylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4 -(Methoxymethyl) benzyl (1RS, 3RS; 1RS, 3SR) -2,2-dimethyl-3- (2- Chill-1-propenyl) cyclopropanecarboxylate and the like,

(4) Nereistoxin compounds Cartap, bensu1tap, thiocyclam, monosultap, bisultap, etc.

(5) Neonicotinoid compounds Imidacloprid (imidac1oprid), Nitenpyram (nitenpyram), Acetamiprid (acetamiprid), thiamethoxam (thiamethoxam), thiacloprid, dinotefuran, clothianidin, etc.

(6) Benzoylurea compounds Chlorfluazuron, bistrifluron, diafenthiuron, diflubenzuron, fluazuron, flucycloxuron, flufenoc Flufenoxuron, hexaflumuron, lufenuron, novaluron, noiflumuron, teflubenzuron, triflumuron, etc.

(7) Phenylpyrazole compounds Acetoprole, ethiprole, fiproni1, fiproni1, vaniliprole, pyriprole, pyrafluprole, etc.

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

(9) Hydrazine compounds Chromafenozide, halofenozide, methoxyfenozide, tebufenozide, etc.

(10) Organochlorine compounds Aldrin, dieldrin, dienochlor, endosulfan, methoxychlor, etc.

(11) Natural insecticide machine oil, nicotine-sulfate, etc.

(12) Other insecticides avermectin-B, bromopropylate, buprofezin, chlorphenapyr, cyromazine, DD (1,3-Dichloropropene), emamectin benzoate ( emamectin-benzoate, fenazaquin, flupyrazofos, hydroprene, indoxacarb, indoxacarb, metoxadiazone, milbemycin-A, pymetrozine, pyridalyl , Pyriproxyfen, spinosad, sulfluramid, tolfenpyrad, triazamate, flubendiamide, SI-0009, cyflumetofen, (Arsenic acid), Benclothiaz, Calcium cyanamide, Calcium polysulfide, chlordane, DDT, DSP, flufenerim, flonicamid, full rim Fen (flurimfen), formetanate, metam-ammonium, metam-sodium, methyl bromide, nidinotefuran, potassium oleate (Potassium oleate), pro Trifenbute (protrifenbute), spiromesifen (spiromesifen), sulfur (Sulfur), metaflumizone (metaflumizone), spirotetramat (spirotetramat), etc.

Acaricides acequinocyl, amitraz, benzoximate, bromopropylate, chinomethionat, chlorobenzilate, CPCBS (chlorfenson), clofentezine ), Kelsen (dicofol), etoxazole, fenbutatin oxide, phenothiocarb, fenpyroximate, fluacrypyrim, fluproxyfen, hexythiazox, hexythiazox propargite: BPPS, polynactins (polynactins), pyridaben, pyrimidifen, tebufenpyrad, tetradifon, spirodiclof Down (spirodiclofen), amide full Met (amidoflumet), bifenazate (Bifenazate), cyflumetofen (Cyflumetofen) or the like,

Nematicide (nematode active ingredient)
DCIP, fosthiazate, levamisol hydrochloride, methyl isothiocyanate, morantel tartarate, etc.

  Hereinafter, the present invention will be described in more detail with reference to production examples, formulation examples, test examples, and the like, but the present invention is not limited to these examples.

  Production examples of production intermediates used in the production of the compound of the present invention are shown in Reference production examples.

Reference production example 1
2- (N-nicotinoylamino) benzoic acid (20.0 g) and acetic anhydride (100 mL) were mixed, and the mixture was stirred with heating under reflux for 1 hour. The reaction mixture was allowed to cool to room temperature, and water and ethyl acetate were added to separate the layers. The obtained organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained residue was washed with methyl = tert-butyl = ether to obtain 18.07 g of 2- (3-pyridinyl) -4H-3,1-benzoxazin-4-one.

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）δ：７．４７（１Ｈ，ｄｄｄ，Ｊ＝８，５，１Ｈｚ），７．５７（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．７３（１Ｈ，ｄｄ，Ｊ＝９，２Ｈｚ），７．８７（１Ｈ，ｄｄｄ，Ｊ＝９，７，１Ｈｚ），８．２７（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．５６（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．８１（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），９．５３（１Ｈ，ｄｄ，Ｊ＝２，１Ｈｚ） 2- (3-pyridinyl) -4H-3,1-benzoxazin-4-one

¹ H-NMR (CDCl ₃ , TMS) δ: 7.47 (1H, ddd, J = 8, 5, 1 Hz), 7.57 (1H, dd, J = 8, 7 Hz), 7.73 (1H, dd, J = 9, 2 Hz), 7.87 (1H, ddd, J = 9, 7, 1 Hz), 8.27 (1H, dd, J = 8, 1 Hz), 8.56 (1H, ddd, J = 8, 2, 2 Hz), 8.81 (1H, dd, J = 5, 2 Hz), 9.53 (1H, dd, J = 2, 1 Hz)

Reference production example 2
2- (3-Pyridinyl) -4H-3,1-benzoxazin-4-one (0.9 g), N, N-dimethylformamide (11 mL) and methylhydrazine (0.37 g) were mixed, and the mixture was stirred at room temperature for 2 hours. . The reaction mixture was mixed with water and ethyl acetate and separated. The obtained organic layer was washed with water, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was washed with methyl = tert-butyl = ether to obtain 0.79 g of N- [2- (N-methylhydrazinocarbonyl) phenyl] -3-pyridinecarboxamide.

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：３．００−３．１９（３Ｈ，ｍ），４．７３−５．１７（２Ｈ，ｍ），７．１４−７．３４（１Ｈ，ｍ），７．３６−７．４５（１Ｈ，ｍ），７．４５−７．５４（１Ｈ，ｍ），７．５８（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．６９−７．８１（１Ｈ，ｍ），８．２２（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７８（１Ｈ，ｄｄ，Ｊ＝５，１Ｈｚ），９．０４（１Ｈ，ｂｒｓ），１０．４２（１Ｈ，ｂｒｓ） N- [2- (N-methylhydrazinocarbonyl) phenyl] -3-pyridinecarboxamide

¹ H-NMR (DMSO-d ₆ , TMS) δ: 3.00-3.19 (3H, m), 4.73-5.17 (2H, m), 7.14-7.34 (1H, m), 7.36-7.45 (1H, m), 7.45-7.54 (1H, m), 7.58 (1H, dd, J = 8, 5 Hz), 7.69-7. 81 (1H, m), 8.22 (1H, d, J = 8 Hz), 8.78 (1H, dd, J = 5, 1 Hz), 9.04 (1H, brs), 10.42 (1H, brs)

Reference production example 3
11.2 g of 2- (3-pyridinyl) -4H-3,1-benzoxazin-4-one, 200 mL of tetrahydrofuran and 5 mL of hydrazine monohydrate were mixed, and the mixture was stirred at room temperature for 3 hours. Water and ethyl acetate were mixed into the reaction mixture and separated. The obtained organic layer was washed with water, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was washed with 50 mL of tetrahydrofuran to obtain 12.0 g of N- [2- (hydrazinocarbonyl) phenyl] -3-pyridinecarboxamide.

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：４．６９（２Ｈ，ｂｒｓ），７．２１（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．５８（１Ｈ，ｄｄ，Ｊ＝７，７Ｈｚ），７．６４（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．８０（１Ｈ，ｄ，Ｊ＝７Ｈｚ），８．２９（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．６１（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．８２（１Ｈ，ｄｄ，Ｊ＝５，１Ｈｚ），９．１３（１Ｈ，ｄ，Ｊ＝２Ｈｚ），１０．２２（１Ｈ，ｂｒｓ），１２．６４（１Ｈ，ｂｒｓ） N- [2- (hydrazinocarbonyl) phenyl] -3-pyridinecarboxamide

¹ H-NMR (DMSO-d ₆ , TMS) δ: 4.69 (2H, brs), 7.21 (1H, dd, J = 8, 7 Hz), 7.58 (1H, dd, J = 7, 7 Hz), 7.64 (1 H, dd, J = 8, 5 Hz), 7.80 (1 H, d, J = 7 Hz), 8.29 (1 H, ddd, J = 8, 2, 2 Hz), 8. 61 (1H, d, J = 8 Hz), 8.82 (1H, dd, J = 5, 1 Hz), 9.13 (1H, d, J = 2 Hz), 10.22 (1H, brs), 12. 64 (1H, brs)

Reference production example 4
N-methyl isatoic anhydride (8.86 g), ethyl carbamate (5.73 g) and ethanol (25 mL) were mixed, and the mixture was stirred with heating under reflux for 2 hours. The reaction mixture was allowed to cool to room temperature and concentrated under reduced pressure. Water and ethyl acetate were mixed with the obtained residue and separated. The obtained organic layer was washed with water, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was washed with methyl = tert-butyl = ether to obtain 5.99 g of N- (2-methylaminobenzoyl) -N′-ethoxycarbonylhydrazine.

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）δ：１．２８（３Ｈ，ｔ，Ｊ＝７Ｈｚ），２．８５（３Ｈ，ｄ，Ｊ＝５Ｈｚ），４．２１（２Ｈ，ｑ，Ｊ＝７Ｈｚ），６．５７（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），６．６６（１Ｈ，ｄ，Ｊ＝８Ｈｚ），６．７９（１Ｈ，ｂｒｓ），７．２７−７．３８（２Ｈ，ｍ），７．４３（１Ｈ，ｄｄ，Ｊ＝８，２Ｈｚ），７．９１（１Ｈ，ｂｒｓ） N- (2-methylaminobenzoyl) -N′-ethoxycarbonylhydrazine

¹ H-NMR (CDCl ₃ , TMS) δ: 1.28 (3H, t, J = 7 Hz), 2.85 (3H, d, J = 5 Hz), 4.21 (2H, q, J = 7 Hz) 6.57 (1H, dd, J = 8, 7 Hz), 6.66 (1H, d, J = 8 Hz), 6.79 (1H, brs), 7.27-7.38 (2H, m) , 7.43 (1H, dd, J = 8, 2 Hz), 7.91 (1H, brs)

Reference production example 5
1.85 g of 2-amino-5-chloro-3-methylbenzoic acid, 0.90 g of triphosgene and 10 ml of tetrahydrofuran were mixed, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was concentrated under reduced pressure, and the resulting solid was washed with water to obtain 1.20 g of 6-chloro-8-methyl-1H-benzo [d] -1,3-oxazine-2,4-dione. It was.

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ（ｐｐｍ）：２．３３（３Ｈ，ｓ），７．６９（１Ｈ，ｄ，Ｊ＝２Ｈｚ），７．７３（１Ｈ，ｄ，Ｊ＝２Ｈｚ），１１．１８（１Ｈ，ｓ） 6-Chloro-8-methyl-1H-benzo [d] -1,3-oxazine-2,4-dione

¹ H-NMR (DMSO-d ₆ , TMS) δ (ppm): 2.33 (3H, s), 7.69 (1H, d, J = 2 Hz), 7.73 (1H, d, J = 2 Hz) ), 11.18 (1H, s)

Reference production example 6
A mixture of 6-chloro-8-methyl-1H-benzo [d] -1,3-oxazine-2,4-dione (1.05 g), methyl carbamate (0.46 g) and methanol (20 ml) was stirred with heating under reflux for 3 hours. . The reaction mixture was allowed to cool to room temperature, water was added, and the mixture was extracted 3 times with ethyl acetate. The obtained organic layer was concentrated under reduced pressure, and the residue was washed with toluene to obtain 0.77 g of N- (2-amino-5-chloro-3-methylbenzoyl) -N′-methoxycarbonylhydrazine.

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ（ｐｐｍ）：２．１０（３Ｈ，ｓ），３．６３（３Ｈ，ｓ），６．３２（２Ｈ，ｂｒｓ），７．１９（１Ｈ，ｄ，Ｊ＝２Ｈｚ），７．４５（１Ｈ，ｄ，Ｊ＝２Ｈｚ），９．１４（１Ｈ，ｂｒｓ），１０．１２（１Ｈ，ｂｒｓ） N- (2-amino-5-chloro-3-methylbenzoyl) -N'-methoxycarbonylhydrazine

¹ H-NMR (DMSO-d ₆ , TMS) δ (ppm): 2.10 (3H, s), 3.63 (3H, s), 6.32 (2H, brs), 7.19 (1H, d, J = 2 Hz), 7.45 (1H, d, J = 2 Hz), 9.14 (1H, brs), 10.12 (1H, brs)

Reference production example 7
A mixture of 1.18 g of nicotinic acid chloride hydrochloride, 1.0 g of 2-amino-4-methylbenzoic acid and 20 ml of acetonitrile was stirred at room temperature for 1 hour. To the reaction mixture, 1.0 g of triethylamine was added and stirred at room temperature for 1 hour, and further 2.0 g of triethylamine was added and stirred at room temperature for 1 hour. Next, 1 g of methanesulfonyl chloride was added to the reaction mixture, and the mixture was stirred at room temperature for 5 hours. Water was poured into the reaction mixture, and the mixture was extracted twice with ethyl acetate. The obtained organic layer was concentrated under reduced pressure, and the residue was washed with ethyl acetate to obtain 1.2 g of 7-methyl-2- (3-pyridinyl) -4H-3,1-benzoxazin-4-one. .

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：２．５１−２．５３（３Ｈ，ｍ），７．４９（１Ｈ，ｄ，Ｊ＝８Ｈｚ），７．５９（１Ｈ，ｓ），７．６４（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），８．０７（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．４９（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．８２（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），９．３１（１Ｈ，ｄ，Ｊ＝２Ｈｚ） 7-Methyl-2- (3-pyridinyl) -4H-3,1-benzoxazin-4-one

¹ H-NMR (DMSO-d ₆ , TMS) δ: 2.51-2.53 (3H, m), 7.49 (1H, d, J = 8 Hz), 7.59 (1H, s), 7 .64 (1H, dd, J = 8, 5 Hz), 8.07 (1H, d, J = 8 Hz), 8.49 (1H, ddd, J = 8, 2, 2 Hz), 8.82 (1H, dd, J = 5, 2 Hz), 9.31 (1H, d, J = 2 Hz)

Hereinafter, production intermediates produced by the production method according to the method described in Reference Production Example 7 will be exemplified.

Compound 1-1
¹ H-NMR (DMSO-d ₆ , TMS) δ: 2.30 (3H, s), 7.55 (1H, dd, J = 8, 8 Hz), 7.65 (1H, dd, J = 8, 5 Hz), 7.85 (1 H, d, J = 8 Hz), 8.02 (1 H, d, J = 8 Hz), 8.53 (1 H, d, J = 8 Hz), 8.83 (1 H, dd, J = 5, 2 Hz), 9.36 (1H, d, J = 2 Hz)
Compound 2-1
¹ H-NMR (DMSO-d ₆ , TMS) δ: 7.66 (1H, dd, J = 8, 5 Hz), 7.71 (1H, dd, J = 8, 2 Hz), 7.86 (1H, d, J = 2 Hz), 8.18 (1 H, d, J = 8 Hz), 8.50 (1 H, ddd, J = 8, 2, 2 Hz), 8.84 (1 H, dd, J = 5, 2 Hz) ), 9.32 (1H, d, J = 2 Hz)
Compound 2-2
¹ H-NMR (DMSO-d ₆ , TMS) δ: 7.65 (1H, dd, J = 8, 5 Hz), 7.78 (1H, d, J = 8 Hz), 7.98-8.03 ( 1H, m), 8.15 (1H, d, J = 2 Hz), 8.50 (1H, ddd, J = 8, 2, 2 Hz), 8.83 (1H, dd, J = 5, 2 Hz), 9.31 (1H, d, J = 2Hz)
Compound 2-3
¹ H-NMR (DMSO-d ₆ , TMS) δ: 7.63-7.67 (1H, m), 7.70 (1H, dd, J = 4, 1 Hz), 7.72 (1H, dd, J = 4, 1 Hz), 7.90 (1H, dd, J = 8, 8 Hz), 8.49 (1H, ddd, J = 8, 2, 2 Hz), 8.84 (1H, dd, J = 5) , 2 Hz), 9.31 (1H, d, J = 2 Hz)

Reference production example 8
7-Methyl-2- (3-pyridinyl) -4H-3,1-benzoxazin-4-one (0.12 g), tetrahydrofuran (10 mL) and hydrazine monohydrate (0.5 mL) were mixed, and the mixture was stirred at room temperature for 3 hours. Stir. Water and ethyl acetate were mixed into the reaction mixture and separated. The obtained organic layer was washed with water, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was washed with methyl = tert-butyl = ether to obtain 0.6 g of N- [2- (hydrazinocarbonyl) -5-methylphenyl] -3-pyridinecarboxamide.

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：２．３８（３Ｈ，ｓ），４．７０（２Ｈ，ｂｒｓ），７．０２（１Ｈ，ｄ，Ｊ＝８Ｈｚ），７．６４（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．７２（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．２８（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．４９（１Ｈ，ｓ），８．８１（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），９．１３（１Ｈ，ｄ，Ｊ＝２Ｈｚ），１０．１５（１Ｈ，ｂｒｓ），１２．８０（１Ｈ，ｂｒｓ） N- [2- (hydrazinocarbonyl) -5-methylphenyl] -3-pyridinecarboxamide

¹ H-NMR (DMSO-d ₆ , TMS) δ: 2.38 (3H, s), 4.70 (2H, brs), 7.02 (1H, d, J = 8 Hz), 7.64 (1H , Dd, J = 8, 5 Hz), 7.72 (1H, d, J = 8 Hz), 8.28 (1H, d, J = 8 Hz), 8.49 (1H, s), 8.81 (1H) , Dd, J = 5, 2 Hz), 9.13 (1H, d, J = 2 Hz), 10.15 (1H, brs), 12.80 (1H, brs)

Hereinafter, production intermediates produced by the production method according to the method described in Reference Production Example 8 will be exemplified.

Compound 3-1
¹ H-NMR (DMSO-d ₆ , TMS) δ: 2.56 (3H, s), 5.71 (2H, s), 6.98-7.41 (1H, m), 7.47 (1H , Dd, J = 8, 8 Hz), 7.54 (1H, ddd, J = 8, 5, 1 Hz), 7.73 (1H, ddd, J = 8, 1, 1 Hz), 8.04 (1H, ddd, J = 8, 1, 1 Hz), 8.27 (1H, ddd, J = 8, 2, 2 Hz), 8.68 (1H, dd, J = 5, 2 Hz), 9.03 (1H, dd) , J = 2, 1 Hz), 9.40-9.74 (1H, m)

Reference production example 9
1H-naphtho [2,3-d] -1, in the same manner as in Reference Production Example 5, using 3-amino-2-naphthoic acid instead of 2-amino-5-chloro-3-methylbenzoic acid 3-Oxazine-2,4-dione was obtained.

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ（ｐｐｍ）：７．４７−７．５４（２Ｈ，ｍ），７．６７（１Ｈ，ｔ，Ｊ＝８Ｈｚ），７．９４（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．１４（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７４（１Ｈ，ｓ），１１．７９（１Ｈ，ｂｒｓ） 1H-naphtho [2,3-d] -1,3-oxazine-2,4-dione

¹ H-NMR (DMSO-d ₆ , TMS) δ (ppm): 7.47-7.54 (2H, m), 7.67 (1H, t, J = 8 Hz), 7.94 (1H, d , J = 8 Hz), 8.14 (1H, d, J = 8 Hz), 8.74 (1H, s), 11.79 (1H, brs)

Reference production example 10
Instead of 6-chloro-8-methyl-1H-benzo [d] -1,3-oxazine-2,4-dione, 1H-naphtho [2,3-d] -1,3-oxazine-2,4- N- (3-amino-2-naphthoyl) -N′-ethoxycarbonylhydrazine was obtained in the same manner as in Reference Production Example 6 using dione and using ethyl carbamate instead of methyl carbamate.

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ（ｐｐｍ）：１．２３（３Ｈ，ｔ，Ｊ＝７Ｈｚ），４．１１（２Ｈ，ｔ，Ｊ＝７Ｈｚ），６．０５（２Ｈ，ｂｒｓ），６．９９（１Ｈ，ｓ），７．１５（１Ｈ，ｔ，Ｊ＝７Ｈｚ），７．３７（１Ｈ，ｔ，Ｊ＝７Ｈｚ），７．４７−７．５６（１Ｈ，ｍ），７．６３−７．７３（１Ｈ，ｍ），８．０５（１Ｈ，ｓ），９．２２（１Ｈ，ｂｒｓ），１０．３０（１Ｈ，ｂｒｓ） N- (3-amino-2-naphthoyl) -N′-ethoxycarbonylhydrazine

¹ H-NMR (DMSO-d ₆ , TMS) δ (ppm): 1.23 (3H, t, J = 7 Hz), 4.11 (2H, t, J = 7 Hz), 6.05 (2H, brs) ), 6.99 (1H, s), 7.15 (1H, t, J = 7 Hz), 7.37 (1H, t, J = 7 Hz), 7.47-7.56 (1H, m), 7.63-7.73 (1H, m), 8.05 (1H, s), 9.22 (1H, brs), 10.30 (1H, brs)

Next, production examples of the compound of the present invention are shown.
Production Example 1
2- (3-pyridinyl) -4H-3,1-benzoxazin-4-one (0.11 g), ethyl carbamate (0.11 g) and N, N-dimethylformamide (10 ml) were mixed and the mixture was stirred at 60 ° C. for 7 hours. Stir and leave at room temperature overnight. Water and saturated aqueous sodium hydrogen carbonate solution were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic phase was washed successively with water and saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 0.06 g of the following present compound (1).

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：１．２５−１．３５（３Ｈ，ｍ），４．１０−４．２７（２Ｈ，ｍ），７．２０（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．５０（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．６０（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．７５−７．８５（１Ｈ，ｍ），８．３３（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．７０−８．７５（２Ｈ，ｍ），９．１９（１Ｈ，ｄ，Ｊ＝２Ｈｚ） Compound (1) of the present invention

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 1.25-1.35 (3H, m), 4.10-4.27 (2H, m), 7.20 (1H, dd, J = 8,7 Hz), 7.50 (1H, dd, J = 8, 5 Hz), 7.60 (1H, dd, J = 8, 7 Hz), 7.75-7.85 (1H, m), 8.33 (1H, ddd, J = 8, 2, 2 Hz), 8.70-8.75 (2H, m), 9.19 (1H, d, J = 2 Hz)

Production Example 2
The following compound (2) of the present invention is obtained in the same manner as in Production Example 1 using formhydrazide instead of ethyl carbamate.
Compound (2) of the present invention

Production Example 3
0.25 g of N- [2- (N-methylhydrazinocarbonyl) phenyl] -3-pyridinecarboxamide and 25 ml of acetonitrile were mixed at 0 ° C., and the mixture was mixed with 0.17 g of methyl chlorocarbonate, 2 mL of pyridine and 1 mL of acetonitrile. Was added dropwise, stirred at 0 ° C. for 4 hours, and further stirred at room temperature for 2 hours. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic phase was washed twice with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was washed with methyl = tert-butyl = ether to obtain 0.11 g of the following present compound (3).

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：３．０８−３．１５（３Ｈ，ｍ），３．５０−３．５６（３Ｈ，ｍ），７．２１−７．２８（１Ｈ，ｍ），７．２９−７．３７（１Ｈ，ｍ），７．４５−７．５１（１Ｈ，ｍ），７．５７−７．６４（１Ｈ，ｍ），７．７４−７．８０（１Ｈ，ｍ），８．２１−８．２８（１Ｈ，ｍ），８．７９（１Ｈ，ｂｒｓ），９．０６（１Ｈ，ｂｒｓ），９．６４（１Ｈ，ｂｒｓ），１０．１０（１Ｈ，ｂｒｓ） Compound (3) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 3.08-3.15 (3H, m), 3.50-3.56 (3H, m), 7.21-7.28 (1H, m), 7.29-7.37 (1H, m), 7.45-7.51 (1H, m), 7.57-7.64 (1H, m), 7.74-7.80 ( 1H, m), 8.21-8.28 (1H, m), 8.79 (1H, brs), 9.06 (1H, brs), 9.64 (1H, brs), 10.10 (1H) , Brs)

Production Example 4
0.25 g of N- [2- (hydrazinocarbonyl) phenyl] -3-pyridinecarboxamide and 10 ml of pyridine were mixed, and 0.10 g of methyl chlorocarbonate was added dropwise at room temperature, followed by stirring at room temperature for 1 hour. Water was poured into the reaction mixture, and the deposited precipitate was collected by filtration and dried to obtain 0.16 g of the present compound (4).

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：３．６４（３Ｈ，ｓ），７．２４（１Ｈ，ｄｄ，Ｊ＝４，４Ｈｚ），７．５６−７．６４（２Ｈ，ｍ），７．８３（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．２４（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．５４（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７４−８．８１（１Ｈ，ｍ），９．０２−９．１１（２Ｈ，ｍ），１０．４６（１Ｈ，ｂｒｓ），１１．７９（１Ｈ，ｂｒｓ） The present compound (4)

¹ H-NMR (DMSO-d ₆ , TMS) δ: 3.64 (3H, s), 7.24 (1H, dd, J = 4, 4 Hz), 7.56-7.64 (2H, m) 7.83 (1H, d, J = 8 Hz), 8.24 (1H, ddd, J = 8, 2, 2 Hz), 8.54 (1H, d, J = 8 Hz), 8.74-8. 81 (1H, m), 9.02-9.11 (2H, m), 10.46 (1H, brs), 11.79 (1H, brs)

Production Example 5
N- (2-methylaminobenzoyl) -N′-ethoxycarbonylhydrazine (0.95 g), nicotinic acid chloride hydrochloride (0.85 g) and acetonitrile (10 ml) were mixed, and the mixture was stirred at 80 ° C. for 8 hours. The reaction mixture was filtered and concentrated under reduced pressure. To the obtained residue were added saturated brine and saturated aqueous sodium hydrogen carbonate solution, and the mixture was extracted twice with ethyl acetate. The obtained organic phases were combined, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was washed with methyl = tert-butyl = ether to obtain 0.46 g of the following present compound (5).

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：１．１４−１．２６（３Ｈ，ｍ），３．２８（３Ｈ，ｓ），３．９９−４．１５（２Ｈ，ｍ），７．１５−７．２４（２Ｈ，ｍ），７．３０−７．４８（３Ｈ，ｍ），７．７９（１Ｈ，ｄ，Ｊ＝７Ｈｚ），８．３８（１Ｈ，ｄ，Ｊ＝４Ｈｚ），８．５５（１Ｈ，ｂｒｓ），９．３０（１Ｈ，ｂｒｓ），１０．２３（１Ｈ，ｂｒｓ） Compound (5) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 1.14-1.26 (3H, m), 3.28 (3H, s), 3.99-4.15 (2H, m), 7 .15-7.24 (2H, m), 7.30-7.48 (3H, m), 7.79 (1H, d, J = 7Hz), 8.38 (1H, d, J = 4Hz) 8.55 (1H, brs), 9.30 (1H, brs), 10.23 (1H, brs)

Production Example 6
N- [2- (hydrazinocarbonyl) phenyl] -3-pyridinecarboxamide (0.13 g), triethylamine (0.10 g), dimethyl sulfoxide (2 ml) and N, N-dimethylcarbamoyl chloride (0.11 g) were mixed and mixed at 30 ° C. for 2 hours. Stir. Water and saturated aqueous sodium hydrogen carbonate solution were added to the reaction mixture, and the mixture was extracted twice with ethyl acetate. The obtained organic phases were combined, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 0.03 g of the following present compound (6).

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：２．８７（６Ｈ，ｓ），７．２６（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．５８−７．６６（２Ｈ，ｍ），７．８２（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．２６（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．５６−８．６５（２Ｈ，ｍ），８．８０（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），９．０８（１Ｈ，ｄ，Ｊ＝２Ｈｚ），１０．３５（１Ｈ，ｂｒｓ），１１．９６（１Ｈ，ｂｒｓ） The present compound (6)

¹ H-NMR (DMSO-d ₆ , TMS) δ: 2.87 (6H, s), 7.26 (1H, dd, J = 8, 7 Hz), 7.58-7.66 (2H, m) 7.82 (1H, dd, J = 8, 1 Hz), 8.26 (1H, ddd, J = 8, 2, 2 Hz), 8.56-8.65 (2H, m), 8.80 ( 1H, dd, J = 5, 2 Hz), 9.08 (1H, d, J = 2 Hz), 10.35 (1H, brs), 11.96 (1H, brs)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：１．０８（６Ｈ，ｔ，Ｊ＝７Ｈｚ），３．２７（４Ｈ，ｑ，Ｊ＝７Ｈｚ），７．２５（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．５６−７．６４（２Ｈ，ｍ），７．８１（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．２６（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．５２（１Ｈ，ｄ，Ｊ＝２Ｈｚ），８．５８（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７９（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），９．０８（１Ｈ，ｄ，Ｊ＝２Ｈｚ），１０．３４（１Ｈ，ｂｒｓ），１１．９１（１Ｈ，ｂｒｓ） Production Example 7
The following compound (7) of the present invention was obtained in the same manner as in Production Example 6 using N, N-diethylcarbamoyl chloride instead of N, N-dimethylcarbamoyl chloride.
Compound (7) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 1.08 (6H, t, J = 7 Hz), 3.27 (4H, q, J = 7 Hz), 7.25 (1H, dd, J = 8,8 Hz), 7.56-7.64 (2H, m), 7.81 (1H, dd, J = 8, 1 Hz), 8.26 (1H, ddd, J = 8, 2, 2 Hz), 8.52 (1H, d, J = 2Hz), 8.58 (1H, d, J = 8Hz), 8.79 (1H, dd, J = 5, 2Hz), 9.08 (1H, d, J = 2Hz), 10.34 (1H, brs), 11.91 (1H, brs)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：３．３７（４Ｈ，ｔ，Ｊ＝５Ｈｚ），３．５９（４Ｈ，ｔ，Ｊ＝５Ｈｚ），７．２６（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．５９−７．６６（２Ｈ，ｍ），７．８４（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．２６（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．５９（１Ｈ，ｄ，Ｊ＝７Ｈｚ），８．８０（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），８．８８（１Ｈ，ｂｒｓ），９．０８（１Ｈ，ｄ，Ｊ＝２Ｈｚ），１０．４１（１Ｈ，ｂｒｓ），１１．９８（１Ｈ，ｂｒｓ） Production Example 8
The following compound (8) of the present invention was obtained in the same manner as in Production Example 6 using 4-morpholinecarbonyl chloride instead of N, N-dimethylcarbamoyl chloride.
The present compound (8)

¹ H-NMR (DMSO-d ₆ , TMS) δ: 3.37 (4H, t, J = 5 Hz), 3.59 (4H, t, J = 5 Hz), 7.26 (1H, dd, J = 8,7 Hz), 7.59-7.66 (2 H, m), 7.84 (1 H, dd, J = 8, 1 Hz), 8.26 (1 H, ddd, J = 8, 2, 2 Hz), 8.59 (1 H, d, J = 7 Hz), 8.80 (1 H, dd, J = 5, 2 Hz), 8.88 (1 H, brs), 9.08 (1 H, d, J = 2 Hz), 10.41 (1H, brs), 11.98 (1H, brs)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）δ：６．８６（１Ｈ，ｄ，Ｊ＝４Ｈｚ），７．０７（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．２７−７．３３（２Ｈ，ｍ），７．３７−７．４７（９Ｈ，ｍ），７．４６−７．５５（１Ｈ，ｍ），７．６５（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．３１（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．７３−８．８０（２Ｈ，ｍ），８．８５（１Ｈ，ｂｒｓ），９．２５（１Ｈ，ｄ，Ｊ＝２Ｈｚ），１１．９２（１Ｈ，ｂｒｓ） Production Example 9
The following compound (9) of the present invention was obtained in the same manner as in Production Example 6 using N, N-diphenylcarbamoyl chloride instead of N, N-dimethylcarbamoyl chloride.
The present compound (9)

¹ H-NMR (CDCl ₃ , TMS) δ: 6.86 (1H, d, J = 4 Hz), 7.07 (1H, dd, J = 8, 7 Hz), 7.27-7.33 (2H, m), 7.37-7.47 (9H, m), 7.46-7.55 (1H, m), 7.65 (1H, d, J = 8 Hz), 8.31 (1H, ddd, J = 8, 2, 2 Hz), 8.73-8.80 (2H, m), 8.85 (1 H, brs), 9.25 (1 H, d, J = 2 Hz), 11.92 (1 H, brs)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）δ：３．３５（３Ｈ，ｓ），６．６４（１Ｈ，ｂｒｓ），７．０６（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．３９−７．５２（７Ｈ，ｍ），７．７０（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．３２（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７２−８．８０（２Ｈ，ｍ），９．１８−９．２６（２Ｈ，ｍ），１２．０３（１Ｈ，ｂｒｓ） Production Example 10
The following compound (10) of the present invention was obtained in the same manner as in Production Example 6 using N-phenyl-N-methylcarbamoyl chloride instead of N, N-dimethylcarbamoyl chloride.
Compound (10) of the present invention

¹ H-NMR (CDCl ₃ , TMS) δ: 3.35 (3H, s), 6.64 (1H, brs), 7.06 (1H, dd, J = 8, 8 Hz), 7.39-7 .52 (7H, m), 7.70 (1H, d, J = 8 Hz), 8.32 (1H, d, J = 8 Hz), 8.72-8.80 (2H, m), 9.18 -9.26 (2H, m), 12.03 (1H, brs)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）δ：０．８８−０．９８（６Ｈ，ｍ），１．８９−２．０４（１Ｈ，ｍ），３．９７（２Ｈ，ｄ，Ｊ＝７Ｈｚ），７．０３−７．１９（２Ｈ，ｍ），７．４０−７．４６（１Ｈ，ｍ），７．５４（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．６９（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．２７−８．３０（１Ｈ，ｍ），８．７４−８．８４（３Ｈ，ｍ），９．２３（１Ｈ，ｄ，Ｊ＝２Ｈｚ），１１．９２（１Ｈ，ｂｒｓ） Production Example 11
The following compound (11) of the present invention was obtained in the same manner as in Production Example 6 using isobutyl chlorocarbonate instead of N, N-dimethylcarbamoyl chloride.
Compound (11) of the present invention

¹ H-NMR (CDCl ₃ , TMS) δ: 0.88-0.98 (6H, m), 1.89-2.04 (1H, m), 3.97 (2H, d, J = 7 Hz) , 7.03-7.19 (2H, m), 7.40-7.46 (1H, m), 7.54 (1H, dd, J = 8, 8 Hz), 7.69 (1H, dd, J = 8, 1 Hz), 8.27-8.30 (1H, m), 8.74-8.84 (3H, m), 9.23 (1 H, d, J = 2 Hz), 11.92 ( 1H, brs)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）δ：５．２０（２Ｈ，ｓ），７．０８−７．１９（２Ｈ，ｍ），７．２７−７．３８（５Ｈ，ｍ），７．４１（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．５６（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．６７（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．２６（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．５７（１Ｈ，ｂｒｓ），８．７３−８．８２（２Ｈ，ｍ），９．２３（１Ｈ，ｄ，Ｊ＝２Ｈｚ），１１．８７（１Ｈ，ｂｒｓ） Production Example 12
The following compound (12) of the present invention was obtained in the same manner as in Production Example 6 using benzyl chlorocarbonate instead of N, N-dimethylcarbamoyl chloride.
The present compound (12)

¹ H-NMR (CDCl ₃ , TMS) δ: 5.20 (2H, s), 7.08-7.19 (2H, m), 7.27-7.38 (5H, m), 7.41 (1H, dd, J = 8, 5 Hz), 7.56 (1H, dd, J = 8, 7 Hz), 7.67 (1H, d, J = 8 Hz), 8.26 (1H, d, J = 8Hz), 8.57 (1H, brs), 8.73-8.82 (2H, m), 9.23 (1H, d, J = 2Hz), 11.87 (1H, brs)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：７．０９（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．２８−７．３８（３Ｈ，ｍ），７．４３−７．５１（１Ｈ，ｍ），７．７０−７．７８（３Ｈ，ｍ），８．１６−８．２３（１Ｈ，ｍ），８．５２−８．６０（２Ｈ，ｍ），９．０２（１Ｈ，ｂｒｓ） Production Example 13
The following compound (13) of the present invention was obtained in the same manner as in Production Example 6 using p-chlorobenzoyl chloride instead of N, N-dimethylcarbamoyl chloride.
Compound (13) of the present invention

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 7.09 (1H, dd, J = 8, 8 Hz), 7.28-7.38 (3H, m), 7.43-7. 51 (1H, m), 7.70-7.78 (3H, m), 8.16-8.23 (1H, m), 8.52-8.60 (2H, m), 9.02 ( 1H, brs)

Production Example 14
N- [2- (hydrazinocarbonyl) phenyl] -3-pyridinecarboxamide 0.13 g, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride 0.12 g, dimethyl sulfoxide 2 ml and 3-bromopropionic acid 0.10 g was mixed and stirred at 30 ° C. for 2 hours. Water and saturated aqueous sodium hydrogen carbonate solution were added to the reaction mixture, and the mixture was extracted twice with ethyl acetate. The obtained organic phases were combined, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 0.05 g of the following present compound (14).

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：２．８３（２Ｈ，ｔ，Ｊ＝６Ｈｚ），３．８５（２Ｈ，ｔ，Ｊ＝６Ｈｚ），７．２０（１Ｈ，ｄｄ，Ｊ＝７，７Ｈｚ），７．５０（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．５９（１Ｈ，ｄｄ，Ｊ＝７，７Ｈｚ），７．７９（１Ｈ，ｄ，Ｊ＝７Ｈｚ），８．３５（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．７１−８．７８（２Ｈ，ｍ），９．１８（１Ｈ，ｂｒｓ） The present compound (14)

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 2.83 (2H, t, J = 6 Hz), 3.85 (2H, t, J = 6 Hz), 7.20 (1H, dd, J = 7, 7 Hz), 7.50 (1H, dd, J = 8, 5 Hz), 7.59 (1H, dd, J = 7, 7 Hz), 7.79 (1H, d, J = 7 Hz), 8.35 (1H, ddd, J = 8, 2, 2 Hz), 8.71-8.78 (2H, m), 9.18 (1H, brs)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：５．７８−５．８５（１Ｈ，ｍ），６．３２−６．４９（２Ｈ，ｍ），７．２１（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．５０（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．５６−７．６４（１Ｈ，ｍ），７．８２（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．３５（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７２−８．７６（２Ｈ，ｍ），９．１９（１Ｈ，ｄ，Ｊ＝１Ｈｚ） Production Example 15
The following present compound (15) was obtained in the same manner as in Production Example 14 using acrylic acid instead of 3-bromopropionic acid.
The present compound (15)

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 5.78-5.85 (1H, m), 6.32-6.49 (2H, m), 7.21 (1H, dd, J = 8,7 Hz), 7.50 (1H, dd, J = 8, 5 Hz), 7.56-7.64 (1H, m), 7.82 (1H, d, J = 8 Hz), 8. 35 (1H, d, J = 8 Hz), 8.72-8.76 (2H, m), 9.19 (1H, d, J = 1 Hz)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）δ：１．００（３Ｈ，ｔ，Ｊ＝７Ｈｚ），１．７１−１．８０（２Ｈ，ｍ），２．３４（２Ｈ，ｔ，Ｊ＝７Ｈｚ），７．１２（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．４４（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．５５（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．６９（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．３０（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．６６−８．８３（３Ｈ，ｍ），９．２２（１Ｈ，ｄ，Ｊ＝２Ｈｚ），９．４９（１Ｈ，ｂｒｓ），１１．９９（１Ｈ，ｂｒｓ） Production Example 16
The following compound (16) of the present invention was obtained in the same manner as in Production Example 14 using butyric acid instead of 3-bromopropionic acid.
The present compound (16)

¹ H-NMR (CDCl ₃ , TMS) δ: 1.00 (3H, t, J = 7 Hz), 1.71-1.80 (2H, m), 2.34 (2H, t, J = 7 Hz) , 7.12 (1H, dd, J = 8, 8 Hz), 7.44 (1H, dd, J = 8, 5 Hz), 7.55 (1H, dd, J = 8, 8 Hz), 7.69 ( 1H, d, J = 8 Hz), 8.30 (1H, d, J = 8 Hz), 8.66-8.83 (3H, m), 9.22 (1H, d, J = 2 Hz), 9. 49 (1H, brs), 11.99 (1H, brs)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：２．１５−２．２１（２Ｈ，ｍ），２．５５（２Ｈ，ｔ，Ｊ＝７Ｈｚ），３．６６（２Ｈ，ｔ，Ｊ＝７Ｈｚ），７．２０（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．５０（１Ｈ，ｄｄｄ，Ｊ＝８，５，１Ｈｚ），７．５６−７．６４（１Ｈ，ｍ），７．７９（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．３４（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．７２−８．７７（２Ｈ，ｍ），９．１８（１Ｈ，ｄ，Ｊ＝２Ｈｚ） Production Example 17
The following compound (17) of the present invention was obtained in the same manner as in Production Example 14 using 4-chlorobutyric acid instead of 3-bromopropionic acid.
The present compound (17)

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 2.15 to 2.21 (2H, m), 2.55 (2H, t, J = 7 Hz), 3.66 (2H, t, J = 7 Hz), 7.20 (1H, dd, J = 8, 7 Hz), 7.50 (1H, ddd, J = 8, 5, 1 Hz), 7.56-7.64 (1H, m), 7.79 (1H, dd, J = 8, 1 Hz), 8.34 (1H, ddd, J = 8, 2, 2 Hz), 8.72-8.77 (2H, m), 9.18 (1H , D, J = 2Hz)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）δ：０．９０（３Ｈ，ｔ，Ｊ＝７Ｈｚ），１．２９−１．３８（４Ｈ，ｍ），１．６７−１．７５（２Ｈ，ｍ），２．３５（２Ｈ，ｔ，Ｊ＝８Ｈｚ），７．１２（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．４４（１Ｈ，ｄｄｄ，Ｊ＝８，５，１Ｈｚ），７．５６（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．６９（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．３０（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．６０−８．８４（３Ｈ，ｍ），９．２３（１Ｈ，ｄ，Ｊ＝２Ｈｚ），１２．００（１Ｈ，ｂｒｓ） Production Example 18
The following present compound (18) was obtained in the same manner as in Production Example 14 using hexanoic acid instead of 3-bromopropionic acid.
Compound (18) of the present invention

¹ H-NMR (CDCl ₃ , TMS) δ: 0.90 (3H, t, J = 7 Hz), 1.29-1.38 (4H, m), 1.67-1.75 (2H, m) , 2.35 (2H, t, J = 8 Hz), 7.12 (1H, dd, J = 8, 7 Hz), 7.44 (1H, ddd, J = 8, 5, 1 Hz), 7.56 ( 1H, dd, J = 8, 7 Hz), 7.69 (1H, dd, J = 8, 1 Hz), 8.30 (1H, ddd, J = 8, 2, 2 Hz), 8.60-8.84 (3H, m), 9.23 (1H, d, J = 2 Hz), 12.00 (1H, brs)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）δ：１．４４−１．５８（２Ｈ，ｍ），１．７０−１．８５（４Ｈ，ｍ），２．３８（２Ｈ，ｔ，Ｊ＝７Ｈｚ），３．５３（２Ｈ，ｔ，Ｊ＝７Ｈｚ），７．１３（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．４５（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．５７（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．６８（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．３０（１Ｈ，ｄｄ，Ｊ＝８，２Ｈｚ），８．７１（１Ｈ，ｂｒｓ），８．７７（１Ｈ，ｄｄ，Ｊ＝５，１Ｈｚ），８．８１（１Ｈ，ｄ，Ｊ＝８Ｈｚ），９．２２（１Ｈ，ｄ，Ｊ＝２Ｈｚ），９．３８（１Ｈ，ｂｒｓ），１１．９８（１Ｈ，ｂｒｓ） Production Example 19
The following compound (19) of the present invention was obtained in the same manner as in Production Example 14 using 6-bromohexanoic acid instead of 3-bromopropionic acid.
Compound (19) of the present invention

¹ H-NMR (CDCl ₃ , TMS) δ: 1.44 to 1.58 (2H, m), 1.70-1.85 (4H, m), 2.38 (2H, t, J = 7 Hz) , 3.53 (2H, t, J = 7 Hz), 7.13 (1H, dd, J = 8, 8 Hz), 7.45 (1H, dd, J = 8, 5 Hz), 7.57 (1H, dd, J = 8, 8 Hz), 7.68 (1H, d, J = 8 Hz), 8.30 (1H, dd, J = 8, 2 Hz), 8.71 (1H, brs), 8.77 ( 1H, dd, J = 5, 1 Hz), 8.81 (1H, d, J = 8 Hz), 9.22 (1H, d, J = 2 Hz), 9.38 (1H, brs), 11.98 ( 1H, brs)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）δ：０．８３−０．８９（３Ｈ，ｍ），１．２０−１．３５（１２Ｈ，ｍ），１．６７−１．７３（２Ｈ，ｍ），２．３５（２Ｈ，ｔ，Ｊ＝８Ｈｚ），７．１２（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．４４（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．５５（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．６８（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．３０（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．６８（１Ｈ，ｓ），８．７６（１Ｈ，ｄ，Ｊ＝２Ｈｚ），８．８１（１Ｈ，ｄ，Ｊ＝８Ｈｚ），９．２３（１Ｈ，ｄ，Ｊ＝２Ｈｚ），１２．００（１Ｈ，ｂｒｓ） Production Example 20
The following compound (20) of the present invention was obtained in the same manner as in Production Example 14 using decanoic acid instead of 3-bromopropionic acid.
Compound (20) of the present invention

¹ H-NMR (CDCl ₃ , TMS) δ: 0.83-0.89 (3H, m), 1.20-1.35 (12H, m), 1.67-1.73 (2H, m) , 2.35 (2H, t, J = 8 Hz), 7.12 (1H, dd, J = 8, 7 Hz), 7.44 (1H, dd, J = 8, 5 Hz), 7.55 (1H, dd, J = 8, 7 Hz), 7.68 (1H, d, J = 8 Hz), 8.30 (1H, ddd, J = 8, 2, 2 Hz), 8.68 (1H, s), 8. 76 (1H, d, J = 2Hz), 8.81 (1H, d, J = 8Hz), 9.23 (1H, d, J = 2Hz), 12.00 (1H, brs)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：０．８５−０．９３（２Ｈ，ｍ），１．００−１．０６（２Ｈ，ｍ），１．６７−１．７１（１Ｈ，ｍ），７．２０（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．５１（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．５８（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．８０（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．３２−８．３８（１Ｈ，ｍ），８．６８−８．７５（２Ｈ，ｍ），９．１８（１Ｈ，ｄ，Ｊ＝２Ｈｚ） Production Example 21
The following compound (21) of the present invention was obtained in the same manner as in Production Example 14 using cyclopropanecarboxylic acid instead of 3-bromopropionic acid.
Compound (21) of the present invention

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 0.85-0.93 (2H, m), 1.00-1.06 (2H, m), 1.67-1.71 ( 1H, m), 7.20 (1H, dd, J = 8, 8 Hz), 7.51 (1H, dd, J = 8, 5 Hz), 7.58 (1H, dd, J = 8, 8 Hz), 7.80 (1H, d, J = 8 Hz), 8.32-8.38 (1 H, m), 8.68-8.75 (2H, m), 9.18 (1 H, d, J = 2 Hz) )

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：０．２４−０．３０（２Ｈ，ｍ），０．５８−０．６６（２Ｈ，ｍ），１．０３−１．１５（１Ｈ，ｍ），２．２９（２Ｈ，ｄ，Ｊ＝７Ｈｚ），７．２２（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．５２（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．６０（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．８２（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．３２−８．３８（１Ｈ，ｍ），８．６８−８．７５（２Ｈ，ｍ），９．１８（１Ｈ，ｄ，Ｊ＝２Ｈｚ） Production Example 22
The following compound (22) of the present invention was obtained in the same manner as in Production Example 14 using cyclopropylacetic acid instead of 3-bromopropionic acid.
Compound (22) of the present invention

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 0.24-0.30 (2H, m), 0.58-0.66 (2H, m), 1.03-1.15 ( 1H, m), 2.29 (2H, d, J = 7 Hz), 7.22 (1H, dd, J = 8, 7 Hz), 7.52 (1H, dd, J = 8, 5 Hz), 7. 60 (1H, dd, J = 8, 8 Hz), 7.82 (1H, d, J = 8 Hz), 8.32-8.38 (1H, m), 8.68-8.75 (2H, m ), 9.18 (1H, d, J = 2 Hz)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：１．９０−１．９９（１Ｈ，ｍ），２．００−２．１１（１Ｈ，ｍ），２．１８−２．２７（２Ｈ，ｍ），２．３１−２．４２（２Ｈ，ｍ），３．１７−３．２７（１Ｈ，ｍ），７．２１（１Ｈ，ｄｄｄ，Ｊ＝４，４，１Ｈｚ），７．５１（１Ｈ，ｄｄｄ，Ｊ＝８，５，１Ｈｚ），７．５６−７．６２（１Ｈ，ｍ），７．８０（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．３４（１Ｈ，ｄｄｄ，Ｊ＝８，１，１Ｈｚ），８．７２−８．７４（２Ｈ，ｍ），９．１８（１Ｈ，ｄｄ，Ｊ＝２，１Ｈｚ） Production Example 23
The following compound (23) of the present invention was obtained in the same manner as in Production Example 14 using cyclobutanecarboxylic acid instead of 3-bromopropionic acid.
Compound (23) of the present invention

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 1.90-1.99 (1H, m), 2.00-2.11 (1H, m), 2.18-2.27 ( 2H, m), 2.31-2.42 (2H, m), 3.17-3.27 (1H, m), 7.21 (1H, ddd, J = 4, 4, 1 Hz), 7. 51 (1H, ddd, J = 8, 5, 1 Hz), 7.56-7.62 (1H, m), 7.80 (1H, dd, J = 8, 1 Hz), 8.34 (1H, ddd) , J = 8, 1, 1 Hz), 8.72-8.74 (2H, m), 9.18 (1H, dd, J = 2, 1 Hz)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：１．５９−１．６８（２Ｈ，ｍ），１．７３−１．９０（４Ｈ，ｍ），１．９１−２．０１（２Ｈ，ｍ），２．７０−２．７９（１Ｈ，ｍ），７．２０（１Ｈ，ｄｄｄ，Ｊ＝４，４，１Ｈｚ），７．５０（１Ｈ，ｄｄｄ，Ｊ＝８，５，１Ｈｚ），７．５６−７．６３（１Ｈ，ｍ），７．７８（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．３５（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．７１−８．７８（２Ｈ，ｍ），９．１９（１Ｈ，ｄｄ，Ｊ＝２，１Ｈｚ） Production Example 24
The following compound (24) of the present invention was obtained in the same manner as in Production Example 14 using cyclopentanecarboxylic acid instead of 3-bromopropionic acid.
Compound (24) of the present invention

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 1.59-1.68 (2H, m), 1.73-1.90 (4H, m), 1.91-2.01 ( 2H, m), 2.70-2.79 (1H, m), 7.20 (1H, ddd, J = 4, 4, 1 Hz), 7.50 (1H, ddd, J = 8, 5, 1 Hz) ), 7.56-7.63 (1H, m), 7.78 (1H, dd, J = 8, 1 Hz), 8.35 (1H, ddd, J = 8, 2, 2 Hz), 8.71 −8.78 (2H, m), 9.19 (1H, dd, J = 2, 1 Hz)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）δ：０．９０−１．０５（２Ｈ，ｍ），１．１０−１．３３（４Ｈ，ｍ），１．６０−１．８０（４Ｈ，ｍ），１．８２−１．８７（１Ｈ，ｍ），２．２０−２．２４（２Ｈ，ｍ），７．０６（１Ｈ，ｄｄｄ，Ｊ＝４，４，１Ｈｚ），７．４３（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．４９（１Ｈ，ｄｄｄ，Ｊ＝４，４，１Ｈｚ），７．７２（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．２９（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．７２−８．８０（２Ｈ，ｍ），８．９２（１Ｈ，ｂｒｓ），９．２０（１Ｈ，ｄ，Ｊ＝２Ｈｚ），９．３４（１Ｈ，ｂｒｓ），１２．０６（１Ｈ，ｂｒｓ） Production Example 25
The following compound (25) of the present invention was obtained in the same manner as in Production Example 14 using cyclohexylacetic acid instead of 3-bromopropionic acid.
Compound (25) of the present invention

¹ H-NMR (CDCl ₃ , TMS) δ: 0.90 to 1.05 (2H, m), 1.10 to 1.33 (4H, m), 1.60 to 1.80 (4H, m) , 1.82-1.87 (1H, m), 2.20-2.24 (2H, m), 7.06 (1H, ddd, J = 4, 4, 1 Hz), 7.43 (1H, dd, J = 8, 5 Hz), 7.49 (1H, ddd, J = 4, 4, 1 Hz), 7.72 (1H, dd, J = 8, 1 Hz), 8.29 (1H, ddd, J = 8, 2, 2 Hz), 8.72-8.80 (2H, m), 8.92 (1 H, brs), 9.20 (1 H, d, J = 2 Hz), 9.34 (1 H, brs) ), 12.06 (1H, brs)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）δ：１．５９−１．７１（１２Ｈ，ｍ），１．９１−２．１２（６Ｈ，ｍ），７．０７（１Ｈ，ｄｄｄ，Ｊ＝４，４，１Ｈｚ），７．４０−７．４６（１Ｈ，ｍ），７．５０（１Ｈ，ｄｄｄ，Ｊ＝４，４，１Ｈｚ），７．７３（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．２９（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．７２−８．８２（２Ｈ，ｍ），９．２１（１Ｈ，ｄ，Ｊ＝２Ｈｚ），９．４６（１Ｈ，ｂｒｓ），１２．１０（１Ｈ，ｂｒｓ） Production Example 26
The following compound (26) of the present invention was obtained in the same manner as in Production Example 14 using 1-adamantaneacetic acid instead of 3-bromopropionic acid.
Compound (26) of the present invention

¹ H-NMR (CDCl ₃ , TMS) δ: 1.59-1.71 (12H, m), 1.91-2.12 (6H, m), 7.07 (1H, ddd, J = 4 4, 1 Hz), 7.40-7.46 (1 H, m), 7.50 (1 H, ddd, J = 4, 4, 1 Hz), 7.73 (1 H, dd, J = 8, 1 Hz), 8.29 (1H, ddd, J = 8, 2, 2 Hz), 8.72-8.82 (2H, m), 9.21 (1H, d, J = 2 Hz), 9.46 (1H, brs) ), 12.10 (1H, brs)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：３．３８（２Ｈ，ｂｒｓ），７．１９（１Ｈ，ｄｄｄ，Ｊ＝４，４，１Ｈｚ），７．２５（２Ｈ，ｄ，Ｊ＝９Ｈｚ），７．４３−７．５４（３Ｈ，ｍ），７．５９（１Ｈ，ｄｄｄ，Ｊ＝４，４，１Ｈｚ），７．７８（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．３３（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．７０−８．７６（２Ｈ，ｍ），９．１８（１Ｈ，ｄｄ，Ｊ＝２，１Ｈｚ） Production Example 27
The following compound (27) of the present invention was obtained in the same manner as in Production Example 14 using p-bromophenylacetic acid instead of 3-bromopropionic acid.
The present compound (27)

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 3.38 (2H, brs), 7.19 (1H, ddd, J = 4, 4, 1 Hz), 7.25 (2H, d, J = 9 Hz), 7.43-7.54 (3H, m), 7.59 (1H, ddd, J = 4, 4, 1 Hz), 7.78 (1H, dd, J = 8, 1 Hz), 8.33 (1H, ddd, J = 8, 2, 2 Hz), 8.70-8.76 (2H, m), 9.18 (1H, dd, J = 2, 1 Hz)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：３．３５−３．４０（２Ｈ，ｍ），７．２０（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．３６−７．３８（１Ｈ，ｍ），７．４１−７．５１（５Ｈ，ｍ），７．５６−７．６２（５Ｈ，ｍ），７．７９（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．３３（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．６８−８．７５（２Ｈ，ｍ），９．１９（１Ｈ，ｄ，Ｊ＝２Ｈｚ） Production Example 28
The following compound (28) of the present invention was obtained in the same manner as in Production Example 14 using 4-biphenylacetic acid instead of 3-bromopropionic acid.
The present compound (28)

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 3.35-3.40 (2H, m), 7.20 (1H, dd, J = 8, 8 Hz), 7.36-7. 38 (1H, m), 7.41-7.51 (5H, m), 7.56-7.62 (5H, m), 7.79 (1H, d, J = 8 Hz), 8.33 ( 1H, d, J = 8 Hz), 8.68-8.75 (2H, m), 9.19 (1H, d, J = 2 Hz)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：４．６７（２Ｈ，ｓ），６．９６（２Ｈ，ｄ，Ｊ＝９Ｈｚ），７．２２（１Ｈ，ｄｄｄ，Ｊ＝４，４，１Ｈｚ），７．３０（２Ｈ，ｄ，Ｊ＝９Ｈｚ），７．５１（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．６１（１Ｈ，ｄｄｄ，Ｊ＝４，４，１Ｈｚ），７．８３（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．３２（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．７２−８．７７（２Ｈ，ｍ），９．１９（１Ｈ，ｄ，Ｊ＝２Ｈｚ） Production Example 29
The following compound (29) of the present invention was obtained in the same manner as in Production Example 14 using p-chlorophenoxyacetic acid instead of 3-bromopropionic acid.
Compound (29) of the present invention

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 4.67 (2H, s), 6.96 (2H, d, J = 9 Hz), 7.22 (1H, ddd, J = 4 4,1 Hz), 7.30 (2H, d, J = 9 Hz), 7.51 (1H, dd, J = 8, 5 Hz), 7.61 (1H, ddd, J = 4, 4, 1 Hz), 7.83 (1H, dd, J = 8, 1 Hz), 8.32 (1H, ddd, J = 8, 2, 2 Hz), 8.72-8.77 (2H, m), 9.19 (1H , D, J = 2Hz)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：３．８７（３Ｈ，ｓ），７．１０（１Ｈ，ｄｄ，Ｊ＝８，２Ｈｚ），７．２２（１Ｈ，ｄｄｄ，Ｊ＝４，４，１Ｈｚ），７．３８（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．４３−７．５２（３Ｈ，ｍ），７．６１（１Ｈ，ｄｄｄ，Ｊ＝４，４，１Ｈｚ），７．８７（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．３４（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．７２（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），８．７６（１Ｈ，ｄ，Ｊ＝８Ｈｚ），９．１９（１Ｈ，ｄ，Ｊ＝２Ｈｚ） Production Example 30
The following present compound (30) was obtained in the same manner as in Production Example 14 using m-methoxybenzoic acid instead of 3-bromopropionic acid.
Compound (30) of the present invention

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 3.87 (3H, s), 7.10 (1H, dd, J = 8, 2 Hz), 7.22 (1H, ddd, J = 4, 4, 1 Hz), 7.38 (1 H, dd, J = 8, 8 Hz), 7.43-7.52 (3 H, m), 7.61 (1 H, ddd, J = 4, 4, 1 Hz) ), 7.87 (1H, d, J = 8 Hz), 8.34 (1H, ddd, J = 8, 2, 2 Hz), 8.72 (1H, dd, J = 5, 2 Hz), 8.76 (1H, d, J = 8 Hz), 9.19 (1H, d, J = 2 Hz)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：６．６６（１Ｈ，ｄ，Ｊ＝１６Ｈｚ），７．２３（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．３６−７．４３（３Ｈ，ｍ），７．５０（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．５３−７．５８（２Ｈ，ｍ），７．６１（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．７３（１Ｈ，ｄ，Ｊ＝１６Ｈｚ），７．８５（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．３６（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７３（１Ｈ，ｄｄ，Ｊ＝４，２Ｈｚ），８．７７（１Ｈ，ｄ，Ｊ＝８Ｈｚ），９．２０（１Ｈ，ｄ，Ｊ＝２Ｈｚ） Production Example 31
The following compound (31) of the present invention was obtained in the same manner as in Production Example 14 using trans-cinnamic acid instead of 3-bromopropionic acid.
Compound (31) of the present invention

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 6.66 (1H, d, J = 16 Hz), 7.23 (1H, dd, J = 8, 8 Hz), 7.36-7. 43 (3H, m), 7.50 (1H, dd, J = 8, 5 Hz), 7.53-7.58 (2H, m), 7.61 (1H, dd, J = 8, 8 Hz), 7.73 (1H, d, J = 16 Hz), 7.85 (1H, d, J = 8 Hz), 8.36 (1H, d, J = 8 Hz), 8.73 (1H, dd, J = 4) , 2 Hz), 8.77 (1 H, d, J = 8 Hz), 9.20 (1 H, d, J = 2 Hz)

Production Example 32
N- [2- (hydrazinocarbonyl) phenyl] -3-pyridinecarboxamide (0.13 g), dimethyl sulfoxide (2 ml) and ethyl isocyanate (0.10 g) were mixed, and the mixture was stirred at 30 ° C. for 2 hours. Water and saturated aqueous sodium hydrogen carbonate solution were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic phase was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 0.13 g of the following present compound (32).

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：１．１４（３Ｈ，ｔ，Ｊ＝７Ｈｚ），３．２４（２Ｈ，ｑ，Ｊ＝７Ｈｚ），７．２１（１Ｈ，ｄｄｄ，Ｊ＝４，４，１Ｈｚ），７．５１（１Ｈ，ｄｄｄ，Ｊ＝８，５，１Ｈｚ），７．５９（１Ｈ，ｄｄｄ，Ｊ＝４，４，１Ｈｚ），７．８１（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．３４（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．６６（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７２（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），９．１７（１Ｈ，ｄｄ，Ｊ＝２，１Ｈｚ） Compound (32) of the present invention

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 1.14 (3H, t, J = 7 Hz), 3.24 (2H, q, J = 7 Hz), 7.21 (1H, ddd, J = 4, 4, 1 Hz), 7.51 (1H, ddd, J = 8, 5, 1 Hz), 7.59 (1H, ddd, J = 4, 4, 1 Hz), 7.81 (1H, dd) , J = 8, 1 Hz), 8.34 (1H, ddd, J = 8, 2, 2 Hz), 8.66 (1H, d, J = 8 Hz), 8.72 (1H, dd, J = 5 2Hz), 9.17 (1H, dd, J = 2, 1 Hz)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：０．９７−１．０４（６Ｈ，ｍ），３．２０−３．２５（１Ｈ，ｍ），７．０８（１Ｈ，ｄｄｄ，Ｊ＝４，４，１Ｈｚ），７．３７（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．４１−７．４７（１Ｈ，ｍ），７．６３−７．６９（１Ｈ，ｍ），８．２１（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．５３（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．５６−８．６１（１Ｈ，ｍ），９．０１−９．０５（１Ｈ，ｍ） Production Example 33
The following compound (33) of the present invention was obtained in the same manner as in Production Example 32 using isopropyl isocyanate instead of ethyl isocyanate.
Compound (33) of the present invention

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 0.97-1.04 (6H, m), 3.20-3.25 (1H, m), 7.08 (1H, ddd, J = 4, 4, 1 Hz), 7.37 (1H, dd, J = 8, 5 Hz), 7.41-7.47 (1H, m), 7.63-7.69 (1H, m), 8.21 (1H, ddd, J = 8, 2, 2 Hz), 8.53 (1H, d, J = 8 Hz), 8.56-8.61 (1H, m), 9.01-9.05 (1H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：０．９１（３Ｈ，ｔ，Ｊ＝７Ｈｚ），１．４５−１．５７（２Ｈ，ｍ），３．１５−３．１９（２Ｈ，ｍ），７．２１（１Ｈ，ｄｄ，Ｊ＝７，７Ｈｚ），７．５０（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．５９（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．７９（１Ｈ，ｄ，Ｊ＝７Ｈｚ），８．３４（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．６９（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７３（１Ｈ，ｄｄ，Ｊ＝５，１Ｈｚ），９．１８（１Ｈ，ｄ，Ｊ＝１Ｈｚ） Production Example 34
The following compound (34) of the present invention was obtained in the same manner as in Production Example 32 using propyl isocyanate instead of ethyl isocyanate.
The present compound (34)

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 0.91 (3H, t, J = 7 Hz), 1.45 to 1.57 (2H, m), 3.15-3.19 ( 2H, m), 7.21 (1H, dd, J = 7, 7 Hz), 7.50 (1H, dd, J = 8, 5 Hz), 7.59 (1H, dd, J = 8, 8 Hz), 7.79 (1H, d, J = 7 Hz), 8.34 (1H, d, J = 8 Hz), 8.69 (1H, d, J = 8 Hz), 8.73 (1H, dd, J = 5) , 1 Hz), 9.18 (1 H, d, J = 1 Hz)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：６．８８（１Ｈ，ｄｄ，Ｊ＝７，７Ｈｚ），７．０３−７．１６（３Ｈ，ｍ），７．２５−７．２８（２Ｈ，ｍ），７．３３（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．４４（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．６８（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．１８（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．５０（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．５４（１Ｈ，ｄ，Ｊ＝５Ｈｚ），９．０１（１Ｈ，ｂｒｓ） Production Example 35
The following compound (35) of the present invention was obtained in the same manner as in Production Example 32 using phenyl isocyanate instead of ethyl isocyanate.
The present compound (35)

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 6.88 (1H, dd, J = 7, 7 Hz), 7.03-7.16 (3H, m), 7.25-7. 28 (2H, m), 7.33 (1H, dd, J = 8, 5 Hz), 7.44 (1H, dd, J = 8, 8 Hz), 7.68 (1H, d, J = 8 Hz), 8.18 (1H, d, J = 8 Hz), 8.50 (1H, d, J = 8 Hz), 8.54 (1H, d, J = 5 Hz), 9.01 (1H, brs)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：７．２２−７．２８（２Ｈ，ｍ），７．３６−７．４２（２Ｈ，ｍ），７．４７−７．５３（３Ｈ，ｍ），７．６２（１Ｈ，ｄｄｄ，Ｊ＝４，４，２Ｈｚ），７．８３（１Ｈ，ｄｄ，Ｊ＝８，２Ｈｚ），８．３２（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．６５（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７３（１Ｈ，ｄｄ，Ｊ＝５，１Ｈｚ），９．１７（１Ｈ，ｄ，Ｊ＝１Ｈｚ） Production Example 36
The following compound (36) of the present invention was obtained in the same manner as in Production Example 32 using phenyl isothiocyanate instead of ethyl isocyanate.
The present compound (36)

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 7.22-7.28 (2H, m), 7.36-7.42 (2H, m), 7.47-7.53 ( 3H, m), 7.62 (1H, ddd, J = 4, 4, 2 Hz), 7.83 (1H, dd, J = 8, 2 Hz), 8.32 (1H, ddd, J = 8, 2 , 2 Hz), 8.65 (1 H, d, J = 8 Hz), 8.73 (1 H, dd, J = 5, 1 Hz), 9.17 (1 H, d, J = 1 Hz)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：０．９７（３Ｈ，ｔ，Ｊ＝７Ｈｚ），３．３９（２Ｈ，ｑ，Ｊ＝７Ｈｚ），７．０３（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．３２（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．３９（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．６１（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．１２（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．３１（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．５１（１Ｈ，ｄ，Ｊ＝５Ｈｚ），８．９４（１Ｈ，ｂｒｓ） Production Example 37
The following compound (37) of the present invention was obtained in the same manner as in Production Example 32 using ethyl isothiocyanate instead of ethyl isocyanate.
Compound (37) of the present invention

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 0.97 (3H, t, J = 7 Hz), 3.39 (2H, q, J = 7 Hz), 7.03 (1H, dd, J = 8, 8 Hz), 7.32 (1H, dd, J = 8, 5 Hz), 7.39 (1H, dd, J = 8, 8 Hz), 7.61 (1H, d, J = 8 Hz), 8.12 (1H, d, J = 8 Hz), 8.31 (1H, d, J = 8 Hz), 8.51 (1H, d, J = 5 Hz), 8.94 (1H, brs)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）δ：０．８５（３Ｈ，ｔ，Ｊ＝６Ｈｚ），１．１１−１．４３（１０Ｈ，ｍ），１．５９−１．６８（２Ｈ，ｍ），３．５８（２Ｈ，ｄ，Ｊ＝６Ｈｚ），６．７７（１Ｈ，ｂｒｓ），７．２０（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．４７（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．６１（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．７８（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．３０（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．７３（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），８．７６−８．８２（２Ｈ，ｍ），９．２１（１Ｈ，ｄ，Ｊ＝２Ｈｚ），９．６９（１Ｈ，ｂｒｓ），１２．００（１Ｈ，ｂｒｓ） Production Example 38
The following compound (38) of the present invention was obtained in the same manner as in Production Example 32 using octyl isothiocyanate instead of ethyl isocyanate.
The present compound (38)

¹ H-NMR (CDCl ₃ , TMS) δ: 0.85 (3H, t, J = 6 Hz), 1.11-1.43 (10H, m), 1.59-1.68 (2H, m) , 3.58 (2H, d, J = 6 Hz), 6.77 (1H, brs), 7.20 (1H, dd, J = 8, 8 Hz), 7.47 (1H, dd, J = 8, 5 Hz), 7.61 (1 H, dd, J = 8, 8 Hz), 7.78 (1 H, d, J = 8 Hz), 8.30 (1 H, ddd, J = 8, 2, 2 Hz), 8. 73 (1H, dd, J = 5, 2 Hz), 8.76-8.82 (2H, m), 9.21 (1H, d, J = 2 Hz), 9.69 (1H, brs), 12. 00 (1H, brs)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：４．０８（２Ｈ，ｄ，Ｊ＝５Ｈｚ），４．９３（１Ｈ，ｄ，Ｊ＝９Ｈｚ），５．０５（１Ｈ，ｄ，Ｊ＝１７Ｈｚ），５．６４−５．７６（１Ｈ，ｍ），７．０８（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．３７（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．４５（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．６５（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．１７（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．４０（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．５７（１Ｈ，ｄ，Ｊ＝５Ｈｚ），９．０１（１Ｈ，ｄ，Ｊ＝２Ｈｚ） Production Example 39
The present compound (39) was obtained in the same manner as in Production Example 32 using allyl isothiocyanate instead of ethyl isocyanate.
The present compound (39)

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 4.08 (2H, d, J = 5 Hz), 4.93 (1H, d, J = 9 Hz), 5.05 (1H, d, J = 17 Hz), 5.64-5.76 (1 H, m), 7.08 (1 H, dd, J = 8, 8 Hz), 7.37 (1 H, dd, J = 8, 5 Hz), 7. 45 (1H, dd, J = 8, 8 Hz), 7.65 (1H, d, J = 8 Hz), 8.17 (1H, ddd, J = 8, 2, 2 Hz), 8.40 (1H, d , J = 8 Hz), 8.57 (1H, d, J = 5 Hz), 9.01 (1H, d, J = 2 Hz)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：１．３４（９Ｈ，ｓ），７．２１（１Ｈ，ｄｄｄ，Ｊ＝４，４，１Ｈｚ），７．５０（１Ｈ，ｄｄｄ，Ｊ＝８，５，１Ｈｚ），７．５６−７．６２（１Ｈ，ｍ），７．７８（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．３５（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．６７−８．７６（２Ｈ，ｍ），９．１８（１Ｈ，ｄｄ，Ｊ＝２，１Ｈｚ） Production Example 40
This invention compound (40) was obtained by the method similar to manufacture example 32 using tert-butyl isocyanate instead of ethyl isocyanate.
Compound (40) of the present invention

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 1.34 (9H, s), 7.21 (1H, ddd, J = 4, 4, 1 Hz), 7.50 (1H, ddd, J = 8, 5, 1 Hz), 7.56-7.62 (1H, m), 7.78 (1H, dd, J = 8, 1 Hz), 8.35 (1H, ddd, J = 8, 2 , 2 Hz), 8.67-8.76 (2H, m), 9.18 (1H, dd, J = 2, 1 Hz)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：３．３８−３．４８（４Ｈ，ｍ），７．０８（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．３８（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．４６（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．６７（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．２１（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．５３（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．５６−８．６０（１Ｈ，ｍ），９．０３（１Ｈ，ｂｒｓ） Production Example 41
The following compound (41) of the present invention was obtained in the same manner as in Production Example 32 using isocyanic acid (2-chloroethyl) instead of ethyl isocyanate.
Compound (41) of the present invention

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 3.38-3.48 (4H, m), 7.08 (1H, dd, J = 8, 8 Hz), 7.38 (1H, dd, J = 8, 5 Hz), 7.46 (1H, dd, J = 8, 8 Hz), 7.67 (1H, d, J = 8 Hz), 8.21 (1H, d, J = 8 Hz), 8.53 (1H, d, J = 8 Hz), 8.56-8.60 (1H, m), 9.03 (1H, brs)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ，ＣＤ_３ＯＤ）δ：１．０５−１．４１（６Ｈ，ｍ），１．６５−１．９９（４Ｈ，ｍ），３．３５−３．４０（１Ｈ，ｍ），７．２２（１Ｈ，ｄｄｄ，Ｊ＝４，４，１Ｈｚ），７．５１（１Ｈ，ｄｄｄ，Ｊ＝８，５，１Ｈｚ），７．５５−７．６４（１Ｈ，ｍ），７．７９（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．３５（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．６８（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７３（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），９．１８（１Ｈ，ｄ，Ｊ＝２Ｈｚ） Production Example 42
The following compound (42) of the present invention was obtained in the same manner as in Production Example 32 using cyclohexyl isocyanate in place of ethyl isocyanate.
Compound (42) of the present invention

¹ H-NMR (CDCl ₃ , TMS, CD ₃ OD) δ: 1.05-1.41 (6H, m), 1.65-1.99 (4H, m), 3.35-3.40 ( 1H, m), 7.22 (1H, ddd, J = 4, 4, 1 Hz), 7.51 (1H, ddd, J = 8, 5, 1 Hz), 7.55-7.64 (1H, m ), 7.79 (1H, dd, J = 8, 1 Hz), 8.35 (1H, ddd, J = 8, 2, 2 Hz), 8.68 (1H, d, J = 8 Hz), 8.73. (1H, dd, J = 5, 2 Hz), 9.18 (1H, d, J = 2 Hz)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：３．２５（６Ｈ，ｓ），７．２９（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．６０−７．６７（２Ｈ，ｍ），７．９６（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．２６（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．５７（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．８１（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），９．０８（１Ｈ，ｄ，Ｊ＝２Ｈｚ），９．５４（１Ｈ，ｂｒｓ），１０．７７（１Ｈ，ｂｒｓ），１１．８９（１Ｈ，ｂｒｓ） Production Example 43
The following compound (43) of the present invention was obtained in the same manner as in Production Example 4 using N, N-dimethylthiocarbamoyl chloride instead of methyl chlorocarbonate.
Compound (43) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 3.25 (6H, s), 7.29 (1H, dd, J = 8, 8 Hz), 7.60-7.67 (2H, m) , 7.96 (1H, dd, J = 8, 1 Hz), 8.26 (1H, ddd, J = 8, 2, 2 Hz), 8.57 (1H, d, J = 8 Hz), 8.81 ( 1H, dd, J = 5, 2 Hz), 9.08 (1H, d, J = 2 Hz), 9.54 (1H, brs), 10.77 (1H, brs), 11.89 (1H, brs)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ），（ｔｅｍｐ＝８０℃）δ：２．２３（３Ｈ，ｓ），７．２７（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．５６−７．６６（２Ｈ，ｍ），７．８５（１Ｈ，ｄｄ，Ｊ＝７，２Ｈｚ），８．２４（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．５１（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７８（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），９．０８（１Ｈ，ｄ，Ｊ＝２Ｈｚ），９．８７（１Ｈ，ｂｒｓ），１０．６５（１Ｈ，ｂｒｓ），１１．６７（１Ｈ，ｂｒｓ） Production Example 44
The following compound (44) of the present invention was obtained in the same manner as in Production Example 4 using methyl chlorothiocarbonate instead of methyl chlorocarbonate.
Compound (44) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS), (temp = 80 ° C.) δ: 2.23 (3H, s), 7.27 (1H, dd, J = 8, 7 Hz), 7.56-7 .66 (2H, m), 7.85 (1H, dd, J = 7, 2 Hz), 8.24 (1H, ddd, J = 8, 2, 2 Hz), 8.51 (1H, d, J = 8 Hz), 8.78 (1 H, dd, J = 5, 2 Hz), 9.08 (1 H, d, J = 2 Hz), 9.87 (1 H, brs), 10.65 (1 H, brs), 11 .67 (1H, brs)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：１．９５（３Ｈ，ｓ），７．２７（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．６０−７．６８（２Ｈ，ｍ），７．８７（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．２６（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．５５（１Ｈ，ｄ，Ｊ＝７Ｈｚ），８．８１（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），９．０９（１Ｈ，ｄ，Ｊ＝２Ｈｚ），１０．０３（１Ｈ，ｂｒｓ），１０．６３（１Ｈ，ｂｒｓ），１２．０２（１Ｈ，ｂｒｓ） Production Example 45
The following compound (45) of the present invention was obtained in the same manner as in Production Example 4 using acetyl chloride instead of methyl chlorocarbonate.
The present compound (45)

¹ H-NMR (DMSO-d ₆ , TMS) δ: 1.95 (3H, s), 7.27 (1H, dd, J = 8, 7 Hz), 7.60-7.68 (2H, m) , 7.87 (1H, dd, J = 8, 1 Hz), 8.26 (1H, ddd, J = 8, 2, 2 Hz), 8.55 (1H, d, J = 7 Hz), 8.81 ( 1H, dd, J = 5, 2 Hz), 9.09 (1H, d, J = 2 Hz), 10.03 (1H, brs), 10.63 (1H, brs), 12.02 (1H, brs)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：４．５５−４．６１（２Ｈ，ｍ），５．２１−５．４１（２Ｈ，ｍ），５．８９−６．００（１Ｈ，ｍ），７．２８（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．６０−７．６９（２Ｈ，ｍ），７．８６（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．２６（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．５７（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．８１（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），９．０９（１Ｈ，ｄ，Ｊ＝２Ｈｚ），９．４８（１Ｈ，ｂｒｓ），１０．７０（１Ｈ，ｂｒｓ），１２．０２（１Ｈ，ｂｒｓ） Production Example 46
The following compound (46) of the present invention was obtained in the same manner as in Production Example 4 using allyl chlorocarbonate instead of methyl chlorocarbonate.
The present compound (46)

¹ H-NMR (DMSO-d ₆ , TMS) δ: 4.55-4.61 (2H, m), 5.21-5.41 (2H, m), 5.89-6.00 (1H, m), 7.28 (1H, dd, J = 8, 7 Hz), 7.60-7.69 (2H, m), 7.86 (1H, d, J = 8 Hz), 8.26 (1H, d, J = 8 Hz), 8.57 (1H, d, J = 8 Hz), 8.81 (1H, dd, J = 5, 2 Hz), 9.09 (1H, d, J = 2 Hz), 9. 48 (1H, brs), 10.70 (1H, brs), 12.02 (1H, brs)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：７．１０−７．１８（２Ｈ，ｍ），７．１８−７．３０（２Ｈ，ｍ），７．３２−７．４３（２Ｈ，ｍ），７．５５−７．６６（２Ｈ，ｍ），７．８６（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．２４（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．５３（１Ｈ，ｄ，Ｊ＝９Ｈｚ），８．７９（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），９．１０（１Ｈ，ｄ，Ｊ＝２Ｈｚ），９．７１（１Ｈ，ｓ），１０．６８（１Ｈ，ｓ），１１．７５（１Ｈ，ｓ） Production Example 47
The following compound (47) of the present invention was obtained in the same manner as in Production Example 4 using phenyl chlorocarbonate instead of methyl chlorocarbonate.
Compound (47) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 7.10-7.18 (2H, m), 7.18-7.30 (2H, m), 7.32-7.43 (2H, m), 7.55-7.66 (2H, m), 7.86 (1H, d, J = 8 Hz), 8.24 (1H, ddd, J = 8, 2, 2 Hz), 8.53 ( 1H, d, J = 9 Hz), 8.79 (1H, dd, J = 5, 2 Hz), 9.10 (1H, d, J = 2 Hz), 9.71 (1H, s), 10.68 ( 1H, s), 11.75 (1H, s)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：０．９８−１．２８（６Ｈ，ｍ），４．７５−４．９０（１Ｈ，ｍ），７．２７（１Ｈ，ｄｄ，Ｊ＝７，７Ｈｚ），７．５９−７．６７（２Ｈ，ｍ），７．７９−７．８８（１Ｈ，ｍ），８．２６（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．５７（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．８１（１Ｈ，ｄ，Ｊ＝３Ｈｚ），９．０８（１Ｈ，ｓ），９．２７（１Ｈ，ｂｒｓ），１０．６２（１Ｈ，ｂｒｓ），１１．９９（１Ｈ，ｂｒｓ） Production Example 48
The following compound (48) of the present invention was obtained in the same manner as in Production Example 4 using isopropyl chlorocarbonate instead of methyl chlorocarbonate.
The present compound (48)

¹ H-NMR (DMSO-d ₆ , TMS) δ: 0.98-1.28 (6H, m), 4.75-4.90 (1H, m), 7.27 (1H, dd, J = 7, 7 Hz), 7.59-7.67 (2H, m), 7.79-7.88 (1 H, m), 8.26 (1 H, d, J = 8 Hz), 8.57 (1 H, d, J = 8 Hz), 8.81 (1H, d, J = 3 Hz), 9.08 (1H, s), 9.27 (1H, brs), 10.62 (1H, brs), 11.99. (1H, brs)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：３．２６（３Ｈ，ｓ），３．５２（２Ｈ，ｔ，Ｊ＝５Ｈｚ），４．１６（２Ｈ，ｔ，Ｊ＝５Ｈｚ），７．２４（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．５４−７．６５（２Ｈ，ｍ），７．８３（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．２４（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．５４（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７８（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），９．０８（１Ｈ，ｄ，Ｊ＝２Ｈｚ），９．１３（１Ｈ，ｂｒｓ），１０．４７（１Ｈ，ｂｒｓ），１１．８１（１Ｈ，ｂｒｓ） Production Example 49
The following compound (49) of the present invention was obtained in the same manner as in Production Example 4 using chlorocarbonate (2-methoxyethyl) instead of methyl chlorocarbonate.
The present compound (49)

¹ H-NMR (DMSO-d ₆ , TMS) δ: 3.26 (3H, s), 3.52 (2H, t, J = 5 Hz), 4.16 (2H, t, J = 5 Hz), 7 .24 (1H, dd, J = 8, 7 Hz), 7.54-7.65 (2H, m), 7.83 (1H, d, J = 8 Hz), 8.24 (1H, ddd, J = 8, 2, 2 Hz), 8.54 (1 H, d, J = 8 Hz), 8.78 (1 H, dd, J = 5, 2 Hz), 9.08 (1 H, d, J = 2 Hz), 9. 13 (1H, brs), 10.47 (1H, brs), 11.81 (1H, brs)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：７．１２−７．３２（２Ｈ，ｍ），７．５１（１Ｈ，ｂｒｓ），７．５７−７．６６（２Ｈ，ｍ），７．８９（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．２４（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．５３（１Ｈ，ｄ，Ｊ＝７Ｈｚ），８．７８（１Ｈ，ｄｄ，Ｊ＝５，１Ｈｚ），９．０８（１Ｈ，ｄ，Ｊ＝２Ｈｚ），１１．６４（１Ｈ，ｂｒｓ） Production Example 50
The following compound (50) of the present invention was obtained in the same manner as in Production Example 4 using trichloroacetyl chloride instead of methyl chlorocarbonate.
Compound (50) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 7.12-7.32 (2H, m), 7.51 (1H, brs), 7.57-7.66 (2H, m), 7 .89 (1H, d, J = 8 Hz), 8.24 (1H, ddd, J = 8, 2, 2 Hz), 8.53 (1H, d, J = 7 Hz), 8.78 (1H, dd, J = 5, 1 Hz), 9.08 (1H, d, J = 2 Hz), 11.64 (1H, brs)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：１．０７（３Ｈ，ｔ，Ｊ＝８Ｈｚ），２．２３（２Ｈ，ｑ，Ｊ＝８Ｈｚ），７．２７（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．５９−７．６８（２Ｈ，ｍ），７．８７（１Ｈ，ｄｄ，Ｊ＝８，１Ｈｚ），８．２６（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．５５（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．８１（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），９．０８（１Ｈ，ｄ，Ｊ＝２Ｈｚ），１０．００（１Ｈ，ｂｒｓ），１０．６３（１Ｈ，ｂｒｓ），１２．０１（１Ｈ，ｂｒｓ） Production Example 51
The following compound (51) of the present invention was obtained in the same manner as in Production Example 4 using propionyl chloride instead of methyl chlorocarbonate.
Compound (51) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 1.07 (3H, t, J = 8 Hz), 2.23 (2H, q, J = 8 Hz), 7.27 (1H, dd, J = 8,7 Hz), 7.59-7.68 (2 H, m), 7.87 (1 H, dd, J = 8, 1 Hz), 8.26 (1 H, ddd, J = 8, 2, 2 Hz), 8.55 (1H, d, J = 8 Hz), 8.81 (1H, dd, J = 5, 2 Hz), 9.08 (1H, d, J = 2 Hz), 10.00 (1H, brs), 10.63 (1H, brs), 12.01 (1H, brs)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：１．２１（９Ｈ，ｓ），７．２３（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．５３−７．６４（２Ｈ，ｍ），７．８４（１Ｈ，ｄ，Ｊ＝６Ｈｚ），８．２４（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．５１−８．５９（１Ｈ，ｍ），８．７７（１Ｈ，ｄｄ，Ｊ＝５，１Ｈｚ），９．０７（１Ｈ，ｄ，Ｊ＝２Ｈｚ），９．４９（１Ｈ，ｂｒｓ），１０．３１（１Ｈ，ｂｒｓ），１１．７１（１Ｈ，ｂｒｓ） Production Example 52
The following compound (52) of the present invention was obtained in the same manner as in Production Example 4 using trimethylacetyl chloride instead of methyl chlorocarbonate.
Compound (52) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 1.21 (9H, s), 7.23 (1H, dd, J = 8, 7 Hz), 7.53 to 7.64 (2H, m) 7.84 (1 H, d, J = 6 Hz), 8.24 (1 H, ddd, J = 8, 2, 2 Hz), 8.51-8.59 (1 H, m), 8.77 (1 H, dd, J = 5, 1 Hz), 9.07 (1H, d, J = 2 Hz), 9.49 (1H, brs), 10.31 (1H, brs), 11.71 (1H, brs)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：３．８４（３Ｈ，ｓ），７．０３（２Ｈ，ｄ，Ｊ＝９Ｈｚ），７．２７（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．５４−７．５９（１Ｈ，ｍ），７．６２（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．８８−７．９４（３Ｈ，ｍ），８．２５（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．５７（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７６（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），９．０８（１Ｈ，ｄ，Ｊ＝２Ｈｚ），１０．２８（１Ｈ，ｂｒｓ），１０．５６（１Ｈ，ｂｒｓ），１１．８２（１Ｈ，ｂｒｓ） Production Example 53
The following compound (53) of the present invention was obtained in the same manner as in Production Example 4 using p-methoxybenzoyl chloride instead of methyl chlorocarbonate.
The present compound (53)

¹ H-NMR (DMSO-d ₆ , TMS) δ: 3.84 (3H, s), 7.03 (2H, d, J = 9 Hz), 7.27 (1H, dd, J = 8, 8 Hz) 7.54-759 (1H, m), 7.62 (1H, dd, J = 8, 8 Hz), 7.88-7.94 (3H, m), 8.25 (1H, d, J = 8 Hz), 8.57 (1H, d, J = 8 Hz), 8.76 (1H, dd, J = 5, 2 Hz), 9.08 (1H, d, J = 2 Hz), 10.28 ( 1H, brs), 10.56 (1H, brs), 11.82 (1H, brs)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：１．４２−１．５２（４Ｈ，ｍ），１．５２−１．６２（２Ｈ，ｍ），３．３４−３．４０（４Ｈ，ｍ），７．２６（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．５８−７．６５（２Ｈ，ｍ），７．８３（１Ｈ，ｄｄ，Ｊ＝８，２Ｈｚ），８．２６（１Ｈ，ｄｄｄ，Ｊ＝８，２，２Ｈｚ），８．５９（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７３（１Ｈ，ｓ），８．８０（１Ｈ，ｄｄ，Ｊ＝５，２Ｈｚ），９．０９（１Ｈ，ｄ，Ｊ＝２Ｈｚ），１０．３５（１Ｈ，ｓ），１１．９９（１Ｈ，ｓ） Production Example 54
The following compound (54) of the present invention was obtained in the same manner as in Production Example 4 using 1-piperidinecarbonyl chloride instead of methyl chlorocarbonate.
The present compound (54)

¹ H-NMR (DMSO-d ₆ , TMS) δ: 1.42-1.52 (4H, m), 1.52-1.62 (2H, m), 3.34-3.40 (4H, m), 7.26 (1H, dd, J = 8, 8 Hz), 7.58-7.65 (2H, m), 7.83 (1H, dd, J = 8, 2 Hz), 8.26 ( 1H, ddd, J = 8, 2, 2 Hz), 8.59 (1H, d, J = 8 Hz), 8.73 (1H, s), 8.80 (1H, dd, J = 5, 2 Hz), 9.09 (1H, d, J = 2 Hz), 10.35 (1H, s), 11.99 (1H, s)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：０．８９（６Ｈ，ｔ，Ｊ＝８Ｈｚ），１．１９−１．３３（４Ｈ，ｍ），１．４３−１．５３（４Ｈ，ｍ），３．２０（４Ｈ，ｔ，Ｊ＝７Ｈｚ），７．２５（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．５５−７．６４（２Ｈ，ｍ），７．８０（１Ｈ，ｄ，Ｊ＝７Ｈｚ），８．２６（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．４９（１Ｈ，ｂｒｓ），８．５８（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７９（１Ｈ，ｄ，Ｊ＝４Ｈｚ），９．０８（１Ｈ，ｄ，Ｊ＝２Ｈｚ），１０．３４（１Ｈ，ｂｒｓ），１１．９４（１Ｈ，ｂｒｓ） Production Example 55
The following compound (55) of the present invention was obtained in the same manner as in Production Example 4 using N, N-dibutylcarbamoyl chloride instead of methyl chlorocarbonate.
The present compound (55)

¹ H-NMR (DMSO-d ₆ , TMS) δ: 0.89 (6H, t, J = 8 Hz), 1.19-1.33 (4H, m), 1.43-1.53 (4H, m), 3.20 (4H, t, J = 7 Hz), 7.25 (1H, dd, J = 8, 8 Hz), 7.55-7.64 (2H, m), 7.80 (1H, d, J = 7 Hz), 8.26 (1H, d, J = 8 Hz), 8.49 (1H, brs), 8.58 (1H, d, J = 8 Hz), 8.79 (1H, d, J = 4 Hz), 9.08 (1H, d, J = 2 Hz), 10.34 (1H, brs), 11.94 (1H, brs)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：１．２０（１２Ｈ，ｄ，Ｊ＝７Ｈｚ），３．７５−３．８１（２Ｈ，ｍ），７．２４（１Ｈ，ｄｄ，Ｊ＝８，８Ｈｚ），７．５４−７．６５（２Ｈ，ｍ），７．７６（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．２５（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．３９（１Ｈ，ｂｒｓ），８．５６（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７８（１Ｈ，ｄ，Ｊ＝５Ｈｚ），９．０８（１Ｈ，ｂｒｓ），１０．２４（１Ｈ，ｂｒｓ），１１．８１（１Ｈ，ｂｒｓ） Production Example 56
The following compound (56) of the present invention was obtained in the same manner as in Production Example 4 using N, N-diisopropylcarbamoyl chloride instead of methyl chlorocarbonate.
The present compound (56)

¹ H-NMR (DMSO-d ₆ , TMS) δ: 1.20 (12H, d, J = 7 Hz), 3.75-3.81 (2H, m), 7.24 (1H, dd, J = 8,8 Hz), 7.54-7.65 (2 H, m), 7.76 (1 H, d, J = 8 Hz), 8.25 (1 H, d, J = 8 Hz), 8.39 (1 H, brs), 8.56 (1H, d, J = 8 Hz), 8.78 (1H, d, J = 5 Hz), 9.08 (1H, brs), 10.24 (1H, brs), 11.81 (1H, brs)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：３．７５（３Ｈ，ｓ），６．８３−７．００（３Ｈ，ｍ），７．３１−７．４４（３Ｈ，ｍ），７．５５−７．６８（３Ｈ，ｍ），８．２３（１Ｈ，ｄ，Ｊ＝６Ｈｚ），８．４９（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７９−８．８５（１Ｈ，ｍ），９．０５（１Ｈ，ｂｒｓ），１１．５１（１Ｈ，ｂｒｓ），１１．５９（１Ｈ，ｂｒｓ） Production Example 57
The following compound (57) of the present invention was obtained in the same manner as in Production Example 4 using o-methoxybenzoyl chloride instead of methyl chlorocarbonate.
Compound (57) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 3.75 (3H, s), 6.83-7.00 (3H, m), 7.31-7.44 (3H, m), 7 .55-7.68 (3H, m), 8.23 (1H, d, J = 6 Hz), 8.49 (1H, d, J = 8 Hz), 8.79-8.85 (1H, m) 9.05 (1H, brs), 11.51 (1H, brs), 11.59 (1H, brs)

Production Example 58
N- (2-amino-5-chloro-3-methylbenzoyl) -N′-methoxycarbonylhydrazine 0.26 g, nicotinic acid chloride hydrochloride 0.18 g, acetonitrile 5 mL, pyridine 5 ml and triethylamine 0.3 g were mixed, The mixture was stirred at room temperature for 10 hours. Water was poured into the reaction mixture, and the deposited precipitate was collected by filtration and dried to obtain 0.21 g of the following present compound (58).

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：２．２５（３Ｈ，ｓ），３．２５−３．４５（３Ｈ，ｍ），７．３６−７．４７（１Ｈ，ｍ），７．５７−７．６７（２Ｈ，ｍ），８．３４（１Ｈ，ｄ，Ｊ＝７Ｈｚ），８．７５−８．８３（１Ｈ，ｍ），９．０８−９．１５（１Ｈ，ｍ），９．２２−９．３０（１Ｈ，ｍ），１０．１２−１０．２１（２Ｈ，ｍ） Compound (58) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 2.25 (3H, s), 3.25-3.45 (3H, m), 7.36-7.47 (1H, m), 7 .57-7.67 (2H, m), 8.34 (1H, d, J = 7 Hz), 8.75-8.83 (1H, m), 9.08-9.15 (1H, m) , 9.22-9.30 (1H, m), 10.12-10.21 (2H, m)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：０．８５−１．２４（３Ｈ，ｍ），２．２４（３Ｈ，ｓ），３．７８−４．１０（２Ｈ，ｍ），７．３０−７．５２（３Ｈ，ｍ），７．５６（１Ｈ，ｄｄ，Ｊ＝８，３Ｈｚ），８．２８（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７６（１Ｈ，ｄ，Ｊ＝４Ｈｚ），９．０７−９．２１（２Ｈ，ｍ），９．９８−１０．１１（２Ｈ，ｍ） Production Example 59
0.25 g of N- [2- (hydrazinocarbonyl) -6-methylphenyl] -3-pyridinecarboxamide and 10 ml of pyridine were mixed, and 0.10 g of ethyl chlorocarbonate was added dropwise to the mixture at room temperature, and 5 hours at room temperature. Stir. Water was added to the reaction mixture, and the deposited precipitate was collected by filtration and dried to obtain 0.14 g of the following present compound (59).
The present compound (59)

¹ H-NMR (DMSO-d ₆ , TMS) δ: 0.85-1.24 (3H, m), 2.24 (3H, s), 3.78-4.10 (2H, m), 7 .30-7.52 (3H, m), 7.56 (1H, dd, J = 8, 3 Hz), 8.28 (1H, d, J = 8 Hz), 8.76 (1H, d, J = 4Hz), 9.07-9.21 (2H, m), 9.98-10.11 (2H, m)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：０．９１−１．２３（６Ｈ，ｍ），２．２４（３Ｈ，ｓ），４．７０−４．７９（１Ｈ，ｍ），７．３０−７．３９（１Ｈ，ｍ），７．３９−７．５１（２Ｈ，ｍ），７．５１−７．６０（１Ｈ，ｍ），８．２５−８．３５（１Ｈ，ｍ），８．７３−８．８０（１Ｈ，ｍ），９．０５−９．１６（２Ｈ，ｍ），９．９５−１０．１２（２Ｈ，ｍ） Production Example 60
The following compound (60) of the present invention was obtained in the same manner as in Production Example 59 using isopropyl chlorocarbonate instead of ethyl chlorocarbonate.
Compound (60) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 0.91-1.23 (6H, m), 2.24 (3H, s), 4.70-4.79 (1H, m), 7 .30-7.39 (1H, m), 7.39-7.51 (2H, m), 7.51-7.60 (1H, m), 8.25-8.35 (1H, m) , 8.73-8.80 (1H, m), 9.05-9.16 (2H, m), 9.95-10.12 (2H, m).

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：０．６５−０．７７（４Ｈ，ｍ），１．６０−１．６９（１Ｈ，ｍ），２．２５（３Ｈ，ｓ），７．３３（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．４３−７．５０（２Ｈ，ｍ），７．５６（１Ｈ，ｄｄ，Ｊ＝８，６Ｈｚ），８．２８（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７６（１Ｈ，ｄ，Ｊ＝４Ｈｚ），９．０５−９．１４（１Ｈ，ｍ），１０．０１−１０．１２（３Ｈ，ｍ） Production Example 61
The following compound (61) of the present invention was obtained in the same manner as in Production Example 59 using cyclopropanecarboxylic acid chloride in place of ethyl chlorocarbonate.
Compound (61) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 0.65-0.77 (4H, m), 1.60-1.69 (1H, m), 2.25 (3H, s), 7 .33 (1H, dd, J = 8, 7 Hz), 7.43-7.50 (2H, m), 7.56 (1H, dd, J = 8, 6 Hz), 8.28 (1H, d, J = 8 Hz), 8.76 (1H, d, J = 4 Hz), 9.05-9.14 (1H, m), 10.01-10.12 (3H, m)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：１．１７−１．２８（３Ｈ，ｍ），２．３５（３Ｈ，ｓ），４．０１−４．１５（２Ｈ，ｍ），７．４６（１Ｈ，ｄ，Ｊ＝９Ｈｚ），７．６２（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．６５−７．７２（１Ｈ，ｍ），８．２４（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．４４（１Ｈ，ｄ，Ｊ＝９Ｈｚ），８．８０（１Ｈ，ｄ，Ｊ＝５Ｈｚ），９．０５−９．１０（１Ｈ，ｍ），９．３４（１Ｈ，ｂｒｓ），１０．６０（１Ｈ，ｂｒｓ），１１．８７（１Ｈ，ｂｒｓ） Production Example 62
0.25 g of N- [2- (hydrazinocarbonyl) -4-methylphenyl] -3-pyridinecarboxamide and 5 ml of pyridine were mixed, and 0.10 g of ethyl chlorocarbonate was added dropwise to the mixture at room temperature for 5 hours at room temperature. Stir. Water was poured into the reaction mixture, and the deposited precipitate was collected by filtration and dried to obtain 0.05 g of the following present compound (62).
Compound (62) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 1.17-1.28 (3H, m), 2.35 (3H, s), 4.01-4.15 (2H, m), 7 .46 (1H, d, J = 9 Hz), 7.62 (1H, dd, J = 8, 5 Hz), 7.65-7.72 (1H, m), 8.24 (1H, d, J = 8 Hz), 8.44 (1 H, d, J = 9 Hz), 8.80 (1 H, d, J = 5 Hz), 9.05-9.10 (1 H, m), 9.34 (1 H, brs) , 10.60 (1H, brs), 11.87 (1H, brs)

Production Example 63
N- [2- (hydrazinocarbonyl) -4-methylphenyl] -3-pyridinecarboxamide (0.25 g) and pyridine (5 ml) were mixed, and 4-morpholinecarbonyl chloride 0.10 g was added dropwise to the mixture at room temperature. For 5 hours. Water was poured into the reaction mixture, and the deposited precipitate was collected by filtration and dried to obtain 0.18 g of the following present compound (63).

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：２．３５（３Ｈ，ｓ），３．３７（４Ｈ，ｔ，Ｊ＝４Ｈｚ），３．５９（４Ｈ，ｔ，Ｊ＝４Ｈｚ），７．４４（１Ｈ，ｄ，Ｊ＝８Ｈｚ），７．６１（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．６７（１Ｈ，ｓ），８．２５（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．４６（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７９（１Ｈ，ｄ，Ｊ＝４Ｈｚ），８．８６（１Ｈ，ｂｒｓ），９．０７（１Ｈ，ｂｒｓ），１０．３４（１Ｈ，ｂｒｓ），１１．８３（１Ｈ，ｂｒｓ） The present compound (63)

¹ H-NMR (DMSO-d ₆ , TMS) δ: 2.35 (3H, s), 3.37 (4H, t, J = 4 Hz), 3.59 (4H, t, J = 4 Hz), 7 .44 (1H, d, J = 8 Hz), 7.61 (1H, dd, J = 8, 5 Hz), 7.67 (1H, s), 8.25 (1H, d, J = 8 Hz), 8 .46 (1H, d, J = 8 Hz), 8.79 (1 H, d, J = 4 Hz), 8.86 (1 H, brs), 9.07 (1 H, brs), 10.34 (1 H, brs) ), 11.83 (1H, brs)

Production Example 64
2- (3-pyridinyl) -4H-3,1-benzoxazin-4-one 0.9 g, 1,2-dimethylhydrazine dihydrochloride 1.6 g, potassium carbonate 1.6 g, 15 drops of water and N, N -12 ml of dimethylformamide were mixed and the mixture was stirred at room temperature for 2 hours. Water and saturated aqueous sodium hydrogen carbonate solution were added to the reaction mixture, and the mixture was extracted 4 times with ethyl acetate. The obtained organic phase was washed successively with water and saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. To the obtained residue, 5 mL of acetonitrile, 0.57 g of methyl chlorocarbonate and 2 mL of pyridine were mixed at 0 ° C. and stirred overnight at room temperature. Water was poured into the reaction mixture, and the mixture was extracted 3 times with ethyl acetate. The obtained organic phase was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 0.14 g of the following present compound (64).

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：２．９４−３．１４（６Ｈ，ｍ），３．５０−３．６９（３Ｈ，ｍ），７．２３−７．７８（５Ｈ，ｍ），８．２２−８．３２（１Ｈ，ｍ），８．７５−８．８１（１Ｈ，ｍ），９．０３−９．１２（１Ｈ，ｍ），１０．３５−１０．６１（１Ｈ，ｍ） Compound (64) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 2.94-3.14 (6H, m), 3.50-3.69 (3H, m), 7.23-7.78 (5H, m), 8.22-8.32 (1H, m), 8.75-8.81 (1H, m), 9.03-9.12 (1H, m), 10.35-10.61 ( 1H, m)

Production Example 65
N- [2- (hydrazinocarbonyl) -3-methylphenyl] -3-pyridinecarboxamide (0.25 g) and pyridine (5 ml) were mixed, and 4-morpholinecarbonyl chloride 0.10 g was added dropwise to the mixture at room temperature. For 5 hours. Water was poured into the reaction mixture, and the deposited precipitate was collected by filtration and dried to obtain 0.20 g of the following present compound (65).

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：２．３２（３Ｈ，ｓ），３．２７−３．３２（４Ｈ，ｍ），３．５４−３．５８（４Ｈ，ｍ），７．０８（１Ｈ，ｄ，Ｊ＝７Ｈｚ），７．３７（１Ｈ，ｄｄ，Ｊ＝８，７Ｈｚ），７．５１（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），８．１４（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．２１（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７２（１Ｈ，ｄ，Ｊ＝４Ｈｚ），９．０１（１Ｈ，ｂｒｓ），９．０６（１Ｈ，ｂｒｓ），１０．１０（１Ｈ，ｂｒｓ），１０．１５（１Ｈ，ｂｒｓ） Compound (65) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 2.32 (3H, s), 3.27-3.32 (4H, m), 3.54-3.58 (4H, m), 7 .08 (1H, d, J = 7 Hz), 7.37 (1H, dd, J = 8, 7 Hz), 7.51 (1H, dd, J = 8, 5 Hz), 8.14 (1H, d, J = 8 Hz), 8.21 (1H, d, J = 8 Hz), 8.72 (1H, d, J = 4 Hz), 9.01 (1H, brs), 9.06 (1H, brs), 10 .10 (1H, brs), 10.15 (1H, brs)

Production Example 66
0.25 g of N- [2- (hydrazinocarbonyl) -5-methylphenyl] -3-pyridinecarboxamide and 10 ml of pyridine were mixed, and 0.10 g of methyl chlorocarbonate was added dropwise to the mixture at room temperature for 5 hours at room temperature. Stir. Water was poured into the reaction mixture, and the deposited precipitate was collected by filtration and dried to obtain 0.17 g of the following present compound (66).

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：２．４０（３Ｈ，ｓ），３．６５（３Ｈ，ｓ），７．０９（１Ｈ，ｄ，Ｊ＝８Ｈｚ），７．６４（１Ｈ，ｄｄ，Ｊ＝８，５Ｈｚ），７．７９（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．２５（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．４８（１Ｈ，ｂｒｓ），８．８１（１Ｈ，ｄ，Ｊ＝５Ｈｚ），９．０９（１Ｈ，ｂｒｓ），９．３７（１Ｈ，ｂｒｓ），１０．６３（１Ｈ，ｂｒｓ），１２．２５（１Ｈ，ｂｒｓ） Compound (66) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 2.40 (3H, s), 3.65 (3H, s), 7.09 (1H, d, J = 8 Hz), 7.64 (1H , Dd, J = 8, 5 Hz), 7.79 (1H, d, J = 8 Hz), 8.25 (1H, d, J = 8 Hz), 8.48 (1H, brs), 8.81 (1H) , D, J = 5 Hz), 9.09 (1H, brs), 9.37 (1H, brs), 10.63 (1H, brs), 12.25 (1H, brs)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：２．４０（３Ｈ，ｓ），３．３５−３．４０（４Ｈ，ｍ），３．５５−３．６５（４Ｈ，ｍ），７．０４−７．１３（１Ｈ，ｍ），７．５８−７．６７（１Ｈ，ｍ），７．７４−７．８２（１Ｈ，ｍ），８．２２−８．２９（１Ｈ，ｍ），８．４５−８．５２（１Ｈ，ｍ），８．７７−８．８７（２Ｈ，ｍ），９．０８（１Ｈ，ｂｒｓ），１０．３６（１Ｈ，ｂｒｓ），１２．２３（１Ｈ，ｂｒｓ） Production Example 67
The following compound (67) of the present invention was obtained in the same manner as in Production Example 66 using 4-morpholinecarbonyl chloride instead of methyl chlorocarbonate.
Compound (67) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 2.40 (3H, s), 3.35-3.40 (4H, m), 3.55 to 3.65 (4H, m), 7 .04-7.13 (1H, m), 7.58-7.67 (1H, m), 7.74-7.82 (1H, m), 8.22-8.29 (1H, m) , 8.45-8.52 (1H, m), 8.77-8.87 (2H, m), 9.08 (1H, brs), 10.36 (1H, brs), 12.23 (1H) , Brs)

Production Example 68
7-Chloro-2- (3-pyridinyl) -4H-3,1-benzoxazin-4-one 0.26 g, methyl carbazate 0.5 g and N, N-dimethylformamide 10 ml were mixed and the mixture was allowed to cool to room temperature. And stirred overnight. Water was poured into the reaction mixture, and the mixture was extracted twice with ethyl acetate. The obtained organic phase was washed with water and saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was washed with methyl = tert-butyl = ether and hexane to obtain 0.18 g of the following present compound (68).

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：３．６０−３．７６（３Ｈ，ｍ），７．３８（１Ｈ，ｄ，Ｊ＝８Ｈｚ），７．６５（１Ｈ，ｄｄ，Ｊ＝７，５Ｈｚ），７．９０（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．２６（１Ｈ，ｄ，Ｊ＝７Ｈｚ），８．６２−８．７３（１Ｈ，ｍ），８．８３（１Ｈ，ｄ，Ｊ＝５Ｈｚ），９．０８（１Ｈ，ｂｒｓ），９．４４（１Ｈ，ｂｒｓ），１０．８０（１Ｈ，ｂｒｓ），１２．２６（１Ｈ，ｂｒｓ） The present compound (68)

¹ H-NMR (DMSO-d ₆ , TMS) δ: 3.60-3.76 (3H, m), 7.38 (1H, d, J = 8 Hz), 7.65 (1H, dd, J = 7, 5 Hz), 7.90 (1 H, d, J = 8 Hz), 8.26 (1 H, d, J = 7 Hz), 8.62-8.73 (1 H, m), 8.83 (1 H, d, J = 5 Hz), 9.08 (1H, brs), 9.44 (1H, brs), 10.80 (1H, brs), 12.26 (1H, brs)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：３．５８−３．７５（３Ｈ，ｍ），７．６０−７．６８（１Ｈ，ｍ），７．７３（１Ｈ，ｄｄ，Ｊ＝７，２Ｈｚ），７．９１（１Ｈ，ｂｒｓ），８．２５（１Ｈ，ｄ，Ｊ＝７Ｈｚ），８．５０−８．５９（１Ｈ，ｍ），８．８０−８．８５（１Ｈ，ｍ），９．０８（１Ｈ，ｂｒｓ），９．４７（１Ｈ，ｂｒｓ），１０．７８（１Ｈ，ｂｒｓ），１１．９１（１Ｈ，ｂｒｓ） Production Example 69
Instead of 7-chloro-2- (3-pyridinyl) -4H-3,1-benzoxazin-4-one, 6-chloro-2- (3-pyridinyl) -4H-3,1-benzoxazine-4-one The following compound (69) of the present invention was obtained in the same manner as in Production Example 68 using ON.
Compound (69) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 3.58-3.75 (3H, m), 7.60-7.68 (1H, m), 7.73 (1H, dd, J = 7, 2 Hz), 7.91 (1 H, brs), 8.25 (1 H, d, J = 7 Hz), 8.50-8.59 (1 H, m), 8.80-8.85 (1 H, m), 9.08 (1H, brs), 9.47 (1H, brs), 10.78 (1H, brs), 11.91 (1H, brs)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：３．５３−３．６３（３Ｈ，ｍ），７．３９（１Ｈ，ｄ，Ｊ＝７Ｈｚ），７．５０−７．６０（２Ｈ，ｍ），８．１３（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．２４（１Ｈ，ｄ，Ｊ＝８Ｈｚ），８．７４−８．８０（１Ｈ，ｍ），９．０３（１Ｈ，ｂｒｓ），９．６３−９．７５（２Ｈ，ｍ），１０．５３（１Ｈ，ｂｒｓ） Production Example 70
Instead of 7-chloro-2- (3-pyridinyl) -4H-3,1-benzoxazin-4-one, 5-chloro-2- (3-pyridinyl) -4H-3,1-benzoxazine-4-one The following compound (70) of the present invention was obtained in the same manner as in Production Example 68 using ON.
Compound (70) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 3.53-3.63 (3H, m), 7.39 (1H, d, J = 7 Hz), 7.50-7.60 (2H, m), 8.13 (1H, d, J = 8 Hz), 8.24 (1H, d, J = 8 Hz), 8.74-8.80 (1H, m), 9.03 (1H, brs) , 9.63-9.75 (2H, m), 10.53 (1H, brs)

^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６，ＴＭＳ）δ：０．９５−１．３４（３Ｈ，ｍ），３．９７−４．２１（２Ｈ，ｍ），７．４５−７．７５（３Ｈ，ｍ），７．９３−８．０５（２Ｈ，ｍ），８．２２−８．５３（２Ｈ，ｍ），８．７１−８．８７（１Ｈ，ｍ），８．９３−９．１９（２Ｈ，ｍ），９．４７（１Ｈ，ｂｒｓ），１０．８９（１Ｈ，ｂｒｓ），１１．７７（１Ｈ，ｂｒｓ） Production Example 71
0.43 g of N- (3-amino-2-naphthoyl) -N′-ethoxycarbonylhydrazine, 0.36 g of nicotinic acid chloride hydrochloride and 3 ml of pyridine were mixed, and the mixture was stirred at room temperature overnight. Water was poured into the reaction mixture, and the mixture was extracted twice with ethyl acetate. The obtained organic phase was washed with water and saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was washed with ethyl acetate to obtain 0.36 g of the following present compound (71).
Compound (71) of the present invention

¹ H-NMR (DMSO-d ₆ , TMS) δ: 0.95-1.34 (3H, m), 3.97-4.21 (2H, m), 7.45-7.75 (3H, m), 7.93-8.05 (2H, m), 8.22-8.53 (2H, m), 8.71-8.87 (1H, m), 8.93-9.19 ( 2H, m), 9.47 (1H, brs), 10.89 (1H, brs), 11.77 (1H, brs)

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

Formulation Example 1
10 parts of each of the compounds (1) to (70) of the present invention are dissolved in a mixture of 35 parts of xylene and 35 parts of N, N-dimethylformamide, and 14 parts of polyoxyethylene styryl phenyl ether and calcium dodecylbenzenesulfonate 6 Add 10 parts and mix by stirring to obtain each 10% emulsion.

Formulation Example 2
20 parts of each of the compounds (1) to (70) of the present invention were added to a mixture of 4 parts of sodium lauryl sulfate, 2 parts of calcium lignin sulfonate, 20 parts of synthetic silicon hydroxide fine powder and 54 parts of diatomaceous earth, and mixed by stirring. To obtain each 20% wettable powder.

Formulation Example 3
To 2 parts of each of the compounds (1) to (70) of the present invention, 1 part of a synthetic silicon hydrous fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are mixed sufficiently. Next, an appropriate amount of water is added to these mixtures, and the mixture is further stirred, granulated with a granulator, and dried by ventilation to obtain 2% granules.

Formulation Example 4
1 part of each of the compounds (1) to (70) of the present invention is dissolved in an appropriate amount of acetone. To this, 5 parts of synthetic silicon hydroxide fine powder, 0.3 part of PAP and 93.7 parts of Fubasami clay are added and stirred and mixed. Acetone is removed by evaporation to obtain each 1% powder.

Formulation Example 5
10 parts of each of the compounds (1) to (70) of the present invention; 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt; and 55 parts of water are mixed and finely pulverized by a wet pulverization method. Obtain each 10% flowable.

Formulation Example 6
0.1 parts of each of the compounds (1) to (70) of the present invention are dissolved in 5 parts of xylene and 5 parts of trichloroethane and mixed with 89.9 parts of deodorized kerosene to obtain each 0.1% oil.

Formulation Example 7
10 mg of each of the compounds (1) to (70) of the present invention is dissolved in 0.5 ml of acetone, and this solution is added to 5 g of animal solid feed powder (solid feed powder CE-2 for breeding, product of Nippon Claire Co., Ltd.). Process and mix evenly. Then, acetone is evaporated to dryness to obtain each poisonous bait.

  Next, harmful arthropod control efficacy of the compounds of the present invention will be shown by test examples.

Test example 1
The compound (1), (3) to (8), (10), (11), (14), (16) to (18), (21) to (26) of the present invention compound obtained in Formulation Example 5. (30), (31), (33), (34), (40), (42), (43), (45), (46), (48), (49), (51) to (54) ), (56), (63), (64), (66), (67) and (69) were diluted with water so that the active ingredient concentration was 500 ppm to prepare a test spray solution.
On the other hand, a cucumber was planted in a polyethylene cup and allowed to grow until the first true leaf developed, and about 30 cotton aphids (Aphis gossypii) were infested there. One day later, the test spray solution was sprayed onto the cucumber at a rate of 20 ml / cup. Six days after spraying, the number of cotton aphids was investigated, and the control value was determined by the following formula.

Control value (%) = {1− (Cb × Tai) / (Cai × Tb)} × 100
[In addition, the character in a formula represents the following meaning. Cb: Number of insects before treatment in the untreated section. Cai: Number of insects when observing the untreated section. Tb: number of insects before treatment in the treatment area. Tai: Number of insects at the time of observation of the treatment area. ]

  As a result, the present compounds (1), (3) to (8), (10), (11), (14), (16) to (18), (21) to (26), (30), (31), (33), (34), (40), (42), (43), (45), (46), (48), (49), (51) to (54), (56 ), (63), (64), (66), (67) and (69), each of the treatment groups of the test spray solution showed a control value of 90% or more.

で示される化合物（以下、比較化合物（Ａ）と記す。）を試験例１と同様の試験に供したところ、比較化合物（Ａ）の試験用散布液の処理区は、防除価３０％未満であった。 Furthermore, the formula (A) described in Journal fuer Praktische Chemie 1927, (116), pages 1-9.

(Hereinafter referred to as Comparative Compound (A)) was subjected to the same test as in Test Example 1, and the treatment group of the test spray solution of Comparative Compound (A) had a control value of less than 30%. there were.

で示される化合物（以下、比較化合物（B）と記す。）を試験例１と同様の試験に供したところ、比較化合物（B）の試験用散布液の処理区は、防除価３０％未満であった。 Furthermore, the formula (B) described in JP-T-09-510471

(Hereinafter referred to as comparative compound (B)) was subjected to the same test as in Test Example 1, the treatment group of the test spray solution of comparative compound (B) was less than the control value of 30%. there were.

  Since the compound of the present invention has an excellent control effect on harmful arthropods, it is useful as an active ingredient of a harmful arthropod control agent.

Claims (7)

Formula (1)

[Where,
A ¹ and A ² each independently represents an oxygen atom or a sulfur atom,
R ¹ is a hydrogen atom, a C1-C6 alkyl group optionally substituted with a halogen atom, a C2-C6 cyanoalkyl group, a C2-C6 alkoxyalkyl group, a C3-C6 alkenyl group optionally substituted with a halogen atom, A C3-C6 alkynyl group optionally substituted with a halogen atom, or a C7-C9 phenylalkyl group in which the benzene ring moiety may be substituted with the following substituent A,
R ² represents a hydrogen atom, a C1-C6 alkyl group which may be substituted with a halogen atom, a C3-C6 alkenyl group which may be substituted with a halogen atom, or a C3-C6 alkynyl group which may be substituted with a halogen atom. , A C2-C6 cyanoalkyl group, a C3-C6 cycloalkyl group optionally substituted with the following substituent D, or a C4-C7 (cycloalkyl) alkyl group,
R ³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted with a halogen atom, a C3-C6 alkenyl group optionally substituted with a halogen atom, or a C3-C6 alkynyl group optionally substituted with a halogen atom. , C2-C6 cyanoalkyl group, or C3-C6 cycloalkyl group, C4-C7 (cycloalkyl) alkyl group, formyl group, C2-C6 alkylcarbonyl group, C2 which may be substituted with the following substituent D Represents a -C6 alkoxycarbonyl group, a C3-C7 dialkylcarbamoyl group, or a phenyl group which may be substituted with the following substituent B; or
R ² and R ³ are combined to make the following U1 to U3
U1: − (CR ⁹ R ¹⁰ ) _m −
^{U2: -CR 11 R 12 -CR 13} = CR 14 -CR 157 R 16 -
_{^{U3 :-( CR 17 R 18) 2}} -Y- (CR 19 R 20) 2 -
(Here, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a hydrogen atom or C1- May represent a C4 alkyl group,
m represents an integer of 3 to 5,
Y represents an oxygen atom, -S (O) _n - or -NR ²¹ - <Here, n represents an integer of 0 to 2, R ²¹ represents a C1-C4 alkyl group. > )
Q is the following Q1-Q4
^{Q1: -C (= A 3)} -R 4
^{Q2: -C (= A 4)} -OR 5
^{Q3: -C (= A 5)} -SR 6
^{Q4: -C (= A 6)} -NR 7 R 8
(Here, A ³ , A ⁴ , A ⁵ and A ⁶ represent an oxygen atom or a sulfur atom,
R ⁴ represents a hydrogen atom, a C1-C10 alkyl group which may be substituted with the following substituent C, a C2-C6 alkenyl group which may be substituted with a halogen atom, or a C2- which is optionally substituted with a halogen atom. A C6-alkynyl group, a C3-C6 cycloalkyl group optionally substituted with the following substituent D, a phenyl group optionally substituted with the following substituent E, and optionally substituted with the following substituent A. A naphthyl group, a 5-6 membered heteroaryl group optionally substituted with the following substituent D, a 3-8 membered non-aromatic heterocyclic group optionally substituted with the following substituent D, the following substitution: C7-C9 phenylalkyl group optionally substituted with benzene ring moiety with group B, C8-C10 phenylalkenyl group optionally substituted with substituent A below, or benzene ring moiety with substituent A below There represents optionally substituted C7-C9 phenoxyalkyl group,
R ⁵ and R ⁶ are a C1-C10 alkyl group which may be substituted with a halogen atom, a C3-C6 alkoxyalkyl group, a C3-C6 alkenyl group which may be substituted with a halogen atom, or a halogen atom. C3-C6 alkynyl group, C3-C6 cycloalkyl group optionally substituted with the following substituent D, phenyl group optionally substituted with the following substituent E, substituted with the following substituent A An optionally substituted 5-6 membered heteroaryl group, or a C7-C9 phenylalkyl group in which the benzene ring moiety may be substituted with the following substituent A,
R ⁷ and R ⁸ are each independently a hydrogen atom, a C1-C10 alkyl group optionally substituted with a halogen atom, a C2-C6 alkoxyalkyl group, or a C3-C6 alkenyl group optionally substituted with a halogen atom. A C3-C6 alkynyl group which may be substituted with a halogen atom, a C3-C6 cycloalkyl group which may be substituted with the following substituent D, a phenyl group which may be substituted with the following substituent E, It represents a 5-6 membered heteroaryl group which may be substituted with the following substituent A, or a C7-C9 phenylalkyl group where the benzene ring moiety may be substituted with the following substituent A. )
Represents
Z ¹ , Z ² , Z ³ and Z ⁴ are each independently substituted with a hydrogen atom, a halogen atom, a cyano group, a nitro group, a C1-C6 alkyl group which may be substituted with a halogen atom, or a halogen atom. C1-C6 alkoxy group which may be substituted, phenyl group which may be substituted with halogen atom, C1-C6 alkylthio group which may be substituted with halogen atom, C1-C6 alkylsulfinyl which may be substituted with halogen atom Represents a group or a C1-C6 alkylsulfonyl group which may be substituted with a halogen atom, or
Z ¹ and Z ² , Z ² and Z ³ , or Z ³ and Z ⁴ together may be a 1,3-butadiene-1,4-diyl group optionally substituted with the following substituent F The propane-1,3-diyl group optionally substituted with the following substituent D, the butane-1,4-diyl group optionally substituted with the following substituent D, or the following substituent D Represents a methylenedioxy group optionally substituted by
Substituent A: a substituent selected from the group consisting of a halogen atom, a cyano group, a nitro group, a C1-C6 alkyl group which may be substituted with a halogen atom, and a C1-C6 alkoxy group which may be substituted with a halogen atom .
Substituent B: A substituent selected from the group consisting of a halogen atom, a cyano group, a nitro group, a phenyl group, and a C1-C6 alkyl group optionally substituted with a halogen atom.
Substituent C: From halogen atom, C1-C6 alkoxy group, C1-C6 alkylthio group, C1-C6 alkylsulfinyl group, C1-C6 alkylsulfonyl group, C2-C6 dialkylamino group, C3-C6 cycloalkyl group and adamantyl group A substituent selected from the group consisting of
Substituent D: A substituent selected from the group consisting of a halogen atom and a C1-C6 alkyl group.
Substituent E: halogen atom, cyano group, nitro group, C1-C6 alkyl group which may be substituted with halogen atom, phenyl group which may be substituted with halogen atom, C1 which may be substituted with halogen atom -C6 alkoxy group, C1-C6 alkylthio group optionally substituted with a halogen atom, C1-C6 alkylsulfinyl group optionally substituted with a halogen atom, C1-C6 alkylsulfonyl optionally substituted with a halogen atom A substituent selected from the group consisting of a group, a C2-C6 dialkylamino group and a C2-C6 alkoxycarbonyl group.
Substituent F: halogen atom, cyano group, nitro group, C1-C6 alkyl group optionally substituted with a halogen atom, C1-C6 alkoxy group optionally substituted with a halogen atom, substituted with a halogen atom A substituent selected from the group consisting of a C1-C6 alkylthio group which may be substituted, a C1-C6 alkylsulfinyl group which may be substituted with a halogen atom, and a C1-C6 alkylsulfonyl group which may be substituted with a halogen atom. ]
A hydrazide compound represented by: The formula (1), wherein Z ¹ , Z ² and Z ⁴ are hydrogen atoms, and Z ³ is a hydrogen atom, a halogen atom or a C1 to C6 alkyl group optionally substituted with a halogen atom. Hydrazide compounds. In formula (1), R ¹ is a hydrogen atom or a C1-C6 alkyl group optionally substituted with a halogen atom, and R ² is a hydrogen atom or C1-optionally substituted with a halogen atom. A C6 alkyl group, R ³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted with a halogen atom, or a C2-C6 alkoxycarbonyl group, A ^{1 to} A ⁶ are oxygen atoms, R ⁴ is a hydrogen atom, a C1-C10 alkyl group which may be substituted with the substituent C, a C2-C6 alkenyl group which may be substituted with a halogen atom, or a C2-C6 alkynyl which may be substituted with a halogen atom. group, the substituent D optionally substituted by C3-C6 cycloalkyl group or a heterocyclic group wherein the substituent substituted 3-8 membered may be non-aromatic in D, is R ⁵ A C1-C10 alkyl group, a C3-C6 alkoxyalkyl group optionally substituted with a rogen atom, a C2-C6 alkenyl group optionally substituted with a halogen atom, or the substituent D may be substituted. A C3-C6 cycloalkyl group, R ⁶ is an optionally substituted C1-C6 alkyl group, and R ⁷ and R ⁸ are each independently substituted with a hydrogen atom or a halogen atom. A C1-C10 alkyl group or a C2-C6 alkoxyalkyl group, wherein Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, or a halogen atom. in optionally substituted C1-C6 be the alkyl group, or whether it is optionally substituted C1-C6 alkoxy group with a halogen atom, or, Z ¹ and Z ^{2, 2} and Z ^3, or, taken together with Z ³ and Z ^4, the substituent F with optionally substituted 1,3-butadiene-1,4-diyl group, said substituted with a substituent D The hydrazide compound according to claim 1, which is a propane-1,3-diyl group which may be present. In formula (1), R ¹ and R ² are hydrogen atoms, R ³ is a hydrogen atom or a C1-C6 alkyl group optionally substituted with a halogen atom, and A ^{1 to} A ⁶ are oxygen atoms. Z ¹ , Z ² and Z ⁴ are hydrogen atoms, and Z ³ is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a C1-C6 alkyl group optionally substituted with a halogen atom, or a halogen atom in an optionally substituted by C1-C6 alkoxy group, R ⁴ is a hydrogen atom, optionally substituted C1-C6 alkyl group by a halogen atom, or the may be substituted with a substituent D 3 An 8-membered non-aromatic heterocyclic group, R ⁵ and R ⁶ are C1-C6 alkyl groups optionally substituted with a halogen atom, and R ⁷ and R ⁸ are each independently a hydrogen atom, halogen, May be replaced by an atom Hydrazide compounds which are C1-C6 alkyl group. A harmful arthropod control agent comprising the hydrazide compound according to any one of claims 1 to 5 as an active ingredient. Use of the hydrazide compound according to any one of claims 1 to 5 as an active ingredient of a harmful arthropod control agent. A method for controlling harmful arthropods, which comprises applying the hydrazide compound according to any one of claims 1 to 5 directly to harmful arthropods or in the habitat of harmful arthropods.