JP4747582B2 - Malononitrile compound having nitrogen-containing 5-membered ring and its use for pest control - Google Patents

Description

  The present invention relates to a malononitrile compound having a nitrogen-containing 5-membered ring and a pest control application thereof.

  For pest control, compounds having pest control effects have been developed and put into practical use.

  An object of the present invention is to provide a compound having an excellent control effect against pests, a pest control agent containing the compound as an active ingredient, and a method for controlling pests using the compound.

〔式中、Ｒ¹は少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基又は水素原子を表し、Ｒ²は少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルコキシ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基、シアノ基又は水素原子を表し、Ｒ³及びＲ⁴は各々、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ５シクロアルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ４−Ｃ５シクロアルケニル基若しくは水素原子を表すか、或いはＲ³とＲ⁴とが互いに末端で結合して少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルカンジイル基、若しくは、少なくとも１個のハロゲン原子で置換されていてもよいＣ４−Ｃ６アルケンジイル基を表し、Ｘ¹、Ｘ²及びＸ³は各々、窒素原子又はＣＲ⁶を表す。
Ｒ⁵及びＲ⁶は各々、ハロゲン原子、シアノ基、ニトロ基、ヒドロキシル基、メルカプト基、ホルミル基、ＳＦ₅基、カルボキシル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ６シクロアルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルコキシ基、少なくとも１個の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、少なくとも１個の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、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルケニルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルキニルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルフィニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルホニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルキルカルボニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルコキシカルボニル基、ＮＲ¹⁰Ｒ¹¹で示される基、Ｃ（＝Ｘ⁵）ＮＲ¹²Ｒ¹³で示される基、（ＣＨ₂）_mＱで示される基、Ｃ（＝ＮＯＲ¹⁷）Ｒ¹⁸で示される基又は水素原子を表す。
なお、１つのＲ⁵及びＲ⁶、或いは２つのＲ⁶の各々が結合する２個の原子が隣接する場合には、隣接した該２個の原子に結合するＲ⁵とＲ⁶とが、又は隣接した該２個の原子に結合する２個のＲ⁶が互いに末端で結合して、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルカンジイル基又はＣ４−Ｃ６アルケンジイル基を表していてもよい。この場合、該アルカンジイル基及び該アルケンジイル基を形成する少なくとも１つのメチレン基は、酸素原子、硫黄原子若しくはＮＲ⁷で置き換えられえていてもよい。
Ｒ⁷は少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ６シクロアルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルキルカルボニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルコキシカルボニル基又は水素原子を表す。
Ｒ¹⁰及びＲ¹¹は各々、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ６シクロアルキル基、（少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルコキシ）Ｃ１−Ｃ３アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルフィニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルホニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルキルカルボニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルコキシカルボニル基又は水素原子を表し、Ｒ¹²及びＲ¹³は各々、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ６シクロアルキル基、（ＣＨ₂）_mＱで示される基若しくは水素原子を表すか、又はＲ¹²とＲ¹³とが互いに末端で結合して、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルカンジイル基、若しくは、少なくとも１個のハロゲン原子で置換されていてもよいＣ４−Ｃ６アルケンジイル基を表し、Ｒ¹⁷及びＲ¹⁸は各々、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ６シクロアルキル基、（ＣＨ₂）_mＱで示される基又は水素原子を表し、Ｑは１個以上ののＲ¹⁴で置換されていてもよいアリール基を表し、Ｒ¹⁴は各々、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ６シクロアルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルコキシ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルケニルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルキニルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルフィニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルホニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルキルカルボニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルコキシカルボニル基又はハロゲン原子を表し、ｍは０から５のいずれかの整数を表し、Ｘ⁵は酸素原子又は硫黄原子を表す。〕で示されるマロノニトリル化合物（以下、本発明化合物と記す）、本発明化合物を有効成分として含有することを特徴とする有害生物防除剤ならびに本発明化合物の有効量を有害生物又は有害生物の生息場所に施用することを特徴とする有害生物の防除方法に関する。 As a result of intensive studies to find a compound having excellent pest control activity, the present inventors have found that a malononitrile compound having a nitrogen-containing 5-membered ring represented by the following formula (I) is harmful insects and harmful mites. The present invention was found to have excellent control activity against harmful arthropods such as harmful insects and harmful pests such as harmful nematodes.
That is, the present invention relates to the formula (I)

[Wherein, R ¹ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, or at least one halogen. Represents an optionally substituted C2-C5 alkynyl group or a hydrogen atom, R ² is a C1-C5 alkyl group optionally substituted with at least one halogen atom, substituted with at least one halogen atom An optionally substituted C1-C5 alkoxy group, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, a cyano group or represents a hydrogen atom, R ³ and R ⁴ each, at least one halogen are optionally may C1-C5 alkyl optionally substituted with atoms A C2-C5 alkenyl group optionally substituted with at least one halogen atom, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, at least one halogen atom or at least one Represents a C3-C5 cycloalkyl group optionally substituted with a C1-C3 alkyl group, a C4-C5 cycloalkenyl group optionally substituted with at least one halogen atom, or a hydrogen atom, or R ³ and R ⁴ is a C2-C6 alkanediyl group which is bonded to each other at the end and may be substituted with at least one halogen atom, or a C4-C6 alkenediyl group which may be substituted with at least one halogen atom. X ¹ , X ² and X ³ each represent a nitrogen atom or CR ⁶ .
R ⁵ and R ⁶ are each a halogen atom, a cyano group, a nitro group, a hydroxyl group, a mercapto group, a formyl group, an SF ₅ group, a carboxyl group, or a C1-C5 alkyl optionally substituted with at least one halogen atom. A group, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, at least one halogen atom or at least one A C1-C3 cycloalkyl group optionally substituted with a C1-C3 alkyl group, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. A C3-C6 alkenyloxy group, C3 optionally substituted by at least one halogen atom C6 alkynyloxy group, C1-C5 alkylthio group optionally substituted with at least one halogen atom, C3-C5 alkenylthio group optionally substituted with at least one halogen atom, at least one halogen atom A C3-C5 alkynylthio group optionally substituted with, a C1-C5 alkylsulfinyl group optionally substituted with at least one halogen atom, a C1-C5 optionally substituted with at least one halogen atom An alkylsulfonyl group, a C2-C6 alkylcarbonyl group optionally substituted with at least one halogen atom, a C2-C5 alkoxycarbonyl group optionally substituted with at least one halogen atom, and represented by NR ¹⁰ R ¹¹ A group represented by C (═X ⁵ ) NR ¹² R ¹³ , (CH ₂ ) _m Q Groups represented represents a group or a hydrogen atom represented by ^{C (= NOR 17) R 18} .
Note that when one of R ⁵ and R ^6, or two atoms which each of the two R ⁶ are attached to adjacent, R ⁵ and R ⁶ which binds to the adjacent said two atoms, or Two R ⁶ bonded to the two adjacent atoms are bonded to each other at the end and represent a C2-C6 alkanediyl group or a C4-C6 alkenediyl group optionally substituted with at least one halogen atom. It may be. In this case, the alkanediyl group and at least one methylene group forming the alkenediyl group may be replaced with an oxygen atom, a sulfur atom or NR ⁷ .
R ⁷ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C3-C5 alkenyl group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. Optionally substituted C3-C5 alkynyl group, at least one halogen atom or at least one C1-C3 alkyl group optionally substituted C3-C6 cycloalkyl group, substituted with at least one halogen atom. A C2-C6 alkylcarbonyl group which may be substituted, a C2-C5 alkoxycarbonyl group which may be substituted with at least one halogen atom, or a hydrogen atom;
R ¹⁰ and R ¹¹ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C3-C5 alkenyl group optionally substituted with at least one halogen atom, at least one A C3-C5 alkynyl group optionally substituted with a halogen atom, a C3-C6 cycloalkyl group optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group, (at least one C1-C5 alkoxy optionally substituted with a halogen atom) C1-C3 alkyl group, C1-C5 alkylsulfinyl group optionally substituted with at least one halogen atom, substituted with at least one halogen atom A C1-C5 alkylsulfonyl group, which may be substituted with at least one halogen atom There C2-C6 alkylcarbonyl group, at least one halogen atom in the optionally substituted C2-C5 alkoxycarbonyl group or a hydrogen atom, R ¹² and R ¹³ are each substituted with at least one halogen atom An optionally substituted C1-C5 alkyl group, a C3-C5 alkenyl group optionally substituted with at least one halogen atom, a C3-C5 alkynyl group optionally substituted with at least one halogen atom, at least 1 Represents a C3-C6 cycloalkyl group optionally substituted with one halogen atom or at least one C1-C3 alkyl group, a group represented by (CH ₂ ) _m Q or a hydrogen atom, or R ¹² and R ¹³ and are bonded to each other at an end, at least one optionally substituted C2-C6 alkanediyl group by a halogen atom, Details, represents at least one of which may also be C4-C6 alkenediyl group optionally substituted with a halogen atom, each R ¹⁷ and R ^18, at least one optionally substituted by C1-C5 alkyl group by a halogen atom A C3-C5 alkenyl group optionally substituted with at least one halogen atom, a C3-C5 alkynyl group optionally substituted with at least one halogen atom, at least one halogen atom or at least one A C3-C6 cycloalkyl group optionally substituted with a C1-C3 alkyl group, a group represented by (CH ₂ ) _m Q or a hydrogen atom, wherein Q may be substituted with one or more R ¹⁴ Each represents a good aryl group, each R ¹⁴ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, at least one halogen atom; Or a C3-C6 cycloalkyl group optionally substituted with at least one C1-C3 alkyl group, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, at least one halogen atom A C1-C5 alkylthio group optionally substituted with, a C3-C5 alkenylthio group optionally substituted with at least one halogen atom, a C3-C5 alkynyl optionally substituted with at least one halogen atom A thio group, a C1-C5 alkylsulfinyl group optionally substituted with at least one halogen atom, a C1-C5 alkylsulfonyl group optionally substituted with at least one halogen atom, and at least one halogen atom; Optionally substituted C2-C6 alkylcarbonyl group, at least one halo Represents a down atoms optionally substituted by a C2-C5 alkoxycarbonyl group or a halogen atom, m represents an integer from 0 to 5, X ⁵ represents an oxygen atom or a sulfur atom. ], A pest control agent characterized by containing the compound of the present invention as an active ingredient, and an effective amount of the compound of the present invention as a habitat of pests or pests The present invention relates to a method for controlling pests, which is characterized by being applied to the above.

  By using the pest control agent of the present invention, pests can be controlled.

In the present invention, “alkanediyl group” means a group having free valences at two different carbon atoms forming a chain-like saturated hydrocarbon, and “alkenediyl group” means one or two double atoms. It represents a group having free valences at two different carbon atoms that form a chain-like hydrocarbon having a bond.
In the present invention, the “fluoroalkyl group” represents an alkyl group substituted with one or more fluorine atoms, and the description such as C1-C6 means the total number of carbon atoms constituting each substituent.

In the compound of the present invention,
Examples of the C1-C5 alkyl group optionally substituted with at least one halogen atom represented by R ¹ and R ² include a methyl group, an ethyl group, a propyl group, and a 1-methylethyl group (hereinafter, i- Propyl group may also be described.), 2,2-dimethylpropyl group, chloromethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group and 1,1 A C1-C3 alkyl group optionally substituted with at least one halogen atom such as 1,2,2-tetrafluoroethyl group; and a 1,1-dimethylethyl group (hereinafter also referred to as a t-butyl group). There are)
Examples of the C2-C5 alkenyl group optionally substituted with at least one halogen atom include a vinyl group, a 2,2-difluorovinyl group, a 1,2,2-trifluorovinyl group, a 1-propenyl group, and 2-propenyl group,
Examples of the C2-C5 alkynyl group optionally substituted with at least one halogen atom include ethynyl group, 1-propynyl group, 2-propynyl group and 3,3,3-trifluoro-1-propynyl group. Can be mentioned.

Examples of the C1-C5 alkoxy group optionally substituted with at least one halogen atom represented by R ² include a methoxy group, an ethoxy group, a 1-methylethoxy group, a trifluoromethoxy group, a difluoromethoxy group, A C1-C3 alkyl group optionally substituted with at least one halogen atom such as a fluoromethoxy group, a 2,2,2-trifluoroethoxy group and a 1,1,2,2-tetrafluoroethoxy group; and butoxy Groups.

Examples of the C1-C5 alkyl group optionally substituted with at least one halogen atom represented by R ³ and R ⁴ include a methyl group, an ethyl group, a 1-methylethyl group, a 2-methylpropyl group, a propyl group, Butyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, fluoromethyl group, chloromethyl group, 2,2-difluoroethyl group, 2,2-dichloroethyl group, 3,3-difluoropropyl group, 3, 3-dichloropropyl group, trifluoromethyl group, trichloromethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, 3,3,3-trifluoropropyl group, 3,3 , 3-trichloropropyl group, 2,2-difluoropropyl group, 3,3-difluorobutyl group, 1-bromo-2,2,2-trifluoroethyl group, 1 -Chloro-2,2,2-trifluoroethyl group, 1,2,2,2-tetrafluoroethyl group, pentafluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1 , 2,2-tetrafluoroethyl group and 2,2,3,3-tetrafluoropropyl group,
Examples of the C2-C5 alkenyl group optionally substituted with at least one halogen atom include a vinyl group, allyl group, 1-propenyl group, 3-butenyl group, 2-methyl-1-propenyl group, and 3-methyl- 2-butenyl group, 3-pentenyl group, 4-pentenyl group, 3-methyl-3-butenyl group, 4-methyl-3-pentenyl group, 1-chlorovinyl group, 2-chlorovinyl group, 1-fluorovinyl group , 2-fluorovinyl group, 2,2-dichlorovinyl group, 2,2-dibromovinyl group, 2,2-difluorovinyl group, 1,2,2-trifluorovinyl group, 1- (trifluoromethyl) vinyl Group, 2-chloro-2-propenyl group, 3-chloro-2-propenyl group, 2-fluoro-2-propenyl group, 3-fluoro-2-propenyl group, 3,3-dichloro 2-propenyl group, 3,3-dibromo-2-propenyl group, 3,3-difluoro-2-propenyl group, 2,3,3-trifluoro-2-propenyl group, 2- (trifluoromethyl) -2 -Propenyl group, 2,3,3,3-tetrafluoro-1-propenyl group, 1,2,3,3,3-pentafluoro-1-propenyl group, 3,4,4-trifluoro-3-butenyl Group, 3,4,4,4-tetrafluoro-2-butenyl group, 2,3,4,4,4-pentafluoro-2-butenyl group and 4,5,5-trifluoro-4-pentenyl group Named,
Examples of the C2-C5 alkynyl group optionally substituted with at least one halogen atom include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 3-methyl-1-butynyl group, 2- Chloro-1-propynyl group, 3-chloro-2-propynyl group, 3,3,3-trifluoro-1-propynyl group and 4,4,4-trifluoro-2-butynyl group,
Examples of the C3-C5 cycloalkyl group optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group include a cyclopropyl group, a 2,2-dichlorocyclopropyl group, and a 2,2-difluoro group. Cyclopropyl group, 2,2,3,3-tetrafluorocyclopropyl group, 2,2-dichlorocyclobutyl group, 2,2-difluorocyclobutyl group, 2,2,3,3-tetrafluorocyclobutyl group, A cyclobutyl group, a cyclopentyl group and a cyclohexyl group,
Examples of the C4-C5 cycloalkenyl group optionally substituted with at least one halogen atom include a 2-fluoro-2-cyclopentenyl group.

Examples of the C2-C6 alkanediyl group optionally substituted with at least one halogen atom represented by the bond with R ³ and R ⁴ include an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group. ,
Examples of the C4-C6 alkenediyl group optionally substituted with at least one halogen atom include a 2-butenylene group and a 2-pentenylene group.
Examples of the halogen atom represented by R ⁵ , R ⁶ and R ¹⁴ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

^{R 5, R 6, R 7} , R 10, R 11, R 12, R 13, R 14, R 17 and at least one optionally substituted by C1-C5 alkyl group by a halogen atom represented by R ¹⁸ For example, methyl group, ethyl group, 1-methylethyl group, 1-ethylethyl group, 1,1-dimethylethyl group, n-propyl group, 1-methylpropyl group, 1-ethylpropyl group, 1,1-dimethyl group Propyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1,2-trimethylpropyl group, n-butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, n -Pentyl, fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, chlorodifluoromethyl, bromodifluoromethyl, trifluoromethyl Group, dichloromethyl group, trichloromethyl group, 1-chloroethyl group, 1-bromoethyl group, 1-iodoethyl group, 1-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-iodoethyl group, 2-fluoroethyl Group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, pentafluoroethyl group, 2,2,2-trifluoro-1-chloroethyl group, 3-fluoropropyl group, 3-chloropropyl group, 1-fluoro-1-methylethyl group, 1-chloro-1-methylethyl group, 2-chloro-1, 1-dimethylethyl group, 2-fluoro-1, 1-dimethylethyl group, heptafluoropropyl group, 1,1,2,2,3,3-hexafluoro-n-propyl group, 4-chlorobutyl group, 4- Examples include a fluorobutyl group, a 5-chloropentyl group, and a 5-fluoropentyl group.

Examples of the C2-C5 alkenyl group optionally substituted with at least one halogen atom represented by R ⁵ and R ⁶ include a vinyl group, a 1-methylvinyl group, a 1-propenyl group, and a 1-methyl-1-propenyl group. Group, 2-methyl-1-propenyl group, 1,2-dimethyl-1-propenyl group, 2-propenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1,1-dimethyl 2-propenyl group, 1,2-dimethyl-2-propenyl group and 2,2-difluorovinyl group, 2-chloro-2-propenyl group, 2,2-dichloro-2-propenyl group, 2-bromo-2 -Propenyl group, 2,2-dibromo-2-propenyl group, 2-fluoro-2-propenyl group and 2,2-difluoro-2-propenyl group.

Examples of the C3-C5 alkenyl group optionally substituted with at least one halogen atom represented by R ⁷ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁷ and R ¹⁸ include 1-methylvinyl Group, 1-propenyl group, 1-methyl-1-propenyl group, 2-methyl-1-propenyl group, 1,2-dimethyl-1-propenyl group, 2-propenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1,1-dimethyl-2-propenyl group, 1,2-dimethyl-2-propenyl group, 2-chloro-2-propenyl group, 2,2-dichloro-2-propenyl group 2-bromo-2-propenyl group, 2,2-dibromo-2-propenyl group, 2-fluoro-2-propenyl group and 2,2-difluoro-2-propenyl group.

Examples of the C2-C5 alkynyl group optionally substituted with at least one halogen atom represented by R ⁵ and R ⁶ include ethynyl group, 1-propynyl group, 2-propynyl group and 3,3,3- A trifluoro-1-propynyl group is mentioned.

Examples of the C3-C5 alkynyl group optionally substituted with at least one halogen atom represented by R ⁷ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁷ , R ¹⁸ include a 1-propynyl group. 2-propynyl group and 3,3,3-trifluoro-1-propynyl group.

Substituted with the ^{R 5, R 6, R 7} , R 10, R 11, R 12, R 13, at least one halogen atom or at least one C1-C3 alkyl group represented by R ^14, R ¹⁷ and R ¹⁸ Examples of the C3-C6 cycloalkyl group which may be used include a cyclopropyl group, 1-methylcyclopropyl group, 2,2-dichlorocyclopropyl group, 2,2-dichloro-1-methylcyclopropyl group, 2 , 2-difluorocyclopropyl group, 2,2-difluoro-1-methylcyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group.

Examples of the C1-C5 alkoxy group optionally substituted with at least one halogen atom represented by R ⁵ , R ⁶ and R ¹⁴ include a methoxy group, an ethoxy group, a propoxy group, a trifluoromethoxy group, and a bromodifluoromethoxy group. , Difluoromethoxy group, chlorodifluoromethoxy group, pentafluoroethoxy group, 2,2,2-trifluoroethoxy group and 1,1,2,2-tetrafluoroethoxy group.

Examples of the C3-C6 alkenyloxy group optionally substituted with at least one halogen atom represented by R ⁵ and R ⁶ include a 1-propenyloxy group, a 2-propenyloxy group, and 2,2-difluoro- A 2-propenyloxy group is mentioned.
The at least one halogen atom may be substituted C3-C6 alkynyloxy group represented by R ⁵ and R ^6, for example, 2-propynyloxy group, 2-butynyloxy group and 3,3,3 A fluoro-1-propynyloxy group is mentioned.

Examples of the C1-C3 alkyl group represented by R ¹⁰ and R ¹¹ (C1-C5 alkoxy optionally substituted with at least one halogen atom) include a methoxymethyl group, an ethoxymethyl group, and a 1-methoxyethyl group. , 1-ethoxyethyl group and trifluoromethoxymethyl.

Examples of the C1-C5 alkylthio group optionally substituted with at least one halogen atom represented by R ⁵ , R ⁶ and R ¹⁴ include a methylthio group, an ethylthio group, a trifluoromethylthio group, a chlorodifluoromethylthio group, Examples include a bromodifluoromethylthio group, a dibromofluoromethylthio group, a 2,2,2-trifluoroethylthio group, a 1,1,2,2, -tetrafluoroethylthio group, and a pentafluoroethylthio group.
The R ^5, R ⁶ and at least one halogen atom may be substituted C3-C5 alkenylthio group shown by R ¹⁴ such as 1-propenylthio group, 2-propenylthio group and 2,2-difluoro A 2-propenylthio group is mentioned.
R ^5, R ⁶ and as at least one halogen atom in the optionally substituted by C3-C5 alkynylthio group represented by R ^14, for example, 2-propynylthio group, 2-butynylthio group and 3,3, A 3-trifluoro-1-propynylthio group is mentioned.

R ^5, R ^6, examples of R ^10, R ¹¹ and at least one halogen atom may be substituted C1-C5 alkylsulfinyl group represented by R ^14, for example, methylsulfinyl group and a trifluoromethyl sulfinyl group Is mentioned.
R ^5, examples of R ^6, R ^10, R ¹¹ and at least one halogen atom may be substituted C1-C5 alkylsulfonyl group represented by R ^14, for example, a methylsulfonyl group and a trifluoromethylsulfonyl group Is mentioned.

Examples of the C2-C6 alkylcarbonyl group optionally substituted by at least one halogen atom represented by R ⁵ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ and R ¹⁴ include an acetyl group, a propionyl group, Examples include 2,2-dimethylpropionyl group and trifluoroacetyl group.
R ^5, as the C2-C5 alkoxycarbonyl group represented by ^{R 6, R 7, R 10} , R 11 and R ^14, for example, a methoxycarbonyl group, an ethoxycarbonyl group, 1-methylethoxy group and t- butoxycarbonyl Groups.

When R ⁵ and R ⁶ bonded to two adjacent atoms, or two R ⁶ bonded to two adjacent atoms are bonded at the terminal, they are represented by R ⁵ and R ⁶ . Examples of the C2-C6 alkanediyl group optionally substituted with at least one halogen atom include propylene group, trimethylene group and tetramethylene group, ethyleneoxy group, dimethyleneoxy group, ethylenethio group and dimethylenethio group. Named,
Examples of the C4-C6 alkenediyl group optionally substituted with at least one halogen atom include 2-butenylene group and 2-pentenylene group.

Examples of the C2-C6 alkanediyl group optionally substituted with at least one halogen atom represented by the bond with R ¹² and R ¹³ include an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group. ,
Examples of the C4-C6 alkenediyl group optionally substituted with at least one halogen atom include 2-butenylene group and 2-pentenylene group.

As an aspect of this invention compound, the following compounds are mentioned, for example.
A malononitrile compound in which R ¹ is a hydrogen atom in formula (I);
A malononitrile compound represented by formula (I), wherein R ² is a methyl group;
A malononitrile compound in which R ¹ and R ² are hydrogen atoms in formula (I);
A malononitrile compound represented by formula (I), wherein R ¹ is a hydrogen atom and R ² is a methyl group;
A malononitrile compound in which R ³ is a hydrogen atom in formula (I);
A malononitrile compound represented by formula (I), wherein R ⁴ is a C2-C5 alkenyl group optionally substituted by at least one halogen atom;
A malononitrile compound in which R ⁴ is a vinyl group in formula (I);
A malononitrile compound represented by formula (I), wherein R ⁴ is a 2-propenyl group;
A malononitrile compound represented by formula (I), wherein R ⁴ is a 2,2-difluorovinyl group;
A malononitrile compound represented by formula (I), wherein R ⁴ is a 1- (trifluoromethyl) vinyl group;
A malononitrile compound represented by formula (I), wherein R ⁴ is a 3,3-difluoro-2-propenyl group;
A malononitrile compound represented by formula (I), wherein R ⁴ is a 2,3,3-trifluoro-2-propenyl group;
A malononitrile compound represented by formula (I), wherein R ⁴ is a 3,3,3-trifluoro-1-propenyl group;
A malononitrile compound represented by formula (I), wherein R ⁴ is a C2-C5 haloalkynyl group optionally substituted by at least one halogen atom;
A malononitrile compound represented by formula (I), wherein R ⁴ is a C1-C5 fluoroalkyl group;
A malononitrile compound represented by formula (I), wherein R ⁴ is a fluoromethyl group;
A malononitrile compound represented by formula (I), wherein R ⁴ is a 2,2-difluoroethyl group;
A malononitrile compound represented by formula (I), wherein R ⁴ is a 2,2,2-trifluoroethyl group;
A malononitrile compound in which R ⁴ is a pentafluoroethyl group in formula (I);
A malononitrile compound represented by formula (I), wherein R ⁴ is a 3,3,3-trifluoropropyl group;
A malononitrile compound represented by formula (I), wherein R ⁴ is a 2,2,3,3,3-pentafluoropropyl group;
A malononitrile compound represented by formula (I), wherein R ⁴ is a C3-C6 cycloalkyl group;
A malononitrile compound in which R ⁴ is a 2,2-dichlorocyclopropyl group in formula (I);
A malononitrile compound represented by formula (I), wherein R ⁴ is a cyclopropyl group;
A malononitrile compound represented by formula (I), wherein R ⁴ is a cyclobutyl group;

A malononitrile compound represented by formula (I), wherein R ³ is a hydrogen atom, and R ⁴ is a vinyl group or a 2-propenyl group;
In the formula (I), R ³ is a hydrogen atom, and R ⁴ is 2,2-difluorovinyl group, 1- (trifluoromethyl) vinyl group, 3,3-difluoro-2-propenyl group, 2,3 A malononitrile compound which is a 1,3-trifluoro-2-propenyl group or a 3,3,3-trifluoro-1-propenyl group;
In the formula (I), R ³ is a hydrogen atom, R ⁴ is a fluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2,2- A malononitrile compound which is a pentafluoroethyl group, a 3,3,3-trifluoropropyl group or a 2,2,3,3,3-pentafluoropropyl group;
A malononitrile compound represented by formula (I), wherein R ³ is a hydrogen atom, and R ⁴ is a cyclopropyl group, a cyclobutyl group, or a 2,2-dichlorocyclopropyl group;
A malononitrile compound represented by formula (I), wherein R ¹ , R ² and R ³ are hydrogen atoms, and R ⁴ is a vinyl group or a 2-propenyl group;
In the formula (I), R ¹ , R ² and R ³ are hydrogen atoms, R ⁴ is a 2,2-difluorovinyl group, 1- (trifluoromethyl) vinyl group, 3,3-difluoro-2-propenyl A malononitrile compound which is a group, 2,3,3-trifluoro-2-propenyl group or 3,3,3-trifluoro-1-propenyl group;
In the formula (I), R ¹ and R ³ are hydrogen atoms, R ² is a methyl group, R ⁴ is a 2,2-difluorovinyl group or 1- (trifluoromethyl) vinyl group, 3,3- A malononitrile compound which is a difluoro-2-propenyl group, a 2,3,3-trifluoro-2-propenyl group or a 3,3,3-trifluoro-1-propenyl group;
In the formula (I), R ¹ , R ² and R ³ are hydrogen atoms, and R ⁴ is a fluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group. A malononitrile compound which is a 3,3,3-trifluoropropyl group or a 2,2,3,3,3-pentafluoropropyl group;
In the formula (I), R ¹ and R ³ are hydrogen atoms, R ² is a methyl group, R ⁴ is a fluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group. A malononitrile compound which is a pentafluoroethyl group, a 3,3,3-trifluoropropyl group or a 2,2,3,3,3-pentafluoropropyl group;
A malononitrile compound in which R ¹ , R ² and R ³ are hydrogen atoms and R ⁴ is a cyclopropyl group, a cyclobutyl group or a 2,2-dichlorocyclopropyl group in the formula (I);

A malononitrile compound represented by formula (I), wherein X ¹ , X ² and X ³ are each CR ⁶ ;
A malononitrile compound represented by the formula (I), wherein X ¹ is a nitrogen atom, and X ² and X ³ are each CR ⁶ ;
A malononitrile compound represented by the formula (I), wherein X ² is a nitrogen atom, and X ¹ and X ³ are each CR ⁶ ;
A malononitrile compound represented by the formula (I), wherein X ³ is a nitrogen atom, and X ¹ and X ² are each CR ⁶ ;
A malononitrile compound represented by formula (I), wherein X ¹ and X ² are nitrogen atoms and X ³ is CR ⁶ ;
A malononitrile compound represented by formula (I), wherein X ¹ and X ³ are nitrogen atoms and X ² is CR ⁶ ;
A malononitrile compound in which X ¹ , X ² and X ³ are nitrogen atoms in formula (I);

In formula (I), X ³ is CR ⁶ , and R ⁶ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with a halogen atom Or a malononitrile compound which is a C2-C5 alkynyl group optionally substituted by at least one halogen atom;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is an ethyl group;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a 1-methylethyl group;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a 1,1-dimethylethyl group;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a 2,2-dimethylpropyl group;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a trifluoromethyl group;
A malononitrile compound represented by formula (I), wherein X ³ is CR ⁶ and R ⁶ is a pentafluoroethyl group;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a 1-methylvinyl group;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is an ethynyl group;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a C3-C6 cycloalkyl group optionally substituted with at least one halogen atom;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a cyclopropyl group;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a 1-methylcyclopropyl group;
In Formula (I), X ³ is CR ⁶ , and R ⁶ is a C1-C5 alkoxy group that may be substituted with at least one halogen atom, and may be substituted with at least one halogen atom. A malononitrile compound which is a C3-C6 alkenyloxy group or a C3-C6 alkynyloxy group optionally substituted by at least one halogen atom;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a propargyloxy group;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a 2-butynyloxy group;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a 3-butynyloxy group;
In the formula (I), X ³ is CR ⁶ , and R ⁶ is a C1-C5 alkylthio group which may be substituted with at least one halogen atom, and may be substituted with at least one halogen atom. A malononitrile compound which is a C1-C5 alkylsulfinyl group or a C1-C5 alkylsulfonyl group optionally substituted by at least one halogen atom;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a methylthio group;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a trifluoromethylthio group;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a propargylthio group;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a methylsulfinyl group;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a trifluoromethylsulfinyl group;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a methylsulfonyl group;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a cyano group;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a halogen atom;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a bromine atom;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a chlorine atom;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a fluorine atom;
A malononitrile compound represented by the formula (I), wherein X ³ is CR ⁶ and R ⁶ is a nitro group;

A malononitrile compound represented by formula (I), which is a R ¹ hydrogen atom, and R ² is a C1-C3 alkyl group which may be substituted with at least one halogen atom or a hydrogen atom;
In the formula (I), R ¹ is a C1-C3 alkyl group which may be substituted with at least one halogen atom or a hydrogen atom, and R ² is C1 which may be substituted with at least one halogen atom. -C3 alkyl group, C1-C3 alkoxy group optionally substituted with at least one halogen atom, C2-C5 alkenyl group optionally substituted with at least one halogen atom, at least one halogen atom A malononitrile compound which is an optionally substituted C2-C5 alkynyl group, a cyano group or a hydrogen atom;

In formula (I), R ³ and R ⁴ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, or a C2-C5 alkenyl optionally substituted with at least one halogen atom. A C2-C5 alkynyl group optionally substituted with at least one halogen atom, a C3-C5 cycloalkyl group optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group Or a malononitrile compound in which R ³ and R ⁴ are bonded to each other at the end and are a C2-C6 alkanediyl group optionally substituted by at least one halogen atom;
In formula (I), R ¹ is a hydrogen atom, R ² is a C1-C3 alkyl group optionally substituted with at least one halogen atom or a hydrogen atom, and R ³ and R ⁴ are each at least A C1-C5 alkyl group optionally substituted with one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, optionally substituted with at least one halogen atom A C2-C5 alkynyl group, a C3-C5 cycloalkyl group optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group, or R ³ and R ⁴ are mutually terminated. A malononitrile compound which is a C2-C6 alkanediyl group optionally bonded and substituted with at least one halogen atom;
In the formula (I), R ¹ is a C1-C3 alkyl group which may be substituted with at least one halogen atom or a hydrogen atom, and R ² is C1 which may be substituted with at least one halogen atom. -C3 alkyl group, C1-C3 alkoxy group optionally substituted with at least one halogen atom, C2-C5 alkenyl group optionally substituted with at least one halogen atom, at least one halogen atom An optionally substituted C2-C5 alkynyl group, a cyano group, or a hydrogen atom, and R ³ and R ⁴ are each at least one C1-C5 alkyl group optionally substituted with at least one halogen atom. A C2-C5 alkenyl group optionally substituted with a halogen atom of C2-C5 optionally substituted with at least one halogen atom Rukiniru group, or at least one halogen atom or at least one C1-C3 alkyl group optionally substituted C3-C5 also be a cycloalkyl group, or R ³ and are and R ⁴ are bonded to each other at an end A malononitrile compound which is a C2-C6 alkanediyl group optionally substituted by at least one halogen atom;

In the formula (I), R ³ is a hydrogen atom, R ⁴ is a C1-C5 alkyl group which may be substituted with at least one halogen atom, and C2 which is optionally substituted with at least one halogen atom. -C5 alkenyl group, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, or a malononitrile in which R ³ and R ⁴ are bonded to each other at the end to form a C2-C6 alkanediyl group Compound;
In the formula (I), R ^{1 is a} hydrogen atom, R ² is a C1-C5 alkyl group which may be substituted with at least one halogen atom or a hydrogen atom, R ³ is a hydrogen atom, and at least 1 R ⁴ is a C1-C3 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, and at least one halogen atom. A malononitrile compound which is an optionally substituted C2-C5 alkynyl group, or wherein R ³ and R ⁴ are bonded to each other at the terminal to form a C2-C6 alkanediyl group;
In the formula (I), R ¹ is a C1-C3 alkyl group which may be substituted with at least one halogen atom or a hydrogen atom, and R ² is C1 which may be substituted with at least one halogen atom. -C3 alkyl group, C1-C3 alkoxy group optionally substituted with at least one halogen atom, C2-C5 alkenyl group optionally substituted with at least one halogen atom, at least one halogen atom An optionally substituted C2-C5 alkynyl group, a cyano group or a hydrogen atom, R ³ is a hydrogen atom, and R ⁴ is a C1-C5 alkyl group optionally substituted by at least one halogen atom; C2-C5 alkenyl group optionally substituted with at least one halogen atom, C optionally substituted with at least one halogen atom -C5 or alkynyl group, or a malononitrile compound R ³ and R ⁴ are C2-C6 alkanediyl group bonded to each other at an end;

〔式中、
Ｒ¹は少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基又は水素原子を表し、
Ｒ²は少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルコキシ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基、シアノ基又は水素原子を表し、
Ｒ³及びＲ⁴は各々、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ５シクロアルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ４−Ｃ５シクロアルケニル基若しくは水素原子を表すか、
或いはＲ³とＲ⁴とが互いに末端で結合して少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルカンジイル基、若しくは、少なくとも１個のハロゲン原子で置換されていてもよいＣ４−Ｃ６アルケンジイル基を表し、
Ｒ⁵及びＲ^6-1は各々、ハロゲン原子、シアノ基、ニトロ基、ヒドロキシル基、メルカプト基、ホルミル基、ＳＦ₅基、カルボキシル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ６シクロアルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルコキシ基、少なくとも１個の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、少なくとも１個の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、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルケニルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルキニルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルフィニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルホニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルキルカルボニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルコキシカルボニル基、フェニル基又は水素原子を表す。〕
で示されるマロノニトリル化合物； Formula (I-1)

[Where,
R ¹ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkynyl group or a hydrogen atom,
R ² is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkenyl group, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, a cyano group or a hydrogen atom;
R ³ and R ⁴ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, at least one C2-C5 alkynyl group optionally substituted with a halogen atom, C3-C5 cycloalkyl group optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group, at least one halogen Represents a C4-C5 cycloalkenyl group or a hydrogen atom optionally substituted by an atom,
Alternatively, R ³ and R ⁴ are bonded to each other at the end and may be substituted with at least one halogen atom, or a C2-C6 alkanediyl group, or C4 may be substituted with at least one halogen atom. Represents a -C6 alkenediyl group,
R ⁵ and R ^6-1 each have a halogen atom, a cyano group, a nitro group, a hydroxyl group, a mercapto group, a formyl group, an SF ₅ group, a carboxyl group, or a C1-optionally substituted C1- A C5 alkyl group, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, at least one halogen atom or at least C1-C6 cycloalkyl group optionally substituted with one C1-C3 alkyl group, C1-C5 alkoxy group optionally substituted with at least one halogen atom, substituted with at least one halogen atom An optionally substituted C3-C6 alkenyloxy group, optionally substituted by at least one halogen atom -C6 alkynyloxy group, C1-C5 alkylthio group optionally substituted with at least one halogen atom, C3-C5 alkenylthio group optionally substituted with at least one halogen atom, at least one halogen C3-C5 alkynylthio group which may be substituted with an atom, C1-C5 alkylsulfinyl group which may be substituted with at least one halogen atom, C1- which may be substituted with at least one halogen atom C5 alkylsulfonyl group, C2-C6 alkylcarbonyl group optionally substituted with at least one halogen atom, C2-C5 alkoxycarbonyl group optionally substituted with at least one halogen atom, phenyl group or hydrogen atom Represents. ]
A malononitrile compound represented by:

In formula (I-1), R ¹ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, at least A C2-C5 alkynyl group or a hydrogen atom optionally substituted by one halogen atom,
R ² is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkenyl group, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, a cyano group or a hydrogen atom,
R ³ and R ⁴ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, at least one C2-C5 alkynyl group optionally substituted with a halogen atom, C3-C5 cycloalkyl group optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group, at least one halogen An optionally substituted C4-C5 cycloalkenyl group or a hydrogen atom,
Alternatively, R ³ and R ⁴ are bonded to each other at the end and may be substituted with at least one halogen atom, or a C2-C6 alkanediyl group, or C4 may be substituted with at least one halogen atom. -C6 alkenediyl group,
R ⁵ is a hydrogen atom,
R ^6-1 is a halogen atom, a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, at least one A C1-C5 alkylthio group optionally substituted with a halogen atom or a malononitrile compound which is a hydrogen atom;

In formula (I-1), R ¹ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, at least A C2-C5 alkynyl group or a hydrogen atom optionally substituted by one halogen atom,
R ² is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkenyl group, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, a cyano group or a hydrogen atom,
R ³ and R ⁴ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, at least one C2-C5 alkynyl group optionally substituted with a halogen atom, C3-C5 cycloalkyl group optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group, at least one halogen An optionally substituted C4-C5 cycloalkenyl group or a hydrogen atom,
R ⁵ is a hydrogen atom,
R ^6-1 is a halogen atom, a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, at least one A C1-C5 alkylthio group optionally substituted with a halogen atom or a malononitrile compound which is a hydrogen atom;

In formula (I-1), R ¹ , R ² , R ³ and R ⁵ are hydrogen atoms,
R ⁴ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, or a C2-C5 alkenyl group optionally substituted with at least one halogen atom;
R ^6-1 is a halogen atom, a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, at least one A C1-C5 alkylthio group which may be substituted with a halogen atom or a malononitrile compound which is a hydrogen atom;
In formula (I-1), R ¹ , R ² , R ³ and R ⁵ are hydrogen atoms,
R ⁴ is 2,2,2-trifluoroethyl group or vinyl group,
R ^6-1 is a halogen atom, a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, at least one A C1-C5 alkylthio group optionally substituted with a halogen atom or a malononitrile compound which is a hydrogen atom;

〔式中、
Ｒ¹は少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基又は水素原子を表し、
Ｒ²は少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルコキシ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基、シアノ基又は水素原子を表し、
Ｒ³及びＲ⁴は各々、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ５シクロアルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ４−Ｃ５シクロアルケニル基若しくは水素原子を表すか、
或いはＲ³とＲ⁴とが互いに末端で結合して少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルカンジイル基、若しくは、少なくとも１個のハロゲン原子で置換されていてもよいＣ４−Ｃ６アルケンジイル基を表し、
Ｒ⁵、Ｒ^6-1及びＲ^6-2は各々、ハロゲン原子、シアノ基、ニトロ基、ヒドロキシル基、メルカプト基、ホルミル基、ＳＦ₅基、カルボキシル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ６シクロアルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルコキシ基、少なくとも１個の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、少なくとも１個の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、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルケニルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルキニルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルフィニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルホニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルキルカルボニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルコキシカルボニル基、フェニル基又は水素原子を表す。〕
で示されるマロノニトリル化合物； Formula (I-2)

[Where,
R ¹ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkynyl group or a hydrogen atom,
R ² is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkenyl group, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, a cyano group or a hydrogen atom;
R ³ and R ⁴ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, at least one C2-C5 alkynyl group optionally substituted with a halogen atom, C3-C5 cycloalkyl group optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group, at least one halogen Represents a C4-C5 cycloalkenyl group or a hydrogen atom optionally substituted by an atom,
Alternatively, R ³ and R ⁴ are bonded to each other at the end and may be substituted with at least one halogen atom, or a C2-C6 alkanediyl group, or C4 may be substituted with at least one halogen atom. Represents a -C6 alkenediyl group,
R ⁵ , R ^6-1 and R ^6-2 are each substituted with a halogen atom, cyano group, nitro group, hydroxyl group, mercapto group, formyl group, SF ₅ group, carboxyl group or at least one halogen atom. An optionally substituted C1-C5 alkyl group, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, at least one A C3-C6 cycloalkyl group optionally substituted with at least one C1-C3 alkyl group, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, at least one A C3-C6 alkenyloxy group optionally substituted with a halogen atom, or substituted with at least one halogen atom Good C3-C6 alkynyloxy group, C1-C5 alkylthio group optionally substituted with at least one halogen atom, at least one C3-C5 alkenylthio group optionally substituted with at least one halogen atom A C3-C5 alkynylthio group optionally substituted with a halogen atom, a C1-C5 alkylsulfinyl group optionally substituted with at least one halogen atom, and optionally substituted with at least one halogen atom A C1-C5 alkylsulfonyl group, a C2-C6 alkylcarbonyl group optionally substituted with at least one halogen atom, a C2-C5 alkoxycarbonyl group optionally substituted with at least one halogen atom, a phenyl group, or Represents a hydrogen atom. ]
A malononitrile compound represented by:

In formula (I-2), R ¹ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, at least A C2-C5 alkynyl group or a hydrogen atom optionally substituted by one halogen atom,
R ² is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkenyl group, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, a cyano group or a hydrogen atom,
R ³ and R ⁴ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, and at least one halogen C2-C5 alkynyl group optionally substituted with atoms, at least one halogen atom or C3-C5 cycloalkyl group optionally substituted with at least one C1-C3 alkyl group, at least one halogen atom A C4-C5 cycloalkenyl group or a hydrogen atom optionally substituted by
Alternatively, R ³ and R ⁴ are bonded to each other at the end and may be substituted with at least one halogen atom, or a C2-C6 alkanediyl group, or C4 may be substituted with at least one halogen atom. -C6 alkenediyl group,
R ⁵ is a hydrogen atom,
R ^6-1 and R ^6-2 are each a halogen atom, a C1-C5 alkyl group optionally substituted with at least one halogen atom, or a C1-C5 optionally substituted with at least one halogen atom. A malononitrile compound which is an alkoxy group, a C1-C5 alkylthio group optionally substituted with at least one halogen atom, or a hydrogen atom;

In formula (I-2), R ¹ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, at least A C2-C5 alkynyl group or a hydrogen atom optionally substituted by one halogen atom,
R ² is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkenyl group, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, a cyano group or a hydrogen atom,
R ³ and R ⁴ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, at least one C2-C5 alkynyl group optionally substituted with a halogen atom, C3-C5 cycloalkyl group optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group, at least one halogen An optionally substituted C4-C5 cycloalkenyl group or a hydrogen atom,
R ⁵ is a hydrogen atom,
R ^6-1 and R ^6-2 are each a halogen atom, a C1-C5 alkyl group optionally substituted with at least one halogen atom, or a C1-C5 optionally substituted with at least one halogen atom. A malononitrile compound which is an alkoxy group, a C1-C5 alkylthio group optionally substituted with at least one halogen atom, or a hydrogen atom;

In the formula (I-2), R ¹ , R ² , R ³ and R ⁵ are hydrogen atoms,
R ⁴ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, or a C2-C5 alkenyl group optionally substituted with at least one halogen atom;
R ^6-1 and R ^6-2 are each a halogen atom, a C1-C5 alkyl group optionally substituted with at least one halogen atom, or a C1-C5 optionally substituted with at least one halogen atom. A malononitrile compound which is an alkoxy group, a C1-C5 alkylthio group optionally substituted with at least one halogen atom, or a hydrogen atom;
In the formula (I-2), R ¹ , R ² , R ³ and R ⁵ are hydrogen atoms,
R ⁴ is 2,2,2-trifluoroethyl group or vinyl group,
R ^6-1 and R ^6-2 are each a halogen atom, a C1-C5 alkyl group optionally substituted with at least one halogen atom, or a C1-C5 optionally substituted with at least one halogen atom. A malononitrile compound which is an alkoxy group, a C1-C5 alkylthio group optionally substituted with at least one halogen atom, or a hydrogen atom;

〔式中、
Ｒ¹は少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基又は水素原子を表し、
Ｒ²は少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルコキシ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基、シアノ基又は水素原子を表し、
Ｒ³及びＲ⁴は各々、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ５シクロアルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ４−Ｃ５シクロアルケニル基若しくは水素原子を表すか、
或いはＲ³とＲ⁴とが互いに末端で結合して少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルカンジイル基、若しくは、少なくとも１個のハロゲン原子で置換されていてもよいＣ４−Ｃ６アルケンジイル基を表し、
Ｒ⁵、Ｒ^6-1及びＲ^6-2は各々、ハロゲン原子、シアノ基、ニトロ基、ヒドロキシル基、メルカプト基、ホルミル基、ＳＦ₅基、カルボキシル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ６シクロアルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルコキシ基、少なくとも１個の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、少なくとも１個の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、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルケニルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルキニルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルフィニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルホニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルキルカルボニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルコキシカルボニル基、フェニル基又は水素原子を表す。〕
で示されるマロノニトリル化合物； Formula (I-3)

[Where,
R ¹ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkynyl group or a hydrogen atom,
R ² is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkenyl group, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, a cyano group or a hydrogen atom;
R ³ and R ⁴ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, at least one C2-C5 alkynyl group optionally substituted with a halogen atom, C3-C5 cycloalkyl group optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group, at least one halogen Represents a C4-C5 cycloalkenyl group or a hydrogen atom optionally substituted by an atom,
Alternatively, R ³ and R ⁴ are bonded to each other at the end and may be substituted with at least one halogen atom, or a C2-C6 alkanediyl group, or C4 may be substituted with at least one halogen atom. Represents a -C6 alkenediyl group,
R ⁵ , R ^6-1 and R ^6-2 are each substituted with a halogen atom, cyano group, nitro group, hydroxyl group, mercapto group, formyl group, SF ₅ group, carboxyl group or at least one halogen atom. An optionally substituted C1-C5 alkyl group, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, at least one A C3-C6 cycloalkyl group optionally substituted with at least one C1-C3 alkyl group, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, at least one A C3-C6 alkenyloxy group optionally substituted with a halogen atom, or substituted with at least one halogen atom Good C3-C6 alkynyloxy group, C1-C5 alkylthio group optionally substituted with at least one halogen atom, at least one C3-C5 alkenylthio group optionally substituted with at least one halogen atom A C3-C5 alkynylthio group optionally substituted with a halogen atom, a C1-C5 alkylsulfinyl group optionally substituted with at least one halogen atom, and optionally substituted with at least one halogen atom A C1-C5 alkylsulfonyl group, a C2-C6 alkylcarbonyl group optionally substituted with at least one halogen atom, a C2-C5 alkoxycarbonyl group optionally substituted with at least one halogen atom, a phenyl group, or Represents a hydrogen atom. ]
A malononitrile compound represented by:

In formula (I-3), R ¹ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, at least A C2-C5 alkynyl group or a hydrogen atom optionally substituted by one halogen atom,
R ² is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkenyl group, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, a cyano group or a hydrogen atom,
R ³ and R ⁴ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, at least one C2-C5 alkynyl group optionally substituted with a halogen atom, C3-C5 cycloalkyl group optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group, at least one halogen An optionally substituted C4-C5 cycloalkenyl group or a hydrogen atom,
Alternatively, R ³ and R ⁴ are bonded to each other at the end and may be substituted with at least one halogen atom, or a C2-C6 alkanediyl group, or C4 may be substituted with at least one halogen atom. -C6 alkenediyl group,
R ⁵ is a hydrogen atom,
R ^6-1 and R ^6-2 are each a halogen atom, a C1-C5 alkyl group optionally substituted with at least one halogen atom, or a C1-C5 optionally substituted with at least one halogen atom. A malononitrile compound which is an alkoxy group, a C1-C5 alkylthio group optionally substituted with at least one halogen atom, or a hydrogen atom;

In formula (I-3), R ¹ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, at least A C2-C5 alkynyl group or a hydrogen atom optionally substituted by one halogen atom,
R ² is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkenyl group, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, a cyano group or a hydrogen atom,
R ⁵ is a hydrogen atom,
R ³ and R ⁴ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, and at least one halogen C2-C5 alkynyl group optionally substituted with atoms, at least one halogen atom or C3-C5 cycloalkyl group optionally substituted with at least one C1-C3 alkyl group, at least one halogen atom A C4-C5 cycloalkenyl group or a hydrogen atom optionally substituted by
R ^6-1 and R ^6-2 are each a halogen atom, a C1-C5 alkyl group optionally substituted with at least one halogen atom, or a C1-C5 optionally substituted with at least one halogen atom. A malononitrile compound which is an alkoxy group, a C1-C5 alkylthio group optionally substituted with at least one halogen atom, or a hydrogen atom;
In formula (I-3), R ¹ , R ² , R ³ and R ⁵ are hydrogen atoms,
R ⁴ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, or a C2-C5 alkenyl group optionally substituted with at least one halogen atom;
R ^6-1 and R ^6-2 are each a halogen atom, a C1-C5 alkyl group optionally substituted with at least one halogen atom, or a C1-C5 optionally substituted with at least one halogen atom. A malononitrile compound which is an alkoxy group, a C1-C5 alkylthio group optionally substituted with at least one halogen atom, or a hydrogen atom;

In formula (I-3), R ¹ , R ² , R ³ , and R ⁵ are hydrogen atoms,
R ⁴ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, or a C2-C5 alkenyl group optionally substituted with at least one halogen atom,
R ^6-1 is a halogen atom, a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, at least one A C1-C5 alkylthio group which may be substituted with a halogen atom or a hydrogen atom,
A malononitrile compound in which R ^6-2 is a halogen atom or a hydrogen atom;
In formula (I-3), R ¹ , R ² , R ³ and R ⁵ are hydrogen atoms,
R ⁴ is 2,2,2-trifluoroethyl group or vinyl group,
R ^6-1 and R ^6-2 are each a halogen atom, a C1-C5 alkyl group optionally substituted with at least one halogen atom, or a C1-C5 optionally substituted with at least one halogen atom. A malononitrile compound which is an alkoxy group, a C1-C5 alkylthio group optionally substituted with at least one halogen atom, or a hydrogen atom;
In formula (I-3), R ¹ , R ² , R ³ and R ⁵ are hydrogen atoms,
R ⁴ is 2,2,2-trifluoroethyl group or vinyl group,
R ^6-1 is a halogen atom, a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, at least one A C1-C5 alkylthio group which may be substituted with a halogen atom or a hydrogen atom,
A malononitrile compound in which R ^6-3 is a halogen atom or a hydrogen atom;

〔式中、
Ｒ¹は少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基又は水素原子を表し、
Ｒ²は少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルコキシ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基、シアノ基又は水素原子を表し、
Ｒ³及びＲ⁴は各々少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ５シクロアルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ４−Ｃ５シクロアルケニル基若しくは水素原子を表すか、
或いはＲ³とＲ⁴とが互いに末端で結合して少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルカンジイル基、若しくは、少なくとも１個のハロゲン原子で置換されていてもよいＣ４−Ｃ６アルケンジイル基を表し、
Ｒ⁵、Ｒ^6-1及びＲ^6-2は各々、ハロゲン原子、シアノ基、ニトロ基、ヒドロキシル基、メルカプト基、ホルミル基、ＳＦ₅基、カルボキシル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ６シクロアルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルコキシ基、少なくとも１個の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、少なくとも１個の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、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルケニルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルキニルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルフィニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルホニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルキルカルボニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルコキシカルボニル基、フェニル基又は水素原子を表す。〕
で示されるマロノニトリル化合物； Formula (I-4)

[Where,
R ¹ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkynyl group or a hydrogen atom,
R ² is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkenyl group, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, a cyano group or a hydrogen atom;
R ³ and R ⁴ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, and at least one halogen. C2-C5 alkynyl group optionally substituted with atoms, at least one halogen atom or C3-C5 cycloalkyl group optionally substituted with at least one C1-C3 alkyl group, at least one halogen atom Represents a C4-C5 cycloalkenyl group or a hydrogen atom optionally substituted by
Alternatively, R ³ and R ⁴ are bonded to each other at the end and may be substituted with at least one halogen atom, or a C2-C6 alkanediyl group, or C4 may be substituted with at least one halogen atom. Represents a -C6 alkenediyl group,
R ⁵ , R ^6-1 and R ^6-2 are each substituted with a halogen atom, cyano group, nitro group, hydroxyl group, mercapto group, formyl group, SF ₅ group, carboxyl group or at least one halogen atom. An optionally substituted C1-C5 alkyl group, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, at least one A C3-C6 cycloalkyl group optionally substituted with at least one C1-C3 alkyl group, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, at least one A C3-C6 alkenyloxy group optionally substituted with a halogen atom, or substituted with at least one halogen atom Good C3-C6 alkynyloxy group, C1-C5 alkylthio group optionally substituted with at least one halogen atom, at least one C3-C5 alkenylthio group optionally substituted with at least one halogen atom A C3-C5 alkynylthio group optionally substituted with a halogen atom, a C1-C5 alkylsulfinyl group optionally substituted with at least one halogen atom, and optionally substituted with at least one halogen atom A C1-C5 alkylsulfonyl group, a C2-C6 alkylcarbonyl group optionally substituted with at least one halogen atom, a C2-C5 alkoxycarbonyl group optionally substituted with at least one halogen atom, a phenyl group, or Represents a hydrogen atom. ]
A malononitrile compound represented by:

In formula (I-4), R ¹ is a C1-alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, at least 1 A C2-C5 alkynyl group or a hydrogen atom optionally substituted by one halogen atom,
R ² is a halogen atom substituted with at least one optionally substituted C1-C5 alkyl group, a halogen atom substituted with at least one optionally substituted C1-C5 alkoxy group, at least one halogen atom substituted An optionally substituted C2-C5 alkenyl group, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, a cyano group or a hydrogen atom,
R ³ and R ⁴ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, and at least one halogen C2-C5 alkynyl group optionally substituted with atoms, at least one halogen atom or C3-C5 cycloalkyl group optionally substituted with at least one C1-C3 alkyl group, at least one halogen atom A C4-C5 cycloalkenyl group or a hydrogen atom optionally substituted by
Alternatively, R ³ and R ⁴ are bonded to each other at the end and may be substituted with at least one halogen atom, or a C2-C6 alkanediyl group, or C4 may be substituted with at least one halogen atom. -C6 alkenediyl group,
R ⁵ is a hydrogen atom,
R ^6-1 and R ^6-2 are each a halogen atom, a C1-C5 alkyl group optionally substituted with at least one halogen atom, or a C1-C5 optionally substituted with at least one halogen atom. A malononitrile compound which is an alkoxy group, a C1-C5 alkylthio group optionally substituted with at least one halogen atom, or a hydrogen atom;

In formula (I-4), R ¹ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, at least A C2-C5 alkynyl group or a hydrogen atom optionally substituted by one halogen atom,
R ² is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkenyl group, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, a cyano group or a hydrogen atom,
R ³ and R ⁴ are each at least one optionally substituted C1-C5 alkyl group, at least one halogen atom optionally substituted C2-C5 alkenyl group, at least one halogen. C2-C5 alkynyl group optionally substituted with atoms, at least one halogen atom or C3-C5 cycloalkyl group optionally substituted with at least one C1-C3 alkyl group, at least one halogen atom A C4-C5 cycloalkenyl group or a hydrogen atom optionally substituted by
R ⁵ is a hydrogen atom,
R ^6-1 and R ^6-2 are each a halogen atom, a C1-C5 alkyl group optionally substituted with at least one halogen atom, or a C1-C5 optionally substituted with at least one halogen atom. A malononitrile compound which is an alkoxy group, a C1-C5 alkylthio group optionally substituted with at least one halogen atom, or a hydrogen atom;

In formula (I-4), R ¹ , R ² , R ³ and R ⁵ are hydrogen atoms,
R ⁴ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, or a C2-C5 alkenyl group optionally substituted with at least one halogen atom;
R ^6-1 and R ^6-2 are each a halogen atom, a C1-C5 alkyl group optionally substituted with at least one halogen atom, or a C1-C5 optionally substituted with at least one halogen atom. A malononitrile compound which is an alkoxy group, a C1-C5 alkylthio group optionally substituted with at least one halogen atom, or a hydrogen atom;
In formula (I-4), R ¹ , R ² , R ³ and R ⁵ are hydrogen atoms,
R ⁴ is 2,2,2-trifluoroethyl group or vinyl group,
R ^6-1 and R ^6-2 are each a halogen atom, a C1-C5 alkyl group optionally substituted with at least one halogen atom, or a C1-C5 optionally substituted with at least one halogen atom. A malononitrile compound, which is an alkoxy group, a C1-C5 alkylthio group which may be substituted with at least one halogen atom, or a hydrogen atom.

In the compounds represented by formulas (I-1) to (I-4), examples of the halogen atom represented by R ^6-1 or R ^6-2 include a fluorine atom, a chlorine atom, and a bromine atom. ,
Examples of the C1-C5 alkyl group which may be substituted with at least one halogen atom include C1-C5 fluoroalkyl groups such as a trifluoromethyl group, 2,2,2-trifluoroethyl group, and i. -Propyl groups, t-butyl groups, 1,1-dimethylpropyl groups, etc., branched alkyl groups such as 1,
Examples of the C1-C5 alkoxy group that may be substituted with at least one halogen atom include a methoxy group, an ethoxy group, and a 1-methylethoxy group.
Examples of the C1-C5 alkylthio group optionally substituted with at least one halogen atom include a methylthio group, an ethylthio group, and a 1-methylethylthio group.

〔式中、
Ｒ¹は少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基又は水素原子を表し、
Ｒ²は少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルコキシ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基、シアノ基又は水素原子を表し、
Ｒ³及びＲ⁴は各々少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ５シクロアルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ４−Ｃ５シクロアルケニル基若しくは水素原子を表すか、
或いはＲ³とＲ⁴とが互いに末端で結合して少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルカンジイル基、若しくは、少なくとも１個のハロゲン原子で置換されていてもよいＣ４−Ｃ６アルケンジイル基を表し、
Ｘ¹、Ｘ²及びＸ³は各々、窒素原子又はＣＲ⁶を表す。
Ｒ⁵及びＲ⁶は各々、ハロゲン原子、シアノ基、ニトロ基、ヒドロキシル基、メルカプト基、ホルミル基、ＳＦ₅基、カルボキシル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ６シクロアルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルコキシ基、少なくとも１個の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、少なくとも１個の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、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルケニルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルキニルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルフィニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルホニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルキルカルボニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルコキシカルボニル基、ＮＲ¹⁰Ｒ¹¹で示される基、Ｃ（＝Ｘ⁵）ＮＲ¹²Ｒ¹³で示される基、（ＣＨ₂）_mＱで示される基、Ｃ（＝ＮＯＲ¹⁷）Ｒ¹⁸で示される基又は水素原子を表す。
なお、１つのＲ⁵及びＲ⁶、或いは２つのＲ⁶の各々が結合する２個の原子が隣接する場合には、隣接した該２個の原子に結合するＲ⁵とＲ⁶とが、又は隣接した該２個の原子に結合する２個のＲ⁶が互いに末端で結合して、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルカンジイル基又はＣ４−Ｃ６アルケンジイル基を表していてもよい。この場合、該アルカンジイル基及び該アルケンジイル基を形成する少なくとも１つのメチレン基は、酸素原子、硫黄原子若しくはＮＲ⁷で置き換えられえていてもよい。
Ｒ⁷は少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ６シクロアルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルキルカルボニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルコキシカルボニル基又は水素原子を表す。
Ｒ¹⁰及びＲ¹¹は各々、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ６シクロアルキル基、（少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルコキシ）Ｃ１−Ｃ３アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルフィニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルホニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルキルカルボニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルコキシカルボニル基又は水素原子を表し、
Ｒ¹²及びＲ¹³は各々、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ６シクロアルキル基、（ＣＨ₂）_mＱで示される基若しくは水素原子を表すか、
又はＲ¹²とＲ¹³とが互いに末端で結合して、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルカンジイル基、若しくは、少なくとも１個のハロゲン原子で置換されていてもよいＣ４−Ｃ６アルケンジイル基を表し、
Ｒ¹⁷及びＲ¹⁸は各々、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルケニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルキニル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ６シクロアルキル基、（ＣＨ₂）_mＱで示される基又は水素原子を表し、
Ｑは１個以上ののＲ¹⁴で置換されていてもよいアリール基を表し、
Ｒ¹⁴は各々、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキル基、少なくとも１個のハロゲン原子又は少なくとも１個のＣ１−Ｃ３アルキル基で置換されていてもよいＣ３−Ｃ６シクロアルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルコキシ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルケニルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ３−Ｃ５アルキニルチオ基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルフィニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ１−Ｃ５アルキルスルホニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルキルカルボニル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルコキシカルボニル基又はハロゲン原子を表し、
ｍは０から５のいずれかの整数を表し、
Ｘ⁵は酸素原子又は硫黄原子を表す。
Ｅ¹は脱離基（例えば塩素、臭素、ヨウ素、メタンスルホニル基、トリフルオロメタンスルホニル基、トルエンスルホニル基、メタンスルホニルオキシ基、トリフルオロメタンスルホニルオキシ基、及びトルエンスルホニルオキシ基等）を表す。〕
該反応は通常溶媒中、塩基の存在下で行われる。
反応に用いられる溶媒としては、例えば、Ｎ，Ｎ−ジメチルホルムアミド等の酸アミド類、ジエチルエーテル、テトラヒドロフラン等のエーテル類、ジメチルスルホキシド、スルホラン等の有機硫黄類、１，２−ジクロロエタン、クロロベンゼン等のハロゲン化炭化水素類、トルエン、キシレン等の芳香族炭化水素類及びそれらの混合物があげられる。
該反応に用いられる塩基としては、例えば、水素化ナトリウム、炭酸ナトリウム、炭酸カリウム等の無機塩基、カリウム−ｔ−ブトキシド等のアルカリ金属アルコキシド、リチウムジイソプロピルアミド等のアルカリ金属アミド類及び４−（ジメチルアミノ）ピリジン、１，４−ジアザビシクロ〔２．２．２〕オクタン、１，８−ジアザビシクロ〔５．４．０〕−７−ウンデセン等の有機塩基があげられる。
反応に用いられる塩基の量は、化合物（ａ）１モルに対して通常１〜１０モルの割合である。
反応に用いられる化合物（ｂ）の量は、化合物（ａ）１モルに対し、通常１〜１０モルの割合である。
該反応の反応温度は通常−２０〜１００℃の範囲であり、反応時間は通常１〜２４時間の範囲である。
反応終了後は、反応混合物を水に注加し、有機溶媒抽出し、抽出液を濃縮する等、反応混合物を後処理操作に付すことにより、式（Ｉ）で示される本発明化合物を単離することができる。単離された式（Ｉ）で示される本発明化合物は必要に応じてクロマトグラフィー、再結晶等で精製することもできる。 Next, a method for producing the compound of the present invention will be described.
The compound of the present invention can be produced, for example, according to the following (Production Method 1) and (Production Method 2).
(Production method 1)
Method for reacting compound (a) with compound (b)

[Where,
R ¹ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkynyl group or a hydrogen atom,
R ² is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkenyl group, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, a cyano group or a hydrogen atom;
R ³ and R ⁴ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, and at least one halogen. C2-C5 alkynyl group optionally substituted with atoms, at least one halogen atom or C3-C5 cycloalkyl group optionally substituted with at least one C1-C3 alkyl group, at least one halogen atom Represents a C4-C5 cycloalkenyl group or a hydrogen atom optionally substituted by
Alternatively, R ³ and R ⁴ are bonded to each other at the end and may be substituted with at least one halogen atom, or a C2-C6 alkanediyl group, or C4 may be substituted with at least one halogen atom. Represents a -C6 alkenediyl group,
X ¹ , X ² and X ³ each represent a nitrogen atom or CR ⁶ .
R ⁵ and R ⁶ are each a halogen atom, a cyano group, a nitro group, a hydroxyl group, a mercapto group, a formyl group, an SF ₅ group, a carboxyl group, or a C1-C5 alkyl optionally substituted with at least one halogen atom. A group, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, at least one halogen atom or at least one A C1-C3 cycloalkyl group optionally substituted with a C1-C3 alkyl group, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. A C3-C6 alkenyloxy group, C3 optionally substituted by at least one halogen atom C6 alkynyloxy group, C1-C5 alkylthio group optionally substituted with at least one halogen atom, C3-C5 alkenylthio group optionally substituted with at least one halogen atom, at least one halogen atom A C3-C5 alkynylthio group optionally substituted with, a C1-C5 alkylsulfinyl group optionally substituted with at least one halogen atom, a C1-C5 optionally substituted with at least one halogen atom An alkylsulfonyl group, a C2-C6 alkylcarbonyl group optionally substituted with at least one halogen atom, a C2-C5 alkoxycarbonyl group optionally substituted with at least one halogen atom, and represented by NR ¹⁰ R ¹¹ A group represented by C (═X ⁵ ) NR ¹² R ¹³ , (CH ₂ ) _m Q Groups represented represents a group or a hydrogen atom represented by ^{C (= NOR 17) R 18} .
Note that when one of R ⁵ and R ^6, or two atoms which each of the two R ⁶ are attached to adjacent, R ⁵ and R ⁶ which binds to the adjacent said two atoms, or Two R ⁶ bonded to the two adjacent atoms are bonded to each other at the end and represent a C2-C6 alkanediyl group or a C4-C6 alkenediyl group optionally substituted with at least one halogen atom. It may be. In this case, the alkanediyl group and at least one methylene group forming the alkenediyl group may be replaced with an oxygen atom, a sulfur atom or NR ⁷ .
R ⁷ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C3-C5 alkenyl group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. Optionally substituted C3-C5 alkynyl group, at least one halogen atom or at least one C1-C3 alkyl group optionally substituted C3-C6 cycloalkyl group, substituted with at least one halogen atom. A C2-C6 alkylcarbonyl group which may be substituted, a C2-C5 alkoxycarbonyl group which may be substituted with at least one halogen atom, or a hydrogen atom;
R ¹⁰ and R ¹¹ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C3-C5 alkenyl group optionally substituted with at least one halogen atom, at least one A C3-C5 alkynyl group optionally substituted with a halogen atom, a C3-C6 cycloalkyl group optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group, (at least one C1-C5 alkoxy optionally substituted with a halogen atom) C1-C3 alkyl group, C1-C5 alkylsulfinyl group optionally substituted with at least one halogen atom, substituted with at least one halogen atom A C1-C5 alkylsulfonyl group, which may be substituted with at least one halogen atom There C2-C6 alkylcarbonyl group, at least one halogen atom may be substituted C2-C5 alkoxycarbonyl group or a hydrogen atom,
R ¹² and R ¹³ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C3-C5 alkenyl group optionally substituted with at least one halogen atom, at least one A C3-C5 alkynyl group optionally substituted with a halogen atom, a C3-C6 cycloalkyl group optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group, (CH ₂ ) _m Represents a group represented by Q or a hydrogen atom,
Alternatively, R ¹² and R ¹³ are bonded to each other at the terminal, and may be substituted with at least one halogen atom, or a C2-C6 alkanediyl group that may be substituted with at least one halogen atom. Represents a C4-C6 alkenediyl group,
R ¹⁷ and R ¹⁸ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C3-C5 alkenyl group optionally substituted with at least one halogen atom, at least one A C3-C5 alkynyl group optionally substituted with a halogen atom, a C3-C6 cycloalkyl group optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group, (CH ₂ ) _m Represents a group represented by Q or a hydrogen atom,
Q represents an aryl group which may be substituted with one or more R ¹⁴ ,
Each R ¹⁴ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, C3-C6 optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group. A cycloalkyl group, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, a C1-C5 alkylthio group optionally substituted with at least one halogen atom, substituted with at least one halogen atom C3-C5 alkenylthio group which may be substituted, C3-C5 alkynylthio group which may be substituted with at least one halogen atom, C1-C5 alkylsulfinyl group which may be substituted with at least one halogen atom Groups, C1-C5 alkylsulfo, optionally substituted by at least one halogen atom Group, represents at least one halogen atom that is substituted may be C2-C6 alkylcarbonyl group, at least one halogen atom may be substituted C2-C5 alkoxycarbonyl group or a halogen atom,
m represents an integer of 0 to 5,
X ⁵ represents an oxygen atom or a sulfur atom.
E ¹ represents a leaving group (for example, chlorine, bromine, iodine, methanesulfonyl group, trifluoromethanesulfonyl group, toluenesulfonyl group, methanesulfonyloxy group, trifluoromethanesulfonyloxy group, toluenesulfonyloxy group, etc.). ]
The reaction is usually performed in a solvent in the presence of a base.
Examples of the solvent used in the reaction include acid amides such as N, N-dimethylformamide, ethers such as diethyl ether and tetrahydrofuran, organic sulfurs such as dimethyl sulfoxide and sulfolane, 1,2-dichloroethane, and chlorobenzene. Examples thereof include halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene, and mixtures thereof.
Examples of the base used in the reaction include inorganic bases such as sodium hydride, sodium carbonate and potassium carbonate, alkali metal alkoxides such as potassium tert-butoxide, alkali metal amides such as lithium diisopropylamide, and 4- (dimethyl And organic bases such as amino) pyridine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene.
The amount of the base used for the reaction is usually 1 to 10 moles relative to 1 mole of the compound (a).
The amount of the compound (b) used in the reaction is usually 1 to 10 moles relative to 1 mole of the compound (a).
The reaction temperature of the reaction is usually in the range of -20 to 100 ° C, and the reaction time is usually in the range of 1 to 24 hours.
After completion of the reaction, the compound of the present invention represented by formula (I) is isolated by subjecting the reaction mixture to post-treatment operations such as pouring the reaction mixture into water, extracting with an organic solvent, and concentrating the extract. can do. The isolated compound of the present invention represented by the formula (I) can be purified by chromatography, recrystallization or the like, if necessary.

〔式中、Ｅ¹、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｘ¹、Ｘ²及びＸ³は前記と同じ意味を表す。〕
該反応は通常溶媒中、塩基の存在下で行われる。
反応に用いられる溶媒としては、例えば、Ｎ，Ｎ−ジメチルホルムアミド等の酸アミド類、ジエチルエーテル、テトラヒドロフラン等のエーテル類、ジメチルスルホキシド、スルホラン等の有機硫黄類、１，２−ジクロロエタン、クロロベンゼン等のハロゲン化炭化水素類、トルエン、キシレン等の芳香族炭化水素類及びそれらの混合物があげられる。
該反応に用いられる塩基としては、例えば、水素化ナトリウム、炭酸ナトリウム、炭酸カリウム等の無機塩基、カリウム−ｔ−ブトキシド等のアルカリ金属アルコキシド、リチウムジイソプロピルアミド等のアルカリ金属アミド類及び４−ジメチルアミノピリジン、１，４−ジアザビシクロ〔２．２．２〕オクタン、１，８−ジアザビシクロ〔５．４．０〕−７−ウンデセン等の有機塩基があげられる。
反応に用いられる塩基の量は、化合物（ｃ）１モルに対して通常１〜１０モルの割合である。
反応に用いられる化合物（ｄ）の量は、化合物（ｃ）１モルに対し、通常１〜１０モルの割合である。
該反応の反応温度は通常−２０〜１００℃の範囲であり、反応時間は通常１〜２４時間の範囲である。
反応終了後は、反応混合物を水に注加し、有機溶媒抽出し、抽出液を濃縮する等、反応混合物を後処理操作に付すことにより、式（Ｉ）で示される本発明化合物を単離することができる。単離され式（Ｉ）で示される本発明化合物は必要に応じてクロマトグラフィー、再結晶等で精製することもできる。 (Production method 2)
Method of reacting compound (c) and compound (d)

[Wherein, E ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X ¹ , X ² and X ³ represent the same meaning as described above. ]
The reaction is usually performed in a solvent in the presence of a base.
Examples of the solvent used in the reaction include acid amides such as N, N-dimethylformamide, ethers such as diethyl ether and tetrahydrofuran, organic sulfurs such as dimethyl sulfoxide and sulfolane, 1,2-dichloroethane, and chlorobenzene. Examples thereof include halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene, and mixtures thereof.
Examples of the base used in the reaction include inorganic bases such as sodium hydride, sodium carbonate, and potassium carbonate, alkali metal alkoxides such as potassium t-butoxide, alkali metal amides such as lithium diisopropylamide, and 4-dimethylamino. And organic bases such as pyridine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene.
The amount of the base used for the reaction is usually 1 to 10 moles relative to 1 mole of the compound (c).
The amount of the compound (d) used in the reaction is usually 1 to 10 moles per 1 mole of the compound (c).
The reaction temperature of the reaction is usually in the range of -20 to 100 ° C, and the reaction time is usually in the range of 1 to 24 hours.
After completion of the reaction, the compound of the present invention represented by formula (I) is isolated by subjecting the reaction mixture to post-treatment operations such as pouring the reaction mixture into water, extracting with an organic solvent, and concentrating the extract. can do. The isolated compound of the present invention represented by the formula (I) can be purified by chromatography, recrystallization or the like, if necessary.

〔式中、Ｒ¹、Ｒ²、Ｒ⁵、Ｘ¹、Ｘ²及びＸ³は前記と同じ意味を表す。〕
（第１工程）
化合物（ｆ）は化合物（ｅ）とマロノニトリルとを反応させることにより製造することができる。
該反応は通常溶媒中で行われる。反応に用いられる溶媒としては例えばＮ，Ｎ−ジメチルホルムアミド等の酸アミド類、ジエチルエーテル、テトラヒドロフラン等のエーテル類、クロロホルム、１，２−ジクロロエタン、クロロベンゼン等のハロゲン化炭化水素類、トルエン、キシレン等の芳香族炭化水素類、メタノール、エタノール、イソプロパノール等のアルコール類及びそれらの混合物が挙げられる。
該反応は必要に応じて塩基存在下で行なわれるが、反応に用いられる塩基としては、例えば水酸化テトラブチルアンモニウム等が挙げられる。
反応に用いられる塩基の量は、化合物（ｅ）１モルに対して通常０．０１〜０．５モルの割合である。
反応に用いられるマロノニトリルの量は、化合物（ｅ）１モルに対して、通常１〜１０モルの割合である。
該反応の反応温度は、通常−２０〜２００℃の範囲であり、反応時間は、通常１〜２４時間の範囲である。
該反応は、必要により反応によって生成する水を反応系外に除きながら行うこともできる。
反応終了後は、反応混合物を水に注加し、有機溶媒抽出し、抽出液を濃縮する等、反応混合物を後処理操作に付すことにより、化合物（ｆ）を単離することができる。単離された化合物（ｆ）は必要に応じてクロマトグラフィー、再結晶等で精製することもできる。
（第２工程）
（１）Ｒ²が少なくとも１個のハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、少なくとも１個のハロゲン原子で置換されていてもよいＣ２−Ｃ５アルケニル基、又は、少なくとも１個のハロゲン原子で置換されていてもよいアルケニル基である場合；
化合物（ａ）は、化合物（ｆ）と有機金属化合物とを反応させることにより製造することができる。
該反応は通常溶媒中で行われる。
反応に用いられる溶媒としては、例えばジエチルエーテル、テトラヒドロフラン等のエーテル類、トルエン、キシレン等の芳香族炭化水素類及びこれらの混合物が挙げられる。
反応に用いられる有機金属化合物としては、例えばヨウ化メチルマグネシウム、臭化エチルマグネシウム、臭化イソプロピルマグネシウム、臭化ビニルマグネシウム、臭化エチニルマグネシウム、ジメチルマグネシウム等の有機マグネシウム化合物、メチルリチウム等の有機リチウム化合物、ジエチル亜鉛等の有機亜鉛化合物及びトリフルオロメチル銅等の有機銅化合物が挙げられる。
反応に用いられる有機金属化合物の量は化合物（ｆ）１モルに対して通常１〜１０モルの割合である。
該反応は必要に応じて銅塩の存在下で行われる。反応に用いられる銅塩としては例えばヨウ化銅（Ｉ）、臭化銅（Ｉ）等が挙げられ、反応に用いられる銅塩の量は化合物（ｆ）１モルに対して通常０．０５〜１モルの割合である。
該反応の反応温度は通常−２０〜１００℃の範囲であり、反応時間通常１〜２４時間の範囲である。
反応終了後は、反応混合物を水に注加し、有機溶媒抽出し、抽出液を濃縮する等、反応混合物を後処理操作に付すことにより、化合物（ａ）を単離することができる。単離された化合物（ａ）は必要に応じてクロマトグラフィー、再結晶等で精製することもできる。
（２）Ｒ²が水素原子である場合
化合物（ａ）は、化合物（ｆ）の還元反応により製造することができる。
該還元反応は通常溶媒中で行われる。
反応に用いられる溶媒としては、例えばジエチルエーテル、テトラヒドロフラン等のエーテル類、トルエン、キシレン等の芳香族炭化水素類、メタノール、エタノール、プロパノール等のアルコール類、水及びそれらの混合物が挙げられる。
反応に用いられる還元剤としては例えば水素化ホウ素ナトリウムが挙げられる。
反応に用いられる還元剤の量は、化合物（ｆ）１モルに対して通常０．２５〜２モルの割合である。
該反応の反応温度は通常０〜５０℃の範囲であり、反応時間は通常瞬時〜２４時間の範囲である。
反応終了後は、反応混合物を水に注加し、有機溶媒抽出して、抽出液を濃縮する等、反応混合物を後処理操作に付すことにより、化合物（ａ）を単離することができる。単離された化合物（ａ）は必要に応じてクロマトグラフィー、再結晶等で精製することもできる。
（３）Ｒ²がシアノ基である場合
化合物（ａ）は、化合物（ｆ）とシアン化物とを反応させることにより製造することができる。
該反応は通常溶媒中で行われる。
反応に用いられる溶媒としては、例えばジエチルエーテル、テトラヒドロフラン等のエーテル類、トルエン、キシレン等の芳香族炭化水素類及びこれらの混合物が挙げられる。
反応に用いられるシアン化物としては、例えばテトラブチルアンモニウムシアニドが挙げられる。
反応に用いられるシアン化物の量は、化合物（ｆ）１モルに対して通常１〜１０モルの割合である。
該反応の反応温度の通常−２０〜１００℃の範囲であり、反応時間は通常１〜２４時間の範囲である。
反応終了後は、反応混合物を水に注加し、有機溶媒抽出し、抽出液を濃縮する等、反応混合物を後処理操作に付すことにより、化合物（ａ）を単離することができる。単離された化合物（ａ）は必要に応じてクロマトグラフィー、再結晶等で精製することもできる。 Next, the production method of the production intermediate will be described as a reference production method.
(Reference production method 1)

[Wherein, R ¹ , R ² , R ⁵ , X ¹ , X ² and X ³ represent the same meaning as described above. ]
(First step)
Compound (f) can be produced by reacting compound (e) with malononitrile.
The reaction is usually performed in a solvent. Examples of the solvent used in the reaction include acid amides such as N, N-dimethylformamide, ethers such as diethyl ether and tetrahydrofuran, halogenated hydrocarbons such as chloroform, 1,2-dichloroethane and chlorobenzene, toluene, xylene and the like. Aromatic hydrocarbons, alcohols such as methanol, ethanol and isopropanol, and mixtures thereof.
The reaction is performed in the presence of a base as necessary. Examples of the base used in the reaction include tetrabutylammonium hydroxide.
The amount of the base used in the reaction is usually 0.01 to 0.5 mol with respect to 1 mol of the compound (e).
The amount of malononitrile used in the reaction is usually 1 to 10 moles per mole of compound (e).
The reaction temperature of the reaction is usually in the range of -20 to 200 ° C, and the reaction time is usually in the range of 1 to 24 hours.
The reaction can be carried out while removing water produced by the reaction from the reaction system, if necessary.
After completion of the reaction, the compound (f) can be isolated by subjecting the reaction mixture to post-treatment operations such as pouring the reaction mixture into water, extraction with an organic solvent, and concentration of the extract. The isolated compound (f) can be purified by chromatography, recrystallization or the like, if necessary.
(Second step)
(1) R ² is at least one halogen atom substituted by C1~C5 may alkyl group, at least one of which may also be C2-C5 alkenyl group substituted with a halogen atom, or at least one An alkenyl group optionally substituted with a halogen atom;
Compound (a) can be produced by reacting compound (f) with an organometallic compound.
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include ethers such as diethyl ether and tetrahydrofuran, aromatic hydrocarbons such as toluene and xylene, and mixtures thereof.
Examples of the organometallic compound used in the reaction include organomagnesium compounds such as methylmagnesium iodide, ethylmagnesium bromide, isopropylmagnesium bromide, vinylmagnesium bromide, ethynylmagnesium bromide, and dimethylmagnesium, and organolithiums such as methyllithium. Examples include compounds, organic zinc compounds such as diethyl zinc, and organic copper compounds such as trifluoromethyl copper.
The amount of the organometallic compound used in the reaction is usually 1 to 10 moles per mole of the compound (f).
The reaction is performed in the presence of a copper salt as necessary. Examples of the copper salt used in the reaction include copper (I) iodide and copper (I) bromide. The amount of the copper salt used in the reaction is usually 0.05 to 1 mol per 1 mol of the compound (f). The ratio is 1 mole.
The reaction temperature is usually in the range of -20 to 100 ° C, and the reaction time is usually in the range of 1 to 24 hours.
After completion of the reaction, the compound (a) can be isolated by subjecting the reaction mixture to post-treatment operations such as pouring the reaction mixture into water, extraction with an organic solvent, and concentration of the extract. The isolated compound (a) can be purified by chromatography, recrystallization or the like, if necessary.
(2) When R ² is a hydrogen atom Compound (a) can be produced by a reduction reaction of compound (f).
The reduction reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include ethers such as diethyl ether and tetrahydrofuran, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol and propanol, water, and mixtures thereof.
Examples of the reducing agent used in the reaction include sodium borohydride.
The amount of the reducing agent used in the reaction is usually in a ratio of 0.25 to 2 mol with respect to 1 mol of the compound (f).
The reaction temperature of the reaction is usually in the range of 0 to 50 ° C., and the reaction time is usually in the range of instantaneous to 24 hours.
After completion of the reaction, the compound (a) can be isolated by subjecting the reaction mixture to post-treatment operations such as pouring the reaction mixture into water, extracting with an organic solvent, and concentrating the extract. The isolated compound (a) can be purified by chromatography, recrystallization or the like, if necessary.
(3) When R ² is a cyano group Compound (a) can be produced by reacting compound (f) with cyanide.
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include ethers such as diethyl ether and tetrahydrofuran, aromatic hydrocarbons such as toluene and xylene, and mixtures thereof.
Examples of the cyanide used for the reaction include tetrabutylammonium cyanide.
The amount of cyanide used in the reaction is usually 1 to 10 moles per mole of compound (f).
The reaction temperature is usually in the range of −20 to 100 ° C., and the reaction time is usually in the range of 1 to 24 hours.
After completion of the reaction, the compound (a) can be isolated by subjecting the reaction mixture to post-treatment operations such as pouring the reaction mixture into water, extraction with an organic solvent, and concentration of the extract. The isolated compound (a) can be purified by chromatography, recrystallization or the like, if necessary.

〔式中、Ｅ¹、Ｒ³及びＲ⁴は前記と同じ意味を表す。〕
該反応は通常溶媒中、塩基の存在下で行われる。
反応に用いられる溶媒としては、例えばＮ，Ｎ−ジメチルホルムアミド等の酸アミド類、ジエチルエーテル、テトラヒドロフラン等のエーテル類、ジメチルスルホキシド、スルホラン等の有機硫黄類、１，２−ジクロロエタン、クロロベンゼン等のハロゲン原子化炭化水素類、トルエン、キシレン等の芳香族炭化水素類及びそれらの混合物があげられる
該反応に用いられる塩基としては、例えば水素化ナトリウム、炭酸ナトリウム、炭酸カリウム等の無機塩基、カリウム−ｔ−ブトキシド等のアルカリ金属アルコキシド、リチウムジイソプロピルアミドなどのアルカリ金属アミド類及びジメチルアミノピリジン、１，４−ジアザビシクロ〔２．２．２〕オクタン、１，８−ジアザビシクロ〔５．４．０〕−７−ウンデセン等の有機塩基があげられる。
反応に用いられる塩基の量は、化合物（ｂ）１モルに対して通常１〜１０モルの割合である。
反応に供されるマロノニトリルの量は、化合物（ｂ）１モルに対し、通常１〜１０モルの割合である。
該反応の反応温度は通常−２０〜１００℃の範囲であり、反応時間は通常１〜２４時間の範囲である。
反応終了後は、反応混合物を水に注加し、有機溶媒抽出し、抽出液を濃縮する等、反応混合物を後処理操作に付すことにより、化合物（ｄ）を単離することができる。単離された化合物（ｄ）は必要に応じてクロマトグラフィー、再結晶等で精製することもできる。 (Reference production method 2)
Compound (d) can be produced by reacting compound (b) with malononitrile.

[Wherein, E ¹ , R ³ and R ⁴ represent the same meaning as described above. ]
The reaction is usually performed in a solvent in the presence of a base.
Examples of the solvent used in the reaction include acid amides such as N, N-dimethylformamide, ethers such as diethyl ether and tetrahydrofuran, organic sulfurs such as dimethyl sulfoxide and sulfolane, and halogens such as 1,2-dichloroethane and chlorobenzene. Atomized hydrocarbons, aromatic hydrocarbons such as toluene and xylene, and mixtures thereof are exemplified. Examples of the base used in the reaction include inorganic bases such as sodium hydride, sodium carbonate, and potassium carbonate, potassium-t. Alkali metal alkoxides such as butoxide, alkali metal amides such as lithium diisopropylamide, and dimethylaminopyridine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7 -Organic bases such as undecene It is done.
The amount of the base used in the reaction is usually 1 to 10 moles relative to 1 mole of the compound (b).
The amount of malononitrile to be subjected to the reaction is usually 1 to 10 mol per 1 mol of the compound (b).
The reaction temperature of the reaction is usually in the range of -20 to 100 ° C, and the reaction time is usually in the range of 1 to 24 hours.
After completion of the reaction, the compound (d) can be isolated by subjecting the reaction mixture to post-treatment operations such as pouring the reaction mixture into water, extracting with an organic solvent, and concentrating the extract. The isolated compound (d) can be purified by chromatography, recrystallization or the like, if necessary.

〔式中、Ｒ³及びＲ⁴は前記と同じ意味を表す。〕
（第１工程）
化合物（ｈ）は、化合物（ｇ）とマロノニトリルとを反応させることにより製造することができる。
該反応は通常溶媒中で行われる。反応に用いられる溶媒としては例えばＮ，Ｎ−ジメチルホルムアミド等の酸アミド類、ジエチルエーテル、テトラヒドロフラン等のエーテル類、クロロホルム、１，２−ジクロロエタン、クロロベンゼン等のハロゲン化炭化水素類、トルエン、キシレン等の芳香族炭化水素類、メタノール、エタノール、イソプロパノール等のアルコール類及びそれらの混合物が挙げられる。
該反応は必要に応じて塩基存在下で行なわれる。反応に用いられる塩基としては、例えば水酸化テトラブチルアンモニウム等が挙げられる。
反応に用いられる塩基の量は、化合物（ｇ）１モルに対して通常０．０１〜０．５モルの割合である。
反応に用いられるマロノニトリルの量は、化合物（ｇ）１モルに対して、通常１〜１０モルの割合である。
該反応の反応温度は、通常−２０〜２００℃の範囲であり、反応時間は、通常１〜２４時間の範囲である。
該反応は、必要により反応によって生成する水を反応系外に除きながら行うこともできる。
反応終了後は、反応混合物を水に注加し、有機溶媒抽出し、抽出液を濃縮する等、反応混合物を後処理操作に付すことにより、化合物（ｈ）を単離することができる。単離した化合物（ｈ）は必要に応じてクロマトグラフィー、再結晶等で精製することもできる。
（第２工程）
化合物（ｄ）は、化合物（ｈ）と還元剤とを反応させることにより製造することもできる。
該反応は通常溶媒中で行われる。
反応に用いられる溶媒としては、例えばメタノール、エタノール、イソプロピルアルコール、ｔ−ブチルアルコール等のアルコール類、ジエチルエーテル、テトラヒドロフラン等のエーテル類、１，２−ジクロロエタン、クロロベンゼン等のハロゲン化炭化水素類、トルエン、キシレン等の芳香族炭化水素類及びそれらの混合物が挙げられる。
該反応に用いられる還元剤としては、例えば、水素化ホウ素ナトリウム、水素化ホウ素リチウム及び水素化ジイソプロピルアルミニウム等が挙げられる。
反応に用いられる還元剤の量は反応に用いられる還元剤によるが、化合物（ｈ）１モルに対して通常０．２５〜５モルの割合である。
該反応の反応温度は通常−２０〜１００℃の範囲であり、反応時間は通常１〜２４時間の範囲である。
反応終了後は、反応混合物を水に注加し、有機溶媒抽出し、抽出液を濃縮する等、反応混合物を後処理操作に付すことにより化合物（ｄ）を単離することができる。単離された化合物（ｄ）は必要に応じてクロマトグラフィー、再結晶等で精製することもできる。 (Reference production method 3)
Compound (d) can also be produced by the method described below.

[Wherein R ³ and R ⁴ represent the same meaning as described above. ]
(First step)
Compound (h) can be produced by reacting compound (g) with malononitrile.
The reaction is usually performed in a solvent. Examples of the solvent used in the reaction include acid amides such as N, N-dimethylformamide, ethers such as diethyl ether and tetrahydrofuran, halogenated hydrocarbons such as chloroform, 1,2-dichloroethane and chlorobenzene, toluene, xylene and the like. Aromatic hydrocarbons, alcohols such as methanol, ethanol and isopropanol, and mixtures thereof.
The reaction is performed in the presence of a base as necessary. Examples of the base used for the reaction include tetrabutylammonium hydroxide.
The amount of the base used for the reaction is usually 0.01 to 0.5 mol with respect to 1 mol of the compound (g).
The amount of malononitrile used in the reaction is usually 1 to 10 moles per mole of the compound (g).
The reaction temperature of the reaction is usually in the range of -20 to 200 ° C, and the reaction time is usually in the range of 1 to 24 hours.
The reaction can be carried out while removing water produced by the reaction from the reaction system, if necessary.
After completion of the reaction, the compound (h) can be isolated by subjecting the reaction mixture to post-treatment operations such as pouring the reaction mixture into water, extraction with an organic solvent, and concentration of the extract. The isolated compound (h) can be purified by chromatography, recrystallization or the like, if necessary.
(Second step)
Compound (d) can also be produced by reacting compound (h) with a reducing agent.
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include alcohols such as methanol, ethanol, isopropyl alcohol and t-butyl alcohol, ethers such as diethyl ether and tetrahydrofuran, halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene, and toluene. , Aromatic hydrocarbons such as xylene, and mixtures thereof.
Examples of the reducing agent used in the reaction include sodium borohydride, lithium borohydride, diisopropylaluminum hydride, and the like.
Although the quantity of the reducing agent used for reaction is based on the reducing agent used for reaction, it is a ratio of 0.25-5 mol normally with respect to 1 mol of compounds (h).
The reaction temperature of the reaction is usually in the range of -20 to 100 ° C, and the reaction time is usually in the range of 1 to 24 hours.
After completion of the reaction, the compound (d) can be isolated by subjecting the reaction mixture to post-treatment operations such as pouring the reaction mixture into water, extraction with an organic solvent, and concentration of the extract. The isolated compound (d) can be purified by chromatography, recrystallization or the like, if necessary.

〔式中、Ｅ¹、Ｒ¹、Ｒ⁵、Ｘ¹、Ｘ²及びＸ³は前記と同じ意味を表す。〕
（第１工程）
化合物（ｊ−１）は化合物（ｃ）とＲ¹−ＣＨＯとを反応させることにより製造することができる。
該反応は溶媒の存在下又は非存在下で行われる。該反応を溶媒の存在下で行う場合、反応に用いられる溶媒としては、例えばトルエン、ベンゼン等の芳香族炭化水素類、クロロベンゼン等のハロゲン化炭化水素類及びこれらの混合物が挙げられる。
該反応は必要により、塩基の存在下で行われる。該反応を塩基の存在下で行う場合、反応に用いられる塩基としては、例えばトリエチルアミン、エチルジイソプロピルアミン等の有機塩基が挙げられ、反応に用いられる塩基の量は、化合物（ｃ）１モルに対して、通常０．５〜５モルの割合である。
反応に用いられるＲ¹−ＣＨＯの量は、化合物（ｋ）1モルに対して、通常１〜１０モルの割合である。
該反応の反応温度は通常５０〜１５０℃の範囲であり、反応時間は通常１〜２４時間の範囲である。
反応終了後は、反応混合物に必要に応じてアセトン等の有機溶媒を加えてから、反応混合物を濾過し、濾液を濃縮する等、反応混合物を後処理操作に付すことにより、化合物（ｊ−１）を単離することができる。単離された化合物（ｄ）は必要に応じてクロマトグラフィー、再結晶等で精製することもできる。
（第２工程）
化合物（ｃ−１）は、化合物（ｊ−１）のハロゲン化（例えば、化合物（ｊ−１）と塩化チオニル、オキシ塩化リン等のハロゲン化剤とを反応させる方法）又はスルホン酸エステル化（例えば、塩基存在下で化合物（ｊ−１）とトリフルオロメタンスルホン酸無水物、メタンスルホニルクロリド、トルエンスルホン酸クロリド等のスルホン酸無水物又はスルホン酸塩化物とを反応させる方法）することにより製造することができる。 (Reference production method 4)
Among the compounds (c), the compound (c-1) in which R ² is a hydrogen atom can be produced, for example, by the method described below.

[Wherein, E ¹ , R ¹ , R ⁵ , X ¹ , X ² and X ³ represent the same meaning as described above. ]
(First step)
Compound (j-1) can be produced by reacting compound (c) with R ¹ —CHO.
The reaction is performed in the presence or absence of a solvent. When the reaction is carried out in the presence of a solvent, examples of the solvent used in the reaction include aromatic hydrocarbons such as toluene and benzene, halogenated hydrocarbons such as chlorobenzene, and mixtures thereof.
The reaction is performed in the presence of a base, if necessary. When the reaction is carried out in the presence of a base, examples of the base used in the reaction include organic bases such as triethylamine and ethyldiisopropylamine. The amount of the base used in the reaction is 1 mol of compound (c). The ratio is usually 0.5 to 5 mol.
The amount of R ¹ —CHO used in the reaction is usually 1 to 10 moles relative to 1 mole of the compound (k).
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, an organic solvent such as acetone is added to the reaction mixture as necessary, and the reaction mixture is subjected to a post-treatment operation such as filtration of the reaction mixture and concentration of the filtrate. ) Can be isolated. The isolated compound (d) can be purified by chromatography, recrystallization or the like, if necessary.
(Second step)
Compound (c-1) is obtained by halogenation of compound (j-1) (for example, a method of reacting compound (j-1) with a halogenating agent such as thionyl chloride or phosphorus oxychloride) or sulfonate esterification ( For example, it is produced by reacting compound (j-1) with sulfonic acid anhydride or sulfonic acid chloride such as trifluoromethanesulfonic acid anhydride, methanesulfonyl chloride, toluenesulfonic acid chloride in the presence of a base). be able to.

In the compounds (c), (e), (k) and (j-1), the compounds in which X ¹ , X ² and X ³ are CR ⁶ are, for example, Houben-Weyl, Methoden der Organischen Chemi, Heterene I, Teil . 1, p. It can be synthesized according to the method described in 556-779.

In the compounds (c), (e), (k), and (j-1), a compound in which X ¹ is a nitrogen atom and X ² and X ³ are nitrogen atoms is, for example, Houben-Weyl, Methoden der Organischen Chemi , Heterene III, Teil. 3, p. It can synthesize | combine according to the method of 399-710.

In the compounds (c), (e), (k) and (j-1), a compound in which X ² is a nitrogen atom and X ¹ and X ³ are CR ⁶ is, for example, Houben-Weyl, Methoden der Organischen Chemi , Heterene III, Teil. 3, p. It can be synthesized according to the method described in 1-192.

In the compounds (c), (e), (k) and (j-1), compounds in which X ¹ and X ² are nitrogen atoms and X ³ is CR ⁶ are, for example, Houben-Weyl, Methoden der Organischen Chemi , Heterene III, Teil. 4, p. It can be synthesized according to the method described in 305-389.

In the compounds (c), (e), (k) and (j-1), compounds in which X ¹ and X ³ are nitrogen atoms and X ² is CR ⁶ are, for example, Houben-Weyl, Methoden der Organischen Chemi , Heterene III, Teil. 4, p. It can be synthesized according to the method described in 479-586.

In the compounds (c), (e), (k) and (j-1), compounds in which X ¹ , X ² and X ³ are nitrogen atoms are, for example, Houben-Weyl, Methoden der Organischen Chemi, Heterene III, Teil . 4, p. It can be synthesized according to the method described in 664-777.

Examples of the pests for which the compound of the present invention exhibits a controlling effect include harmful arthropods and harmful nematodes such as harmful insects and harmful mites. More specifically, the following are mentioned.
Hemiptera: Laodelphax striatellus, Japanese green planthopper (Nilaparvata lugens), Japanese green planthoppers (Sogatella furcifera) and other leafhoppers (Nephotettix cincticeps), Nephotettixvis , Aphids such as Myzus persicae, Nezara antennata, Riptortus clavetus, Eysarcoris lewisi, Eysarcoris parvus, P. stali), stink bugs such as Halyomorpha mista, whitefly (Trialeurodes vaporariorum), whiteflies such as Bemisia argentifolii, Aonidiella aurantii, Sanho Scale insects such as Zephyllus (Comstockaspis perniciosa), citrus snow scale (Unaspis citri), ruby weevil (Ceroplastes rubens), Icerya purchasi, etc .;

Lepidopterous insects: Chilo suppressalis, Cnaphalocrocis medinalis, Notarcha derogata, Plodia interpunctella, etc., Spodoptera litura, Psedia, Psedia, Heliotis genus, Helicobelpa genus moths, white butterflies (Pieris rapae), white butterflies, Adoxofies genus, Nashihime shinshin oyster (Grapholita molesta), codling moth (Cydia pomonella) scallop moth, Carposina niponensis, etc Anemone such as genus Anatolia, Limantria genus, Euprocutis genus, etc., Suga, such as Plutella xylostella, Pterinophora gossypiella, etc., Shirohitori (Hyphantria cunea), etc. Common moths such as moths, moths (Tinea translucens), moths (Tineola bisselliella), etc .;

Diptera: Culex pipiens pallens, Culex tritaeniorhynchus, Culex quinquefasciatus, etc., Aedes aegypti, Aedes albopics, etc. Anopheles, chironomids, Musca domestica, Muscina stabulans and other house flies, black flies, sphagnum flies, fly flies, fly flies such as fly flies (Delia platura), fly flies (Delia antiqua), flies Drosophila, butterflies, flyfish, abs, sand flies, leafworms, etc .;

Coleoptera: Western corn root worm (Diabrotica virgifera virgifera), corn root worms such as Southern corn root worm (Diabrotica undecimpunctata howardi); Weevil such as Sitophilus zeamais, rice weevil (Lissorhoptrus oryzophilus), weevil (Callosobruchuys chienensis), weevil (A), euphorus oleum (Tribo) femoralis, potato beetle (Phyllotreta striolata), Colorado potato beetle (Leptinotarsa decemlineata) and other potato beetles, beetles, Epilachna vigintioctopunctata and other epilacunas Takikuimushi acids, Naga Shinkuimushi acids, Cerambycidae such, Aoba ants backlash Staphylinidae (Paederus fuscipes), etc.;

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

Thrips of the order: Thrips palmi, Thrips tabaci, Frankliniella occidentalis, Frankliniella intonsa, etc .;
Hymenoptera: insects, hornets, scallops, bees such as Athalia japonica;

Straight-eyed pests: vignetting, grasshoppers, etc.
Lepidoptera: Cat fleas (Ctenocephalides felis), Dog fleas (Ctenocephalides canis), Human fleas (Pulex irritans), Xenopsylla cheopis, etc.
Lice insect pests: white lice (Pediculus humanus corporis), white lice (Phthirus pubis), cattle lice (Haematopinus eurysternus), sheep lice (Dalmalinia ovis), etc.
Termite pests: Yamato termites (Reticulitermes speratus), termites (Coptotermes formosanus), etc.

Acarina: Tetranychus urticae, Kanzawa spider mite (Tetranychus kanzawai), citrus spider mite (Panonychus citri), apple spider mite (Panonychus ulmi), spider mites (Aculops pelekt), ali Dust mites, mite mites (Polyphagotarsonemus latus), etc., spider mites, mite mites (Haemaphysalis longicornis), tick mites (Haemaphysalis flava), Dermacentor taxodes mites (Dermacentor taxodes mites) ), Ticks such as Boophilus microplus, mites such as Tyrophagus putrescentiae, Dermatophagoides farinae, Dermatophagoides ptrenyssnus, etc. Youhidani acids, Hosotsumedani (Cheyletus eruditus), Beetle Tsumedani (Cheyletus malaccensis), Tsumedani such as southern Tsumedani (Cheyletus moorei), chicken mites, and the like;
Spiders: Chiracanthium japonicum, Latrodectus hasseltii, etc .;

Lip and leg class: Gezi (Thereuonema hilgendorfi), Tobismukade (Scolopendra subspinipes), etc .;
Double-legged class: Japanese red millipede (Oxidus gracilis), Japanese red millipede (Nedyopus tambanus), etc .;
Isopods: Armadillidium vulgare, etc .;
Gastropods: Limax marginatus, Limax flavus, etc .;
Nematodes: Southern nematode nematode (Pratylenchus coffeae), Red beetle nematode (Pratylenchus fallax), Soy bean nematode (Heterodera glycines), Potato cyst nematode (Globodera rostochiensis), Red beetle nematode (Meloidogyne moth) etc.

The pest control agent of the present invention contains an effective amount of the compound of the present invention and an inert carrier. Usually, the compound of the present invention is mixed with a carrier such as a solid carrier, a liquid carrier and / or a gaseous carrier, and if necessary, a surfactant or other formulation adjuvant is added to prepare a formulation. Examples of such preparations include emulsions, oils, shampoos, flowables, powders, wettable powders, granules, paste preparations, microcapsule preparations, foams, aerosol preparations, carbon dioxide preparations, tablets, and resin preparations. Can be mentioned. These preparations may be used after being processed into poison baits, mosquito coils, electric mosquito mats, fumigants, fumigants, and sheets.
The pest control agent of the present invention usually contains 0.1 to 95% by weight of the compound of the present invention.

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

  Examples of the liquid carrier include aromatic or aliphatic hydrocarbons (xylene, toluene, alkylnaphthalene, phenylxylylethane, kerosene, light oil, hexane, cyclohexane, etc.), halogenated hydrocarbons (chlorobenzene, dichloromethane, dichloroethane, trichloroethane). Etc.), alcohols (methanol, ethanol, isopropyl alcohol, butanol, hexanol, ethylene glycol, etc.), ethers (diethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, tetrahydrofuran, dioxane, etc.) ), Esters (ethyl acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl keto) , Methyl isobutyl ketone, cyclohexanone, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), sulfoxides (dimethyl sulfoxide, etc.), acid amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), vegetable oil (Soybean oil, cottonseed oil, etc.), vegetable essential oils (orange oil, hyssop oil, lemon oil, etc.) and water.

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

  Examples of the surfactant include alkyl sulfate ester salts, alkyl sulfonate salts, alkyl aryl sulfonate salts, alkyl aryl ethers and polyoxyethylenated products thereof, polyethylene glycol ethers, polyhydric alcohol esters, and sugar alcohol derivatives. It is done.

  Other formulation adjuvants include fixing agents, dispersants and stabilizers, such as casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, saccharides, Synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.), PAP (isopropyl acid phosphate), BHT (2,6-di-t-butyl-4-methylphenol), BHA (2-t- Butyl-4-methoxyphenol and 3-t-butyl-4-methoxyphenol), vegetable oils, mineral oils, fatty acids and fatty acid esters.

  Examples of the base material of the resin preparation include vinyl chloride polymers, polyurethanes, etc., and these base materials include phthalic acid esters (dimethyl phthalate, dioctyl phthalate, etc.) and adipic acid esters as necessary. Further, a plasticizer such as stearic acid may be added. The resin formulation is obtained by kneading the compound in the base material using a normal kneading apparatus, and then molding by injection molding, extrusion molding, press molding, etc., and if necessary, through steps such as molding, cutting, It can be processed into resin preparations such as plate, film, tape, net, and string. These resin preparations are processed, for example, as animal collars, animal ear tags, sheet preparations, attracting strings, or gardening supports.

  Examples of the base material for poison bait include cereal flour, vegetable oil, sugar, crystalline cellulose, and the like. Further, if necessary, the base material includes antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, and dehydroacetic acid. Preservatives such as pepper, anti-fouling agent for children and pets such as pepper powder, cheese flavor, onion flavor and pest-attractive flavor such as peanut oil are added.

  A pest can be controlled by applying an effective amount of the compound of the present invention directly to the pest and / or to a habitat (plant, animal body, soil, etc.) of the pest. Usually, the preparation of the pest control agent of the present invention is used in the pest control method of the present invention.

  When the pest control agent of the present invention is used for controlling agricultural and forestry pests, the application amount is usually 1 to 10000 g / ha, preferably 10 to 1000 g / ha as the amount of active ingredient. Emulsions, wettable powders, flowables, microcapsule preparations and the like are usually diluted with water so that the active ingredient concentration is 1 to 10,000 ppm, and powders, granules and the like are usually used as they are. These preparations may be applied directly to plants to be protected from pests. By treating these preparations in the soil, pests that live in the soil can be controlled, and these preparations can be treated in the nursery before planting, or they can be treated in planting holes and stocks at the time of planting. You can also. Furthermore, the sheet preparation of the pest control agent of the present invention can be applied by a method such as wrapping around a plant, installing in the vicinity of the plant, or laying on the soil surface of the plant source.

When the pest control agent of the present invention is used for epidemics, the application amount is usually 0.001 to 10 mg / m ³ as an active ingredient amount when applied to a space, and 0.001 when applied to a plane. ˜100 mg / m ² . Emulsions, wettable powders, flowables, microcapsules, etc. are usually diluted with water so that the active ingredient concentration is 0.01 to 10,000 ppm, and oils, aerosols, smoke agents, poison baits, etc. are usually applied as they are. To do.
When the pesticidal agent of the present invention is used for controlling ectoparasites of domestic animals such as cattle, horses, pigs, sheep, goats and chickens, and small animals such as dogs, cats, rats and mice, a method known in veterinary medicine Can be used on animals. Specifically, in systemic control, for example, tablets, feed mixing, suppositories, injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.) are administered, and non-systemic suppression (non- In systemic control), for example, spraying oil or aqueous solution, pour-on treatment or spot-on treatment, washing animals with shampoo preparations, and using resin preparations as collars or ear tags Used by attaching to animals. When the pest control agent of the present invention is administered to an animal body, the amount is usually in the range of 0.1 to 1000 mg / kg with respect to 1 kg of the body weight of the animal.

The pest control agent of the present invention is mixed with other insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil improvers, animal feeds, etc. It can also be used together.
Examples of active ingredients of such other insecticides and acaricides include, for example, allethrin, tetramethrin, praretrin, phenothrin, resmethrin, ciphenothrin, permethrin, cypermethrin, alpha cypermethrin, zetacypermethrin, deltamethrin, tralomethrin, cyfluthrin, beta Cyfluthrin, cyhalothrin, lambda cihalothrin, framethrin, imiprotorin, etofenprox, fenvalerate, esfenvalerate, fenpropatoline, silafluophene, bifenthrin, transfluthrin, flucitrinate, taufulvalinate, acrinathrin, tefluthrin, etc. Pyrethroid compounds, dichlorvos, fenitrothion, cyanophos, profenophos, sulprophos, phentoate, isocyanate Organic phosphorus compounds such as thione, tetrachlorobinphos, fenthion, chlorpyrifos, diazinon, acephate, terbufos, folate, chlorethoxyphos, phosthiazete, etoprophos, kazusafos, methidathion, propoxer, carbaryl, methoxadiazone, fenocarb, mesomil, thiodicarb, aradicarb Carbamate compounds such as benfuracarb, oxamyl, aldicarb, and methiocarb, benzoylphenylurea compounds such as lufenuron, chlorfluazuron, hexaflumuron, diflubenzuron, triflumuron, teflubenzuron, flufenoxuron, fluazuron, novallon, and triazuron, pyriproxyfen, metoprene Juvenile hormone-like substances such as hydroprene and phenoxycarb Neonicotinoid compounds such as acetamiprid, nitenpyram, thiacloprid, thiamethoxam, dinotefuran, N-phenylpyrazole compounds such as acetoprole, ethiprole, benzoylhydrazine compounds such as tebufenozide, chromafenozide, methoxyphenozide, halofenozide, diafenthiuron, pymetrozine, Flonicamid, triazamate, buprofezin, spinosad, emamectin benzoate, chlorfenapyr, indoxacarb MP, pyridalyl, cyromazine, fenpyroximate, tebufenpyrad, tolfenpyrad, pyridaben, pyrimidifene, fluacrylpyrim, etoxazole, phenazafen, acetidin, acetidin , Zicohol, Propal Tsu door, avermectin, milbemectin, amitraz, cartap, bensultap, thiocyclam, endosulfan, spirodiclofen, and azadirachtin, and the like.

  Examples of the active ingredient of such other fungicides include, for example, strobilurin compounds such as azoxystrobin, organophosphorus compounds such as triclofosmethyl, azole compounds such as triflumizole, pefrazoate, difenoconazole, fusalide, flutolanil, validamycin, probenazole , Dichromedin, pencyclon, dazomet, kasugamycin, IBP, pyroxylone, oxolinic acid, tricyclazole, ferrimzone, mepronil, EDDP, isoprothiolane, carpropamide, diclocimet, flametopir, fludioxonil, procymidone and dietofencarb.

Next, although this invention is further demonstrated by a manufacture example, a formulation example, a test example, etc., this invention is not limited to these Examples.
First, the manufacture example of this invention compound is shown.

（以下、本発明化合物（１）と記す。）０．３６ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．２１−２．２７（２Ｈ、ｍ）、２．４７−２．５９（２Ｈ、ｍ）、４．７６（２Ｈ、ｓ）、６．４２（１Ｈ、ｔ）、７．６３−７．６４（２Ｈ、ｍ） Production Example 1
0.76 g of 1- (chloromethyl) -1H-pyrazole hydrochloride and 0.81 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 10 ml of N, N-dimethylformamide. To the stirred solution under ice cooling, 1.38 g of potassium carbonate was added, and the mixture was further stirred at room temperature for 5 hours. Water was added to the reaction mixture, and the mixture was extracted with methyl t-butyl ether (hereinafter sometimes referred to as MTBE). The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was recrystallized from hexane-ethyl acetate and (1H-pyrazol-1-ylmethyl) (3,3,3-trifluoropropyl) malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (1).) 0.36 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.21-2.27 (2H, m), 2.47-2.59 (2H, m), 4.76 (2H, s) 6.42 (1H, t), 7.63-7.64 (2H, m)

（以下、本発明化合物（２）と記す。）０．４２ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．２４（６Ｈ、ｄ）、２．２０−２．２４（２Ｈ、ｍ）、２．４７−２．５８（２Ｈ、ｍ）、２．９３−３．００（１Ｈ、ｍ）、４．３４（２Ｈ、ｓ）、６．２０（１Ｈ、ｄ）、７．５０（１Ｈ、ｄ） Production Example 2
0.77 g of 3-i-propyl-1- (chloromethyl) -1H-pyrazole hydrochloride and 0.64 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 8 ml of N, N-dimethylformamide. To the stirred solution under ice cooling, 1.54 g of potassium carbonate was added, and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, recrystallized from hexane-ethyl acetate, and [(3-i-propyl-1H-pyrazol-1-yl) methyl] (3,3,3- Trifluoropropyl) malononitrile

(Hereinafter referred to as the present compound (2).) 0.42 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.24 (6H, d), 2.20-2.24 (2H, m), 2.47-2.58 (2H, m) 2.93-3.00 (1H, m), 4.34 (2H, s), 6.20 (1H, d), 7.50 (1H, d)

（以下、本発明化合物（３）と記す。）０．６３ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．２８（９Ｈ、ｓ）、２．１９−２．２４（２Ｈ、ｍ）、２．４８−２．５７（２Ｈ、ｍ）、４．６４（２Ｈ、ｓ）、６．２３（１Ｈ、ｄ）、７．４９（１Ｈ、ｄ） Production Example 3
1.16 g of 3-t-butyl-1- (chloromethyl) -1H-pyrazole hydrochloride and 0.98 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 17 ml of N, N-dimethylformamide. To the stirred solution under ice cooling, 1.54 g of potassium carbonate was added, and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and [(3-t-butyl-1H-pyrazol-1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (3).) 0.63 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.28 (9H, s), 2.19-2.24 (2H, m), 2.48-2.57 (2H, m) 4.64 (2H, s), 6.23 (1H, d), 7.49 (1H, d)

（以下、本発明化合物（４）と記す。）０．３８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３０（９Ｈ、ｓ）、２．６９（２Ｈ、ｄｄ）、４．５８（２Ｈ、ｓ）、５．４５−５．５１（２Ｈ、ｍ）、５．８８−５．９９（１Ｈ、ｍ）、６．２１（１Ｈ、ｄ）、７．４８（１Ｈ、ｄ） Production Example 4
1.24 g of 3-t-butyl-1- (chloromethyl) -1H-pyrazole hydrochloride and 0.63 g of allylmalononitrile were dissolved in 18 ml of N, N-dimethylformamide. 1.63 g of potassium carbonate was added and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and allyl [(3-t-butyl-1H-pyrazol-1-yl) methyl] malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (4).) 0.38 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.30 (9H, s), 2.69 (2H, dd), 4.58 (2H, s), 5.45-5.51 (2H, m), 5.88-5.99 (1H, m), 6.21 (1H, d), 7.48 (1H, d)

（以下、本発明化合物（５）と記す。）０．２７ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．２４（６Ｈ、ｓ）２．１５−２．２３（４Ｈ、ｍ）、２．４２−２．６５（４Ｈ、ｍ）、５．９７（２Ｈ、ｓ）、７．１５（１Ｈ、ｓ） Production Example 5
2- (chloromethyl) -6,6-dimethyl-2,4,5,6-tetrahydrocyclopenta [c] pyrazole hydrochloride 0.58 g and (3,3,3-trifluoropropyl) malononitrile 0.43 g Dissolved in 8 ml of N, N-dimethylformamide. To the stirred solution under ice cooling, 0.73 g of potassium carbonate was added, and the mixture was further stirred overnight at room temperature. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and represented by the following formula: [(6,6-dimethyl-5,6-dihydro-cyclopenta [c] pyrazol-2 (4H) -yl) methyl] (3,3,3 -Trifluoropropyl) malononitrile

(Hereinafter referred to as the present compound (5).) 0.27 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.24 (6H, s) 2.15-2.23 (4H, m), 2.42-2.65 (4H, m), 5.97 (2H, s), 7.15 (1H, s)

（以下、本発明化合物（６）と記す。）０．８７ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．２５−２．２９（２Ｈ、ｍ）、２．５０−２．６１（２Ｈ、ｍ）、４．７５（２Ｈ、ｓ）、６．７０（１Ｈ、ｓ）、７．７２（１Ｈ、ｓ） Production Example 6
1.44 g of 1- (chloromethyl) -3- (trifluoromethyl) -1H-pyrazole and 1.30 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 16 ml of N, N-dimethylformamide. To the solution stirred under ice cooling, 2.21 g of potassium carbonate was added, and the mixture was further stirred overnight at room temperature. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was recrystallized from hexane-ethyl acetate, and {[3- (trifluoromethyl) -1H-pyrazol-1-yl] methyl} (3,3,3-trifluoropropyl) malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (6).) 0.87 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.25-2.29 (2H, m), 2.50-2.61 (2H, m), 4.75 (2H, s) 6.70 (1H, s), 7.72 (1H, s)

（以下、本発明化合物（７）と記す。）０．５７ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．７４（２Ｈ、ｄ）、４．６９（２Ｈ、ｓ）、５．４９−５．５４（２Ｈ、ｍ）、５．８７−５．９８（１Ｈ、ｍ）、６．６７（１Ｈ、ｓ）、７．７１（１Ｈ、ｓ） Production Example 7
1.33 g of 1- (chloromethyl) -3- (trifluoromethyl) -1H-pyrazole and 0.76 g of allylmalononitrile were dissolved in 21 ml of N, N-dimethylformamide. To the stirred solution under ice-cooling, 1.99 g of potassium carbonate was added, and the mixture was further stirred overnight at room temperature. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was recrystallized from hexane-ethyl acetate, and allyl {[3- (trifluoromethyl) -1H-pyrazol-1-yl] methyl} malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (7).) 0.57 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.74 (2H, d), 4.69 (2H, s), 5.49-5.54 (2H, m), 5.87 -5.98 (1H, m), 6.67 (1H, s), 7.71 (1H, s)

（以下、本発明化合物（８）と記す。）０．０５ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．２８−２．３４（２Ｈ、ｍ）、２．５２−２．６３（２Ｈ、ｍ）４．７７（２Ｈ、ｓ）、６．９３（１Ｈ、ｓ）、７．７０（１Ｈ、ｓ）、９．９９（１Ｈ、ｓ） Production Example 8
1-Chloromethyl-3-formylpyrazole hydrochloride (1.57 g) and (3,3,3-trifluoropropyl) malononitrile (1.52 g) were dissolved in N, N-dimethylformamide (30 ml), and the solution was stirred under ice-cooling. 2.76 g of potassium carbonate was added and the mixture was further stirred at room temperature for 5 hours. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and represented by the following formula [(3-formyl-1H-pyrazol-1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile

(Hereinafter referred to as the present compound (8).) 0.05 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.28-2.34 (2H, m), 2.52-2.63 (2H, m) 4.77 (2H, s), 6.93 (1H, s), 7.70 (1H, s), 9.99 (1H, s)

（以下、本発明化合物（９）と記す。）１．１１ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．２３−２．２７（２Ｈ、ｍ）、２．４９−２．６０（２Ｈ、ｍ）、４．７５（２Ｈ、ｓ）、７．６０（１Ｈ、ｓ）、７．６６（１Ｈ、ｓ） Production Example 9
1.00 g of 1- (chloromethyl) -3-cyano-1H-pyrazole and 1.15 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 21 ml of N, N-dimethylformamide. To the solution stirred under ice cooling, 1.96 g of potassium carbonate was added, and the mixture was further stirred at room temperature for 5 hours. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and represented by the following formula [(3-cyano-1H-pyrazol-1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile

(Hereinafter referred to as the present compound (9).) 1.11 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.23 to 2.27 (2H, m), 2.49-2.60 (2H, m), 4.75 (2H, s) 7.60 (1H, s), 7.66 (1H, s)

（以下、本発明化合物（１０）と記す。）０．６６ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．３３−２．３７（２Ｈ、ｍ）、２．５３−２．６２（２Ｈ、ｍ）、４．７３（２Ｈ、ｓ）、６．７０（１Ｈ、ｄ）、７．３３−７．４４（３Ｈ、ｍ）、７．６４（１Ｈ、ｄ）、７．７８−７．８０（２Ｈ、ｍ） Production Example 10
2.01 g of 1- (chloromethyl) -3-phenyl-1H-pyrazole hydrochloride and 1.42 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 27 ml of N, N-dimethylformamide. To the stirred solution under ice cooling, 2.43 g of potassium carbonate was added, and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and [(3-phenyl-1H-pyrazol-1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (10).) 0.66 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.33-2.37 (2H, m), 2.53-2.62 (2H, m), 4.73 (2H, s) 6.70 (1H, d), 7.33-7.44 (3H, m), 7.64 (1H, d), 7.78-7.80 (2H, m)

（以下、本発明化合物（１１）と記す。）０．９１ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．２５（６Ｈ、ｄ）、２．２０−２．２９（２Ｈ、ｍ）、２．５１−２．５８（２Ｈ、ｍ）、３．００−３．０６（１Ｈ、ｍ）４．６０（２Ｈ、ｓ）、７．５６（１Ｈ、ｓ） Production Example 11
4-bromo-3-i-propyl-1- (chloromethyl) -1H-pyrazole hydrochloride 1.38 g and (3,3,3-trifluoropropyl) malononitrile 0.81 g in 15 ml of N, N-dimethylformamide Dissolved. To the stirred solution under ice-cooling, 1.38 g of potassium carbonate was added, and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and [(4-bromo-3-i-propyl-1H-pyrazol-1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (11).) 0.91 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.25 (6H, d), 2.20-2.29 (2H, m), 2.51-2.58 (2H, m) 3.00-3.06 (1H, m) 4.60 (2H, s), 7.56 (1H, s)

（以下、本発明化合物（１２）と記す。）１．９１ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３８（９Ｈ、ｓ）、２．２０−２．２３（２Ｈ、ｍ）、２．４９−２．６１（２Ｈ、ｍ）、４．５７（２Ｈ、ｓ）、７．５７（１Ｈ、ｓ） Production Example 12
4-bromo-3-tert-butyl-1- (chloromethyl) -1H-pyrazole hydrochloride 1.85 g and (3,3,3-trifluoropropyl) malononitrile 1.18 g in 21 ml of N, N-dimethylformamide Dissolved. To the stirred solution under ice cooling, 2.02 g of potassium carbonate was added, and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and [(4-bromo-3-tert-butyl-1H-pyrazol-1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (12).) 1.91 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.38 (9H, s), 2.20-2.23 (2H, m), 2.49-2.61 (2H, m) 4.57 (2H, s), 7.57 (1H, s)

（以下、本発明化合物（１３）と記す。）０．４０ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３６（９Ｈ、ｓ）、２．２０−２．２４（２Ｈ、ｍ）、２．４９−２．６１（２Ｈ、ｍ）、４．５６（２Ｈ、ｓ）、７．５４（１Ｈ、ｓ） Production Example 13
0.98 g of 4-chloro-3-t-butyl-1- (chloromethyl) -1H-pyrazole hydrochloride and 0.65 g of (3,3,3-trifluoropropyl) malononitrile in 12 ml of N, N-dimethylformamide Dissolved. To the stirred solution under ice cooling, 1.11 g of potassium carbonate was added, and the mixture was further stirred overnight at room temperature. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and [(4-chloro-3-tert-butyl-1H-pyrazol-1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (13).) 0.40 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.36 (9H, s), 2.20-2.24 (2H, m), 2.49-2.61 (2H, m) 4.56 (2H, s), 7.54 (1H, s)

（以下、本発明化合物（１４）と記す。）０．８４ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．４０（９Ｈ、ｓ）、２．７１（２Ｈ、ｄ）、４．５１（２Ｈ、ｓ）、５．４３−５．５２（２Ｈ、ｍ）、５．８７−５．９８（１Ｈ、ｍ）、７．５６（１Ｈ、ｓ） Production Example 14
4-Bromo-3-tert-butyl-1- (chloromethyl) -1H-pyrazole hydrochloride 1.84 g and allylmalononitrile 0.77 g were dissolved in 21 ml of N, N-dimethylformamide. To the stirred solution under ice cooling, 2.02 g of potassium carbonate was added, and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and allyl [(4-bromo-3-t-butyl-1H-pyrazol-1-yl) methyl] malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (14).) 0.84 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.40 (9H, s), 2.71 (2H, d), 4.51 (2H, s), 5.43-5.52. (2H, m), 5.87-5.98 (1H, m), 7.56 (1H, s)

（以下、本発明化合物（１５）と記す。）０．９７ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．２５−２．３０（２Ｈ、ｍ）、２．４９−２．６２（２Ｈ、ｍ）、４．７０（２Ｈ、ｓ）、７．７７（１Ｈ、ｓ） Production Example 15
1.67 g of 4-bromo-1- (chloromethyl) -3-trifluoromethyl-1H-pyrazole and 1.03 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 18 ml of N, N-dimethylformamide. . To the stirred solution under ice-cooling, 1.74 g of potassium carbonate was added, and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and [(4-bromo-3-trifluoromethyl-1H-pyrazol-1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (15).) 0.97 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.25-2.30 (2H, m), 2.49-12.62 (2H, m), 4.70 (2H, s) , 7.77 (1H, s)

（以下、本発明化合物（１６）と記す。）０．９０ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．７５（２Ｈ、ｄ）、４．６３（２Ｈ、ｓ）、５．５０−５．５５（２Ｈ、ｍ）、５．８６−５．９７（１Ｈ、ｍ）、７．７６（１Ｈ、ｓ） Production Example 16
1.67 g of 4-bromo-1- (chloromethyl) -3- (trifluoromethyl) -1H-pyrazole and 0.67 g of allylmalononitrile were dissolved in 18 ml of N, N-dimethylformamide. To the stirred solution under ice-cooling, 1.74 g of potassium carbonate was added, and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and allyl {[4-bromo-3- (trifluoromethyl) -1H-pyrazol-1-yl] methyl} malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (16).) 0.90 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.75 (2H, d), 4.63 (2H, s), 5.50-5.55 (2H, m), 5.86 -5.97 (1H, m), 7.76 (1H, s)

（以下、本発明化合物（１７）と記す。）０．４５ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．２３（３Ｈ、ｓ）、２．３７（３Ｈ、ｓ）、２．４１−２．６１（４Ｈ、ｍ）、４．５２（２Ｈ、ｓ）、５．９１（１Ｈ、ｓ） Production Example 17
0.93 g of 1- (chloromethyl) -3,5-dimethyl-1H-pyrazole hydrochloride and 0.81 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 15 ml of N, N-dimethylformamide. To the stirred solution under ice cooling, 1.38 g of potassium carbonate was added, and the mixture was further stirred at room temperature for 4 hours. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and represented by the following formula [(3,5-dimethyl-1H-pyrazol-1-yl)] (3,3,3-trifluoropropyl) malononitrile

(Hereinafter referred to as the present compound (17).) 0.45 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.23 (3H, s), 2.37 (3H, s), 2.41-2.61 (4H, m), 4.52 (2H, s), 5.91 (1H, s)

（以下、本発明化合物（１８）と記す。）０．８３ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．１１（３Ｈ、ｓ）、２．２０−２．２４（２Ｈ、ｍ）、２．４６−２．５８（２Ｈ、ｍ）、４．６４（２Ｈ、ｓ）、７．３８（１Ｈ、ｓ）、７．４２（Ｈ、ｓ） Production Example 18
1.46 g of 1- (chloromethyl) -4-methyl-1H-pyrazole hydrochloride and 1.42 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 30 ml of N, N-dimethylformamide. To the stirred solution under ice-cooling, 2.40 g of potassium carbonate was added, and the mixture was further stirred overnight at room temperature. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and [(4-methyl-1H-pyrazol-1-yl)] (3,3,3-trifluoropropyl) malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (18).) 0.83 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.11 (3H, s), 2.20-2.24 (2H, m), 2.46-2.58 (2H, m) 4.64 (2H, s), 7.38 (1H, s), 7.42 (H, s)

（以下、本発明化合物（１９）と記す。）１．７３ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．１７−２．３１（２Ｈ、ｍ）、２．４６−２．６０（２Ｈ、ｍ）、４．６４（２Ｈ、ｓ）、７．５７（１Ｈ、ｓ）、７．６３（１Ｈ、ｓ） Production Example 19
1.44 g of 4-chloro-1- (chloromethyl) -1H-pyrazole hydrochloride and 1.56 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 30 ml of N, N-dimethylformamide. To the stirred solution under ice cooling, 2.76 g of potassium carbonate was added, and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and [(4-chloro-1H-pyrazol-1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (19).) 1.73 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.17-2.31 (2H, m), 2.46-2.60 (2H, m), 4.64 (2H, s) 7.57 (1H, s), 7.63 (1H, s)

（以下、本発明化合物（２０）と記す。）１．２２ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．７２（２Ｈ、ｄ）、４．５８（２Ｈ、ｓ）、５．４６−５．５２（２Ｈ、ｍ）、５．８７−５．９８（１Ｈ、ｍ）、７．５７（１Ｈ、ｓ）、７．６３（１Ｈ、ｓ） Production Example 20
4-Chloro-1- (chloromethyl) -1H-pyrazole hydrochloride (1.43 g) and allylmalononitrile (1.01 g) were dissolved in N, N-dimethylformamide (30 ml). To the stirred solution under ice cooling, 2.76 g of potassium carbonate was added, and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and allyl [(4-chloro-1H-pyrazol-1-yl) methyl] malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (20).) 1.22 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.72 (2H, d), 4.58 (2H, s), 5.46-5.52 (2H, m), 5.87 -5.98 (1H, m), 7.57 (1H, s), 7.63 (1H, s)

（以下、本発明化合物（２１）と記す。）３．２８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．１７−２．２７（２Ｈ、ｍ）、２．４８−２．６０（２Ｈ、ｍ）、４．６６（２Ｈ、ｓ）、７．６０（１Ｈ、ｓ）、７．６５（１Ｈ、ｓ） Production Example 21
4.27 g of 4-bromo-1- (chloromethyl) -1H-pyrazole hydrochloride and 2.29 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 28 ml of N, N-dimethylformamide. To the stirred solution under ice cooling, 3.89 g of potassium carbonate was added, and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and [(4-bromo-1H-pyrazol-1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (21).) 3.28 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.17-2.27 (2H, m), 2.48-2.60 (2H, m), 4.66 (2H, s) 7.60 (1H, s), 7.65 (1H, s)

（以下、本発明化合物（２２）と記す。）０．１９ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．２８−２．３２（２Ｈ、ｍ）、２．５３−２．５７（２Ｈ、ｍ）、４．７１（２Ｈ、ｓ）、７．８５（１Ｈ、ｓ）、７．９３（１Ｈ、ｓ） Production Example 22
0.60 g of 1- (chloromethyl) -4- (trifluoromethyl) -1H-pyrazole and 0.54 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 10 ml of N, N-dimethylformamide. To the stirred solution under ice cooling, 0.99 g of potassium carbonate was added, and the mixture was further stirred overnight at room temperature. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, recrystallized from hexane-chloroform, and represented by {[4- (trifluoromethyl) -1H-pyrazol-1-yl] methyl} (3, 3, 3 -Trifluoropropyl) malononitrile

(Hereinafter referred to as the present compound (22).) 0.19 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.28-2.32 (2H, m), 2.53-2.57 (2H, m), 4.71 (2H, s) 7.85 (1H, s), 7.93 (1H, s)

（以下、本発明化合物（２３）と記す。）０．４８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．２７−２．３２（２Ｈ、ｍ）、２．４７−２．６２（２Ｈ、ｍ）、３．８６（３Ｈ、ｓ）、４．７１（２Ｈ、ｓ）、８．０３（１Ｈ、ｓ）、８．１２（１Ｈ、ｓ） Production Example 23
0.80 g of 1- (chloromethyl) -4-methoxycarbonyl-1H-pyrazole and 0.75 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 15 ml of N, N-dimethylformamide. To the solution stirred under ice cooling was added 1.27 g of potassium carbonate, and the mixture was further stirred overnight at room temperature. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, recrystallized from hexane-chloroform, and {[4- (methoxycarbonyl) -1H-pyrazol-1-yl] methyl} (3,3,3- Trifluoropropyl) malononitrile

(Hereinafter referred to as the present compound (23).) 0.48 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.27-2.32 (2H, m), 2.47-2.62 (2H, m), 3.86 (3H, s) 4.71 (2H, s), 8.03 (1H, s), 8.12 (1H, s)

（以下、本発明化合物（２４）と記す。）０．５０ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．７６（２Ｈ，ｄ）、３．８５（３Ｈ、ｓ）、４．６４（２Ｈ、ｓ）、５．４７−５．５４（２Ｈ、ｍ）、５．８５−５．９９（１Ｈ、ｍ）８．０２（１Ｈ、ｓ）、８．１１（１Ｈ、ｓ） Production Example 24
0.79 g of 1- (chloromethyl) -4-methoxycarbonyl-1H-pyrazole and 0.49 g of allylmalononitrile were dissolved in 15 ml of N, N-dimethylformamide. To the stirred solution under ice cooling, 1.26 g of potassium carbonate was added, and the mixture was further stirred overnight at room temperature. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography. Thereafter, recrystallization from hexane-chloroform and allyl {[4- (methoxycarbonyl) -1H-pyrazol-1-yl] methyl} malononitrile represented by the following formula

(Hereinafter referred to as the present compound (24).) 0.50 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.76 (2H, d), 3.85 (3H, s), 4.64 (2H, s), 5.47-5.54 (2H, m), 5.85-5.99 (1H, m) 8.02 (1H, s), 8.11 (1H, s)

（以下、本発明化合物（２５）と記す。）０．３０ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３７（３Ｈ、ｔ）、２．３０−２．３４（２Ｈ、ｍ）、２．５２−２．６３（２Ｈ、ｍ）、４．３５（２Ｈ、ｑ）、４．７３（２Ｈ、ｓ）、８．２４（１Ｈ、ｓ） Production Example 25
1- (Chloromethyl) -3- (trifluoromethyl) -4-ethoxycarbonyl-1H-pyrazole (1.13 g) and (3,3,3-trifluoropropyl) malononitrile (0.71 g) were added to N, N-dimethylformamide (13 ml). Dissolved in. To the stirred solution under ice cooling, 1.22 g of potassium carbonate was added, and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and {[4-ethoxycarbonyl-3- (trifluoromethyl) -pyrazol-1H-yl] methyl} (3,3,3-trifluoropropyl) malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (25).) 0.30 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.37 (3H, t), 2.30-2.34 (2H, m), 2.52-2.63 (2H, m) 4.35 (2H, q), 4.73 (2H, s), 8.24 (1H, s)

（以下、本発明化合物（２６）と記す。）０．１４ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３６（３Ｈ、ｔ）、２．８０（２Ｈ、ｄ）、４．３０（２Ｈ、ｑ）、４．６８（２Ｈ、ｓ）、５．４６−５．５６（２Ｈ、ｍ）、５．８８−５．９８（１Ｈ、ｍ）、８．２４（１Ｈ、ｓ） Production Example 26
1.25 g of 1- (chloromethyl) -3- (trifluoromethyl) -4-ethoxycarbonyl-1H-pyrazole and 0.52 g of allylmalononitrile were dissolved in 15 ml of N, N-dimethylformamide. To the solution stirred under ice-cooling, 1.35 g of potassium carbonate was added, and the mixture was further stirred overnight at room temperature. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, recrystallized from hexane, and allyl {[4-ethoxycarbonyl-3- (trifluoromethyl) -pyrazol-1H-yl] methyl} malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (26).) 0.14 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.36 (3H, t), 2.80 (2H, d), 4.30 (2H, q), 4.68 (2H, s) ), 5.46-5.56 (2H, m), 5.88-5.98 (1H, m), 8.24 (1H, s)

（以下、本発明化合物（２７）と記す。）０．４２ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．３１−２．３７（２Ｈ、ｍ）、２．５２−２．６３（２Ｈ、ｍ）、４．７７（２Ｈ、ｓ）、８．０９（１Ｈ、ｓ）、８．３３（１Ｈ、ｓ） Production Example 27
0.77 g of 1- (chloromethyl) -1H-1,2,4-triazole hydrochloride and 0.81 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 15 ml of N, N-dimethylformamide. To the stirred solution under ice-cooling, 1.38 g of potassium carbonate was added, and the mixture was further stirred at room temperature for 7 hours. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was recrystallized from hexane-MTBE and represented by the following formula [(1H-1,2,4-triazole -1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile

(Hereinafter referred to as the present compound (27).) 0.42 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.31-2.37 (2H, m), 2.52-2.63 (2H, m), 4.77 (2H, s) , 8.09 (1H, s), 8.33 (1H, s)

（以下、本発明化合物（２８）と記す。）０．３１ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３２（６Ｈ，ｄ）、２．３１−２．３５（２Ｈ、ｍ）、２．４５−２．６３（２Ｈ、ｍ）、３．０６−３．１３（１Ｈ、ｍ）、４．６８（２Ｈ、ｓ）、８．１９（１Ｈ、ｓ） Production Example 28
3-i-Propyl-1- (chloromethyl) -1H-1,2,4-triazole hydrochloride 0.78 g and (3,3,3-trifluoropropyl) malononitrile 0.65 g were added to N, N-dimethylformamide. Dissolved in 12 ml. To the stirred solution under ice-cooling, 1.10 g of potassium carbonate was added, and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was recrystallized from hexane-MTBE and represented by the following formula [(3-i-propyl-1H-1 , 2,4-Triazol-1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile

(Hereinafter referred to as the present compound (28).) 0.31 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.32 (6H, d), 2.31-2.35 (2H, m), 2.45-2.63 (2H, m) 3.06-3.13 (1H, m), 4.68 (2H, s), 8.19 (1H, s)

（以下、本発明化合物（２９）と記す。）０．７７ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３７（９Ｈ、ｓ）、２．３１−２．３４（２Ｈ、ｍ）、２．５１−２．６３（２Ｈ、ｍ）、４．６７（２Ｈ、ｓ）、８．１８（１Ｈ、ｓ） Production Example 29
1.61 g of 3-t-butyl-1- (chloromethyl) -1H-1,2,4-triazole hydrochloride and 1.24 g of (3,3,3-trifluoropropyl) malononitrile were mixed with N, N-dimethylformamide. Dissolved in 22 ml. To the solution stirred under ice-cooling, 2.13 g of potassium carbonate was added, and the mixture was further stirred at room temperature for 4 hours. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, the residue was recrystallized from hexane-MTBE, and represented by the following formula [(3-t-butyl-1H-1 , 2,4-Triazol-1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile

(Hereinafter referred to as the present compound (29).) 0.77 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.37 (9H, s), 2.31-2.34 (2H, m), 2.51-2.63 (2H, m) 4.67 (2H, s), 8.18 (1H, s)

（以下、本発明化合物（３０）と記す。）０．２９ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：０．７２（３Ｈ、ｔ）、１．３３（６Ｈ、ｓ）、１．６９（２Ｈ、ｑ）、２．３１−２．３５（２Ｈ、ｍ）、２．５１−２．６３（２Ｈ、ｍ）、４．６８（２Ｈ、ｓ）、８．１９（１Ｈ、ｓ） Production Example 30
0.98 g of 3- (1,1-dimethylpropyl) -1- (chloromethyl) -1H-1,2,4-triazole hydrochloride and 0.65 g of (3,3,3-trifluoropropyl) malononitrile were added to N , N-dimethylformamide was dissolved in 12 ml. To the stirred solution under ice cooling, 1.11 g of potassium carbonate was added, and the mixture was further stirred overnight at room temperature. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, the residue was recrystallized from hexane-MTBE, and represented by the following formula {[3- (1,1-dimethylpropyl ) -1H-1,2,4-triazol-1-yl] methyl} (3,3,3-trifluoropropyl) malononitrile

(Hereinafter referred to as the present compound (30).) 0.29 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 0.72 (3H, t), 1.33 (6H, s), 1.69 (2H, q), 2.31-2.35 (2H, m), 2.51-2.63 (2H, m), 4.68 (2H, s), 8.19 (1H, s)

（以下、本発明化合物（３１）と記す。）０．１６ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３８（９Ｈ、ｓ）、２．７９（２Ｈ、ｄ）、４．６１（２Ｈ、ｓ）、５．５０−５．５４（２Ｈ、ｍ）、５．８９−６．００（１Ｈ、ｍ）、８．１６（１Ｈ、ｓ） Production Example 31
1- (Chloromethyl) -3-tert-butyl-1H-1,2,4-triazole hydrochloride 1.28 g and allylmalononitrile 0.77 g were dissolved in 21 ml of N, N-dimethylformamide. To the solution stirred under ice cooling, 1.01 g of potassium carbonate was added, and the mixture was further stirred at room temperature for 4 hours. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, the residue was recrystallized from hexane-MTBE, and allyl represented by the following formula [(3-t-butyl-1H- 1,2,4-triazol-1-yl) methyl] malononitrile

(Hereinafter referred to as the present compound (31).) 0.16 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.38 (9H, s), 2.79 (2H, d), 4.61 (2H, s), 5.50-5.54 (2H, m), 5.89-6.00 (1H, m), 8.16 (1H, s)

（以下、本発明化合物（３２）と記す。）０．７６ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３４（９Ｈ、ｓ）、２．４０−２．４５（２Ｈ、ｍ）、２．５１−２．６４（２Ｈ、ｍ）、４．６２（２Ｈ、ｓ） Production Example 32
2.03 g of 5-bromo-3-tert-butyl-1- (chloromethyl) -1H-1,2,4-triazole hydrochloride and 1.30 g of (3,3,3-trifluoropropyl) malononitrile were mixed with N, Dissolved in 24 ml of N-dimethylformamide. To the solution stirred under ice cooling, 2.21 g of potassium carbonate was added, and the mixture was further stirred overnight at room temperature. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and [(5-bromo-3-tert-butyl-1H-1,2,4-triazol-1-yl) methyl] (3,3,3- Trifluoropropyl) malononitrile

(Hereinafter referred to as the present compound (32).) 0.76 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.34 (9H, s), 2.40-2.45 (2H, m), 2.51-2.64 (2H, m) 4.62 (2H, s)

（以下、本発明化合物（３３）と記す。）０．１５ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．３４−２．３８（２Ｈ、ｍ）、２．５１−２．６５（２Ｈ、ｍ）、４．８２（２Ｈ、ｓ）、８．４５（１Ｈ、ｓ） Production Example 33
1- (Chloromethyl) -3- (trifluoromethyl) -1H-1,2,4-triazole (1.56 g) and (3,3,3-trifluoropropyl) malononitrile (1.38 g) were mixed with N, N-dimethylformamide. Dissolved in 25 ml. To the solution stirred under ice cooling, 2.35 g of potassium carbonate was added, and the mixture was further stirred at room temperature for 4 hours. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, the residue was recrystallized from hexane-MTBE, and represented by the following formula {[3- (trifluoromethyl) -1H -1,2,4-triazol-1-yl] methyl} (3,3,3-trifluoropropyl) malononitrile

(Hereinafter referred to as the present compound (33).) 0.15 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.34-2.38 (2H, m), 2.51-2.65 (2H, m), 4.82 (2H, s) , 8.45 (1H, s)

（以下、本発明化合物（３４）と記す。）０．２５ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．３２−２．３６（２Ｈ、ｍ）、２．５２−２．６４（２Ｈ、ｍ）、４．８４（２Ｈ、ｓ）、８．４７（１Ｈ、ｓ） Production Example 34
1.74 g of 1- (chloromethyl) -3- (pentafluoroethyl) -1H-1,2,4-triazole and 1.20 g of (3,3,3-trifluoropropyl) malononitrile were added to N, N-dimethylformamide Dissolved in 21 ml. To the stirred solution under ice cooling, 2.04 g of potassium carbonate was added, and the mixture was further stirred at room temperature for 4 hours. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was recrystallized from hexane-MTBE and represented by the following formula {[3- (pentafluoroethyl) -1H -1,2,4-triazol-1-yl] methyl} (3,3,3-trifluoropropyl) malononitrile

(Hereinafter referred to as the present compound (34).) 0.25 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.32-2.36 (2H, m), 2.52-2.64 (2H, m), 4.84 (2H, s) , 8.47 (1H, s)

（以下、本発明化合物（３５）と記す。）０．５４ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．８１（２Ｈ、ｄ）、４．７６（２Ｈ、ｓ）、５．５３−５．５９（２Ｈ、ｍ）、５．８８−５．９７（１Ｈ、ｍ）、８．４５（１Ｈ、ｓ） Production Example 35
1.24 g of 1- (chloromethyl) -3- (pentafluoroethyl) -1H-1,2,4-triazole and 1.02 g of allylmalononitrile were dissolved in 28 ml of N, N-dimethylformamide. To the stirred solution under ice cooling, 2.76 g of potassium carbonate was added, and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, then subjected to preparative high performance liquid chromatography, and allyl {[3- (pentafluoroethyl) -1H-1,2,4-triazole-1- Yl] methyl} malononitrile

(Hereinafter referred to as the present compound (35).) 0.54 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.81 (2H, d), 4.76 (2H, s), 5.53-5.59 (2H, m), 5.88 -5.97 (1H, m), 8.45 (1H, s)

（以下、本発明化合物（３６）と記す。）１．３１ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．２３−２．２７（２Ｈ、ｍ）、２．４９−２．５９（２Ｈ、ｍ）、４．７７（２Ｈ、ｓ）、６．７２（１Ｈ、ｄ）、７．７５（１Ｈ、ｄ） Production Example 36
2.01 g of 1- (chloromethyl) -3- (pentafluoroethyl) -1H-pyrazole and 1.39 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 25 ml of N, N-dimethylformamide. To the stirred solution under ice cooling, 2.38 g of potassium carbonate was added, and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and {[3- (pentafluoroethyl) -1H-pyrazol-1-yl] methyl} (3,3,3-trifluoropropyl) malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (36).) 1.31 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.23 to 2.27 (2H, m), 2.49-1.59 (2H, m), 4.77 (2H, s) 6.72 (1H, d), 7.75 (1H, d)

（以下、本発明化合物（３７）と記す。）７．１５ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．２４−２．２９（２Ｈ、ｍ）、２．４９−２．６１（２Ｈ、ｍ）、４．７５（２Ｈ、ｓ）、７．８１（１Ｈ、ｓ） Production Example 37
4-Bromo-1- (chloromethyl) -3- (pentafluoroethyl) -1H-pyrazole 6.84 g and (3,3,3-trifluoropropyl) malononitrile 3.54 g were added to 60 ml of N, N-dimethylformamide. Dissolved. To the stirred solution under ice cooling, 6.08 g of potassium carbonate was added, and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and [(4-bromo-3- (pentafluoroethyl) -1H-pyrazol-1-yl) methyl] (3,3,3-trifluoropropyl) represented by the following formula: Malononitrile

(Hereinafter referred to as the present compound (37).) 7.15 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.24-2.29 (2H, m), 2.49-2.61 (2H, m), 4.75 (2H, s) 7.81 (1H, s)

（以下、本発明化合物（３８）と記す。）１．１２ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．２４−２．２８（２Ｈ、ｍ）、２．５４−２．６５（２Ｈ、ｍ）、４．５３（２Ｈ、ｓ）、７．５０（１Ｈ、ｓ）、７．７３（１Ｈ、ｓ） Production Example 38
1.90 g of 1- (chloromethyl) -4- (trifluoromethyl) -1H-imidazole hydrochloride and 2.11 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 39 ml of N, N-dimethylformamide. . To the stirred solution under ice cooling, 3.59 g of potassium carbonate was added, and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and {[4- (trifluoromethyl) -1H-imidazol-1-yl] methyl} (3,3,3-trifluoropropyl) malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (38).) 1.12 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.24-2.28 (2H, m), 2.54-2.65 (2H, m), 4.53 (2H, s) 7.50 (1H, s), 7.73 (1H, s)

（以下、本発明化合物（３９）と記す。）１．４８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．２８−２．３２（２Ｈ、ｍ）、２．５１−２．６３（２Ｈ、ｍ）、４．７８（２Ｈ、ｓ）、７．３７−７．４７（２Ｈ、ｍ）、７．５３（１Ｈ、ｄ）、７．８０−７．８３（２Ｈ、ｍ） Production Example 39
1.70 g of 1- (chloromethyl) -3-cyano-1H-indole and 1.45 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 27 ml of N, N-dimethylformamide. To the solution stirred under ice cooling, 2.49 g of potassium carbonate was added, and the mixture was further stirred at room temperature for 7 hours. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and {[3-cyano-1H-indol-1-yl] methyl} (3,3,3-trifluoropropyl) malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (39).) 1.48 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.28-2.32 (2H, m), 2.51-2.63 (2H, m), 4.78 (2H, s) 7.37-7.47 (2H, m), 7.53 (1H, d), 7.80-7.83 (2H, m)

（以下、本発明化合物（４０）と記す。）２．６８ｇを得た。
¹Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ₆、ＴＭＳ、δ（ｐｐｍ））：２．３３−２．５１（２Ｈ、ｍ）、２．５９−２．７５（２Ｈ、ｍ）、５．２９（２Ｈ、ｓ）、７．３０−７．４０（２Ｈ、ｍ）、７．９７（１Ｈ、ｄ）、８．１４（１Ｈ、ｄ）、８．３６（１Ｈ、ｓ）、１０．０４（１Ｈ、ｓ） Production Example 40
3.02 g of 1- (chloromethyl) -3-formyl-1H-indole and 2.53 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 45 ml of N, N-dimethylformamide. To the stirred solution under ice cooling, 4.35 g of potassium carbonate was added, and the mixture was further stirred at room temperature for 3 hours. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and {[3-formyl-1H-indol-1-yl] methyl} (3,3,3-trifluoropropyl) malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (40).) 2.68 g was obtained.
¹ H-NMR (DMSO-d ₆ , TMS, δ (ppm)): 2.33-2.51 (2H, m), 2.59-2.75 (2H, m), 5.29 (2H, s), 7.30-7.40 (2H, m), 7.97 (1H, d), 8.14 (1H, d), 8.36 (1H, s), 10.04 (1H, s) )

（以下、本発明化合物（４１）と記す。）３．０６ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．３３−２．３７（２Ｈ、ｍ）、２．５３−２．６５（２Ｈ、ｍ）、４．８５（２Ｈ、ｓ）、７．４４−７．５０（２Ｈ、ｍ）、７．５２−７．５７（１Ｈ、ｍ）、８．１６（１Ｈ、ｓ）、８．４４−８．４７（１Ｈ、ｍ） Production Example 41
3.53 g of 1- (chloromethyl) -3- (trifluoroacetyl) -1H-indole and 2.19 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 27 ml of N, N-dimethylformamide. To the stirred solution under ice-cooling, 3.74 g of potassium carbonate was added, and the mixture was further stirred at room temperature overnight. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and {[3- (trifluoroacetyl) -1H-indol-1-yl] methyl} (3,3,3-trifluoropropyl) malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (41).) 3.06 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.33-2.37 (2H, m), 2.53-2.65 (2H, m), 4.85 (2H, s) 7.44-7.50 (2H, m), 7.52-7.57 (1H, m), 8.16 (1H, s), 8.44-8.47 (1H, m)

（以下、本発明化合物（４２）と記す。）１．７１ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．０４−２．２７（２Ｈ、ｍ）、２．４８（２Ｈ、ｍ）、４．６９（２Ｈ、ｓ）、７．６５（１Ｈ、ｓ）、７．６７（１Ｈ、ｓ） Production Example 42
1.21 g of [(1H-pyrazol-1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (the present compound (1)) is dissolved in 50 ml of acetonitrile, and ammonium cerium (IV) is added to the solution. 2.19 g of nitrite and 1.02 g of iodine were added and stirred at room temperature for 10 hours. The reaction mixture was concentrated under reduced pressure, the residue was subjected to silica gel column chromatography, and [(4-iodo-1H-pyrazol-1-yl) methyl] (3,3,3-trifluoropropyl) represented by the following formula: Malononitrile

(Hereinafter referred to as the present compound (42).) 1.71 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.04-2.27 (2H, m), 2.48 (2H, m), 4.69 (2H, s), 7.65 (1H, s), 7.67 (1H, s)

（以下、本発明化合物（４３）と記す。）０．０６ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．２４−２．３３（２Ｈ、ｍ）、２．４９−２．５９（２Ｈ、ｍ）、５．４３（２Ｈ、ｓ）、７．８３（１Ｈ、ｓ）、７．９６（１Ｈ、ｓ） Production Example 43
Dissolve 0.21 g of 1- (chloromethyl) -4-[(dichlorofluoromethyl) thio] -1H-pyrazole and 0.14 g of (3,3,3-trifluoropropyl) malononitrile in 2 ml of N, N-dimethylformamide. did. To this solution was added 0.12 g of potassium carbonate under ice cooling, and the mixture was further stirred overnight at room temperature. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then filtered. The filtrate was concentrated under reduced pressure. [(4-{(Dichlorofluoromethyl) thio} -1H-pyrazol-1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile represented by the following formula

(Hereinafter referred to as the present compound (43).) 0.06 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.24-2.33 (2H, m), 2.49-1.59 (2H, m), 5.43 (2H, s) 7.83 (1H, s), 7.96 (1H, s)

（以下、本発明化合物（４４）と記す。）０．６５ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．０５−２．２８（２Ｈ、ｍ）、２．４９−２．６０（２Ｈ、ｍ）、４．８０（２Ｈ、ｓ）、７．３４−７．４２（２Ｈ、ｍ）、７．５０（１Ｈ、ｄ）、７．６７（１Ｈ、ｓ）、７．８６（１Ｈ、ｓ） Production Example 44
Dissolve 0.61 g of 1- (chloromethyl) -3-{[dichlorofluoromethyl] thio} -1H-indole and 0.35 g of (3,3,3-trifluoropropyl) malononitrile in 2 ml of N, N-dimethylformamide. did. To the solution was added 0.28 g of potassium carbonate under ice cooling, and the mixture was further stirred overnight at room temperature. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then filtered. The filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and [(3-{[dichlorofluoromethyl] thio} -1H-indol-1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile represented by the following formula:

(Hereinafter referred to as the present compound (44).) 0.65 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.05-2.28 (2H, m), 2.49-2.60 (2H, m), 4.80 (2H, s) , 7.34-7.42 (2H, m), 7.50 (1H, d), 7.67 (1H, s), 7.86 (1H, s)

（以下、本発明化合物（４５）と記す。）０．８０ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．２２−２．２６（２Ｈ、ｍ）、２．５２−２．６３（２Ｈ、ｍ）、４．４６（２Ｈ、ｓ）、６．８１−６．８３（１Ｈ、ｍ）、６．８８（１Ｈ、ｔ）、７．６９（１Ｈ、ｄ） Production Example 45
0.61 g of 1-chloromethyl-3-nitro-1H-pyrrole and 0.65 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 10 ml of N, N-dimethylformamide. To the solution was added 0.28 g of potassium carbonate under ice cooling, and the mixture was further stirred overnight at room temperature. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and represented by the following formula: [(3-nitro-1H-pyrrol-1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile

(Hereinafter referred to as the present compound (45).) 0.80 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.22-2.26 (2H, m), 2.52-2.63 (2H, m), 4.46 (2H, s) 6.81-6.83 (1H, m), 6.88 (1H, t), 7.69 (1H, d)

（以下、本発明化合物（４６）と記す。）０．３３ｇを得た。
¹Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ₆、ＴＭＳ、δ（ｐｐｍ））：２．４５−２．５１（２Ｈ、ｍ）、２．６２−２．７４（２Ｈ、ｍ）、４．９８（２Ｈ、ｓ）、７．７６−７．７７（１Ｈ、ｍ）、８．０４（１Ｈ、ｄ） Production Example 46
0.80 g of 1-chloromethyl-3-cyano-4-trifluoromethyl-1H-pyrrole and 0.67 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 10 ml of N, N-dimethylformamide. To the solution, 0.57 g of potassium carbonate was added under ice cooling, and the mixture was further stirred overnight at room temperature. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and represented by the following formula [(3-cyano-4-trifluoromethyl-1H-pyrrol-1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile

(Hereinafter referred to as the present compound (46).) 0.33 g was obtained.
¹ H-NMR (DMSO-d ₆ , TMS, δ (ppm)): 2.45-2.51 (2H, m), 2.62-2.74 (2H, m), 4.98 (2H, s), 7.76-7.77 (1H, m), 8.04 (1H, d)

（以下、本発明化合物（４７）と記す。）０．２０ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３５（３Ｈ、ｔ）、２．２１−２．２６（２Ｈ、ｍ）、２．５６−２．６３（２Ｈ、ｍ）、４．３５（２Ｈ、ｑ）、４．４５（２Ｈ、ｓ）、７．２０（１Ｈ、ｄ）、７．５３（１Ｈ、ｄ） Production Example 47
0.23 g of 1-chloromethyl-4-trifluoromethyl-3-ethoxycarbonyl-1H-pyrrole and 0.15 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 2 ml of N, N-dimethylformamide. To the solution was added 0.13 g of potassium carbonate under ice cooling, and the mixture was further stirred overnight at room temperature. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and represented by the following formula: [(3-ethoxycarbonyl-4-trifluoromethyl-1H-pyrrol-1-yl) methyl] (3,3,3-trifluoropropyl) malononitrile

(Hereinafter referred to as the present compound (47).) 0.20 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.35 (3H, t), 2.21-2.26 (2H, m), 2.56-2.63 (2H, m) 4.35 (2H, q), 4.45 (2H, s), 7.20 (1H, d), 7.53 (1H, d)

（以下、本発明化合物（４８）と記す。）０．３７ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．１８−２．２３（２Ｈ、ｍ）、２．４６−２．６４（２Ｈ、ｍ）、４．４６（２Ｈ、ｓ）、６．５８−６．５９（１Ｈ、ｍ）、６．８７−６．８８（１Ｈ、ｍ）、７．３３−７．３５（１Ｈ、ｍ） Production Example 48
0.27 g of 1-chloromethyl-3-cyano-1H-pyrrole and 0.34 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 3 ml of N, N-dimethylformamide. To the solution was added 0.29 g of potassium carbonate under ice cooling, and the mixture was further stirred at room temperature for 1 hour. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography. [(3-Cyano-1H-pyrrol-1-yl) methyl] (3,3,3-trifluoropropyl) represented by the following formula: Malononitrile

(Hereinafter referred to as the present compound (48).) 0.37 g was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.18-2.23 (2H, m), 2.46-2.64 (2H, m), 4.46 (2H, s) , 6.58-6.59 (1H, m), 6.87-6.88 (1H, m), 7.33-7.35 (1H, m)

ピラゾール２．０４ｇ、パラホルムアルデヒド２．００ｇ及びトリエチルアミン１ｍｌの混合物を１３０℃で１０時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加え、その混合物をろ過した。ろ液を減圧下濃縮した。残渣にヘキサンを加えることにより結晶が生成した。該結晶を集めて、１Ｈ−ピラゾール−１−イルメタノール３．１０ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．５１（２Ｈ、ｓ）、６．３０（１Ｈ、ｔ）７．５８−７．６１（２Ｈ、ｍ） Next, production examples of intermediate compounds are shown as reference production examples.
Reference Production Example 1-1
1H-pyrazol-1-ylmethanol

A mixture of 2.04 g of pyrazole, 2.00 g of paraformaldehyde and 1 ml of triethylamine was stirred at 130 ° C. for 10 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture, and the mixture was filtered. The filtrate was concentrated under reduced pressure. Crystals were formed by adding hexane to the residue. The crystals were collected to obtain 3.10 g of 1H-pyrazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.51 (2H, s), 6.30 (1H, t) 7.58-7.61 (2H, m)

１Ｈ−ピラゾール−１−イルメタノール３．１０ｇをジクロロメタン１００ｍｌに溶解した。該溶液に塩化チオニル６．８ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮した。残渣をヘキサン−クロロホルムから再結晶して、１−（クロロメチル）−１Ｈ−ピラゾール塩酸塩２．６６ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．９１（２Ｈ、ｓ）、６．３８（１Ｈ、ｔ）、７．６１−７．６８（２Ｈ、ｍ） Reference production example 1-2
1- (Chloromethyl) -1H-pyrazole hydrochloride

1H-pyrazol-1-ylmethanol 3.10 g was dissolved in 100 ml of dichloromethane. To the solution was added 6.8 ml of thionyl chloride, and the mixture was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure. The residue was recrystallized from hexane-chloroform to obtain 2.66 g of 1- (chloromethyl) -1H-pyrazole hydrochloride.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.91 (2H, s), 6.38 (1H, t), 7.61-7.68 (2H, m)

窒素雰囲気下、イソプロピルメチルケトン１７．２３ｇ及びギ酸メチル１２．０１ｇの混合物を０℃に冷却し、該混合物にテトラヒドロフラン２００ｍｌに溶解したｔ−ブトキシカリウム２２．４４ｇを１時間かけて加えた。この間、該混合物の温度は２０℃以下に保たれた。その後、反応混合物を３０℃で５時間攪拌した。室温まで冷却した反応混合物にジエチルエーテル２００ｍｌを加えた結果、固体をが生成した。その固体をろ過により集め、ジエチルエーテル２０ｍｌで洗浄した。得られた固体を減圧下乾燥させることで、１−ヒドロキシ−４−メチル−１−ペンテン−３−オンカリウム塩１４．１４ｇを得た。
１−ヒドロキシ−４，４−ジメチル−１−ペンテン−３−オンカリウム塩１４．１４ｇをエタノール９０ｍｌに懸濁した。該懸濁液にヒドラジン・一水和物５．１１ｇを加え、７時間加熱還流した。室温まで冷却した反応混合物に水３０ｍｌを加え、該混合液を３０ｍｌまで減圧下濃縮した。脳宿駅を酢酸エチルで抽出した。有機層を無水硫酸マグネシウムで乾燥した後、ろ過し、減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィーに付し、３−ｉ−プロピル−１Ｈ−ピラゾール６．８３ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））： １．２９（６Ｈ、ｄ）、３．０１−３．０８（１Ｈ、ｍ）、６．１０（１Ｈ、ｓ）、７．４９（１Ｈ、ｓ） Reference Production Example 2-1
3-i-propyl-1H-pyrazole

Under a nitrogen atmosphere, a mixture of 17.23 g of isopropyl methyl ketone and 12.01 g of methyl formate was cooled to 0 ° C., and 22.44 g of potassium t-butoxy dissolved in 200 ml of tetrahydrofuran was added to the mixture over 1 hour. During this time, the temperature of the mixture was kept below 20 ° C. The reaction mixture was then stirred at 30 ° C. for 5 hours. As a result of adding 200 ml of diethyl ether to the reaction mixture cooled to room temperature, a solid was formed. The solid was collected by filtration and washed with 20 ml of diethyl ether. The obtained solid was dried under reduced pressure to obtain 14.14 g of 1-hydroxy-4-methyl-1-penten-3-one potassium salt.
14.14 g of 1-hydroxy-4,4-dimethyl-1-penten-3-one potassium salt was suspended in 90 ml of ethanol. To the suspension, 5.11 g of hydrazine monohydrate was added, and the mixture was heated to reflux for 7 hours. 30 ml of water was added to the reaction mixture cooled to room temperature, and the mixture was concentrated to 30 ml under reduced pressure. The brain station was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 6.83 g of 3-i-propyl-1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.29 (6H, d), 3.01-3.08 (1H, m), 6.10 (1H, s), 7.49 (1H, s)

３−ｉ−プロピル−１Ｈ−ピラゾール１．１５ｇ、パラホルムアルデヒド０．９４ｇ及びトリエチルアミン０．１４ｇの混合物を１３０℃で７時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。その混合物をろ過した。ろ液を減圧下濃縮した。残渣にヘキサンを加えることによって結晶が生成した。該結晶を集めて、３−ｉ−プロピル−１Ｈ−ピラゾール−１−イルメタノール１．２８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．２４（６Ｈ、ｄ）、２．９４−３．０２（１Ｈ、ｍ）、５．４８（２Ｈ、ｓ）、６．１０（１Ｈ、ｄ）、７．４７（１Ｈ、ｄ） Reference production example 2-2
3-i-propyl-1H-pyrazol-1-ylmethanol

A mixture of 1.15 g of 3-i-propyl-1H-pyrazole, 0.94 g of paraformaldehyde and 0.14 g of triethylamine was stirred at 130 ° C. for 7 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. The mixture was filtered. The filtrate was concentrated under reduced pressure. Crystals were formed by adding hexane to the residue. The crystals were collected to obtain 1.28 g of 3-i-propyl-1H-pyrazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.24 (6H, d), 2.94-3.02 (1H, m), 5.48 (2H, s), 6.10 (1H, d), 7.47 (1H, d)

３−ｉ−プロピル−１Ｈ−ピラゾール−１−イルメタノール１．２８ｇをジクロロメタン２０ｍｌに溶解した。該溶液に塩化チオニル２ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮して、３−ｉ−プロピル−１−（クロロメチル）−１Ｈ−ピラゾール塩酸塩１．５８ｇを得た。 Reference production example 2-3
3-i-propyl-1- (chloromethyl) -1H-pyrazole hydrochloride

1.28 g of 3-i-propyl-1H-pyrazol-1-ylmethanol was dissolved in 20 ml of dichloromethane. 2 ml of thionyl chloride was added to the solution and stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to obtain 1.58 g of 3-i-propyl-1- (chloromethyl) -1H-pyrazole hydrochloride.

ピナコロン５０．００ｇ及びギ酸メチル４２．００ｇの混合物を窒素雰囲気下０℃に冷却し、該混合物にｔ−ブトキシカリウム５６．００ｇを３時間かけて加えた。この間、該混合物の温度は２０℃以下に保たれた。反応混合物を３０℃で５時間攪拌した。室温まで冷却した反応混合物にジエチルエーテルを加えた結果、固体が生成した。この固体をろ過により集め、減圧下乾燥することで、１−ヒドロキシ−４，４−ジメチル−１−ペンテン−３−オンカリウム塩３２．１２ｇを得た。１−ヒドロキシ−４，４−ジメチル−１−ペンテン−３−オンカリウム塩２１．６１ｇをエタノール１５０ｍｌに懸濁した。該懸濁液にヒドラジン・一水和物６．５２ｇを加え、７時間加熱還流した。室温まで冷却した。反応混合物に水５０ｍｌを加えた。該混合物を４０ｍｌまで減圧下濃縮した。濃縮液を酢酸エチルで抽出した。有機層を無水硫酸マグネシウムで乾燥した後、ろ過し、減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィーに付し、３−ｔ−ブチル−１Ｈ−ピラゾール６．８３ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３４（９Ｈ、ｓ）、６．１１（１Ｈ、ｄ）、７．４７（１Ｈ、ｄ） Reference Production Example 3-1
3-t-butyl-1H-pyrazole

A mixture of 50.00 g of pinacolone and 42.00 g of methyl formate was cooled to 0 ° C. under a nitrogen atmosphere, and 56.00 g of potassium t-butoxy was added to the mixture over 3 hours. During this time, the temperature of the mixture was kept below 20 ° C. The reaction mixture was stirred at 30 ° C. for 5 hours. Diethyl ether was added to the reaction mixture cooled to room temperature, resulting in the formation of a solid. This solid was collected by filtration and dried under reduced pressure to obtain 32.12 g of 1-hydroxy-4,4-dimethyl-1-penten-3-one potassium salt. 21.61 g of 1-hydroxy-4,4-dimethyl-1-penten-3-one potassium salt was suspended in 150 ml of ethanol. 6.52 g of hydrazine monohydrate was added to the suspension, and the mixture was heated to reflux for 7 hours. Cooled to room temperature. 50 ml of water was added to the reaction mixture. The mixture was concentrated under reduced pressure to 40 ml. The concentrate was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 6.83 g of 3-t-butyl-1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.34 (9H, s), 6.11 (1H, d), 7.47 (1H, d)

３−ｔ−ブチル−１Ｈ−ピラゾール１．２８ｇ、パラホルムアルデヒド０．６６ｇ及びトリエチルアミン０．３ｇの混合物を１３０℃で７時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。その混合物をろ過した。ろ液を減圧下濃縮した。残渣にヘキサンを加えることにより結晶が生成した。該結晶を集めて、３−ｔ−ブチル−１Ｈ−ピラゾール−１−イルメタノール１．０７ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．２８（９Ｈ、ｓ）、５．５０（２Ｈ、ｓ）、６．１３（１Ｈ、ｓ）、７．４６（１Ｈ、ｓ） Reference Production Example 3-2
3-t-butyl-1H-pyrazol-1-ylmethanol

A mixture of 1.28 g of 3-t-butyl-1H-pyrazole, 0.66 g of paraformaldehyde and 0.3 g of triethylamine was stirred at 130 ° C. for 7 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. The mixture was filtered. The filtrate was concentrated under reduced pressure. Crystals were formed by adding hexane to the residue. The crystals were collected to obtain 1.07 g of 3-t-butyl-1H-pyrazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.28 (9H, s), 5.50 (2H, s), 6.13 (1H, s), 7.46 (1H, s) )

３−ｔ−ブチル−１Ｈ−ピラゾール−１−イルメタノール１．０７ｇをジクロロメタン１４０ｍｌに溶解し、該溶液に塩化チオニル２ｍｌを加え、室温で一晩攪拌した。反応混合物を、減圧下濃縮し、３−ｔ−ブチル−１−（クロロメチル）−１Ｈ−ピラゾール塩酸塩１．６６ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：６．２５（２Ｈ、ｓ）、６．４０（１Ｈ、ｄ）、７．６９（１Ｈ、ｄ） Reference Production Example 3-3
3-t-butyl-1- (chloromethyl) -1H-pyrazole hydrochloride

1.07 g of 3-t-butyl-1H-pyrazol-1-ylmethanol was dissolved in 140 ml of dichloromethane, 2 ml of thionyl chloride was added to the solution, and the mixture was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to obtain 1.66 g of 3-t-butyl-1- (chloromethyl) -1H-pyrazole hydrochloride.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 6.25 (2H, s), 6.40 (1H, d), 7.69 (1H, d)

２，２−ジメチルシクロペンタノン１２．２２ｇ及びギ酸メチル６．０１ｇの混合物を窒素雰囲気下０℃に冷却し、該混合物にｔ−ブトキシカリウム６．７４ｇを１時間かけて加えた。この間、該混合物の温度は２０℃以下に保たれた。その後、反応混合物を室温で１８時間攪拌した。反応混合物にジエチルエーテルを加えた結果、固体が生成した。その固体をろ過により集めた。得られた固体を減圧下乾燥させることで、１−ヒドロキシメチレン−５，５−ジメチルシクロペンタノンカリウム塩９．９４ｇを得た。１−ヒドロキシメチレン−５，５−ジメチルシクロペンタノンカリウム塩９．９４ｇをエタノール８０ｍｌに懸濁した。該懸濁液にヒドラジン・一水和物２．８０ｇを加え、５時間加熱還流した。室温まで冷却した反応混合物に水５０ｍｌを加えた。該混合液を４０ｍｌまで減圧下濃縮した。濃縮液を酢酸エチルで抽出した。有機層を無水硫酸マグネシウムで乾燥した後、ろ過し、減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィーに付し、６，６−ジメチル−２，４、５，６−テトラヒドロシクロペンタ〔ｃ〕ピラゾール１．６８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３２（６Ｈ、ｓ）、２．２３−２．２８（２Ｈ、ｔ）、２．６０−２．６４（２Ｈ、ｔ）、７．１１（１Ｈ、ｓ） Reference production example 4-1
6,6-dimethyl-2,4,5,6-tetrahydrocyclopenta [c] pyrazole

A mixture of 12.22 g of 2,2-dimethylcyclopentanone and 6.01 g of methyl formate was cooled to 0 ° C. under a nitrogen atmosphere, and 6.74 g of potassium t-butoxy was added to the mixture over 1 hour. During this time, the temperature of the mixture was kept below 20 ° C. The reaction mixture was then stirred at room temperature for 18 hours. Diethyl ether was added to the reaction mixture, resulting in the formation of a solid. The solid was collected by filtration. The obtained solid was dried under reduced pressure to obtain 9.94 g of 1-hydroxymethylene-5,5-dimethylcyclopentanone potassium salt. 9.94 g of 1-hydroxymethylene-5,5-dimethylcyclopentanone potassium salt was suspended in 80 ml of ethanol. 2.80 g of hydrazine monohydrate was added to the suspension, and the mixture was heated to reflux for 5 hours. 50 ml of water was added to the reaction mixture cooled to room temperature. The mixture was concentrated to 40 ml under reduced pressure. The concentrate was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 1.68 g of 6,6-dimethyl-2,4,5,6-tetrahydrocyclopenta [c] pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.32 (6H, s), 2.23-2.28 (2H, t), 2.60-2.64 (2H, t) 7.11 (1H, s)

６，６−ジメチル−２，４、５，６−テトラヒドロシクロペンタ〔ｃ〕ピラゾール１．６８ｇ、パラホルムアルデヒド０．４１ｇ及びトリエチルアミン０．２ｇの混合物を１３０℃で５時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。その混合物をろ過した。ろ液を減圧下濃縮た。得られた残渣にヘキサンを加えることにより、結晶が生成した。該結晶を集めて、｛６，６−ジメチル−５，６−ジヒドロシクロペンタ〔ｃ〕ピラゾール−２（４Ｈ）−イル｝メタノール０．３１ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．２８（６Ｈ、ｓ）、２．１８（２Ｈ、ｔ）、２．５９（２Ｈ、ｔ）、５．４４（２Ｈ、ｓ）、７．１３（１Ｈ、ｓ） Reference production example 4-2
{6,6-dimethyl-5,6-dihydrocyclopenta [c] pyrazol-2 (4H) -yl} methanol

A mixture of 1.68 g of 6,6-dimethyl-2,4,5,6-tetrahydrocyclopenta [c] pyrazole, 0.41 g of paraformaldehyde and 0.2 g of triethylamine was stirred at 130 ° C. for 5 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. The mixture was filtered. The filtrate was concentrated under reduced pressure. Crystals were produced by adding hexane to the resulting residue. The crystals were collected to obtain 0.31 g of {6,6-dimethyl-5,6-dihydrocyclopenta [c] pyrazol-2 (4H) -yl} methanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.28 (6H, s), 2.18 (2H, t), 2.59 (2H, t), 5.44 (2H, s) ), 7.13 (1H, s)

（６，６−ジメチル−５，６−ジヒドロシクロペンタ〔ｃ〕ピラゾール−２（４Ｈ）−イル）メタノール０．３１ｇをジクロロメタン５ｍｌに溶解した。該溶液に塩化チオニル１ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮して、１−（クロロメチル）−６，６−ジメチル−５，６−ジヒドロシクロペンタ〔ｃ〕ピラゾール塩酸塩０．５８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．４６（６Ｈ、ｓ）、２．３３（２Ｈ、ｔ）、２．７３（２Ｈ、ｔ）、６．１８（２Ｈ、ｓ）、７．４５（１Ｈ、ｓ） Reference production example 4-3
1- (Chloromethyl) -6,6-dimethyl-5,6-dihydrocyclopenta [c] pyrazole hydrochloride

0.31 g of (6,6-dimethyl-5,6-dihydrocyclopenta [c] pyrazol-2 (4H) -yl) methanol was dissolved in 5 ml of dichloromethane. 1 ml of thionyl chloride was added to the solution and stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to obtain 0.58 g of 1- (chloromethyl) -6,6-dimethyl-5,6-dihydrocyclopenta [c] pyrazole hydrochloride.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.46 (6H, s), 2.33 (2H, t), 2.73 (2H, t), 6.18 (2H, s) ), 7.45 (1H, s)

３−（トリフルオロメチル）−１Ｈ−ピラゾール４．０８ｇ、パラホルムアルデヒド２．００ｇ及びトリエチルアミン１ｍｌの混合物を８０℃で５時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。その混合物をろ過した。ろ液を減圧下濃縮した。残渣にヘキサンを加えることにより結晶が生成した。該結晶を集めて、３−（トリフルオロメチル）−１Ｈ−ピラゾール−１−イルメタノール４．３１ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：４．７３（１Ｈ、ｂｒ．ｓ）、５．５８（２Ｈ、ｓ）、６．５８（１Ｈ、ｓ）、７．６６（１Ｈ、ｓ） Reference Production Example 5-1
3- (Trifluoromethyl) -1H-pyrazol-1-ylmethanol

A mixture of 4.08 g of 3- (trifluoromethyl) -1H-pyrazole, 2.00 g of paraformaldehyde and 1 ml of triethylamine was stirred at 80 ° C. for 5 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. The mixture was filtered. The filtrate was concentrated under reduced pressure. Crystals were formed by adding hexane to the residue. The crystals were collected to obtain 4.31 g of 3- (trifluoromethyl) -1H-pyrazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 4.73 (1H, br.s), 5.58 (2H, s), 6.58 (1H, s), 7.66 (1H , S)

３−（トリフルオロメチル）−１Ｈ−ピラゾール−１−イルメタノール１．３３ｇをジクロロメタン４０ｍｌに溶解した。該溶液に塩化チオニル２．７ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮し、１−（クロロメチル）−３−（トリフルオロメチル）−１Ｈ−ピラゾール１．４４ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．８８（２Ｈ、ｓ）、６．６２（１Ｈ、ｄ）、７．６８（１Ｈ、ｄ） Reference production example 5-2
1- (Chloromethyl) -3- (trifluoromethyl) -1H-pyrazole

1.33 g of 3- (trifluoromethyl) -1H-pyrazol-1-ylmethanol was dissolved in 40 ml of dichloromethane. 2.7 ml of thionyl chloride was added to the solution and stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to obtain 1.44 g of 1- (chloromethyl) -3- (trifluoromethyl) -1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.88 (2H, s), 6.62 (1H, d), 7.68 (1H, d)

３−ホルミル−１Ｈ−ピラゾール０．９６ｇ、パラホルムアルデヒド０．６０ｇ及びトリエチルアミン０．３ｍｌの混合物を１００℃で５時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。その混合物をろ過した後、ろ液を減圧下濃縮し、１−（ヒドロキシメチル）−３−ホルミル−１Ｈ−ピラゾール１．２１ｇを得た。本粗生成物を精製することなく次工程に供した。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．６３（２Ｈ、ｓ）、６．８４（１Ｈ、ｄ）、７．６７（１Ｈ、ｄ）、９．９６（１Ｈ、ｓ） Reference Production Example 6-1
1- (hydroxymethyl) -3-formyl-1H-pyrazole

A mixture of 0.96 g of 3-formyl-1H-pyrazole, 0.60 g of paraformaldehyde and 0.3 ml of triethylamine was stirred at 100 ° C. for 5 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. After the mixture was filtered, the filtrate was concentrated under reduced pressure to obtain 1.21 g of 1- (hydroxymethyl) -3-formyl-1H-pyrazole. This crude product was subjected to the next step without purification.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.63 (2H, s), 6.84 (1H, d), 7.67 (1H, d), 9.96 (1H, s )

１−（ヒドロキシメチル）−３−ホルミル−１Ｈ−ピラゾール１．２１ｇをジクロロメタン５０ｍｌに溶解した。該溶液に塩化チオニル２．４ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮し、１−（クロロメチル）−３−ホルミル−１Ｈ−ピラゾール塩酸塩１．５７ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．９２（２Ｈ、ｓ）、６．８８（１Ｈ、ｓ）、７．６７（１Ｈ、ｓ）、１０．００（１Ｈ、ｓ） Reference production example 6-2
1- (Chloromethyl) -3-formyl-1H-pyrazole hydrochloride

1.21 g of 1- (hydroxymethyl) -3-formyl-1H-pyrazole was dissolved in 50 ml of dichloromethane. To the solution, 2.4 ml of thionyl chloride was added and stirred at room temperature overnight. The reaction mixture was concentrated under reduced pressure to obtain 1.57 g of 1- (chloromethyl) -3-formyl-1H-pyrazole hydrochloride.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.92 (2H, s), 6.88 (1H, s), 7.67 (1H, s), 10.00 (1H, s )

３−ホルミル−１Ｈ−ピラゾール２．１８ｇをピリジン１２ｍｌに溶解し、該溶液にヒドロキシルアミン塩酸塩１．５８ｇを加え、室温で５時間攪拌した。反応混合物を減圧下濃縮した。残渣に無水酢酸３０ｍｌを加え、１００℃で５時間攪拌した。反応混合物を室温まで冷却後、減圧下濃縮した。残渣にエタノール３０mlを加え、該混合物を１００℃で３時間攪拌した。反応混合物を室温まで冷却し、減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィーに付し、３−シアノ−１Ｈ−ピラゾール０．８６ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：６．７９（１Ｈ、ｄ）、７．７５（１Ｈ、ｄ） Reference Production Example 7-1
3-Cyano-1H-pyrazole

2.18 g of 3-formyl-1H-pyrazole was dissolved in 12 ml of pyridine, 1.58 g of hydroxylamine hydrochloride was added to the solution, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was concentrated under reduced pressure. 30 ml of acetic anhydride was added to the residue and stirred at 100 ° C. for 5 hours. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. 30 ml of ethanol was added to the residue and the mixture was stirred at 100 ° C. for 3 hours. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.86 g of 3-cyano-1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 6.79 (1H, d), 7.75 (1H, d)

３−シアノ−１Ｈ−ピラゾール０．８６ｇ及びパラホルムアルデヒド０．５５ｇの混合物を１３０℃で７時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。その混合物をろ過した後、ろ液を減圧下濃縮し、１−（ヒドロキシメチル）−３−シアノ−１Ｈ−ピラゾール０．８９ｇを得た。
¹Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ₆、ＴＭＳ、δ（ｐｐｍ））：５．５４（２Ｈ、ｓ）、６．７０（１Ｈ、ｄ）、７．７２（１Ｈ、ｄ） Reference Production Example 7-2
1- (hydroxymethyl) -3-cyano-1H-pyrazole

A mixture of 0.86 g of 3-cyano-1H-pyrazole and 0.55 g of paraformaldehyde was stirred at 130 ° C. for 7 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. After the mixture was filtered, the filtrate was concentrated under reduced pressure to obtain 0.89 g of 1- (hydroxymethyl) -3-cyano-1H-pyrazole.
¹ H-NMR (DMSO-d ₆ , TMS, δ (ppm)): 5.54 (2H, s), 6.70 (1H, d), 7.72 (1H, d)

１−（ヒドロキシメチル）−３−シアノ−１Ｈ−ピラゾール０．８９ｇをジクロロメタン３０ｍｌに溶解した。該溶液に塩化チオニル１．６ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮し、３−シアノ−１−（クロロメチル）−１Ｈ−ピラゾール１．００ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．８７（２Ｈ、ｓ）、６．７６（１Ｈ、ｓ）、７．７２（１Ｈ、ｓ） Reference Production Example 7-3
3-Cyano-1- (chloromethyl) -1H-pyrazole

0.89 g of 1- (hydroxymethyl) -3-cyano-1H-pyrazole was dissolved in 30 ml of dichloromethane. 1.6 ml of thionyl chloride was added to the solution and stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to obtain 1.00 g of 3-cyano-1- (chloromethyl) -1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.87 (2H, s), 6.76 (1H, s), 7.72 (1H, s)

３−フェニル−１Ｈ−ピラゾール２．８８ｇ、パラホルムアルデヒド０．６７ｇ及びトリエチルアミン０．３ｍｌの混合物を１３０℃で５時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。その混合物をろ過した後、ろ液にヘキサンを加えることにより結晶が生成した。該結晶を集めて、３−フェニル−１Ｈ−ピラゾール−１−イルメタノール２．６４ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．５６（２Ｈ、ｓ）、６．５８（１Ｈ、ｄ）、７．３１−７．４２（３Ｈ、ｍ）、７．５９（１Ｈ、ｄ）、７．７６−７．７９（２Ｈ、ｍ） Reference production example 8-1
3-Phenyl-1H-pyrazol-1-ylmethanol

A mixture of 2.88 g of 3-phenyl-1H-pyrazole, 0.67 g of paraformaldehyde and 0.3 ml of triethylamine was stirred at 130 ° C. for 5 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. After filtering the mixture, hexane was added to the filtrate to produce crystals. The crystals were collected to obtain 2.64 g of 3-phenyl-1H-pyrazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.56 (2H, s), 6.58 (1H, d), 7.31-7.42 (3H, m), 7.59 (1H, d), 7.76-7.79 (2H, m)

３−フェニル−１Ｈ−ピラゾール−１−イルメタノール１．７４ｇをジクロロメタン５０ｍｌに溶解した。該溶液に塩化チオニル３．４ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮し、残渣にヘキサン及びクロロホルムを加えることにより結晶が生成した。この結晶を集めて、１−（クロロメチル）−３−フェニル−１Ｈ−ピラゾール塩酸塩２．０１ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：６．１５（２Ｈ，ｓ），６．７６（１Ｈ、ｄ）、７．３９−７．４９（３Ｈ、ｍ）、７．７６（１Ｈ、ｄ）、７．９０−７．９４（２Ｈ、ｍ） Reference Production Example 8-2
1- (Chloromethyl) -3-phenyl-1H-pyrazole hydrochloride

1.74 g of 3-phenyl-1H-pyrazol-1-ylmethanol was dissolved in 50 ml of dichloromethane. To the solution, 3.4 ml of thionyl chloride was added and stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure, and hexane and chloroform were added to the residue to produce crystals. The crystals were collected to obtain 2.01 g of 1- (chloromethyl) -3-phenyl-1H-pyrazole hydrochloride.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 6.15 (2H, s), 6.76 (1H, d), 7.39-7.49 (3H, m), 7.76 (1H, d), 7.90-7.94 (2H, m)

３−ｉ−プロピル−１Ｈ−ピラゾール１．１０ｇを水２０mlに懸濁させた後、ここに５０％水酸化ナトリウム水溶液１．６ｇを加えた。該混合物を０℃に冷却し、該混合物に臭素１．７６gを加え、室温で５時間攪拌した。反応混合物を酢酸エチルで抽出した。有機層を水で洗浄し、無水硫酸マグネシウムで乾燥後、ろ過し、減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィーに付し、４−ブロモ−３−ｉ−プロピル−１Ｈ−ピラゾール１．８８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））： １．３１（６Ｈ、ｄ）、３．０７−３．１８（１Ｈ、ｍ）、７．４９（１Ｈ、ｓ） Reference production example 9-1
4-Bromo-3-i-propyl-1H-pyrazole

After suspending 1.10 g of 3-i-propyl-1H-pyrazole in 20 ml of water, 1.6 g of 50% aqueous sodium hydroxide solution was added thereto. The mixture was cooled to 0 ° C., 1.76 g of bromine was added to the mixture, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 1.88 g of 4-bromo-3-i-propyl-1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.31 (6H, d), 3.07-3.18 (1H, m), 7.49 (1H, s)

４−ブロモ−３−ｉ−プロピル−１Ｈ−ピラゾール１．８８ｇ、パラホルムアルデヒド０．６０ｇ及びトリエチルアミン０．１０ｇの混合物を１３０℃で５時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。この混合物をろ過した後、ろ液を減圧下濃縮し、４−ブロモ−３−ｉ−プロピル−１Ｈ−ピラゾール−１−イルメタノール１．２９ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））： １．２６（６Ｈ、ｄ）、３．０２−３．１１（１Ｈ、ｍ）、５．４３（２Ｈ、ｓ）、７．５４（１Ｈ、ｓ） Reference Production Example 9-2
4-Bromo-3-i-propyl-1H-pyrazol-1-ylmethanol

A mixture of 1.88 g of 4-bromo-3-i-propyl-1H-pyrazole, 0.60 g of paraformaldehyde and 0.10 g of triethylamine was stirred at 130 ° C. for 5 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. After filtering this mixture, the filtrate was concentrated under reduced pressure to obtain 1.29 g of 4-bromo-3-i-propyl-1H-pyrazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.26 (6H, d), 3.02-3.11 (1H, m), 5.43 (2H, s), 7.54 (1H, s)

４−ブロモ−３−ｉ−プロピル−１Ｈ−ピラゾール−１−イルメタノール１．２９ｇをジクロロメタン２０ｍｌに溶解し、該溶液に塩化チオニル２ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮し、４−ブロモ−３−ｉ−プロピル−１−（クロロメチル）−１Ｈ−ピラゾール塩酸塩１．２８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．２９（６Ｈ、ｄ）、２．９９−３．１０（１Ｈ、ｍ）、５．７５（２Ｈ、ｓ）、７．５４（１Ｈ、ｓ） Reference production example 9-3
4-Bromo-3-i-propyl-1- (chloromethyl) -1H-pyrazole hydrochloride

4-Bromo-3-i-propyl-1H-pyrazol-1-ylmethanol (1.29 g) was dissolved in 20 ml of dichloromethane, 2 ml of thionyl chloride was added to the solution, and the mixture was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to obtain 1.28 g of 4-bromo-3-i-propyl-1- (chloromethyl) -1H-pyrazole hydrochloride.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.29 (6H, d), 2.99-3.10 (1H, m), 5.75 (2H, s), 7.54 (1H, s)

３−t−ブチル−１Ｈ−ピラゾール２．４８ｇを水３５mlに懸濁させた後、ここに５０％水酸化ナトリウム水溶液２．５ｇを加えた。該混合物を０℃に冷却し、該混合物に臭素３．５０gを加え、室温で７時間攪拌した。反応混合物を酢酸エチルで抽出した。有機層を水で洗浄し、無水硫酸マグネシウムで乾燥後、ろ過し、減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィーヘキサン−酢酸エチルに付し、４−ブロモ−３−t−ブチル−１Ｈ−ピラゾール３．１４を得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．４５（９Ｈ、ｓ）、７．４８（１Ｈ、ｓ） Reference Production Example 10-1
4-Bromo-3-t-butyl-1H-pyrazole

After suspending 2.48 g of 3-t-butyl-1H-pyrazole in 35 ml of water, 2.5 g of 50% aqueous sodium hydroxide solution was added thereto. The mixture was cooled to 0 ° C., 3.50 g of bromine was added to the mixture, and the mixture was stirred at room temperature for 7 hours. The reaction mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography hexane-ethyl acetate to obtain 4-bromo-3-tert-butyl-1H-pyrazole 3.14.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.45 (9H, s), 7.48 (1H, s)

４−ブロモ−３−t−ブチル−１Ｈ−ピラゾール３．１４ｇ、パラホルムアルデヒド０．９３ｇ及びトリエチルアミン０．１１ｇの混合物を１３０℃で７時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。その混合物をろ過した。ろ液を減圧下濃縮して得られた残渣にヘキサンを加えた結果、結晶が生じた。その結晶を集めることにより、４−ブロモ−３−t−ブチル−１Ｈ−ピラゾール−１−イルメタノール３．７９ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３７（９Ｈ、ｓ）、５．４０（２Ｈ、ｓ）、７．５５（１Ｈ、ｓ） Reference production example 10-2
4-Bromo-3-t-butyl-1H-pyrazol-1-ylmethanol

A mixture of 3.14 g of 4-bromo-3-tert-butyl-1H-pyrazole, 0.93 g of paraformaldehyde and 0.11 g of triethylamine was stirred at 130 ° C. for 7 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. The mixture was filtered. As a result of adding hexane to the residue obtained by concentrating the filtrate under reduced pressure, crystals were formed. The crystals were collected to obtain 3.79 g of 4-bromo-3-t-butyl-1H-pyrazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.37 (9H, s), 5.40 (2H, s), 7.55 (1H, s)

４−ブロモ−３−t−ブチル−１Ｈ−ピラゾール−１−メタノール３．７９ｇをジクロロメタン４５ｍｌに溶解した。該溶液に塩化チオニル３．４ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮した。生じた固体をヘキサンとクロロホルムとの混合物で洗浄して、４−ブロモ−３−t−ブチル−１−（クロロメチル）−１Ｈ−ピラゾール塩酸塩３．６９ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．４０（９Ｈ、ｓ）、５．７６（２Ｈ、ｓ）、７．５６（１Ｈ、ｓ） Reference production example 10-3
4-Bromo-3-t-butyl-1- (chloromethyl) -1H-pyrazole hydrochloride

4-Bromo-3-t-butyl-1H-pyrazole-1-methanol (3.79 g) was dissolved in dichloromethane (45 ml). To the solution, 3.4 ml of thionyl chloride was added and stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure. The resulting solid was washed with a mixture of hexane and chloroform to give 3.69 g of 4-bromo-3-tert-butyl-1- (chloromethyl) -1H-pyrazole hydrochloride.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.40 (9H, s), 5.76 (2H, s), 7.56 (1H, s)

３−t−ブチル−１Ｈ−ピラゾール１．４２ｇをクロロホルム２３０ｍｌに溶解した。該溶液にＮ−クロロコハク酸イミド１．５５ｇを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮し、残渣をシリカゲルカラムクロマトグラフィーに付し、３−t−ブチル−４−クロロ−１Ｈ−ピラゾール０．６２を得た。 Reference Production Example 11-1
3-t-butyl-4-chloro-1H-pyrazole

1.42 g of 3-t-butyl-1H-pyrazole was dissolved in 230 ml of chloroform. To this solution, 1.55 g of N-chlorosuccinimide was added and stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography to obtain 3-t-butyl-4-chloro-1H-pyrazole 0.62.

３−t−ブチル−４−クロロ−１Ｈ−ピラゾール０．６２ｇ、パラホルムアルデヒド０．２４ｇ及びトリエチルアミン０．１０ｇの混合物を１３０℃で７時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。その混合物をろ過した。ろ液を減圧下濃縮して得られた残渣にヘキサンを加えた結果、結晶が生成した。その結晶を集めることにより、３−t−ブチル−４−クロロ−１Ｈ−ピラゾール−１−イルメタノール０．８２ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３８（９Ｈ、ｓ）、５．３９（２Ｈ、ｓ）、７．５１（１Ｈ、ｓ） Reference Production Example 11-2
3-t-butyl-4-chloro-1H-pyrazol-1-ylmethanol

A mixture of 0.62 g of 3-t-butyl-4-chloro-1H-pyrazole, 0.24 g of paraformaldehyde and 0.10 g of triethylamine was stirred at 130 ° C. for 7 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. The mixture was filtered. As a result of adding hexane to the residue obtained by concentrating the filtrate under reduced pressure, crystals were formed. By collecting the crystals, 0.82 g of 3-t-butyl-4-chloro-1H-pyrazol-1-ylmethanol was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.38 (9H, s), 5.39 (2H, s), 7.51 (1H, s)

３−t−ブチル−４−クロロ−１Ｈ−４−クロロ−ピラゾール−１−イルメタノール０．８２ｇをジクロロメタン４５ｍｌに溶解した。、該溶液に塩化チオニル３．４ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮し、３−t−ブチル−４−クロロ−１−（クロロメチル）−１Ｈ−ピラゾール塩酸塩０．９８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３９（９Ｈ、ｓ）、５．７５（２Ｈ、ｓ）、７．５２（１Ｈ、ｓ） Reference production example 11-3
3-t-butyl-4-chloro-1- (chloromethyl) -1H-pyrazole hydrochloride

0.82 g of 3-t-butyl-4-chloro-1H-4-chloro-pyrazol-1-ylmethanol was dissolved in 45 ml of dichloromethane. To the solution, 3.4 ml of thionyl chloride was added and stirred at room temperature overnight. The reaction mixture was concentrated under reduced pressure to obtain 0.98 g of 3-t-butyl-4-chloro-1- (chloromethyl) -1H-pyrazole hydrochloride.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.39 (9H, s), 5.75 (2H, s), 7.52 (1H, s)

３−（トリフルオロメチル）−１Ｈ−ピラゾール３．５０ｇを水４５mlに懸濁させた後、ここに５０％水酸化ナトリウム水溶液３．２ｇを加えた。該混合物を０℃に冷却し、該混合物に臭素３．２０gを加え、室温で７時間攪拌した。反応混合物を酢酸エチルで抽出した。有機層を水で洗浄し、無水硫酸マグネシウムで乾燥後、ろ過し、減圧下濃縮した。残渣にヘキサンを加えた結果、結晶が生成した。その結晶を集めて、４−ブロモ−３−（トリフルオロメチル）−１Ｈ−ピラゾール３．３８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：７．７２（１Ｈ、ｓ） Reference Production Example 12-1
4-Bromo-3- (trifluoromethyl) -1H-pyrazole

After suspending 3.50 g of 3- (trifluoromethyl) -1H-pyrazole in 45 ml of water, 3.2 g of a 50% aqueous sodium hydroxide solution was added thereto. The mixture was cooled to 0 ° C., 3.20 g of bromine was added to the mixture, and the mixture was stirred at room temperature for 7 hours. The reaction mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. As a result of adding hexane to the residue, crystals were formed. The crystals were collected to obtain 3.38 g of 4-bromo-3- (trifluoromethyl) -1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 7.72 (1H, s)

４−ブロモ−３−（トリフルオロメチル）−１Ｈ−ピラゾール３．３８ｇ及びパラホルムアルデヒド０．６６ｇの混合物を１４０℃で５時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。その混合物をろ過した。ろ液を減圧下濃縮して得られた残渣にヘキサンを加えた結果、結晶が生成した。その結晶を集めて、４−ブロモ−３−（トリフルオロメチル）−１Ｈ−ピラゾール−１−イルメタノール３．２８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．５２（２Ｈ、ｓ）、７．７１（１Ｈ、ｓ） Reference Production Example 12-2
4-Bromo-3- (trifluoromethyl) -1H-pyrazol-1-ylmethanol

A mixture of 3.38 g of 4-bromo-3- (trifluoromethyl) -1H-pyrazole and 0.66 g of paraformaldehyde was stirred at 140 ° C. for 5 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. The mixture was filtered. As a result of adding hexane to the residue obtained by concentrating the filtrate under reduced pressure, crystals were formed. The crystals were collected to obtain 3.28 g of 4-bromo-3- (trifluoromethyl) -1H-pyrazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.52 (2H, s), 7.71 (1H, s)

４−ブロモ−３−（トリフルオロメチル）−１Ｈ−ピラゾール−１−イルメタノール３．２８ｇをジクロロメタン４０ｍｌに溶解した。該溶液に塩化チオニル２．９ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮した。生じた固体をヘキサンとクロロホルムとの混合物で洗浄して、４−ブロモ−１−（クロロメチル）−３−（トリフルオロメチル）−１Ｈ−ピラゾール３．３３ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．８２（２Ｈ、ｓ）、７．７４（１Ｈ、ｓ） Reference Production Example 12-3
4-Bromo-1- (chloromethyl) -3- (trifluoromethyl) -1H-pyrazole

4-Bromo-3- (trifluoromethyl) -1H-pyrazol-1-ylmethanol (3.28 g) was dissolved in dichloromethane (40 ml). 2.9 ml of thionyl chloride was added to the solution and stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure. The resulting solid was washed with a mixture of hexane and chloroform to give 3.33 g of 4-bromo-1- (chloromethyl) -3- (trifluoromethyl) -1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.82 (2H, s), 7.74 (1H, s)

３，５−ジメチル−１Ｈ−ピラゾール−１−イルメタノール０．６３ｇをジクロロメタン２５ｍｌに溶解した。該溶液に塩化チオニル１．２ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮し、１−（クロロメチル）−３，５−ジメチルピラゾール塩酸塩０．９３ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．４９（３Ｈ、ｓ）、２．５０（３Ｈ、ｓ）、６．２０（３Ｈ、ｓ） Reference production example 13
1- (Chloromethyl) -3,5-dimethylpyrazole hydrochloride

0.63 g of 3,5-dimethyl-1H-pyrazol-1-ylmethanol was dissolved in 25 ml of dichloromethane. To the solution, 1.2 ml of thionyl chloride was added and stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to obtain 0.93 g of 1- (chloromethyl) -3,5-dimethylpyrazole hydrochloride.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.49 (3H, s), 2.50 (3H, s), 6.20 (3H, s)

４−メチル−１Ｈ−ピラゾール１．９３ｇ、パラホルムアルデヒド０．９７ｇ及びトリエチルアミン０．４ｍｌの混合物を１３０℃で５時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。その混合物をろ過した。ろ液を減圧下濃縮して得られた残渣にヘキサンを加えた結果、結晶が生成した。その結晶を集めることにより、４−メチル−１Ｈ−ピラゾール−１−イルメタノール１．７２ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：２．０８（３Ｈ、ｓ）、５．４３（２Ｈ、ｓ）、７．３６（２Ｈ、ｓ） Reference Production Example 14-1
4-Methyl-1H-pyrazol-1-ylmethanol

A mixture of 1.93 g of 4-methyl-1H-pyrazole, 0.97 g of paraformaldehyde and 0.4 ml of triethylamine was stirred at 130 ° C. for 5 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. The mixture was filtered. As a result of adding hexane to the residue obtained by concentrating the filtrate under reduced pressure, crystals were formed. By collecting the crystals, 1.72 g of 4-methyl-1H-pyrazol-1-ylmethanol was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.08 (3H, s), 5.43 (2H, s), 7.36 (2H, s)

４−メチル−１Ｈ−ピラゾール−１−イルメタノール１．１２ｇをジクロロメタン５０ｍｌに溶解した。該溶液に塩化チオニル３．４ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮し、１−（クロロメチル）−４−メチル−１Ｈ−ピラゾール塩酸塩１．６１ｇを得た。 Reference Production Example 14-2
1- (Chloromethyl) -4-methyl-1H-pyrazole hydrochloride

4-methyl-1H-pyrazol-1-ylmethanol 1.12 g was dissolved in 50 ml of dichloromethane. To the solution, 3.4 ml of thionyl chloride was added and stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to obtain 1.61 g of 1- (chloromethyl) -4-methyl-1H-pyrazole hydrochloride.

４−クロロピラゾール２．０５ｇ、パラホルムアルデヒド０．６６ｇ及びトリエチルアミン０．１１ｇの混合物を１３０℃で５時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。その混合物をろ過した。ろ液を減圧下濃縮して得られた残渣にヘキサンを加えた結果、結晶が生成した。その結晶を集めることにより、４−クロロ−１Ｈ−ピラゾール−１−イルメタノール２．７３ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．４５（２Ｈ、ｓ）、７．４９（１Ｈ、ｓ）、７．６０（１Ｈ，ｓ） Reference Production Example 15-1
4-Chloro-1H-pyrazol-1-ylmethanol

A mixture of 2.05 g of 4-chloropyrazole, 0.66 g of paraformaldehyde and 0.11 g of triethylamine was stirred at 130 ° C. for 5 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. The mixture was filtered. As a result of adding hexane to the residue obtained by concentrating the filtrate under reduced pressure, crystals were formed. The crystals were collected to obtain 2.73 g of 4-chloro-1H-pyrazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.45 (2H, s), 7.49 (1H, s), 7.60 (1H, s)

４−クロロ−１Ｈ−ピラゾール−１−イルメタノール２．７３ｇをジクロロメタン２０ｍｌに溶解した。該溶液に塩化チオニル４．４ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮し、４−クロロ−１−（クロロメチル）−１Ｈ−ピラゾール塩酸塩２．９０ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．８１（２Ｈ、ｓ）、７．５３（１Ｈ、ｓ）、７．６０（１Ｈ、ｓ） Reference Production Example 15-2
4-Chloro-1- (chloromethyl) -1H-pyrazole hydrochloride

4-Chloro-1H-pyrazol-1-ylmethanol (2.73 g) was dissolved in dichloromethane (20 ml). To the solution, 4.4 ml of thionyl chloride was added and stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to obtain 2.90 g of 4-chloro-1- (chloromethyl) -1H-pyrazole hydrochloride.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.81 (2H, s), 7.53 (1H, s), 7.60 (1H, s)

４−ブロモ−１Ｈ−ピラゾール２．９４ｇ、パラホルムアルデヒド０．６６ｇ及びトリエチルアミン０．３ｍｌの混合物を１３０℃で4時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。この混合物をろ過した。ろ液を減圧下濃縮して得られた残渣にヘキサンを加えた結果、結晶が生成した。その結晶を集めることにより、４−ブロモ−１Ｈ−ピラゾール−１−イルメタノール２．９７ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．４６（２Ｈ、ｓ）、７．５３（１Ｈ、ｓ）、７．６３（１Ｈ、ｓ） Reference Production Example 16-1
4-Bromo-1H-pyrazol-1-ylmethanol

A mixture of 2.94 g of 4-bromo-1H-pyrazole, 0.66 g of paraformaldehyde and 0.3 ml of triethylamine was stirred at 130 ° C. for 4 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. This mixture was filtered. As a result of adding hexane to the residue obtained by concentrating the filtrate under reduced pressure, crystals were formed. The crystals were collected to obtain 2.97 g of 4-bromo-1H-pyrazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.46 (2H, s), 7.53 (1H, s), 7.63 (1H, s)

４−ブロモ−１Ｈ−ピラゾール−１−イルメタノール２．９７ｇをジクロロメタン１００ｍｌに溶解した。該溶液に塩化チオニル５ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮し、４−ブロモ−１−（クロロメチル）−１Ｈ−ピラゾール塩酸塩（３．２７ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．８３（２Ｈ、ｓ）、７．５７（１Ｈ、ｓ）、７．６３（１Ｈ、ｓ） Reference Production Example 16-2
4-Bromo-1- (chloromethyl) -1H-pyrazole hydrochloride

4-Bromo-1H-pyrazol-1-ylmethanol 2.97 g was dissolved in 100 ml of dichloromethane. To the solution was added 5 ml of thionyl chloride, and the mixture was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to obtain 4-bromo-1- (chloromethyl) -1H-pyrazole hydrochloride (3.27 g).
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.83 (2H, s), 7.57 (1H, s), 7.63 (1H, s)

上記化合物はTetrahedron Letters，p．１８２９（１９９６）に記載の方法にて製造した。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：７．８５（２Ｈ、ｓ） Reference Production Example 17-1
4- (Trifluoromethyl) -1H-pyrazole

The above compounds are described in Tetrahedron Letters, p. 1829 (1996).
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 7.85 (2H, s)

４−（トリフルオロメチル）−１Ｈ−ピラゾール０．５９ｇ及びパラホルムアルデヒド０．２６ｇの混合物を１３０℃で4時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。この混合物をろ過した。減圧下濃縮し、４−（トリフルオロメチル）−１Ｈ−ピラゾール−１−イルメタノール０．６０ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．５８（２Ｈ、ｓ）、７．７７（１Ｈ、ｓ）、７．９０（１Ｈ、ｓ） Reference Production Example 17-2
4- (Trifluoromethyl) -1H-pyrazol-1-ylmethanol

A mixture of 0.59 g of 4- (trifluoromethyl) -1H-pyrazole and 0.26 g of paraformaldehyde was stirred at 130 ° C. for 4 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. This mixture was filtered. Concentration under reduced pressure gave 0.60 g of 4- (trifluoromethyl) -1H-pyrazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.58 (2H, s), 7.77 (1H, s), 7.90 (1H, s)

４−（トリフルオロメチル）−１Ｈ−ピラゾール−１−イルメタノール０．６０ｇをジクロロメタン１０ｍｌに溶解し、該溶液に塩化チオニル１ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮し、１−（クロロメチル）−４−（トリフルオロメチル）−１Ｈ−ピラゾール０．６０ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．８９（２Ｈ、ｓ）、７．８０（１Ｈ、ｓ）、７．９１（１Ｈ、ｓ） Reference Production Example 17-3
1- (Chloromethyl) -4- (trifluoromethyl) -1H-pyrazole

0.60 g of 4- (trifluoromethyl) -1H-pyrazol-1-ylmethanol was dissolved in 10 ml of dichloromethane, 1 ml of thionyl chloride was added to the solution, and the mixture was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to obtain 0.60 g of 1- (chloromethyl) -4- (trifluoromethyl) -1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.89 (2H, s), 7.80 (1H, s), 7.91 (1H, s)

３，３−ジメトキシプロピオン酸メチル４４．４５ｇ及びギ酸メチル４５ｍｌをジメトキシエタン１８０ｍｌに溶解し、窒素雰囲気下、該溶液に６０％水素化ナトリウム１２．８ｇを、その間、該溶液の温度を４０〜５０℃に保ちながらを加えた。さらに該混合物を室温で１８時間攪拌した。反応混合物にジエチルエーテル１８０ｍｌを加えた結果、固体が生成した。その固体をろ過により集め、ジエチルエーテル６０ｍｌで洗浄した。得られた固体を減圧下、一晩乾燥し、２−（ジメトキシメチル）−３−ヒドロキシ−アクリル酸メチルナトリウム塩４９．４１ｇを得た。２−（ジメトキシメチル）−３−ヒドロキシアクリル酸メチルナトリウム塩９．９１ｇをエタノール１００ｍｌに懸濁した。該懸濁液にヒドラジン・一水和物２．５０ｇを加え、室温で３時間、８０℃で１時間攪拌した。室温まで冷却した反応混合液に、水１００ｍｌを加えた。該混合液を減圧下１００mlまで濃縮した。濃縮物を酢酸エチルで抽出した。有機層を、飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥した後、ろ過し、減圧下濃縮した。残渣を酢酸エチルに溶解し、この溶液に活性炭を加え、一晩攪拌した。この懸濁液をろ過し、ろ液を減圧下濃縮した。残渣をヘキサン−酢酸エチルから再結晶し、４−メトキシカルボニル−１Ｈ−ピラゾール１．４０ｇを得た。
¹Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ₆、ＴＭＳ、δ（ｐｐｍ））：３．７４（３Ｈ、ｓ）、８．０８（２Ｈ、ｓ）、１３．４３（１Ｈ、ｓ） Reference Production Example 18-1
4-methoxycarbonyl-1H-pyrazole

44.45 g of methyl 3,3-dimethoxypropionate and 45 ml of methyl formate are dissolved in 180 ml of dimethoxyethane, and 12.8 g of 60% sodium hydride is added to the solution under a nitrogen atmosphere. While keeping at ℃. The mixture was further stirred at room temperature for 18 hours. As a result of adding 180 ml of diethyl ether to the reaction mixture, a solid was formed. The solid was collected by filtration and washed with 60 ml of diethyl ether. The obtained solid was dried overnight under reduced pressure to obtain 49.41 g of 2- (dimethoxymethyl) -3-hydroxy-acrylic acid methyl sodium salt. 9.91 g of methyl 2- (dimethoxymethyl) -3-hydroxyacrylate was suspended in 100 ml of ethanol. To the suspension was added 2.50 g of hydrazine monohydrate, and the mixture was stirred at room temperature for 3 hours and at 80 ° C. for 1 hour. To the reaction mixture cooled to room temperature, 100 ml of water was added. The mixture was concentrated to 100 ml under reduced pressure. The concentrate was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was dissolved in ethyl acetate, activated carbon was added to this solution, and the mixture was stirred overnight. This suspension was filtered, and the filtrate was concentrated under reduced pressure. The residue was recrystallized from hexane-ethyl acetate to obtain 1.40 g of 4-methoxycarbonyl-1H-pyrazole.
¹ H-NMR (DMSO-d ₆ , TMS, δ (ppm)): 3.74 (3H, s), 8.08 (2H, s), 13.43 (1H, s)

４−メトキシカルボニル−１Ｈ−ピラゾール１．４０ｇ、パラホルムアルデヒド０．３７ｇ及びトリエチルアミン０．１１ｇの混合物を１３０℃で１時間攪拌した。この混合物にパラホルムアルデヒド０．７４ｇ及びトリエチルアミン２ｍｌを追加し、１３０℃で２時間攪拌した。反応混合物を室温まで冷却後、アセトンを加えた。この混合物をろ過した後、ろ液を減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィーに付し、１−（ヒドロキシメチル）−４−メトキシカルボニル−１Ｈ−ピラゾール１．３８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：３．８４（３Ｈ、ｓ）、５．５３（２Ｈ、ｓ）、７．９６（１Ｈ、ｓ）、８．０８（１Ｈ、ｓ） Reference Production Example 18-2
1- (hydroxymethyl) -4-methoxycarbonyl-1H-pyrazole

A mixture of 1.40 g of 4-methoxycarbonyl-1H-pyrazole, 0.37 g of paraformaldehyde and 0.11 g of triethylamine was stirred at 130 ° C. for 1 hour. To this mixture, 0.74 g of paraformaldehyde and 2 ml of triethylamine were added, and the mixture was stirred at 130 ° C. for 2 hours. After the reaction mixture was cooled to room temperature, acetone was added. After the mixture was filtered, the filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 1.38 g of 1- (hydroxymethyl) -4-methoxycarbonyl-1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 3.84 (3H, s), 5.53 (2H, s), 7.96 (1H, s), 8.08 (1H, s )

１−（ヒドロキシメチル）−４−メトキシカルボニル−１Ｈ−ピラゾール１．３８ｇをジクロロメタン１０ｍｌに溶解し、該溶液に塩化チオニル１ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮し、１−（クロロメチル）−４−メトキシカルボニル−１Ｈ−ピラゾール１．５９ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：３．８５（３Ｈ、ｓ）、５．８５（２Ｈ、ｓ）、７．９８（１Ｈ、ｓ）、８．１０（１Ｈ、ｓ） Reference Production Example 18-3
1- (Chloromethyl) -4-methoxycarbonyl-1H-pyrazole

1.38 g of 1- (hydroxymethyl) -4-methoxycarbonyl-1H-pyrazole was dissolved in 10 ml of dichloromethane, 1 ml of thionyl chloride was added to the solution, and the mixture was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to obtain 1.59 g of 1- (chloromethyl) -4-methoxycarbonyl-1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 3.85 (3H, s), 5.85 (2H, s), 7.98 (1H, s), 8.10 (1H, s )

３−（トリフルオロメチル）−４−エトキシカルボニル−１Ｈ−ピラゾール２．０８ｇ及びパラホルムアルデヒド０．６６ｇの混合物を１５０℃で４時間攪拌した。反応混合物を室温まで冷却後、アセトンを加えた。この混合物をろ過した後、ろ液を減圧下濃縮し、１−（ヒドロキシメチル）−３−（トリフルオロメチル）−４−エトキシカルボニル−１Ｈ−ピラゾール２．２３ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３４（３Ｈ、ｔ）、４．３０（２Ｈ、ｑ）、５．５８（２Ｈ、ｓ）、８．２１（１Ｈ、ｓ） Reference Production Example 19-1
1- (Hydroxymethyl) -3- (trifluoromethyl) -4-ethoxycarbonyl-1H-pyrazole

A mixture of 2.08 g of 3- (trifluoromethyl) -4-ethoxycarbonyl-1H-pyrazole and 0.66 g of paraformaldehyde was stirred at 150 ° C. for 4 hours. After the reaction mixture was cooled to room temperature, acetone was added. After filtering this mixture, the filtrate was concentrated under reduced pressure to obtain 2.23 g of 1- (hydroxymethyl) -3- (trifluoromethyl) -4-ethoxycarbonyl-1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.34 (3H, t), 4.30 (2H, q), 5.58 (2H, s), 8.21 (1H, s )

１−（ヒドロキシメチル）−３−（トリフルオロメチル）−４−エトキシカルボニル−１Ｈ−ピラゾール２．２３ｇをジクロロメタン３０ｍｌに溶解し、該溶液に塩化チオニル１．４ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮し、１−（クロロメチル）−３−（トリフルオロメチル）−４−エトキシカルボニル−１Ｈ−ピラゾール２．３８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３１（３Ｈ、ｔ）、４．３１（２Ｈ、ｑ）、５．８５（２Ｈ、ｓ）、８．２０（１Ｈ、ｓ） Reference Production Example 19-2
1- (Chloromethyl) -3- (trifluoromethyl) -4-ethoxycarbonyl-1H-pyrazole

1- (Hydroxymethyl) -3- (trifluoromethyl) -4-ethoxycarbonyl-1H-pyrazole (2.23 g) was dissolved in 30 ml of dichloromethane, 1.4 ml of thionyl chloride was added to the solution, and the mixture was stirred overnight at room temperature. . The reaction mixture was concentrated under reduced pressure to obtain 2.38 g of 1- (chloromethyl) -3- (trifluoromethyl) -4-ethoxycarbonyl-1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.31 (3H, t), 4.31 (2H, q), 5.85 (2H, s), 8.20 (1H, s )

上記化合物は特開昭５７−１６５３７４号に記載の方法にて製造した。
¹Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ₆、ＴＭＳ、δ（ｐｐｍ））：６．２６（２Ｈ、ｓ）、８．１６（１Ｈ、ｓ）、８．８５（１Ｈ、ｓ） Reference Production Example 20
1-chloromethyl-1H-1,2,4-triazole hydrochloride

The above compound was produced by the method described in JP-A-57-165374.
¹ H-NMR (DMSO-d ₆ , TMS, δ (ppm)): 6.26 (2H, s), 8.16 (1H, s), 8.85 (1H, s)

上記化合物は特開平６−８７８３９号に記載の方法に準じて製造した。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３９（６Ｈ、ｄ）、３．１４−３．７４（１Ｈ、ｍ）、７．９９（１Ｈ、ｓ） Reference Production Example 21-1
3-i-propyl-1H-1,2,4-triazole

The above compound was produced according to the method described in JP-A-6-87839.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.39 (6H, d), 3.14-3.74 (1H, m), 7.9 (1H, s)

３−ｉ−プロピル−１Ｈ−１，２，４−トリアゾール１．１５ｇ、パラホルムアルデヒド０．９４ｇ及びトリエチルアミン０．１４ｇの混合物を１５０℃で５時間攪拌した。反応混合物を室温まで冷却後、アセトンを加えた。この混合物をろ過した。ろ液を減圧下濃縮した。得られた残渣にヘキサンを加えた結果、結晶が生成した。結晶を集めることにより、３−ｉ−プロピル−１Ｈ−トリアゾール−１−イルメタノール１．２８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３２（６Ｈ、ｄ）、３．０４−３．１２（１Ｈ、ｍ）、５．５４（２Ｈ、ｓ）、８．１４（１Ｈ、ｓ） Reference Production Example 21-2
3-i-propyl-1H-1,2,4-triazol-1-ylmethanol

A mixture of 1.15 g of 3-i-propyl-1H-1,2,4-triazole, 0.94 g of paraformaldehyde and 0.14 g of triethylamine was stirred at 150 ° C. for 5 hours. After the reaction mixture was cooled to room temperature, acetone was added. This mixture was filtered. The filtrate was concentrated under reduced pressure. As a result of adding hexane to the obtained residue, crystals were formed. By collecting the crystals, 1.28 g of 3-i-propyl-1H-triazol-1-ylmethanol was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.32 (6H, d), 3.04-3.12 (1H, m), 5.54 (2H, s), 8.14 (1H, s)

３−ｉ−プロピル−１Ｈ−１，２，４−トリアゾール−１−イルメタノール１．２８ｇをジクロロメタン２０ｍｌに溶解し、該溶液に塩化チオニル２ｍｌを加え、室温で８時間攪拌した。反応混合物を減圧下濃縮した。残渣にジエチルエーテルを加えた結果、結晶が生成した。その結晶を集めることにより、１−（クロロメチル）−３−ｉ−プロピル−１Ｈ−１，２，４−トリアゾール塩酸塩１．５８ｇを得た。 Reference Production Example 21-3
1- (Chloromethyl) -3-i-propyl-1H-1,2,4-triazole hydrochloride

1.28 g of 3-i-propyl-1H-1,2,4-triazol-1-ylmethanol was dissolved in 20 ml of dichloromethane, 2 ml of thionyl chloride was added to the solution, and the mixture was stirred at room temperature for 8 hours. The reaction mixture was concentrated under reduced pressure. As a result of adding diethyl ether to the residue, crystals were formed. The crystals were collected to give 1.58 g of 1- (chloromethyl) -3-i-propyl-1H-1,2,4-triazole hydrochloride.

上記化合物は特開平６−８７８３９号に記載の方法にて製造した。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．４５（９Ｈ、ｓ）、８．２５（１Ｈ、ｓ） Reference Production Example 22-1
3-t-butyl-1H-1,2,4-triazole

The above compound was produced by the method described in JP-A-6-87839.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.45 (9H, s), 8.25 (1H, s)

３−ｔ−ブチル−１Ｈ−１，２，４−トリアゾール３．７６ｇ、パラホルムアルデヒド１．００ｇ及びトリエチルアミン０．３ｍｌの混合物を１５０℃で５時間攪拌した。反応混合物を室温まで冷却後、アセトンを加えた。この混合物をろ過した。ろ液を減圧下濃縮した。残渣にヘキサンを加えた結果、結晶が生成した。その結晶を集めることにより、３−ｔ−ブチル−１Ｈ−トリアゾール−１−イルメタノール１．３８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３７（９Ｈ、ｓ）、１．８１（１Ｈ、ｂｒ．ｓ）、５．５５（２Ｈ、ｓ）、８．１６（１Ｈ，ｓ） Reference Production Example 22-2
3-t-butyl-1H-1,2,4-triazol-1-ylmethanol

A mixture of 3-t-butyl-1H-1,2,4-triazole (3.76 g), paraformaldehyde (1.00 g) and triethylamine (0.3 ml) was stirred at 150 ° C. for 5 hours. After the reaction mixture was cooled to room temperature, acetone was added. This mixture was filtered. The filtrate was concentrated under reduced pressure. As a result of adding hexane to the residue, crystals were formed. By collecting the crystals, 1.38 g of 3-t-butyl-1H-triazol-1-ylmethanol was obtained.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.37 (9H, s), 1.81 (1H, br.s), 5.55 (2H, s), 8.16 (1H , S)

３−ｔ−ブチル−１Ｈ−１，２，４−トリアゾール−１−イルメタノール１．３８ｇと塩化チオニル２．７ｍｌとの混合物を加熱還流下３時間攪拌した。反応混合物を室温まで冷却した後、反応混合物を減圧下濃縮した。残渣をヘキサンから再結晶することで、３−ｔ−ブチル−１−（クロロメチル）−１Ｈ−１，２，４−トリアゾール塩酸塩１．７２ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３６（９Ｈ、ｓ）、５．８３（２Ｈ，ｓ）、８．１７（１Ｈ、ｓ） Reference Production Example 22-3
3-t-butyl-1- (chloromethyl) -1H-1,2,4-triazole hydrochloride

A mixture of 1.38 g of 3-t-butyl-1H-1,2,4-triazol-1-ylmethanol and 2.7 ml of thionyl chloride was stirred with heating under reflux for 3 hours. After the reaction mixture was cooled to room temperature, the reaction mixture was concentrated under reduced pressure. The residue was recrystallized from hexane to obtain 1.72 g of 3-t-butyl-1- (chloromethyl) -1H-1,2,4-triazole hydrochloride.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.36 (9H, s), 5.83 (2H, s), 8.17 (1H, s)

上記化合物は特開平６−８７８３９号に記載の方法に準じて製造した。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：０．７７（３Ｈ、ｔ）、１．４０（６Ｈ、ｓ）１．７４（２Ｈ、ｑ）、７．９８（１Ｈ、ｓ） Reference Production Example 23-1
3- (1,1-Dimethylpropyl) -1H-1,2,4-triazole

The above compound was produced according to the method described in JP-A-6-87839.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 0.77 (3H, t), 1.40 (6H, s) 1.74 (2H, q), 7.98 (1H, s)

３−（１，１−ジメチルプロピル）−１Ｈ−１，２，４−トリアゾール０．８６ｇ、パラホルムアルデヒド０．３７ｇ及びトリエチルアミン０．６３ｇの混合物を１５０℃で５時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。この混合物をろ過した。ろ液を減圧下濃縮し、３−（１、１−ジメチルプロピル）−１Ｈ−トリアゾール−１−イルメタノール１．１０ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：０．７３（３Ｈ、ｔ）、１．３３（６Ｈ、ｓ）、１．７１（２Ｈ、ｑ）、５．５４（２Ｈ、ｓ）、８．１６（１Ｈ、ｓ） Reference Production Example 23-2
3- (1,1-Dimethylpropyl) -1H-1,2,4-triazol-1-ylmethanol

A mixture of 0.86 g of 3- (1,1-dimethylpropyl) -1H-1,2,4-triazole, 0.37 g of paraformaldehyde and 0.63 g of triethylamine was stirred at 150 ° C. for 5 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. This mixture was filtered. The filtrate was concentrated under reduced pressure to obtain 1.10 g of 3- (1,1-dimethylpropyl) -1H-triazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 0.73 (3H, t), 1.33 (6H, s), 1.71 (2H, q), 5.54 (2H, s ), 8.16 (1H, s)

３−（１，１−ジメチルプロピル）−１Ｈ−１，２，４−トリアゾール−１−イルメタノール１．１０ｇをジクロロメタン１８ｍｌに溶解した。該溶液に塩化チオニル１．８ｍｌを加え、室温で８時間攪拌した。反応混合物を減圧下濃縮し、１−（クロロメチル）−３−（１、１−ジメチルプロピル）−１Ｈ−１，２，４−トリアゾール塩酸塩１．４７ｇを得た。 Reference Production Example 23-3
1- (Chloromethyl) -3- (1,1-dimethylpropyl) -1H-1,2,4-triazole hydrochloride

1.10 g of 3- (1,1-dimethylpropyl) -1H-1,2,4-triazol-1-ylmethanol was dissolved in 18 ml of dichloromethane. To the solution, 1.8 ml of thionyl chloride was added and stirred at room temperature for 8 hours. The reaction mixture was concentrated under reduced pressure to obtain 1.47 g of 1- (chloromethyl) -3- (1,1-dimethylpropyl) -1H-1,2,4-triazole hydrochloride.

３−ｔ−ブチル−１Ｈ−１，２，４−トリアゾール２．５１ｇ、水３５ｍｌ及び５０％水酸化ナトリウム２．５ｍｌの混合物を０℃に冷却し、ここに臭素３．５ｇを加えた。室温で３時間攪拌した。反応混合物を酢酸エチルで抽出し、無水硫酸ナトリウムで乾燥し、減圧下濃縮した。残渣をヘキサンから再結晶し、５−ブロモ−３−ｔ−ブチル−１Ｈ−１，２，４−トリアゾール３．８０ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．４１（９Ｈ、ｓ）、１１．６０（１Ｈ、ｂｒ．ｓ） Reference Production Example 24-1
5-Bromo-3-tert-butyl-1H-1,2,4-triazole

A mixture of 2.51 g of 3-t-butyl-1H-1,2,4-triazole, 35 ml of water and 2.5 ml of 50% sodium hydroxide was cooled to 0 ° C., and 3.5 g of bromine was added thereto. Stir at room temperature for 3 hours. The reaction mixture was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was recrystallized from hexane to obtain 3.80 g of 5-bromo-3-t-butyl-1H-1,2,4-triazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.41 (9H, s), 11.60 (1H, br.s)

５−ブロモ−３−ｔ−ブチル−１Ｈ−１，２，４−トリアゾール３．４５ｇ、パラホルムアルデヒド０．６１ｇ及びトリエチルアミン０．１７ｇの混合物を１３０℃で５時間攪拌した。反応混合物を室温まで冷却後、アセトンを加えた。この混合物をろ過した。残渣にヘキサンを加え、ろ過した。ろ液を減圧下濃縮し、５−ブロモ−３−ｔ−ブチル−１Ｈ−１，２，４−トリアゾール−１−イルメタノール２．８８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３４（９Ｈ、ｓ）、５．５５（２Ｈ、ｓ） Reference Production Example 24-2
5-Bromo-3-tert-butyl-1H-1,2,4-triazol-1-ylmethanol

A mixture of 3.45 g of 5-bromo-3-tert-butyl-1H-1,2,4-triazole, 0.61 g of paraformaldehyde and 0.17 g of triethylamine was stirred at 130 ° C. for 5 hours. After the reaction mixture was cooled to room temperature, acetone was added. This mixture was filtered. Hexane was added to the residue and filtered. The filtrate was concentrated under reduced pressure to obtain 2.88 g of 5-bromo-3-t-butyl-1H-1,2,4-triazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.34 (9H, s), 5.55 (2H, s)

５−ブロモ−３−ｔ−ブチル−１Ｈ−１，２，４−トリアゾール−１−イルメタノール２．８８ｇをジクロロメタン１００ｍｌに溶解し、該溶液に塩化チオニル４．２ｍｌを加え、室温で３時間攪拌した。反応混合物を減圧下濃縮した。残渣にクロロホルムを加え、ろ過した。ろ液を減圧下濃縮し、５−ブロモ−３−ｔ−ブチル−１−（クロロメチル）−１Ｈ−１，２，４−トリアゾール塩酸塩２．０３ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３５（９Ｈ、ｓ）、５．７９（２Ｈ、ｓ） Reference Production Example 24-3
5-Bromo-3-tert-butyl-1- (chloromethyl) -1H-1,2,4-triazole hydrochloride

Dissolve 2.88 g of 5-bromo-3-tert-butyl-1H-1,2,4-triazol-1-ylmethanol in 100 ml of dichloromethane, add 4.2 ml of thionyl chloride to the solution, and stir at room temperature for 3 hours. did. The reaction mixture was concentrated under reduced pressure. Chloroform was added to the residue and filtered. The filtrate was concentrated under reduced pressure to obtain 2.03 g of 5-bromo-3-t-butyl-1- (chloromethyl) -1H-1,2,4-triazole hydrochloride.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.35 (9H, s), 5.79 (2H, s)

ヒドラジン一水和物４．７６ｇをエタノール１６０ｍｌに溶解し、０℃に冷却した。ここに２，２，２−トリフルオロ酢酸エチル１４．２１ｇを３０分間かけて滴下し、０℃で１時間攪拌した。反応混合物にホルムアミジン酢酸塩９．８９ｇを加え、室温で３０分間攪拌した。反応混合物を減圧下濃縮した。残渣に酢酸２００ｍｌを加え、１００℃で５時間攪拌した。室温まで冷却した反応混合物を減圧下濃縮した。残渣に飽和炭酸水素ナトリウム水溶液を加え、ｐＨ６とした後、酢酸エチルで抽出した。有機層を無水硫酸ナトリウムで乾燥し、減圧下濃縮した。残渣をヘキサンから再結晶し、３−（トリフルオロメチル）−１Ｈ−１，２，４−トリアゾール５．４４ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：８．４５（１Ｈ、ｓ）、１２．４７（１Ｈ、ｂｒ．ｓ） Reference Production Example 25-1
3- (Trifluoromethyl) -1H-1,2,4-triazole

4.76 g of hydrazine monohydrate was dissolved in 160 ml of ethanol and cooled to 0 ° C. 14.21 g of 2,2,2-trifluoroacetic acid ethyl was dripped here over 30 minutes, and it stirred at 0 degreeC for 1 hour. 9.89 g of formamidine acetate was added to the reaction mixture, and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was concentrated under reduced pressure. To the residue, 200 ml of acetic acid was added and stirred at 100 ° C. for 5 hours. The reaction mixture cooled to room temperature was concentrated under reduced pressure. A saturated aqueous sodium hydrogen carbonate solution was added to the residue to adjust the pH to 6, followed by extraction with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was recrystallized from hexane to obtain 5.44 g of 3- (trifluoromethyl) -1H-1,2,4-triazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 8.45 (1H, s), 12.47 (1H, br.s)

３−（トリフルオロメチル）−１Ｈ−１，２，４−トリアゾール２．７４ｇ、パラホルムアルデヒド１．２０ｇの混合物を１５０℃で５時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加え、この混合物をろ過した。ろ液を減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィーに付し、３−（トリフルオロメチル）−１Ｈ−１，２，４−トリアゾール−１−イルメタノール３．１５ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：４．０４（１Ｈ、ｔ）、５．６７（２Ｈ、ｄ）、８．３７（１Ｈ、ｓ） Reference Production Example 25-2
3- (Trifluoromethyl) -1H-1,2,4-triazol-1-ylmethanol

A mixture of 2.74 g of 3- (trifluoromethyl) -1H-1,2,4-triazole and 1.20 g of paraformaldehyde was stirred at 150 ° C. for 5 hours. After cooling the reaction mixture to room temperature, acetone was added to the reaction mixture, and the mixture was filtered. The filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 3.15 g of 3- (trifluoromethyl) -1H-1,2,4-triazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 4.04 (1H, t), 5.67 (2H, d), 8.37 (1H, s)

３−（トリフルオロメチル）−１Ｈ−１，２，４−トリアゾール−１−イルメタノール１．５２ｇをジクロロメタン５０ｍｌに溶解し、該溶液に塩化チオニル２．７ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮し、１−（クロロメチル）−３−（トリフルオロメチル）−１Ｈ−１，２，４−トリアゾール１．３６ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．９２（２Ｈ、ｓ）、８．４４（１Ｈ、ｓ） Reference Production Example 25-3
1- (Chloromethyl) -3- (trifluoromethyl) -1H-1,2,4-triazole

1.52 g of 3- (trifluoromethyl) -1H-1,2,4-triazol-1-ylmethanol was dissolved in 50 ml of dichloromethane, 2.7 ml of thionyl chloride was added to the solution, and the mixture was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to obtain 1.36 g of 1- (chloromethyl) -3- (trifluoromethyl) -1H-1,2,4-triazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.92 (2H, s), 8.44 (1H, s)

ヒドラジン一水和物１．２５ｇをエタノール４５ｍｌに溶解し、０℃に冷却した。該溶液に、２，２，３，３，３−ペンタフルオロプロピオン酸エチル５．３８ｇを１５分間かけて滴下し、０℃で１時間攪拌した。反応混合物にホルムアミジン酢酸塩２．６１ｇを加え、室温で３０分間攪拌した。反応混合物を減圧下濃縮した。残渣に酢酸５０ｍｌを加え、この混合物を１００℃で５時間攪拌した。反応混合物を減圧下濃縮した。残渣に飽和炭酸水素ナトリウム水溶液を加え、約ｐＨ６とした後、酢酸エチルで抽出した。有機層を無水硫酸ナトリウムで乾燥し、減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィーに付し、３−ペンタフルオロエチル−１Ｈ−１，２，４−トリアゾール２．９８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：８．４７（１Ｈ、ｓ）、１２．３９（１Ｈ、ｂｒ．ｓ） Reference Production Example 26-1
3-Pentafluoroethyl-1H-1,2,4-triazole

1.25 g of hydrazine monohydrate was dissolved in 45 ml of ethanol and cooled to 0 ° C. To this solution, 5.38 g of ethyl 2,2,3,3,3-pentafluoropropionate was added dropwise over 15 minutes and stirred at 0 ° C. for 1 hour. To the reaction mixture, 2.61 g of formamidine acetate was added and stirred at room temperature for 30 minutes. The reaction mixture was concentrated under reduced pressure. 50 ml of acetic acid was added to the residue, and the mixture was stirred at 100 ° C. for 5 hours. The reaction mixture was concentrated under reduced pressure. A saturated aqueous sodium hydrogen carbonate solution was added to the residue to adjust the pH to about 6, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 2.98 g of 3-pentafluoroethyl-1H-1,2,4-triazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 8.47 (1H, s), 12.39 (1H, br.s)

３−（ペンタフルオロエチル）−１Ｈ−１，２，４−トリアゾール１．４５ｇ及びパラホルムアルデヒド０．４６ｇの混合物を１５０℃で５時間攪拌した。反応混合物を室温まで冷却後、アセトンを加えた。この混合物をろ過した。ろ液を濃縮した。残渣にヘキサンを加えた結果、結晶が生成した。その結晶を集めて、３−（ペンタフルオロエチル）−１Ｈ−１，２，４−トリアゾール−１−イルメタノール１．５２ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．６９（２Ｈ、ｓ）、８．４１（１Ｈ、ｓ） Reference Production Example 26-2
3- (Pentafluoroethyl) -1H-1,2,4-triazol-1-ylmethanol

A mixture of 1.45 g of 3- (pentafluoroethyl) -1H-1,2,4-triazole and 0.46 g of paraformaldehyde was stirred at 150 ° C. for 5 hours. After the reaction mixture was cooled to room temperature, acetone was added. This mixture was filtered. The filtrate was concentrated. As a result of adding hexane to the residue, crystals were formed. The crystals were collected to obtain 1.52 g of 3- (pentafluoroethyl) -1H-1,2,4-triazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.69 (2H, s), 8.41 (1H, s)

３−（ペンタフルオロエチル）−１Ｈ−１，２，４−トリアゾール−１−イルメタノール１．５２ｇをジクロロメタン５０ｍｌに溶解し、該溶液に塩化チオニル２．７ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮し、１−（クロロメチル）−３−（ペンタフルオロエチル）−１Ｈ−１，２，４−トリアゾール１．３６ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．９３（２Ｈ、ｓ）、８．４４（１Ｈ、ｓ） Reference Production Example 26-3
1- (Chloromethyl) -3- (pentafluoroethyl) -1H-1,2,4-triazole

1.52 g of 3- (pentafluoroethyl) -1H-1,2,4-triazol-1-ylmethanol was dissolved in 50 ml of dichloromethane, 2.7 ml of thionyl chloride was added to the solution, and the mixture was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to obtain 1.36 g of 1- (chloromethyl) -3- (pentafluoroethyl) -1H-1,2,4-triazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.93 (2H, s), 8.44 (1H, s)

３−（ペンタフルオロエチル）−１Ｈ−ピラゾール１．８６ｇ、パラホルムアルデヒド０．６０ｇの混合物を１３０℃で５時間攪拌した。反応混合物を室温まで冷却後、アセトンを加えた。この混合物をろ過した。ろ液を減圧下濃縮し、３−（ペンタフルオロエチル）−１Ｈ−ピラゾール−１−イルメタノール１．９８ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：４．５４（１Ｈ、ｂｒ．ｓ）、５．５８（２Ｈ、ｄ）、６．６０（１Ｈ、ｄ）、７．６８（１Ｈ、ｄ） Reference Production Example 27-1
3- (Pentafluoroethyl) -1H-pyrazol-1-ylmethanol

A mixture of 1.86 g of 3- (pentafluoroethyl) -1H-pyrazole and 0.60 g of paraformaldehyde was stirred at 130 ° C. for 5 hours. After the reaction mixture was cooled to room temperature, acetone was added. This mixture was filtered. The filtrate was concentrated under reduced pressure to obtain 1.98 g of 3- (pentafluoroethyl) -1H-pyrazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 4.54 (1H, br.s), 5.58 (2H, d), 6.60 (1H, d), 7.68 (1H D)

Reference Production Example 27-2
1- (chloromethyl) -3- (pentafluoroethyl)-1H-Pirazo Le
1.98 g of 3- (pentafluoroethyl) -1H-pyrazol-1-ylmethanol was dissolved in 20 ml of dichloromethane. To the solution, 1.5 ml of thionyl chloride was added and stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to obtain 2.01 g of 1- (chloromethyl) -3- (pentafluoroethyl) -1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.89 (2H, s), 6.65 (1H, d), 7.71 (1H, d)

３−（ペンタフルオロエチル）−１Ｈ−ピラゾール９．３０ｇを水９０mlに懸濁し、この懸濁液に５０％水酸化ナトリウム水溶液６．０ｇを加えた。該混合物を０℃に冷却し、該混合物に臭素８．７９gを加え、室温で７時間攪拌した。反応混合物を酢酸エチルで抽出した。有機層を水で洗浄し、無水硫酸マグネシウムで乾燥後、ろ過し、減圧下濃縮し、４−ブロモ−３−（ペンタフルオロエチル）−１Ｈ−ピラゾール１３．７２ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：７．７１（１Ｈ、ｓ） Reference Production Example 28-1
4-Bromo-3- (pentafluoroethyl) -1H-pyrazole

9.30 g of 3- (pentafluoroethyl) -1H-pyrazole was suspended in 90 ml of water, and 6.0 g of 50% aqueous sodium hydroxide solution was added to this suspension. The mixture was cooled to 0 ° C., 8.79 g of bromine was added to the mixture, and the mixture was stirred at room temperature for 7 hours. The reaction mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 13.72 g of 4-bromo-3- (pentafluoroethyl) -1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 7.71 (1H, s)

４−ブロモ−３−（ペンタフルオロエチル）−１Ｈ−ピラゾール１３．７２ｇ及びパラホルムアルデヒド３．００ｇの混合物を１３０℃で５時間攪拌した。反応混合物を室温まで冷却後、アセトンを加えた。この混合物をろ過した後、ろ液を減圧下濃縮した。残渣にヘキサンを加えた結果、結晶が生成した。この結晶を集めて、４−ブロモ−３−（ペンタフルオロエチル）−１Ｈ−ピラゾール−１−イルメタノール７．６９ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：３．５３（１H,ｂｒ．ｓ）、５．５４（２Ｈ、ｓ）、７．７３（１Ｈ、ｓ） Reference Production Example 28-2
4-Bromo-3- (pentafluoroethyl) -1H-pyrazol-1-ylmethanol

A mixture of 13.72 g of 4-bromo-3- (pentafluoroethyl) -1H-pyrazole and 3.00 g of paraformaldehyde was stirred at 130 ° C. for 5 hours. After the reaction mixture was cooled to room temperature, acetone was added. After the mixture was filtered, the filtrate was concentrated under reduced pressure. As a result of adding hexane to the residue, crystals were formed. The crystals were collected to obtain 7.69 g of 4-bromo-3- (pentafluoroethyl) -1H-pyrazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 3.53 (1H, br.s), 5.54 (2H, s), 7.73 (1H, s)

４−ブロモ−３−（ペンタフルオロエチル）−１Ｈ−ピラゾール−１−イルメタノール６．４９ｇをジクロロメタン６０ｍｌに溶解した。該溶液に塩化チオニル３．２ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮し、４−ブロモ−１−（クロロメチル）−３−（ペンタフルオロエチル）−１Ｈ−ピラゾール６．８４ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．８２（２Ｈ、ｓ）、７．７５（１Ｈ、ｓ） Reference Production Example 28-3
4-Bromo-1- (chloromethyl) -3- (pentafluoroethyl) -1H-pyrazole

6.49 g of 4-bromo-3- (pentafluoroethyl) -1H-pyrazol-1-ylmethanol was dissolved in 60 ml of dichloromethane. To the solution was added 3.2 ml of thionyl chloride, and the mixture was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to obtain 6.84 g of 4-bromo-1- (chloromethyl) -3- (pentafluoroethyl) -1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.82 (2H, s), 7.75 (1H, s)

４−（トリフルオロメチル）−１Ｈ−イミダゾール１．８０ｇ、パラホルムアルデヒド０．７８ｇの混合物を１４０℃で４時間攪拌した。反応混合物を室温まで冷却後、アセトンを加えた。この混合物をろ過した後、ろ液を減圧下濃縮し、４−（トリフルオロメチル）−１Ｈ−イミダゾール−１−イルメタノール２．１６ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．３９（２Ｈ、ｄ）、７．４４（１Ｈ、ｓ）、７．６１（１Ｈ、ｓ） Reference Production Example 29-1
4- (Trifluoromethyl) -1H-imidazol-1-ylmethanol

A mixture of 1.80 g of 4- (trifluoromethyl) -1H-imidazole and 0.78 g of paraformaldehyde was stirred at 140 ° C. for 4 hours. After the reaction mixture was cooled to room temperature, acetone was added. After filtering this mixture, the filtrate was concentrated under reduced pressure to obtain 2.16 g of 4- (trifluoromethyl) -1H-imidazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.39 (2H, d), 7.44 (1H, s), 7.61 (1H, s)

４−（トリフルオロメチル）−１Ｈ−イミダゾール−１−イルメタノール２．１６ｇをジクロロメタン４０ｍｌに溶解した。該溶液に塩化チオニル１．９ｍｌを加え、室温で一晩攪拌した。反応混合物を減圧下濃縮し、１−（クロロメチル）−４−（トリフルオロメチル）−１Ｈ−イミダゾール塩酸塩２．９０ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：６．１２（２Ｈ、ｓ）、８．１０（１Ｈ、ｓ）、８．１６（１Ｈ、ｓ） Reference Production Example 29-2
1- (Chloromethyl) -4- (trifluoromethyl) -1H-imidazole hydrochloride

2.16 g of 4- (trifluoromethyl) -1H-imidazol-1-ylmethanol was dissolved in 40 ml of dichloromethane. 1.9 ml of thionyl chloride was added to the solution and stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to obtain 2.90 g of 1- (chloromethyl) -4- (trifluoromethyl) -1H-imidazole hydrochloride.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 6.12 (2H, s), 8.10 (1H, s), 8.16 (1H, s)

３−シアノ−１Ｈ−インドール１．４２ｇ、パラホルムアルデヒド０．６０ｇ及びトリエチルアミン０．１ｇの混合物を１３０℃で１時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。この混合物をろ過した。ろ液を減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィーに付し、３−シアノ−１Ｈ−インドール−１−イルメタノール１．６９ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：３．７３（１Ｈ，ｂｒ．ｓ）、５．６４（２Ｈ、ｄ）、７．２９−７．３９（２Ｈ、ｍ）、７．５６−７．５９（１Ｈ、ｍ）、７．７１−７．７５（２Ｈ、ｍ） Reference Production Example 30-1
3-Cyano-1H-indol-1-ylmethanol

A mixture of 1.42 g of 3-cyano-1H-indole, 0.60 g of paraformaldehyde and 0.1 g of triethylamine was stirred at 130 ° C. for 1 hour. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. This mixture was filtered. The filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 1.69 g of 3-cyano-1H-indol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 3.73 (1H, br.s), 5.64 (2H, d), 7.29-7.39 (2H, m), 7 .56-7.59 (1H, m), 7.71-7.75 (2H, m)

３−シアノ−１Ｈ−インドール−１−イルメタノール１．６９ｇをジクロロメタン３０ｍｌに溶解した。該溶液に塩化チオニル１．４ｍｌを加え、室温で３時間攪拌した。反応混合物を減圧下濃縮し、１−（クロロメチル）−３−シアノ−１Ｈ−インドール１．７０ｇを得た。
¹Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ₆、ＴＭＳ、δ（ｐｐｍ））：６．４４（２Ｈ、ｓ）、７．３４−７．４８（２Ｈ、ｍ）、７．６４−７．７４（１Ｈ、ｍ）、７．８３（１Ｈ、ｄ）、８．４７（１Ｈ、ｓ） Reference Production Example 30-2
1- (Chloromethyl) -3-cyano-1H-indole

1.69 g of 3-cyano-1H-indol-1-ylmethanol was dissolved in 30 ml of dichloromethane. To the solution was added 1.4 ml of thionyl chloride, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure to obtain 1.70 g of 1- (chloromethyl) -3-cyano-1H-indole.
¹ H-NMR (DMSO-d ₆ , TMS, δ (ppm)): 6.44 (2H, s), 7.34-7.48 (2H, m), 7.64-7.74 (1H, m), 7.83 (1H, d), 8.47 (1H, s)

３−ホルミル−１Ｈ−インドール５．８１ｇ、パラホルムアルデヒド１．８０ｇ及びトリエチルアミン０．４０ｇの混合物を１２０℃で３時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。この混合物をろ過した後、ろ液を減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィーに付し、３−ホルミル−１Ｈ−インドール−１−イルメタノール３．０８ｇを得た。
¹Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ₆、ＴＭＳ、δ（ｐｐｍ））：５．６１（２Ｈ、ｄ）、６．７８（１Ｈ、ｔ）、７．２１−７．３４（２Ｈ、ｍ）、７．４９（１Ｈ、ｄ）、８．０８（１Ｈ、ｄ）、８．３４（１Ｈ、ｓ）、９．９４（１Ｈ、ｓ） Reference Production Example 31-1
3-Formyl-1H-indol-1-ylmethanol

A mixture of 5.81 g of 3-formyl-1H-indole, 1.80 g of paraformaldehyde and 0.40 g of triethylamine was stirred at 120 ° C. for 3 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. After the mixture was filtered, the filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 3.08 g of 3-formyl-1H-indol-1-ylmethanol.
¹ H-NMR (DMSO-d ₆ , TMS, δ (ppm)): 5.61 (2H, d), 6.78 (1H, t), 7.21-7.34 (2H, m), 7 .49 (1H, d), 8.08 (1H, d), 8.34 (1H, s), 9.94 (1H, s)

３−ホルミル−１Ｈ−インドール−１−イルメタノール３．０８ｇをジクロロメタン６０ｍｌに溶解した。該溶液に塩化チオニル２．５ｍｌを加え、室温で３時間攪拌した。反応混合物を減圧下濃縮し、１−（クロロメチル）−３−ホルミル−１Ｈ−インドール３．０２ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．９９（２Ｈ、ｓ）、７．３５−７．５２（３Ｈ、ｍ）、７．８１（１Ｈ、ｓ）、７．８３（１Ｈ、ｄ）、８．３２（１Ｈ、ｄ）、１０．０５（１Ｈ、ｓ） Reference Production Example 31-2
1- (Chloromethyl) -3-formyl-1H-indole

3.08 g of 3-formyl-1H-indol-1-ylmethanol was dissolved in 60 ml of dichloromethane. To the solution was added 2.5 ml of thionyl chloride, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure to obtain 3.02 g of 1- (chloromethyl) -3-formyl-1H-indole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.99 (2H, s), 7.35-7.52 (3H, m), 7.81 (1H, s), 7.83 (1H, d), 8.32 (1H, d), 10.05 (1H, s)

３−（トリフルオロアセチル）−１Ｈ−インドール４．８０ｇ、パラホルムアルデヒド１．３５ｇ及びトリエチルアミン０．１０ｇの混合物を１３０℃で２時間攪拌した。反応混合物を室温まで冷却後、反応混合物にアセトンを加えた。この混合物をろ過した後、ろ液を減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィーに付した後、残渣にヘキサンを加えた結果、結晶が生成した。この結晶を集めて、３−（トリフルオロアセチル）−１Ｈ−インドール−１−イルメタノール５．３６ｇを得た。
¹Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ₆、ＴＭＳ、δ（ｐｐｍ））：５．７１（２Ｈ、ｄ）、６．９２（１Ｈ、ｔ）、７．３６−７．４３（２Ｈ、ｍ）、７．７６（１Ｈ、ｄ）、８．１９（１Ｈ、ｄ）、８．３１（１Ｈ、ｓ） Reference Production Example 32-1
3- (Trifluoroacetyl) -1H-indol-1-ylmethanol

A mixture of 4.80 g of 3- (trifluoroacetyl) -1H-indole, 1.35 g of paraformaldehyde and 0.10 g of triethylamine was stirred at 130 ° C. for 2 hours. After the reaction mixture was cooled to room temperature, acetone was added to the reaction mixture. After the mixture was filtered, the filtrate was concentrated under reduced pressure. After the residue was subjected to silica gel column chromatography, hexane was added to the residue, resulting in crystals. The crystals were collected to obtain 5.36 g of 3- (trifluoroacetyl) -1H-indol-1-ylmethanol.
¹ H-NMR (DMSO-d ₆ , TMS, δ (ppm)): 5.71 (2H, d), 6.92 (1H, t), 7.36-7.43 (2H, m), 7 .76 (1H, d), 8.19 (1H, d), 8.31 (1H, s)

３−（トリフルオロアセチル）−１Ｈ−インドール−１−イルメタノール５．３６ｇをジクロロメタン６０ｍｌに溶解した。該溶液に塩化チオニル２．５ｍｌを加え、室温で３時間攪拌した。反応混合物を減圧下濃縮し、残渣をヘキサン−クロロホルムから結晶化し、１−（クロロメチル）−３−（トリフルオロアセチル）−１Ｈ−インドール３．７９ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：６．００（２Ｈ、ｓ）、７．３０−７．５７（３Ｈ、ｍ）、８．０５（１Ｈ、ｓ）、８．３９−８．４１（１Ｈ、ｍ） Reference Production Example 32-2
1- (Chloromethyl) -3- (trifluoroacetyl) -1H-indole

3- (Trifluoroacetyl) -1H-indol-1-ylmethanol (5.36 g) was dissolved in dichloromethane (60 ml). To the solution was added 2.5 ml of thionyl chloride, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure, and the residue was crystallized from hexane-chloroform to obtain 3.79 g of 1- (chloromethyl) -3- (trifluoroacetyl) -1H-indole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 6.00 (2H, s), 7.30-7.57 (3H, m), 8.05 (1H, s), 8.39 -8.41 (1H, m)

カリウムチオシアネート３．８９ｇをメタノール４０ｍｌに懸濁させた。この懸濁液に、窒素雰囲気下−７８℃に冷却した。ここにメタノール４０ｍｌに溶解した臭素１．７６ｇを３０分かけて滴下し、３０分間攪拌した。次いで、メタノール１０ｍｌに溶解した２−（４−メトキシベンジル）−２Ｈ−ピラゾール−３−イルアミン２．０３ｇを１０分間かけて滴下し、−７８℃で１時間、室温で８時間攪拌した。反応混合物を減圧下濃縮した。残渣に水を加え、酢酸エチルで抽出した。有機層を無水硫酸ナトリウムで乾燥した後、濃縮した。残渣をシリカゲルカラムクロマトグラフィーに付し、２−（４−メトキシベンジル）−４−チオシアナト−２Ｈ−ピラゾール−３−イルアミン１．５４ｇを得た。
¹Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ₆、ＴＭＳ、δ（ｐｐｍ））：３．７２（３Ｈ、ｓ）、５．０７（２Ｈ、ｓ）、６．３７（２Ｈ、ｂ．ｓ．）、６．８７（２Ｈ、ｄ）、７．１４（２Ｈ、ｄ）、７．４２（１Ｈ、ｓ） Reference Production Example 33-1
2- (4-Methoxybenzyl) -4-thiocyanato-2H-pyrazol-3-ylamine

3.89 g of potassium thiocyanate was suspended in 40 ml of methanol. The suspension was cooled to −78 ° C. under a nitrogen atmosphere. Here, 1.76 g of bromine dissolved in 40 ml of methanol was dropped over 30 minutes and stirred for 30 minutes. Next, 2.03 g of 2- (4-methoxybenzyl) -2H-pyrazol-3-ylamine dissolved in 10 ml of methanol was added dropwise over 10 minutes, and the mixture was stirred at -78 ° C for 1 hour and at room temperature for 8 hours. The reaction mixture was concentrated under reduced pressure. Water was added to the residue and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated. The residue was subjected to silica gel column chromatography to obtain 1.54 g of 2- (4-methoxybenzyl) -4-thiocyanato-2H-pyrazol-3-ylamine.
¹ H-NMR (DMSO-d ₆ , TMS, δ (ppm)): 3.72 (3H, s), 5.07 (2H, s), 6.37 (2H, bs), 6. 87 (2H, d), 7.14 (2H, d), 7.42 (1H, s)

２−（４−メトキシベンジル）−４−チオシアナト−２Ｈ−ピラゾール−３−イルアミン１．４２ｇを１０％水酸化ナトリウム水溶液２０ｍｌに加え、該混合物を２時間加熱還流した。反応混合物を室温まで冷却した結果、結晶が生成した。この結晶をろ過により集めた。その結晶を水３０ｍｌで３回洗浄した。その結晶を減圧下乾燥し、４−｛〔５−アミノ−１−（４−メトキシベンジル）−１Ｈ−ピラゾール−４−イル〕ジチオ｝−１−（４−メトキシベンジル）−１Ｈ−ピラゾール−５−アミン１．２７ｇを得た。
¹Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ₆、ＴＭＳ、δ（ｐｐｍ））：３．７１（６Ｈ、ｓ）、５．０７（４Ｈ、ｓ）、５．７３（４Ｈ、ｂｒｓ．）、６．８３（４Ｈ、ｄ）、６．９８（２Ｈ、ｓ）、７．０７（４Ｈ、ｄ） Reference Production Example 33-2
4-{[5-Amino-1- (4-methoxybenzyl) -1H-pyrazol-4-yl] dithio} -1- (4-methoxybenzyl) -1H-pyrazol-5-amine

1.42 g of 2- (4-methoxybenzyl) -4-thiocyanato-2H-pyrazol-3-ylamine was added to 20 ml of 10% aqueous sodium hydroxide solution, and the mixture was heated to reflux for 2 hours. The reaction mixture was cooled to room temperature, resulting in the formation of crystals. The crystals were collected by filtration. The crystals were washed 3 times with 30 ml of water. The crystals were dried under reduced pressure to give 4-{[5-amino-1- (4-methoxybenzyl) -1H-pyrazol-4-yl] dithio} -1- (4-methoxybenzyl) -1H-pyrazole-5. -1.27 g of amine was obtained.
¹ H-NMR (DMSO-d ₆ , TMS, δ (ppm)): 3.71 (6H, s), 5.07 (4H, s), 5.73 (4H, brs.), 6.83 ( 4H, d), 6.98 (2H, s), 7.07 (4H, d)

４−｛〔５−アミノ−１−（４−メトキシベンジル）−１Ｈ−ピラゾール−４−イル〕ジチオ｝−１−（４−メトキシベンジル）−１Ｈ−ピラゾール−５−アミン１．５８ｇをＮ，Ｎ−ジメチルホルムアミド２０ｍｌ溶解した。この溶液に氷冷下で水２０ｍｌ、炭酸水素ナトリウム１．４２ｇ及びハイドロサルファイトナトリウム２．９３ｇを加えた。この混合物にトリクロロフルオロメタン５．２８ｇを加え、室温で１５時間攪拌した。反応混合物に水を加え、酢酸エチルで抽出した。有機層を水で洗浄し、硫酸ナトリウムで乾燥し、ろ過した。ろ液を減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィーに付し、４−｛〔ジクロロフルオロメチル〕チオ｝−１−（４−メトキシベンジル）−１Ｈ−ピラゾール−５−アミン１．０４ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：３．７９（３Ｈ、ｓ）、３．９９（２Ｈ、ｂ．ｓ．）、５．１６（２Ｈ、ｓ）、６．８６（２Ｈ、ｄ）、７．１１（２Ｈ、ｄ）、７．５２（１Ｈ、ｓ） Reference Production Example 33-3
4-{[dichlorofluoromethyl] thio} -1- (4-methoxybenzyl) -1H-pyrazol-5-amine

4-{[5-amino-1- (4-methoxybenzyl) -1H-pyrazol-4-yl] dithio} -1- (4-methoxybenzyl) -1H-pyrazol-5-amine (1.58 g) 20 ml of N-dimethylformamide was dissolved. Under ice-cooling, 20 ml of water, 1.42 g of sodium hydrogencarbonate and 2.93 g of hydrosulfite sodium were added to this solution. To this mixture was added 5.28 g of trichlorofluoromethane, and the mixture was stirred at room temperature for 15 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over sodium sulfate and filtered. The filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 1.04 g of 4-{[dichlorofluoromethyl] thio} -1- (4-methoxybenzyl) -1H-pyrazol-5-amine.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 3.79 (3H, s), 3.99 (2H, bs), 5.16 (2H, s), 6.86 ( 2H, d), 7.11 (2H, d), 7.52 (1H, s)

４−｛〔ジクロロフルオロメチル〕チオ｝−１−（４−メトキシベンジル）−１Ｈ−ピラゾール−５−アミン１．０４ｇをテトラヒドロフラン２０ｍｌ溶解した。該溶液に、亜硝酸ｔ−ブチル１．５５ｇを加え、３時間加熱還流した。反応混合物を室温まで冷却後、反応混合物に水を加え、ジエチルエーテルで抽出した。有機層を水洗、硫酸ナトリウムで乾燥し、ろ過した。ろ液を減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィーに付し、４−｛〔ジクロロフルオロメチル〕チオ｝−１−（４−メトキシベンジル）−１Ｈ−ピラゾール０．９４ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：３．８１（３Ｈ、ｓ）、５．２７（２Ｈ、ｓ）、６．８９（２Ｈ、ｄ）、７．１９（２Ｈ、ｄ）、７．６０（１Ｈ、ｓ）、７．７２（１Ｈ、ｓ） Reference Production Example 33-4
4-{[dichlorofluoromethyl] thio} -1- (4-methoxybenzyl) -1H-pyrazole

20 ml of tetrahydrofuran was dissolved in 1.04 g of 4-{[dichlorofluoromethyl] thio} -1- (4-methoxybenzyl) -1H-pyrazol-5-amine. To this solution, 1.55 g of t-butyl nitrite was added and heated to reflux for 3 hours. The reaction mixture was cooled to room temperature, water was added to the reaction mixture, and the mixture was extracted with diethyl ether. The organic layer was washed with water, dried over sodium sulfate and filtered. The filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.94 g of 4-{[dichlorofluoromethyl] thio} -1- (4-methoxybenzyl) -1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 3.81 (3H, s), 5.27 (2H, s), 6.89 (2H, d), 7.19 (2H, d ), 7.60 (1H, s), 7.72 (1H, s)

４−｛〔ジクロロフルオロメチル〕チオ｝−１−（４−メトキシベンジル）−１Ｈ−ピラゾール１．０４ｇをトリフルオロ酢酸６ｍｌに溶解し、６５℃で３時間攪拌した。反応混合物を室温まで冷却後、飽和炭酸水素ナトリウム水溶液に加えた。該混合物を酢酸エチルで抽出した。有機層を無水硫酸ナトリウムで乾燥し、ろ過した。ろ液を減圧下濃縮し、残渣をシリカゲルカラムクロマトグラフィーに付し、４−｛〔ジクロロフルオロメチル〕チオ｝−１Ｈ−ピラゾール０．１９ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：７．８８（２Ｈ、ｓ） Reference Production Example 33-5
4-{[dichlorofluoromethyl] thio} -1H-pyrazole

1.04 g of 4-{[dichlorofluoromethyl] thio} -1- (4-methoxybenzyl) -1H-pyrazole was dissolved in 6 ml of trifluoroacetic acid and stirred at 65 ° C. for 3 hours. The reaction mixture was cooled to room temperature and then added to a saturated aqueous sodium hydrogen carbonate solution. The mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography to obtain 0.19 g of 4-{[dichlorofluoromethyl] thio} -1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 7.88 (2H, s)

４−｛〔ジクロロフルオロメチル〕チオ｝−１Ｈ−ピラゾール０．１９ｇをテトラヒドロフラン５ｍｌに溶解した。該溶液に３６％ホルムアルデヒド水溶液５ｍｌ及び１０％テトラブチルアンモニウムヒドロキシド水溶液０．１ｍｌを加え、室温で４時間攪拌した。反応混合物に水を加え、ＭＴＢＥで抽出した。有機層を水で洗浄し、無水硫酸マグネシウムで乾燥した後、ろ過した。ろ液を減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィーに付し、４−｛〔ジクロロフルオロメチル〕チオ｝−１Ｈ−ピラゾール−１−イルメタノール０．２２ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．５７（２Ｈ、ｓ）、７．７７（１Ｈ、ｓ）、７．９０（１Ｈ、ｓ） Reference Production Example 33-6
4-{[dichlorofluoromethyl] thio} -1H-pyrazol-1-ylmethanol

0.19 g of 4-{[dichlorofluoromethyl] thio} -1H-pyrazole was dissolved in 5 ml of tetrahydrofuran. To this solution, 5 ml of 36% aqueous formaldehyde solution and 0.1 ml of 10% tetrabutylammonium hydroxide aqueous solution were added and stirred at room temperature for 4 hours. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then filtered. The filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.22 g of 4-{[dichlorofluoromethyl] thio} -1H-pyrazol-1-ylmethanol.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.57 (2H, s), 7.77 (1H, s), 7.90 (1H, s)

４−｛〔ジクロロフルオロメチル〕チオ｝−１Ｈ−ピラゾール−１−イルメタノール０．２２ｇをクロロホルム１０ｍｌに溶解した。該溶液に塩化チオニル０．３ｍｌを加え、４時間加熱還流した。反応混合物を減圧下濃縮し、１−（クロロメチル）−４−｛〔ジクロロフルオロメチル〕チオ｝−１Ｈ−ピラゾール０．２１ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．８８（２Ｈ、ｓ）、７．７９（１Ｈ、ｓ）、７．９２（１Ｈ、ｓ） Reference Production Example 33-7
1- (Chloromethyl) -4-{[dichlorofluoromethyl] thio} -1H-pyrazole

0.22 g of 4-{[dichlorofluoromethyl] thio} -1H-pyrazol-1-ylmethanol was dissolved in 10 ml of chloroform. To the solution, 0.3 ml of thionyl chloride was added and heated to reflux for 4 hours. The reaction mixture was concentrated under reduced pressure to obtain 0.21 g of 1- (chloromethyl) -4-{[dichlorofluoromethyl] thio} -1H-pyrazole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.88 (2H, s), 7.79 (1H, s), 7.92 (1H, s)

３−｛〔ジクロロフルオロメチル〕チオ｝−１Ｈ−インドール０．５０ｇをテトラヒドロフラン１０ｍｌに溶解した。この溶液に３６％ホルムアルデヒド水溶液１０ｍｌ及び１０％テトラブチルアンモニウムヒドロキシド水溶液０．４ｍｌを加え、室温で３０分間攪拌した。反応混合物に水を加え、ＭＴＢＥで抽出した。有機層を水で洗浄し、無水硫酸マグネシウムで乾燥した後、ろ過した。ろ液を減圧下濃縮し、３−｛〔ジクロロフルオロメチル〕チオ｝−１Ｈ−インドール−１−イルメタノール０．５４ｇを得た。
¹Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ₆、ＴＭＳ、δ（ｐｐｍ））：５．６１（２Ｈ、ｄ）、６．７３（１Ｈ、ｔ）、７．２３−７．３３（２Ｈ、ｍ）、７．６６−７．７０（２Ｈ、ｍ）、８．０４（１Ｈ、ｓ） Reference Production Example 34-1
3-{[dichlorofluoromethyl] thio} -1H-indol-1-ylmethanol

0.50 g of 3-{[dichlorofluoromethyl] thio} -1H-indole was dissolved in 10 ml of tetrahydrofuran. To this solution, 10 ml of 36% aqueous formaldehyde solution and 0.4 ml of 10% tetrabutylammonium hydroxide aqueous solution were added and stirred at room temperature for 30 minutes. Water was added to the reaction mixture and extracted with MTBE. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then filtered. The filtrate was concentrated under reduced pressure to obtain 0.54 g of 3-{[dichlorofluoromethyl] thio} -1H-indol-1-ylmethanol.
¹ H-NMR (DMSO-d ₆ , TMS, δ (ppm)): 5.61 (2H, d), 6.73 (1H, t), 7.23-7.33 (2H, m), 7 .66-7.70 (2H, m), 8.04 (1H, s)

３−｛〔ジクロロフルオロメチル〕チオ｝−１Ｈ−インドール−１−イルメタノール０．５４ｇをクロロホルム１０ｍｌに溶解し、塩化チオニル０．３ｍｌを加え、４時間加熱還流した。反応混合物を減圧下濃縮し、１−（クロロメチル）−３−｛〔ジクロロフルオロメチル〕チオ｝−１Ｈ−インドール０．６１ｇを得た。 Reference Production Example 34-2
1- (Chloromethyl) -3-{[dichlorofluoromethyl] thio} -1H-indole

0.54 g of 3-{[dichlorofluoromethyl] thio} -1H-indol-1-ylmethanol was dissolved in 10 ml of chloroform, 0.3 ml of thionyl chloride was added, and the mixture was heated to reflux for 4 hours. The reaction mixture was concentrated under reduced pressure to obtain 0.61 g of 1- (chloromethyl) -3-{[dichlorofluoromethyl] thio} -1H-indole.

３−ニトロ−１Ｈ−ピロール８４０ｍｇ、テトラヒドロフラン１５ｍｌ及び３６％ホルムアルデヒド１５ｍｌを混合した。この混合物に室温で１０％テトラブチルアンモニウムヒドロキシド水溶液０．５ｍｌを加え、室温で３０分間攪拌した。反応混合物を、氷水に注加し、酢酸エチルで抽出した。有機層を飽和食塩水にて洗浄し、無水硫酸マグネシウムで乾燥し、ろ過した。ろ液を減圧下濃縮し、１−ヒドロキシメチル−３−ニトロ−１Ｈ−ピロールを得た。
得られた１−ヒドロキシメチル−３−ニトロ−１Ｈ−ピロールを、クロロホルム３ｍｌに溶解し、塩化チオニル３ｍｌを加え室温で１時間攪拌した。反応混合物を０℃に冷却後、氷水に注加した。この混合物を酢酸エチルで抽出した。有機層を飽和炭酸水素ナトリウム水溶液にて洗浄し、無水硫酸マグネシウムで乾燥し、ろ過した。ろ液を減圧下濃縮した。残渣をシリカゲルカラムクロマトグラフィーに付し、１−クロロメチル−３−ニトロ−１Ｈ−ピロール６２０ｍｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．６３（２Ｈ、ｓ）、６．７７−６．７８（２Ｈ、ｍ）、７．６８−７．６９（１Ｈ、ｍ） Reference Production Example 35
1-chloromethyl-3-nitro-1H-pyrrole

840 mg of 3-nitro-1H-pyrrole, 15 ml of tetrahydrofuran and 15 ml of 36% formaldehyde were mixed. To this mixture, 0.5 ml of 10% tetrabutylammonium hydroxide aqueous solution was added at room temperature, and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure to obtain 1-hydroxymethyl-3-nitro-1H-pyrrole.
The obtained 1-hydroxymethyl-3-nitro-1H-pyrrole was dissolved in 3 ml of chloroform, 3 ml of thionyl chloride was added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was cooled to 0 ° C. and poured into ice water. This mixture was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 620 mg of 1-chloromethyl-3-nitro-1H-pyrrole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.63 (2H, s), 6.77-6.78 (2H, m), 7.68-7.69 (1H, m)

３−シアノ−４−トリフルオロメチル−１Ｈ−ピロール５８５ｍｇ、テトラヒドロフラン１０ｍｌ、及び３６％ホルムアルデヒド１０ｍｌを混合した。この混合物に室温にて１０％テトラブチルアンモニウムヒドロキシド水溶液０．１ｍｌを加え、室温で３０分間攪拌した。反応混合物を、氷水に注加し、酢酸エチルで抽出した。有機層を飽和食塩水にて洗浄し、無水硫酸マグネシウムで乾燥し、ろ過した。ろ液を減圧下濃縮し、１−ヒドロキシメチル−３−シアノ−４−トリフルオロメチル−１Ｈ−ピロールを得た。
得られた１−ヒドロキシメチル−３−シアノ−４−トリフルオロメチル−１Ｈ−ピロールを、クロロホルム３ｍｌに溶解し、塩化チオニル３ｍｌを加え室温で１時間攪拌した。反応混合物を０℃に冷却後、氷水に注加した。この混合物を酢酸エチルで抽出した。有機層を飽和炭酸水素ナトリウム水溶液にて洗浄し、無水硫酸マグネシウムで乾燥し、ろ過した。ろ液を減圧下濃縮し、１−クロロメチル−３−シアノ−４−トリフルオロメチル−１Ｈ−ピロール８００ｍｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．６２（２Ｈ、ｓ）、７．２１（１Ｈ、ｄ）、７．３９（１Ｈ、ｄ） Reference Production Example 36
1-chloromethyl-3-cyano-4-trifluoromethyl-1H-pyrrole

585 mg of 3-cyano-4-trifluoromethyl-1H-pyrrole, 10 ml of tetrahydrofuran, and 10 ml of 36% formaldehyde were mixed. To this mixture, 0.1 ml of a 10% tetrabutylammonium hydroxide aqueous solution was added at room temperature, and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure to obtain 1-hydroxymethyl-3-cyano-4-trifluoromethyl-1H-pyrrole.
The obtained 1-hydroxymethyl-3-cyano-4-trifluoromethyl-1H-pyrrole was dissolved in 3 ml of chloroform, 3 ml of thionyl chloride was added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was cooled to 0 ° C. and poured into ice water. This mixture was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure to obtain 800 mg of 1-chloromethyl-3-cyano-4-trifluoromethyl-1H-pyrrole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.62 (2H, s), 7.21 (1H, d), 7.39 (1H, d)

４−トリフルオロメチル−３−エトキシカルボニル−１Ｈ−ピロール２０７ｍｇ、テトラヒドロフラン５ｍｌ及び３６％ホルムアルデヒド５ｍｌを混合した。この混合物に室温にて１０％テトラブチルアンモニウムヒドロキシド水溶液０．２ｍｌを加え、室温で１０分間攪拌した。反応混合物を、氷水に注加し、酢酸エチルで抽出した。有機層を飽和食塩水にて洗浄し、無水硫酸マグネシウムで乾燥し、ろ過した。ろ液を減圧下濃縮し、１−ヒドロキシメチル−４−トリフルオロメチル−３−エトキシカルボニル−１Ｈ−ピロールの粗生成物を得た。
得られた１−ヒドロキシメチル−４−トリフルオロメチル−３−エトキシカルボニル−１Ｈ−ピロールを、クロロホルム３ｍｌに溶解し、塩化チオニル４ｍｌを加え３０分間加熱還流した。反応混合物を０℃に冷却後、氷水に注加した。この混合物を酢酸エチルで抽出した。有機層を飽和炭酸水素ナトリウム水溶液にて洗浄し、無水硫酸マグネシウムで乾燥し、ろ過した。ろ液を減圧下濃縮し、１−クロロメチル−４−トリフルオロメチル−３−エトキシカルボニル−１Ｈ−ピロール２２５ｍｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：１．３５（３Ｈ、ｔ）、４．３１（２Ｈ、ｑ）、５．６４（２Ｈ、ｓ）、７．１７（１Ｈ、ｄ）、７．５１（１Ｈ、ｄ） Reference Production Example 37
1-chloromethyl-4-trifluoromethyl-3-ethoxycarbonyl-1H-pyrrole

207 mg of 4-trifluoromethyl-3-ethoxycarbonyl-1H-pyrrole, 5 ml of tetrahydrofuran and 5 ml of 36% formaldehyde were mixed. To this mixture, 0.2 ml of a 10% tetrabutylammonium hydroxide aqueous solution was added at room temperature, and the mixture was stirred at room temperature for 10 minutes. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure to obtain a crude product of 1-hydroxymethyl-4-trifluoromethyl-3-ethoxycarbonyl-1H-pyrrole.
The obtained 1-hydroxymethyl-4-trifluoromethyl-3-ethoxycarbonyl-1H-pyrrole was dissolved in 3 ml of chloroform, 4 ml of thionyl chloride was added, and the mixture was heated to reflux for 30 minutes. The reaction mixture was cooled to 0 ° C. and poured into ice water. This mixture was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure to obtain 225 mg of 1-chloromethyl-4-trifluoromethyl-3-ethoxycarbonyl-1H-pyrrole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.35 (3H, t), 4.31 (2H, q), 5.64 (2H, s), 7.17 (1H, d ), 7.51 (1H, d)

３−シアノ−１Ｈ−ピロール６７０ｍｇ、テトラヒドロフラン１０ｍｌ、及び３６％ホルムアルデヒド１０ｍｌを混合した。この混合物に室温にて１０％テトラブチルアンモニウムヒドロキシド水溶液０．１ｍｌを加え、室温で３０分間攪拌した。反応混合物を、氷水に注加し、酢酸エチルで抽出した。有機層を飽和食塩水にて洗浄し、無水硫酸マグネシウムで乾燥し、ろ過した。ろ液を減圧下濃縮し、１−ヒドロキシメチル−３−シアノ−１Ｈ−ピロールを得た。
得られた１−ヒドロキシメチル−３−シアノ−１Ｈ−ピロールを、クロロホルム３ｍｌに溶解し、塩化チオニル２ｍｌを加え室温で１時間攪拌した。反応混合物を０℃に冷却後、氷水に注加し酢酸エチルで抽出した。有機層を飽和炭酸水素ナトリウム水溶液にて洗浄し、無水硫酸マグネシウムで乾燥し、ろ過した。ろ液を減圧下濃縮後、シリカゲルカラムクロマトグラフィーに付し、１−クロロメチル−３−シアノ−１Ｈ−ピロール２９０ｍｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ、δ（ｐｐｍ））：５．６６（２Ｈ、ｓ）、６．４６−６．４７（１Ｈ、ｍ）、６．８４（１Ｈ、ｄ）、７．３２−７．３３（１Ｈ、ｍ） Reference Production Example 38
1-chloromethyl-3-cyano-1H-pyrrole

670 mg of 3-cyano-1H-pyrrole, 10 ml of tetrahydrofuran, and 10 ml of 36% formaldehyde were mixed. To this mixture, 0.1 ml of a 10% tetrabutylammonium hydroxide aqueous solution was added at room temperature, and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure to obtain 1-hydroxymethyl-3-cyano-1H-pyrrole.
The obtained 1-hydroxymethyl-3-cyano-1H-pyrrole was dissolved in 3 ml of chloroform, 2 ml of thionyl chloride was added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was cooled to 0 ° C., poured into ice water, and extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure and subjected to silica gel column chromatography to obtain 290 mg of 1-chloromethyl-3-cyano-1H-pyrrole.
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 5.66 (2H, s), 6.46-6.47 (1H, m), 6.84 (1H, d), 7.32 -7.33 (1H, m)

Next, formulation examples are shown. In addition, a part represents a weight part. The compound of the present invention is represented by the above compound number.
Formulation Example 1
9 parts of the present compounds (1) to (48) were dissolved in 37.5 parts of xylene and 37.5 parts of dimethylformamide. To this mixture, 10 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate are added and mixed well to obtain an emulsion.

Formulation Example 2
Inventive compounds (1) to (48) 40 parts of Solpol 5060 (registered trademark of Toho Chemical Co., Ltd.) is added and mixed well. ) Add 32 parts, 23 parts of 300 mesh diatomaceous earth and mix with a juice mixer to obtain a wettable powder.

Formulation Example 3
Add 3 parts of the compounds (1) to (48) of the present invention, 5 parts of a fine powder of hydrous silicon oxide, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 57 parts of clay, and mix well with stirring. An appropriate amount of water is added, further stirred, granulated with a granulator, and dried by ventilation to obtain granules.

Formulation Example 4
The present compounds (1) to (48) 4.5 parts, 1 part of synthetic hydrous silicon fine powder, 1 part of Doreles B (manufactured by Sankyo) as a flocculant, and 7 parts of clay were mixed well in a mortar and then mixed with a juice mixer. Stir and mix. 86.5 parts of cut clay is added to the resulting mixture and mixed well with stirring to obtain a powder.

Formulation Example 5
This invention compound (1)-(48) 10 parts, 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt, and 55 parts of water are mixed, and a formulation is obtained by pulverizing by a wet grinding method. .

Formulation Example 6
0.5 parts of the compounds (1) to (48) of the present invention are dissolved in 10 parts of dichloromethane and mixed with 89.5 parts of Isopar M (isoparaffin: Exxon Chemical Registered Trademark) to obtain an oil.

Formulation Example 7
This invention compound (1)-(48) 0.1 part and neothiozole (Chuo Kasei Co., Ltd.) 49.9 parts were put into the aerosol can, and the aerosol valve was equipped to this can. Next, 25 parts of dimethyl ether and 25 parts of LPG are filled, shaken, and an oily aerosol is obtained by mounting the actuator.

Formulation Example 8
Compound (1) to (48) of the present invention 0.6 parts, BHT 0.01 parts, xylene 5 parts, deodorized kerosene 3.39 parts and emulsifier {Atmos 300 (registered trademark of Atmos Chemical)} 1 part are mixed and dissolved. did. The obtained solution and 50 parts of distilled water are filled in an aerosol container, a valve part is attached, and 40 parts of propellant (LPG) is pressurized and filled through the valve to obtain an aqueous aerosol.

  Next, test examples show that the compound of the present invention is effective as an active ingredient of a pest control composition. In addition, this invention compound is represented by the said compound number.

Test example 1
The present compound (2), (3), (4), (5), (6), (7), (8), (9), (11), (12), obtained by Formulation Example 5 (13), (14), (15), (16), (18), (20), (21), (22), (26), (28), (29), (30), (31 ), (32), (33), (34), (35), (36), (37), (38), (39), (45) and (48), each having an active ingredient concentration of 500 ppm. A test chemical solution was prepared.
On the other hand, 50 g of soil soil bonsol 2 (manufactured by Sumitomo Chemical Co., Ltd.) was placed in a polyethylene cup, and 10 to 15 rice seeds were sown. Rice was grown until the second true leaf developed, and then the height was cut to 5 cm. The test chemical solution prepared as described above was sprayed on the rice at a rate of 20 ml / cup. After the chemical sprayed on the rice was dried, it was placed in a plastic cup to prevent escape of the test insects, and 30 first-instar larvae of Nilaparvata lugens were released and capped. Thereafter, the plastic was left in a greenhouse <25 ° C.>. Six days after releasing the green planthopper larvae, the number of the green planthopper parasitic on the rice was investigated.
As a result, the present compounds (2), (3), (4), (5), (6), (7), (8), (9), (11), (12), (13), (14), (15), (16), (18), (20), (21), (22), (26), (28), (29), (30), (31), (32 ), (33), (34), (35), (36), (37), (38), (39), (45) and (48), the number of parasitic insects is 3 or less. there were.

Test example 2
The present compound (2), (4), (6), (8), (9), (11), (12), (13), (15), (18), obtained by Formulation Example 5 (21), (22), (28), (29), (30), (31), (32), (33), (34), (35), (36), (37), (38 ), (44), (46) and (47) were diluted with water so that the active ingredient concentration was 500 ppm, respectively, to prepare test chemicals.
On the other hand, a cucumber was planted in a polyethylene cup and allowed to grow until the first true leaf developed, and about 20 cotton aphids (Aphis gossypii) were infested there. One day later, the test chemical was sprayed onto the cucumber at a rate of 20 ml / cup. Six days after spraying, the number of cotton aphids was examined.
As a result, the present compounds (2), (4), (6), (8), (9), (11), (12), (13), (15), (18), (21), (22), (28), (29), (30), (31), (32), (33), (34), (35), (36), (37), (38), (44 In each of the treatments (46), (46) and (47), the number of insects parasitized after 6 days of treatment was 3 or less.

Test example 3
The present compound (2), (3), (4), (6), (7), (8), (11), (12), (13), (15), obtained by Formulation Example 5 (16), (19), (20), (21), (22), (28), (29), (30), (31), (32), (33), (34), (36 ), (37), (38) and (39) were diluted with water so that the active ingredient concentration was 500 ppm, respectively, to prepare a test drug solution.
A filter paper of the same diameter was laid on the bottom of a polyethylene cup having a diameter of 5.5 cm, 0.7 ml of the test chemical solution was dropped on the filter paper, and 30 mg of sucrose was uniformly added as a bait thereon. 10 female Musca domestica females were released into the polyethylene cup and capped. After 24 hours, the life-and-death of the house fly was investigated to determine the death rate.
As a result, the present compounds (2), (3), (4), (6), (7), (8), (11), (12), (13), (15), (16), (19), (20), (21), (22), (28), (29), (30), (31), (32), (33), (34), (36), (37 ), (38) and (39) showed a death rate of 90% or more.

Test example 4
The present compound (2), (3), (4), (6), (7), (8), (9), (11), (12), (13), obtained by Formulation Example 5 (15), (16), (18), (19), (20), (21), (22), (27), (28), (29), (30), (31), (32 ), (33), (34), (35), (36), (37), (38), (43) and (43) are diluted with water so that the active ingredient concentration is 500 ppm. Then, a test chemical solution was prepared.
A filter paper of the same diameter was laid on the bottom of a polyethylene cup having a diameter of 5.5 cm, 0.7 ml of the test chemical solution was dropped on the filter paper, and 30 mg of sucrose was uniformly added as a bait thereon. Two adult male cockroaches (Blattalla germanica) were released into the polyethylene cup and covered. Six days later, the death and death of German cockroaches were investigated to determine the death rate.
As a result, the present compounds (2), (3), (4), (6), (7), (8), (9), (11), (12), (13), (15), (16), (18), (19), (20), (21), (22), (27), (28), (29), (30), (31), (32), (33) ), (34), (35), (36), (37), (38), (43) and (43) showed a mortality rate of 100%.

Test Example 5
The present compound (1), (2), (3), (4), (5), (6), (7), (8), (9), (10), obtained by Formulation Example 5 (11), (12), (13), (14), (15), (16), (17), (18), (19), (20), (21), (22), (23 ), (25), (27), (28), (29), (50), (31), (32), (33), (34), (35), (36), (37), (38), (39), (41), (44), (45), (46), (47) and (48) are diluted with water so that the active ingredient concentration is 500 ppm, and used for the test. A drug solution was prepared.
0.7 ml of the test chemical solution was added to 100 ml of ion-exchanged water (active ingredient concentration: 3.5 ppm). Twenty dead larvae of Culex pipiens pallens were released into the liquid, and the viability was investigated one day later to determine the death rate.
As a result, the present compounds (1), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16), (17), (18), (19), (20), (21), (22), (23), (25 ), (27), (28), (29), (50), (31), (32), (33), (34), (35), (36), (37), (38), In the treatments (39), (41), (44), (45), (46), (47), and (48), the death rate was 95% or more.

Claims (7)

Formula (I)

[Where,
R ¹ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkynyl group or a hydrogen atom,
R ² is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. An optionally substituted C2-C5 alkenyl group, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, a cyano group or a hydrogen atom;
R ³ represents a hydrogen atom,
R ⁴ represents a 2,2,2-trifluoroethyl group or a vinyl group,
X ¹ , X ² and X ³ each represent a nitrogen atom or CR ⁶ .
R ⁵ and R ⁶ are each a halogen atom, a cyano group, a nitro group, a hydroxyl group, a mercapto group, a formyl group, an SF ₅ group, a carboxyl group, or a C1-C5 alkyl optionally substituted with at least one halogen atom. A group, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, at least one halogen atom or at least one A C1-C3 cycloalkyl group optionally substituted with a C1-C3 alkyl group, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. A C3-C6 alkenyloxy group, C3 optionally substituted by at least one halogen atom C6 alkynyloxy group, C1-C5 alkylthio group optionally substituted with at least one halogen atom, C3-C5 alkenylthio group optionally substituted with at least one halogen atom, at least one halogen atom A C3-C5 alkynylthio group optionally substituted with, a C1-C5 alkylsulfinyl group optionally substituted with at least one halogen atom, a C1-C5 optionally substituted with at least one halogen atom An alkylsulfonyl group, a C2-C6 alkylcarbonyl group optionally substituted with at least one halogen atom, a C2-C5 alkoxycarbonyl group optionally substituted with at least one halogen atom, and represented by NR ¹⁰ R ¹¹ A group represented by C (═X ⁵ ) NR ¹² R ¹³ , (CH ₂ ) _m Q Groups represented represents a group or a hydrogen atom represented by ^{C (= NOR 17) R 18} .
Note that when one of R ⁵ and R ^6, or two atoms which each of the two R ⁶ are attached to adjacent, R ⁵ and R ⁶ which binds to the adjacent said two atoms, or Two R ⁶ bonded to the two adjacent atoms are bonded to each other at the end and represent a C2-C6 alkanediyl group or a C4-C6 alkenediyl group optionally substituted with at least one halogen atom. It may be. In this case, the alkanediyl group and at least one methylene group forming the alkenediyl group may be replaced with an oxygen atom, a sulfur atom or NR ⁷ .
R ⁷ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C3-C5 alkenyl group optionally substituted with at least one halogen atom, and substituted with at least one halogen atom. Optionally substituted C3-C5 alkynyl group, at least one halogen atom or at least one C1-C3 alkyl group optionally substituted C3-C6 cycloalkyl group, substituted with at least one halogen atom. A C2-C6 alkylcarbonyl group which may be substituted, a C2-C5 alkoxycarbonyl group which may be substituted with at least one halogen atom, or a hydrogen atom;
R ¹⁰ and R ¹¹ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C3-C5 alkenyl group optionally substituted with at least one halogen atom, at least one A C3-C5 alkynyl group optionally substituted with a halogen atom, a C3-C6 cycloalkyl group optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group, (at least one C1-C5 alkoxy optionally substituted with a halogen atom) C1-C3 alkyl group, C1-C5 alkylsulfinyl group optionally substituted with at least one halogen atom, substituted with at least one halogen atom A C1-C5 alkylsulfonyl group, which may be substituted with at least one halogen atom There C2-C6 alkylcarbonyl group, at least one halogen atom may be substituted C2-C5 alkoxycarbonyl group or a hydrogen atom,
R ¹² and R ¹³ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C3-C5 alkenyl group optionally substituted with at least one halogen atom, at least one A C3-C5 alkynyl group optionally substituted with a halogen atom, a C3-C6 cycloalkyl group optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group, (CH ₂ ) _m Represents a group represented by Q or a hydrogen atom,
Alternatively, R ¹² and R ¹³ are bonded to each other at the terminal, and may be substituted with at least one halogen atom, or a C2-C6 alkanediyl group that may be substituted with at least one halogen atom. Represents a C4-C6 alkenediyl group,
R ¹⁷ and R ¹⁸ are each a C1-C5 alkyl group optionally substituted with at least one halogen atom, a C3-C5 alkenyl group optionally substituted with at least one halogen atom, at least one A C3-C5 alkynyl group optionally substituted with a halogen atom, a C3-C6 cycloalkyl group optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group, (CH ₂ ) _m Represents a group represented by Q or a hydrogen atom,
Q represents an aryl group which may be substituted with one or more R ¹⁴ ,
Each R ¹⁴ is a C1-C5 alkyl group optionally substituted with at least one halogen atom, C3-C6 optionally substituted with at least one halogen atom or at least one C1-C3 alkyl group. A cycloalkyl group, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, a C1-C5 alkylthio group optionally substituted with at least one halogen atom, substituted with at least one halogen atom C3-C5 alkenylthio group which may be substituted, C3-C5 alkynylthio group which may be substituted with at least one halogen atom, C1-C5 alkylsulfinyl group which may be substituted with at least one halogen atom Groups, C1-C5 alkylsulfo, optionally substituted by at least one halogen atom Group, represents at least one halogen atom that is substituted may be C2-C6 alkylcarbonyl group, at least one halogen atom may be substituted C2-C5 alkoxycarbonyl group or a halogen atom,
m represents an integer of 0 to 5,
X ⁵ represents an oxygen atom or a sulfur atom. ]
A malononitrile compound represented by: Formula (I-1)

[Where,
R ¹ , R ² , R ³ and R ⁴ have the same meaning as defined in claim 1,
R ⁵ and R ^6-1 each have a halogen atom, a cyano group, a nitro group, a hydroxyl group, a mercapto group, a formyl group, an SF ₅ group, a carboxyl group, or a C1-optionally substituted C1- A C5 alkyl group, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, at least one halogen atom or at least C1-C6 cycloalkyl group optionally substituted with one C1-C3 alkyl group, C1-C5 alkoxy group optionally substituted with at least one halogen atom, substituted with at least one halogen atom An optionally substituted C3-C6 alkenyloxy group, optionally substituted by at least one halogen atom -C6 alkynyloxy group, C1-C5 alkylthio group optionally substituted with at least one halogen atom, C3-C5 alkenylthio group optionally substituted with at least one halogen atom, at least one halogen C3-C5 alkynylthio group which may be substituted with an atom, C1-C5 alkylsulfinyl group which may be substituted with at least one halogen atom, C1- which may be substituted with at least one halogen atom C5 alkylsulfonyl group, C2-C6 alkylcarbonyl group optionally substituted with at least one halogen atom, C2-C5 alkoxycarbonyl group optionally substituted with at least one halogen atom, phenyl group or hydrogen atom Represents. ]
The malononitrile compound of Claim 1 shown by these. Formula (I-2)

[Where,
R ¹ , R ² , R ³ and R ⁴ have the same meaning as defined in claim 1,
R ⁵ , R ^6-1 and R ^6-2 are each substituted with a halogen atom, cyano group, nitro group, hydroxyl group, mercapto group, formyl group, SF ₅ group, carboxyl group or at least one halogen atom. An optionally substituted C1-C5 alkyl group, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, at least one A C3-C6 cycloalkyl group optionally substituted with at least one C1-C3 alkyl group, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, at least one A C3-C6 alkenyloxy group optionally substituted with a halogen atom, or substituted with at least one halogen atom Good C3-C6 alkynyloxy group, C1-C5 alkylthio group optionally substituted with at least one halogen atom, at least one C3-C5 alkenylthio group optionally substituted with at least one halogen atom A C3-C5 alkynylthio group optionally substituted with a halogen atom, a C1-C5 alkylsulfinyl group optionally substituted with at least one halogen atom, and optionally substituted with at least one halogen atom A C1-C5 alkylsulfonyl group, a C2-C6 alkylcarbonyl group optionally substituted with at least one halogen atom, a C2-C5 alkoxycarbonyl group optionally substituted with at least one halogen atom, a phenyl group, or Represents a hydrogen atom. ]
The malononitrile compound of Claim 1 shown by these. Formula (I-3)

[Where,
R ¹ , R ² , R ³ and R ⁴ have the same meaning as defined in claim 1,
R ⁵ , R ^6-1 and R ^6-2 are each substituted with a halogen atom, cyano group, nitro group, hydroxyl group, mercapto group, formyl group, SF ₅ group, carboxyl group or at least one halogen atom. An optionally substituted C1-C5 alkyl group, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, at least one A C3-C6 cycloalkyl group optionally substituted with at least one C1-C3 alkyl group, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, at least one A C3-C6 alkenyloxy group optionally substituted with a halogen atom, or substituted with at least one halogen atom Good C3-C6 alkynyloxy group, C1-C5 alkylthio group optionally substituted with at least one halogen atom, at least one C3-C5 alkenylthio group optionally substituted with at least one halogen atom A C3-C5 alkynylthio group optionally substituted with a halogen atom, a C1-C5 alkylsulfinyl group optionally substituted with at least one halogen atom, and optionally substituted with at least one halogen atom A C1-C5 alkylsulfonyl group, a C2-C6 alkylcarbonyl group optionally substituted with at least one halogen atom, a C2-C5 alkoxycarbonyl group optionally substituted with at least one halogen atom, a phenyl group, or Represents a hydrogen atom. ]
The malononitrile compound of Claim 1 shown by these. Formula (I-4)

[Where,
R ¹ , R ² , R ³ and R ⁴ have the same meaning as defined in claim 1,
R ⁵ , R ^6-1 and R ^6-2 are each substituted with a halogen atom, cyano group, nitro group, hydroxyl group, mercapto group, formyl group, SF ₅ group, carboxyl group or at least one halogen atom. An optionally substituted C1-C5 alkyl group, a C2-C5 alkenyl group optionally substituted with at least one halogen atom, a C2-C5 alkynyl group optionally substituted with at least one halogen atom, at least one A C3-C6 cycloalkyl group optionally substituted with at least one C1-C3 alkyl group, a C1-C5 alkoxy group optionally substituted with at least one halogen atom, at least one A C3-C6 alkenyloxy group optionally substituted with a halogen atom, or substituted with at least one halogen atom Good C3-C6 alkynyloxy group, C1-C5 alkylthio group optionally substituted with at least one halogen atom, at least one C3-C5 alkenylthio group optionally substituted with at least one halogen atom A C3-C5 alkynylthio group optionally substituted with a halogen atom, a C1-C5 alkylsulfinyl group optionally substituted with at least one halogen atom, and optionally substituted with at least one halogen atom A C1-C5 alkylsulfonyl group, a C2-C6 alkylcarbonyl group optionally substituted with at least one halogen atom, a C2-C5 alkoxycarbonyl group optionally substituted with at least one halogen atom, a phenyl group, or Represents a hydrogen atom. ]
The malononitrile compound of Claim 1 shown by these. The pest control agent which contains the malononitrile compound of any one of Claims 1-5 as an active ingredient. A method for controlling pests, wherein an effective amount of the malononitrile compound according to any one of claims 1 to 5 is applied to pests or habitats of pests (excluding human bodies).