JP4670355B2 - Malononitrile compound having nitrogen-containing 6-membered ring and use thereof - Google Patents

Description

  The present invention relates to a malononitrile compound having a nitrogen-containing 6-membered ring and a pest control application thereof.

  In order to control pests, 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、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、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、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、ハロゲン原子で置換されていてもよいＣ５〜Ｃ６シクロアルケニル基又は水素原子を表すか、或いはＲ³とＲ⁴とが一緒になって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。但し、Ｘ¹、Ｘ²及びＸ³のうち、２つ又は３つは窒素原子を表す。
Ｒ⁶は水素原子又はＲ⁵を表し、ｍは０〜２の整数を表し、Ｒ⁵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、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ６アルケニルオキシ基、ハロゲン原子で置換されていてもよいＣ３〜Ｃ６アルキニルオキシ基、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、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、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、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、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、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、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、−ＡＱ¹で示される基又は−Ｃ（＝ＮＯＲ¹⁴）Ｒ¹⁵で示される基を表す。但し、ｍが２であり、２つのＲ⁵が結合する２つの炭素原子が隣接する場合には、該当する２つのＲ⁵が一緒になって、Ｃ３〜Ｃ６アルカンジイル基もしくはＣ３〜Ｃ６アルケンジイル基を表してもよく、該Ｃ３〜Ｃ６アルカンジイル基及び該Ｃ３〜Ｃ６アルケンジイル基を形成するメチレン基はＯ、Ｓ(Ｏ)_rもしくはＮＲ¹⁶で置き換わっていてもよく、該Ｃ３〜Ｃ６アルカンジイル基及び該Ｃ３〜Ｃ６アルケンジイル基を形成する炭素原子は、ハロゲン原子もしくはハロゲン原子で置換されていてもよいＣ１〜Ｃ３アルコキシ基と結合していてもよい。
Ｒ¹⁰及びＲ¹¹は各々、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、（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、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、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、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か、或いは、Ｒ¹⁰とＲ¹¹とが一緒になり、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す。
Ｒ¹²及びＲ¹³は各々、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、−（ＣＨ₂）_nＱ²で示される基若しくは水素原子を表すか、又はＲ¹²とＲ¹³とが一緒になり、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す。
Ａは酸素原子、硫黄原子又は（ＣＨ₂）_nを表し、Ｒ¹⁴及びＲ¹⁵は各々、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、−（ＣＨ₂）_nＱ³で示される基又は水素原子を表す。
Ｑ¹、Ｑ²及びＱ³は各々、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキルチオ基及びハロゲン原子からなる群より選ばれる基で置換されていてもよいフェニル基を表し、Ｒ¹⁶はＣ１〜Ｃ３アルキル基を表し、ｎは０〜３の整数を表し、ｒは０〜２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及び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を提供する。 As a result of intensive studies to find a compound having an excellent control effect against pests, the present inventors have found that a malononitrile compound having a nitrogen-containing 6-membered ring represented by the following formula (I) is harmful insects and harmful It has been found that it has an excellent control effect against harmful arthropods such as mites and pests such as harmful nematodes.
That is, the present invention relates to the formula (I)

[Wherein, R ¹ is a C1 to C5 alkyl group optionally substituted with a halogen atom, a C2 to C5 alkenyl group optionally substituted with a halogen atom, or C2 to C5 optionally substituted with a halogen atom. Represents an alkynyl group or a hydrogen atom, and R ² may be a C1-C5 alkyl group which may be substituted with a halogen atom, a C1-C5 alkoxy group which may be substituted with a halogen atom, or a halogen atom. Represents a C2-C5 alkenyl group, a C2-C5 alkynyl group optionally substituted with a halogen atom, a cyano group or a hydrogen atom, and R ³ and R ⁴ each represent C1-C5 optionally substituted with a halogen atom An alkyl group, a C2-C5 alkenyl group optionally substituted with a halogen atom, a C2-C5 alkynyl group optionally substituted with a halogen atom, a halo Emissions atoms substituted by C3~C5 may cycloalkyl group, or represents a substituted C5~C6 may cycloalkenyl group or a hydrogen atom with a halogen atom, or R ³ and R ⁴ together A C2-C6 alkanediyl group optionally substituted with a halogen atom or a C4-C6 alkenediyl group optionally substituted with a halogen atom; X ¹ , X ² and X ³ each represent a nitrogen atom or CR ⁶ To express. However, two or three of X ¹ , X ² and X ³ represent nitrogen atoms.
R ⁶ represents a hydrogen atom or R ⁵ , m represents an integer of 0 to 2, and R ⁵ represents 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, respectively. A C1-C5 alkyl group optionally substituted with a halogen atom, a C2-C5 alkenyl group optionally substituted with a halogen atom, a C2-C5 alkynyl group optionally substituted with a halogen atom, or a halogen atom A C3-C5 cycloalkyl group which may be substituted, a C1-C5 alkoxy group which may be substituted with a halogen atom, a C3-C6 alkenyloxy group which may be substituted with a halogen atom, and a halogen atom. C3-C6 alkynyloxy group which may be substituted, C1-C5 alkylthio group which may be substituted with halogen atom, substituted with halogen atom An optionally substituted C3-C5 alkenylthio group, a C3-C5 alkynylthio group optionally substituted with a halogen atom, a C1-C5 alkylsulfinyl group optionally substituted with a halogen atom, and a halogen atom. A C1-C5 alkylsulfonyl group which may be substituted, a C2-C6 alkylcarbonyl group which may be substituted with a halogen atom, a C2-C5 alkoxycarbonyl group which may be substituted with a halogen atom, or a group represented by —NR ¹⁰ R ¹¹ represents a -C (= X ⁵⁾ a group represented by NR ¹² R ^13, a group represented by the group or -C (= NOR ¹⁴⁾ R ¹⁵ represented by -AQ ^1. However, when m is 2 and two carbon atoms to which two R ⁵ are bonded are adjacent to each other, the corresponding two R ⁵ are combined to form a C3 to C6 alkanediyl group or a C3 to C6 alkenediyl group. And the methylene group forming the C3-C6 alkanediyl group and the C3-C6 alkenediyl group may be replaced by O, S (O) _r or NR ¹⁶ , and the C3-C6 alkanediyl group And the carbon atom forming the C3-C6 alkenediyl group may be bonded to a halogen atom or a C1-C3 alkoxy group which may be substituted with a halogen atom.
R ¹⁰ and R ¹¹ are each a C1-C5 alkyl group optionally substituted with a halogen atom, a C3-C5 alkenyl group optionally substituted with a halogen atom, or a C3-C5 optionally substituted with a halogen atom. Alkynyl group, C3-C5 cycloalkyl group optionally substituted with a halogen atom, (C1-C5 alkoxy optionally substituted with a halogen atom) C1-C3 alkyl group, C1 optionally substituted with a halogen atom Represents a C2-alkylsulfonyl group, a C2-C6 alkylcarbonyl group optionally substituted with a halogen atom, a C2-C5 alkoxycarbonyl group optionally substituted with a halogen atom, or a hydrogen atom, or R ¹⁰ and R ¹¹ and it is together, by C2~C6 may alkanediyl group or a halogen-substituted with a halogen atom original In it represents the optionally substituted C4~C6 alkenediyl group.
R ¹² and R ¹³ are each a C1-C5 alkyl group optionally substituted with a halogen atom, a C3-C5 alkenyl group optionally substituted with a halogen atom, or a C3-C5 optionally substituted with a halogen atom. alkynyl group, optionally substituted C3~C5 cycloalkyl group with a halogen _{atom, - (CH 2) n Q} 2 in or a group or a hydrogen atom shown, or the R ¹² and R ¹³ come together, A C2-C6 alkanediyl group which may be substituted with a halogen atom or a C4-C6 alkenediyl group which may be substituted with a halogen atom is represented.
A represents an oxygen atom, a sulfur atom or (CH ₂ ) _n , and R ¹⁴ and R ¹⁵ are each a C1 to C5 alkyl group optionally substituted with a halogen atom, or C3 optionally substituted with a halogen atom. A C5 alkenyl group, a C3-C5 alkynyl group optionally substituted with a halogen atom, a C3-C5 cycloalkyl group optionally substituted with a halogen atom, a group represented by — (CH ₂ ) _n Q ³ , or a hydrogen atom Represents.
Q ¹ , Q ² and Q ³ may each be a C1-C5 alkyl group which may be substituted with a halogen atom, a C1-C5 alkoxy group which may be substituted with a halogen atom, or a halogen atom. C1~C5 alkylthio group and a phenyl group which may be substituted by a group selected from the group consisting of halogen atom, R ¹⁶ represents a C1~C3 alkyl group, n represents an integer of 0 to 3, r is Represents an integer of 0 to 2, and 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 in the presence of pests or pests Provided is a pest control method characterized by being applied to a place.

  Pests can be controlled by using a pesticidal agent containing the compound of the present invention as an active ingredient.

  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 compound of the present invention,
As ^{R 1, R 2, R 3} , R 4, R 5, R 10, R 11, R 12, R 13, R 14 and C1~C5 alkyl group which may be substituted with halogen atom represented by R ¹⁵ Is, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2,2-dimethylpropyl, chloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2 -Trifluoroethyl group and 1,1,2,2-tetrafluoroethyl group,
Examples of the C2-C5 alkenyl group optionally substituted by the halogen atom represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ include a vinyl group, 2,2-difluorovinyl group, 1,2, A 2-trifluorovinyl group, a 1-propenyl group and an allyl group,
Examples of the C2-C5 alkynyl group optionally substituted by the halogen atom represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ include an ethynyl group, a 1-propynyl group, a propargyl group, and 3, 3, A 3-trifluoro-1-propynyl group,
Examples of the C1-C5 alkoxy group optionally substituted with a halogen atom represented by R ² and R ⁵ include a methoxy group, an ethoxy group, a 1-methylethoxy group, a trifluoromethoxy group, a difluoromethoxy group, 2,2 , 2-trifluoroethoxy group and 1,1,2,2-tetrafluoroethoxy group,
Examples of the C3-C5 cycloalkyl group optionally substituted with a halogen atom represented by R ³ , R ⁴ , R ⁵ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ include cyclopropyl Group, 2,2-dichlorocyclopropyl group, 2,2-difluorocyclopropyl group, 2,2,3,3-tetrafluorocyclopropyl group, 2,2-dichlorocyclobutyl group, 2,2-difluorocyclobutyl Group, 2,2,3,3-tetrafluorocyclobutyl group, cyclobutyl group, and cyclopentyl group,
Examples of the C5-C6 cycloalkenyl group optionally substituted with a halogen atom represented by R ³ and R ⁴ include a 2-fluoro-2-cyclopentenyl group,
Examples of the C2-C6 alkanediyl group optionally substituted with a halogen atom represented by a combination of R ³ and R ⁴ , a combination of R ¹⁰ and R ^11, and a combination of R ¹² and R ¹³ include ethylene Groups, propylene groups, trimethylene groups and tetramethylene groups,
Examples of the C4-C6 alkenediyl group optionally substituted with a halogen atom represented by a combination of R ³ and R ⁴ , a combination of R ¹⁰ and R ^11, and a combination of R ¹² and R ¹³ include 2- Butene-1,4-diyl group and 2-pentene-1,5-diyl group,
Examples of the C3-C6 alkenyloxy group optionally substituted with a halogen atom represented by R ⁵ include allyloxy group, 1-methyl-2-propenyloxy group, 1,1-dimethyl-2-propenyloxy group, 2 -Methyl-2-propenyloxy group, 1-butenyloxy group, 2-butenyloxy group, 3-butenyloxy group, 1-chloro-2-propenyloxy group, 1-bromo-2-propenyloxy group, 2-chloro-2- A propenyloxy group and a 3,3-dichloro-2-propenyloxy group,
Examples of the C3-C6 alkynyloxy group optionally substituted by the halogen atom represented by R ⁵ include propargyloxy group, 2-butynyloxy group, 3-butynyloxy group, 2-pentynyloxy group, and 3-pentynyloxy group. Group, 3-chloro-2-propynyloxy group, 3-bromo-2-propynyloxy group, 1-methyl-2-propynyloxy group, 4-chloro-2-butynyloxy group, 4,4-difluoro-2-butynyloxy group Group, 4,4,4-trifluoro-2-butynyloxy group and 1,1-dimethyl-2-propynyloxy group,
Examples of the C1-C5 alkylthio group optionally substituted with a halogen atom represented by R ⁵ include a methylthio group, a trifluoromethylthio group, a 2,2,2-trifluoroethylthio group, and 1,1,2,2 -Tetrafluoroethylthio group,
Examples of the C3-C5 alkenylthio group optionally substituted with a halogen atom represented by R ⁵ include a 2-propenylthio group and a 2,2-difluoro-2-propenylthio group,
Examples of the C3-C5 alkynylthio group optionally substituted with a halogen atom represented by R ⁵ include a 2-propynylthio group and a 2-butynylthio group,
Examples of the C1-C5 alkylsulfinyl group optionally substituted with a halogen atom represented by R ⁵ include a methylsulfinyl group and a trifluoromethylsulfinyl group,
The R ^5, R ¹⁰ and R ¹¹ optionally substituted by C1~C5 alkylsulfonyl group by a halogen atom represented by, for example, include a methyl sulfonyl group and a trifluoromethyl sulfonyl group,
R ^5, R ¹⁰ and halogen atom-substituted as the C2~C6 alkyl group may be for example an acetyl group represented by R ^11, include a propionyl group and a trifluoroacetyl group,
Examples of the C2-C5 alkoxycarbonyl group optionally substituted with a halogen atom represented by R ⁵ , R ¹⁰ and R ¹¹ include a methoxycarbonyl group and a 2,2,2-trifluoroethoxycarbonyl group,
Examples of the C3-C5 alkenyl group optionally substituted by the halogen atom represented by R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ include a 1-propenyl group and an allyl group,
Examples of the C3-C5 alkynyl group optionally substituted by the halogen atom represented by R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ include a 1-propynyl group, a propargyl group and 3, 3, A 3-trifluoro-1-propynyl group,
Examples of the C1-C3 alkyl group represented by R ¹⁰ and R ¹¹ (C1-C5 alkoxy optionally substituted with a halogen atom) include a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, and 1-ethoxyethyl. Group, trifluoromethoxymethyl group,
When two carbon atoms to which two R ⁵ are bonded are adjacent to each other, examples of the C3-C6 alkanediyl group in which the two corresponding R ⁵ are shown together include, for example, a trimethylene group, a propylene group, 2,2- A dimethylpropane-1,4-diyl group, a 1,1-dimethylpropane-1,3-diyl group and a tetramethylene group;
When two carbon atoms to which two R ⁵ are bonded are adjacent to each other, the C3 to C6 alkenediyl group in which two corresponding R ⁵ are shown together include a 2-butene-1,4-diyl group and 2 A pentene-1,5-diyl group,
Examples of the C1-C3 alkyl group represented by R ¹⁶ include a methyl group, an ethyl group, and a propyl group.

Examples of the compound of the present invention include the following compounds.
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 with a 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 to C5 alkynyl group optionally substituted with a halogen atom;

A malononitrile compound in which R ⁴ is a C1-C5 fluoroalkyl group in formula (I);
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 to C5 cycloalkyl group optionally substituted with a halogen atom;
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;

In the formula (I), R ³ is a hydrogen atom and R ⁴ is a C1-C5 alkyl group which may be substituted with a halogen atom, a C2-C5 alkenyl group which may be substituted with a halogen atom, or a halogen atom. A C2-C5 alkynyl group which may be substituted, a malononitrile compound which is a C3-C5 cycloalkyl group which may be substituted with a halogen atom, or a malononitrile which is a C5-C6 cycloalkenyl group which may be substituted with a halogen atom Compound;
In the formula (I), R ³ is a hydrogen atom, and R ⁴ is a C2-C5 alkenyl group optionally substituted with a halogen atom, a C2-C5 alkynyl group optionally substituted with a halogen atom, or a halogen atom. A malononitrile compound which is an optionally substituted C3-C5 cycloalkyl group;
In the formula (I), R ³ is a hydrogen atom, and R ⁴ is a C2-C5 alkenyl group optionally substituted with a halogen atom, a C2-C5 alkynyl group optionally substituted with a halogen atom, or a halogen atom. A malononitrile compound which is an optionally substituted C3-C5 cycloalkyl group, X ¹ and X ² are nitrogen atoms, and X ³ is CR ⁶ ;
In the formula (I), R ³ is a hydrogen atom, and R ⁴ is a C2-C5 alkenyl group optionally substituted with a halogen atom, a C2-C5 alkynyl group optionally substituted with a halogen atom, or a halogen atom. A malononitrile compound which is an optionally substituted C3-C5 cycloalkyl group, X ¹ and X ³ are nitrogen atoms, and X ² is CR ⁶ ;
In the formula (I), R ³ is a hydrogen atom, and R ⁴ is a C2-C5 alkenyl group optionally substituted with a halogen atom, a C2-C5 alkynyl group optionally substituted with a halogen atom, or a halogen atom. A malononitrile compound which is an optionally substituted C3-C5 cycloalkyl group, X ² and X ³ are nitrogen atoms, and X ¹ is CR ⁶ ;
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 a 2,2-difluorovinyl group, 1- (trifluoromethyl) vinyl group, 3,3-difluoro-2-propenyl group, 2,3, A malononitrile compound which is a 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;

In the formula (I), R ¹ , R ² and R ³ are hydrogen atoms, R ⁴ is a C2 to C5 alkenyl group optionally substituted with a halogen atom, and C2 to C5 optionally substituted with a halogen atom. A malononitrile compound which is a C3-C5 cycloalkyl group optionally substituted with an alkynyl group or a halogen atom;
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 3,3,3-trifluoropropyl group or a 2,2,3,3,3-pentafluoropropyl group, a malononitrile compound;
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);
In formula (I), R ¹ and R ³ are hydrogen atoms, and R ⁴ is a C2-C5 alkenyl group optionally substituted with a halogen atom, a C2-C5 alkynyl group optionally substituted with a halogen atom, or A malononitrile compound which is a C3-C5 cycloalkyl group optionally substituted with a halogen atom;

A malononitrile compound in which X ¹ , X ² or X ³ is CR ⁶ and R ⁶ is a hydrogen atom in formula (I);
A malononitrile compound in which X ¹ is CR ⁶ and R ⁶ is a hydrogen atom in formula (I);
A malononitrile compound represented by the formula (I), wherein X ² is CR ⁶ and R ⁶ is a hydrogen atom;
A malononitrile compound represented by formula (I), wherein X ³ is CR ⁶ and R ⁶ is a hydrogen atom;
A malononitrile compound represented by formula (I), wherein X ³ is CR ⁶ and R ⁶ is R ⁵ ;
In the formula (I), X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, R ⁵ is a nitro group, a C1-C5 alkyl group optionally substituted with a halogen atom, halogen C2-C5 alkenyl group optionally substituted with atoms, C2-C5 alkynyl group optionally substituted with halogen atoms, C1-C5 alkoxy groups optionally substituted with halogen atoms, substituted with halogen atoms A C3-C6 alkenyloxy group which may be substituted, a C3-C6 alkynyloxy group which may be substituted with a halogen atom, a C1-C5 alkylthio group which may be substituted with a halogen atom, or a halogen atom. A malononitrile compound which is a C1-C5 alkylsulfonyl group which may be substituted with a C1-C5 alkylsulfinyl group or a halogen atom;

A malononitrile compound represented by formula (I), wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a cyano group;
A malononitrile compound represented by formula (I), wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a fluorine atom;
A malononitrile compound represented by formula (I), wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a chlorine atom;
A malononitrile compound represented by formula (I) wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a bromine atom;
A malononitrile compound represented by formula (I), wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a methyl group;
A malononitrile compound in which X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is an ethyl group in the formula (I);
A malononitrile compound represented by formula (I), wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is an isopropyl group;
A malononitrile compound represented by the formula (I), wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a t-butyl group;
In the formula (I), a malononitrile compound in which X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a 1-fluoro-1-methylethyl group ;
A malononitrile compound in which X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a trifluoromethyl group in the formula (I);
A malononitrile compound represented by formula (I), wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a pentafluoroethyl group;
A malononitrile compound represented by the formula (I), wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a propargyl group;
A malononitrile compound represented by formula (I), wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a vinyl group;
A malononitrile compound represented by formula (I), wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a propargyloxy group;
A malononitrile compound in which X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a 2-butynyloxy group in the formula (I);
A malononitrile compound represented by formula (I), wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a 3-butynyloxy group;

A malononitrile compound represented by formula (I), wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a methoxy group;
A malononitrile compound represented by formula (I), wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a methylthio group;
A malononitrile compound represented by formula (I), wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a trifluoromethylthio group;
A malononitrile compound represented by the formula (I), wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a trifluoromethylsulfinyl group;
A malononitrile compound represented by formula (I), wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a trifluoromethylsulfonyl group;
A malononitrile compound represented by formula (I), wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a nitro group;
A malononitrile compound represented by formula (I), wherein X ¹ , X ² or X ³ is CR ⁶ , R ⁶ is a hydrogen atom, m is 1 and R ⁵ is a dimethylamino group;

In the formula (I), X ¹ , X ² and X ³ are nitrogen atoms, R ⁵ is a nitro group, a C1-C5 alkyl group which may be substituted with a halogen atom, or a halogen atom. C2-C5 alkenyl group, C2-C5 alkynyl group optionally substituted with a halogen atom, C1-C5 alkoxy group optionally substituted with a halogen atom, C3-C6 alkenyloxy optionally substituted with a halogen atom A C3-C6 alkynyloxy group optionally substituted with a halogen atom, a C1-C5 alkylthio group optionally substituted with a halogen atom, a C1-C5 alkylsulfinyl group optionally substituted with a halogen atom, or a halogen A malononitrile compound which is a C1-C5 alkylsulfonyl group optionally substituted by an atom;

〔式中、
Ｒ¹は、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、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、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、ハロゲン原子で置換されていてもよいＣ５〜Ｃ６シクロアルケニル基又は水素原子を表すか、
或いはＲ³とＲ⁴とが一緒になって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、
Ｒ^5aは水素原子、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、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ６アルケニルオキシ基、ハロゲン原子で置換されていてもよいＣ３〜Ｃ６アルキニルオキシ基、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、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、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、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、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、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、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、−ＡＱ¹で示される基又は−Ｃ（＝ＮＯＲ¹⁴）Ｒ¹⁵で示される基を表す。
Ｒ¹⁰及びＲ¹¹は各々、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、（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、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、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、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か、
或いは、Ｒ¹⁰とＲ¹¹とが一緒になり、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す。
Ｒ¹²及びＲ¹³は各々、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、−（ＣＨ₂）_nＱ²で示される基若しくは水素原子を表すか、
又はＲ¹²とＲ¹³とが一緒になり、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す。
Ａは酸素原子、硫黄原子又は（ＣＨ₂）_nを表し、
Ｒ¹⁴及びＲ¹⁵は各々、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、−（ＣＨ₂）_nＱ³で示される基又は水素原子を表す。
Ｑ¹、Ｑ²及びＱ³は各々、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキルチオ基及びハロゲン原子からなる群より選ばれる基で置換されていてもよいフェニル基を表し、
ｎは０〜３の整数を表し、
Ｘ⁵は酸素原子又は硫黄原子を表す。〕 A malononitrile compound represented by the formula (XI);

[Where,
R ¹ is a C1-C5 alkyl group optionally substituted with a halogen atom, a C2-C5 alkenyl group optionally substituted with a halogen atom, a C2-C5 alkynyl group optionally substituted with a halogen atom, or hydrogen Represents an atom,
R ² represents a C1-C5 alkyl group optionally substituted with a halogen atom, a C1-C5 alkoxy group optionally substituted with a halogen atom, a C2-C5 alkenyl group optionally substituted with a halogen atom, a halogen Represents a C2-C5 alkynyl group optionally substituted with an atom, a cyano group or a hydrogen atom,
R ³ and R ⁴ are each a C1-C5 alkyl group optionally substituted with a halogen atom, a C2-C5 alkenyl group optionally substituted with a halogen atom, or a C2-C5 optionally substituted with a halogen atom. An alkynyl group, a C3-C5 cycloalkyl group optionally substituted with a halogen atom, a C5-C6 cycloalkenyl group optionally substituted with a halogen atom, or a hydrogen atom,
Alternatively, R ³ and R ⁴ together represent a C2 to C6 alkanediyl group which may be substituted with a halogen atom or a C4 to C6 alkenediyl group which may be substituted with a halogen atom,
R ^5a is a hydrogen atom, 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, a C1-C5 alkyl group optionally substituted with a halogen atom, or a halogen atom. An optionally substituted C2-C5 alkenyl group, an optionally substituted C2-C5 alkynyl group, an optionally substituted C3-C5 cycloalkyl group, or a halogen atom. Good C1-C5 alkoxy group, C3-C6 alkenyloxy group optionally substituted with a halogen atom, C3-C6 alkynyloxy group optionally substituted with a halogen atom, C1-C1 optionally substituted with a halogen atom C5 alkylthio group, C3-C5 alkenylthio group optionally substituted with halogen atom, halogen An optionally substituted C3-C5 alkynylthio group, an optionally substituted C1-C5 alkylsulfinyl group, an optionally substituted C1-C5 alkylsulfonyl group, a halogen atom substituted C2~C6 may alkylcarbonyl group, an optionally substituted C2~C5 alkoxycarbonyl group with a halogen atom, a group represented by ^{-NR 10 R 11, -C (=} X 5) NR 12 R 13 Represents a group represented by -AQ ¹ or a group represented by -C (= NOR ¹⁴ ) R ¹⁵ .
R ¹⁰ and R ¹¹ are each a C1-C5 alkyl group optionally substituted with a halogen atom, a C3-C5 alkenyl group optionally substituted with a halogen atom, or a C3-C5 optionally substituted with a halogen atom. Alkynyl group, C3-C5 cycloalkyl group optionally substituted with a halogen atom, (C1-C5 alkoxy optionally substituted with a halogen atom) C1-C3 alkyl group, C1 optionally substituted with a halogen atom Represents a -C5 alkylsulfonyl group, a C2-C6 alkylcarbonyl group optionally substituted with a halogen atom, a C2-C5 alkoxycarbonyl group optionally substituted with a halogen atom, or a hydrogen atom,
Alternatively, R ¹⁰ and R ¹¹ together represent a C2 to C6 alkanediyl group which may be substituted with a halogen atom or a C4 to C6 alkenediyl group which may be substituted with a halogen atom.
R ¹² and R ¹³ are each a C1-C5 alkyl group optionally substituted with a halogen atom, a C3-C5 alkenyl group optionally substituted with a halogen atom, or a C3-C5 optionally substituted with a halogen atom. alkynyl group, a substituted C3~C5 may cycloalkyl group with a halogen atom, - (CH ₂₎ represent a group or a hydrogen atom represented by _n Q ^2,
Alternatively, R ¹² and R ¹³ together represent a C2 to C6 alkanediyl group which may be substituted with a halogen atom or a C4 to C6 alkenediyl group which may be substituted with a halogen atom.
A represents an oxygen atom, a sulfur atom or (CH ₂ ) _n ;
R ¹⁴ and R ¹⁵ are each a C1-C5 alkyl group optionally substituted with a halogen atom, a C3-C5 alkenyl group optionally substituted with a halogen atom, or a C3-C5 optionally substituted with a halogen atom. alkynyl, C3-C5 cycloalkyl group optionally substituted by a halogen atom, - represents a (CH ₂₎ group or a hydrogen atom represented by _n Q ^3.
Q ¹ , Q ² and Q ³ may each be a C1-C5 alkyl group which may be substituted with a halogen atom, a C1-C5 alkoxy group which may be substituted with a halogen atom, or a halogen atom. Represents a phenyl group which may be substituted with a group selected from the group consisting of a C1-C5 alkylthio group and a halogen atom;
n represents an integer of 0 to 3,
X ⁵ represents an oxygen atom or a sulfur atom. ]

〔式中、
Ｒ¹は、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、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、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、ハロゲン原子で置換されていてもよいＣ５〜Ｃ６シクロアルケニル基又は水素原子を表すか、
或いはＲ³とＲ⁴とが一緒になって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、
ｍは０〜２の整数を表し、
Ｒ⁵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、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ６アルケニルオキシ基、ハロゲン原子で置換されていてもよいＣ３〜Ｃ６アルキニルオキシ基、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、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、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、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、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、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、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、−ＡＱ¹で示される基又は−Ｃ（＝ＮＯＲ¹⁴）Ｒ¹⁵で示される基を表す。
Ｒ¹⁰及びＲ¹¹は各々、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、（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、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、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、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か、
或いは、Ｒ¹⁰とＲ¹¹とが一緒になり、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す。
Ｒ¹²及びＲ¹³は各々、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、−（ＣＨ₂）_nＱ²で示される基若しくは水素原子を表すか、
又はＲ¹²とＲ¹³とが一緒になり、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す。
Ａは酸素原子、硫黄原子又は（ＣＨ₂）_nを表し、
Ｒ¹⁴及びＲ¹⁵は各々、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、−（ＣＨ₂）_nＱ³で示される基又は水素原子を表す。
Ｑ¹、Ｑ²及びＱ³は各々、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキルチオ基及びハロゲン原子からなる群より選ばれる基で置換されていてもよいフェニル基を表し、
ｎは０〜３の整数を表し、
Ｘ⁵は酸素原子又は硫黄原子を表す。〕 A malononitrile compound represented by the formula (XII);

[Where,
R ¹ is a C1-C5 alkyl group optionally substituted with a halogen atom, a C2-C5 alkenyl group optionally substituted with a halogen atom, a C2-C5 alkynyl group optionally substituted with a halogen atom, or hydrogen Represents an atom,
R ² represents a C1-C5 alkyl group optionally substituted with a halogen atom, a C1-C5 alkoxy group optionally substituted with a halogen atom, a C2-C5 alkenyl group optionally substituted with a halogen atom, a halogen Represents a C2-C5 alkynyl group optionally substituted with an atom, a cyano group or a hydrogen atom,
R ³ and R ⁴ are each a C1-C5 alkyl group optionally substituted with a halogen atom, a C2-C5 alkenyl group optionally substituted with a halogen atom, or a C2-C5 optionally substituted with a halogen atom. An alkynyl group, a C3-C5 cycloalkyl group optionally substituted with a halogen atom, a C5-C6 cycloalkenyl group optionally substituted with a halogen atom, or a hydrogen atom,
Alternatively, R ³ and R ⁴ together represent a C2 to C6 alkanediyl group which may be substituted with a halogen atom or a C4 to C6 alkenediyl group which may be substituted with a halogen atom,
m represents an integer of 0 to 2,
R ⁵ is each substituted with 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, an optionally substituted C1-C5 alkyl group, or a halogen atom. An optionally substituted C2-C5 alkenyl group, a C2-C5 alkynyl group optionally substituted with a halogen atom, a C3-C5 cycloalkyl group optionally substituted with a halogen atom, and optionally substituted with a halogen atom C1-C5 alkoxy group, C3-C6 alkenyloxy group optionally substituted with a halogen atom, C3-C6 alkynyloxy group optionally substituted with a halogen atom, C1-C5 optionally substituted with a halogen atom Alkylthio group, C3-C5 alkenylthio group optionally substituted with halogen atom, halogen atom C3-C5 alkynylthio group optionally substituted with, C1-C5 alkylsulfinyl group optionally substituted with a halogen atom, C1-C5 alkylsulfonyl group optionally substituted with a halogen atom, substituted with a halogen atom by C2~C6 may alkylcarbonyl group, an optionally substituted C2~C5 alkoxycarbonyl group with a halogen atom, a group represented by -NR ¹⁰ R ^11, with ^{-C (= X 5) NR 12} R 13 A group represented by the formula: -AQ ¹ or a group represented by -C (= NOR ¹⁴ ) R ¹⁵ .
R ¹⁰ and R ¹¹ are each a C1-C5 alkyl group optionally substituted with a halogen atom, a C3-C5 alkenyl group optionally substituted with a halogen atom, or a C3-C5 optionally substituted with a halogen atom. Alkynyl group, C3-C5 cycloalkyl group optionally substituted with a halogen atom, (C1-C5 alkoxy optionally substituted with a halogen atom) C1-C3 alkyl group, C1 optionally substituted with a halogen atom Represents a -C5 alkylsulfonyl group, a C2-C6 alkylcarbonyl group optionally substituted with a halogen atom, a C2-C5 alkoxycarbonyl group optionally substituted with a halogen atom, or a hydrogen atom,
Alternatively, R ¹⁰ and R ¹¹ together represent a C2 to C6 alkanediyl group which may be substituted with a halogen atom or a C4 to C6 alkenediyl group which may be substituted with a halogen atom.
R ¹² and R ¹³ are each a C1-C5 alkyl group optionally substituted with a halogen atom, a C3-C5 alkenyl group optionally substituted with a halogen atom, or a C3-C5 optionally substituted with a halogen atom. alkynyl group, a substituted C3~C5 may cycloalkyl group with a halogen atom, - (CH ₂₎ represent a group or a hydrogen atom represented by _n Q ^2,
Alternatively, R ¹² and R ¹³ together represent a C2 to C6 alkanediyl group which may be substituted with a halogen atom or a C4 to C6 alkenediyl group which may be substituted with a halogen atom.
A represents an oxygen atom, a sulfur atom or (CH ₂ ) _n ;
R ¹⁴ and R ¹⁵ are each a C1-C5 alkyl group optionally substituted with a halogen atom, a C3-C5 alkenyl group optionally substituted with a halogen atom, or a C3-C5 optionally substituted with a halogen atom. alkynyl, C3-C5 cycloalkyl group optionally substituted by a halogen atom, - represents a (CH ₂₎ group or a hydrogen atom represented by _n Q ^3.
Q ¹ , Q ² and Q ³ may each be a C1-C5 alkyl group which may be substituted with a halogen atom, a C1-C5 alkoxy group which may be substituted with a halogen atom, or a halogen atom. Represents a phenyl group which may be substituted with a group selected from the group consisting of a C1-C5 alkylthio group and a halogen atom;
n represents an integer of 0 to 3,
X ⁵ represents an oxygen atom or a sulfur atom. ]

〔式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴及びＲ⁵は式（ＸＩＩ）における定義と同じ意味を表し、ｍは０〜３の整数を表す。〕 A malononitrile compound represented by the formula (XIII);

[Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent the same meaning as defined in formula (XII), and m represents an integer of 0 to 3. ]

〔式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴及びＲ⁵は式（ＸＩＩ）における定義と同じ意味を表し、ｍは０〜２の整数を表す。〕 A malononitrile compound represented by the formula (XIV);

[Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent the same meaning as defined in formula (XII), and m represents an integer of 0 to 2. ]

〔式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴及びＲ^5aは式（ＸＩ）における定義と同じ意味を表す。〕 A malononitrile compound represented by the formula (XV);

[Wherein R ¹ , R ² , R ³ , R ⁴ and R ^5a represent the same meaning as defined in formula (XI). ]

〔式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴及びＲ⁵は式（ＸＩＩ）における定義と同じ意味を表し、ｍは０〜２の整数を表す。〕 A malononitrile compound represented by the formula (XVI);

[Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent the same meaning as defined in formula (XII), and m represents an integer of 0 to 2. ]

In the formula (XI), R ³ is a hydrogen atom and R ⁴ is a C1-C5 alkyl group which may be substituted with a halogen atom, a C2-C5 alkenyl group which may be substituted with a halogen atom, or a halogen atom. A C2-C5 alkynyl group which may be substituted, a malononitrile compound which is a C3-C5 cycloalkyl group which may be substituted with a halogen atom, or a malononitrile which is a C5-C6 cycloalkenyl group which may be substituted with a halogen atom Compound;
In the formula (XII), R ³ is a hydrogen atom, R ⁴ is substituted C1~C5 may be an alkyl group with a halogen atom, optionally substituted C2~C5 alkenyl with a halogen atom, a halogen atom A C2-C5 alkynyl group which may be substituted, a malononitrile compound which is a C3-C5 cycloalkyl group which may be substituted with a halogen atom, or a malononitrile which is a C5-C6 cycloalkenyl group which may be substituted with a halogen atom Compound;
In the formula (XIII), R ³ is a hydrogen atom and R ⁴ is a C1-C5 alkyl group which may be substituted with a halogen atom, a C2-C5 alkenyl group which may be substituted with a halogen atom, or a halogen atom. A C2-C5 alkynyl group which may be substituted, a malononitrile compound which is a C3-C5 cycloalkyl group which may be substituted with a halogen atom, or a malononitrile which is a C5-C6 cycloalkenyl group which may be substituted with a halogen atom Compound;

In the formula (XIV), R ³ is a hydrogen atom, and R ⁴ is a C1-C5 alkyl group optionally substituted with a halogen atom, a C2-C5 alkenyl group optionally substituted with a halogen atom, or a halogen atom A C2-C5 alkynyl group which may be substituted, a malononitrile compound which is a C3-C5 cycloalkyl group which may be substituted with a halogen atom, or a malononitrile which is a C5-C6 cycloalkenyl group which may be substituted with a halogen atom Compound;
In the formula (XV), R ³ is a hydrogen atom, and R ⁴ is a C1-C5 alkyl group which may be substituted with a halogen atom, a C2-C5 alkenyl group which may be substituted with a halogen atom, or a halogen atom. A C2-C5 alkynyl group which may be substituted, a malononitrile compound which is a C3-C5 cycloalkyl group which may be substituted with a halogen atom, or a malononitrile which is a C5-C6 cycloalkenyl group which may be substituted with a halogen atom Compound;
In the formula (XVI), R ³ is a hydrogen atom, and R ⁴ is a C1-C5 alkyl group which may be substituted with a halogen atom, a C2-C5 alkenyl group which may be substituted with a halogen atom, or a halogen atom. A C2-C5 alkynyl group which may be substituted, a malononitrile compound which is a C3-C5 cycloalkyl group which may be substituted with a halogen atom, or a malononitrile which is a C5-C6 cycloalkenyl group which may be substituted with a halogen atom Compound;

In formula (XI), formula (XII) or formula (XIII), R ⁵ or R ^5a is a nitro group, a C1-C5 alkyl group optionally substituted with a halogen atom, or a C2 optionally substituted with a halogen atom -C5 alkenyl group, C2-C5 alkynyl group optionally substituted with a halogen atom, C1-C5 alkoxy group optionally substituted with a halogen atom, C3-C6 alkenyloxy group optionally substituted with a halogen atom A C3-C6 alkynyloxy group optionally substituted with a halogen atom, a C1-C5 alkylthio group optionally substituted with a halogen atom, a C1-C5 alkylsulfinyl group optionally substituted with a halogen atom, or a halogen atom A malononitrile compound which is a C1-C5 alkylsulfonyl group optionally substituted by:

A malononitrile compound represented by the formula (XI) or the formula (XII), wherein R ⁵ or R ^5a is a cyano group;
A malononitrile compound in which R ⁵ or R ^5a is a fluorine atom in formula (XI) or formula (XII);
A malononitrile compound in which R ⁵ or R ^5a is a chlorine atom in formula (XI) or formula (XII);
A malononitrile compound represented by the formula (XI) or the formula (XII), wherein R ⁵ or R ^5a is a bromine atom;
A malononitrile compound in which R ⁵ or R ^5a is a methyl group in formula (XI) or formula (XII);
A malononitrile compound represented by the formula (XI) or the formula (XII), wherein R ⁵ or R ^5a is an ethyl group;
A malononitrile compound represented by the formula (XI) or the formula (XII), wherein R ⁵ or R ^5a is an isopropyl group;
A malononitrile compound in which R ⁵ or R ^5a is a t-butyl group in formula (XI) or formula (XII);
A malononitrile compound represented by the formula (XI) or the formula (XII), wherein R ⁵ or R ^5a is a 1-fluoro-1-methylethyl group;
A malononitrile compound represented by the formula (XI) or the formula (XII), wherein R ⁵ or R ^5a is a trifluoromethyl group;
A malononitrile compound represented by the formula (XI) or the formula (XII), wherein R ⁵ or R ^5a is a pentafluoroethyl group;
A malononitrile compound represented by the formula (XI) or the formula (XII), wherein R ⁵ or R ^5a is an ethynyl group;
A malononitrile compound in which R ⁵ or R ^5a is a propargyl group in formula (XI) or formula (XII);
A malononitrile compound represented by the formula (XI) or the formula (XII), wherein R ⁵ or R ^5a is a vinyl group;
A malononitrile compound represented by the formula (XI) or the formula (XII), wherein R ⁵ or R ^5a is a propargyloxy group;
A malononitrile compound represented by the formula (XI) or the formula (XII), wherein R ⁵ or R ^5a is a 2-butynyloxy group;
A malononitrile compound represented by the formula (XI) or the formula (XII), wherein R ⁵ or R ^5a is a 3-butynyloxy group;
A malononitrile compound represented by the formula (XI) or the formula (XII), wherein R ⁵ or R ^5a is a methoxy group;
A malononitrile compound represented by the formula (XI) or the formula (XII), wherein R ⁵ or R ^5a is a methylthio group;
A malononitrile compound represented by the formula (XI) or the formula (XII), wherein R ⁵ or R ^5a is a trifluoromethylthio group;
A malononitrile compound represented by the formula (XI) or the formula (XII), wherein R ⁵ or R ^5a is a trifluoromethylsulfinyl group;
A malononitrile compound represented by the formula (XI) or the formula (XII), wherein R ⁵ or R ^5a is a trifluoromethylsulfonyl group;
A malononitrile compound represented by the formula (XI) or the formula (XII), wherein R ⁵ or R ^5a is a nitro group;
And the malononitrile compound whose R ^{< 5} > or R ^<5a> is a dimethylamino group in Formula (XI) or Formula (XII).

Next, the manufacturing method of this invention compound is demonstrated.
The compound of the present invention can be produced, for example, according to the following (Production Method 1) to (Production Method 3).

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｘ¹、Ｘ²及びＸ³は前記と同じ意味を表し、ｍは０〜２の整数を表し、Ｚはハロゲン原子、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又はトルエンスルホニルオキシ基を表す。］
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挙げられる。
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挙げられる。
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、有機溶媒抽出してから、濃縮する等の後処理操作を行うことにより、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。 (Production method 1)

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X ¹ , X ² and X ³ represent the same meaning as described above, m represents an integer of 0 to 2, Z represents a halogen atom, A methanesulfonyloxy group, a trifluoromethanesulfonyloxy group or a toluenesulfonyloxy group is represented. ]
The reaction is usually performed in a solvent in the presence of a base.
Examples of the solvent used in the reaction include amides such as N, N-dimethylformamide, ethers such as diethyl ether and tetrahydrofuran, organic sulfurs such as dimethyl sulfoxide and sulfolane, and halogenation such as 1,2-dichloroethane and chlorobenzene. Examples thereof include 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 and 4-dimethylaminopyridine, 1,4-diazabicyclo [2.2. .2] organic bases such as octane and 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 the formula (I) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating. . 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、Ｒ³、Ｒ⁴、Ｒ⁵、Ｘ¹、Ｘ²及びＸ³は前記と同じ意味を表し、ｍは０〜２の整数を表し、Ｚはハロゲン原子、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又はトルエンスルホニルオキシ基を表す。］
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挙げられる。
該反応で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（ｑ）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（ｒ）の量は、化合物（ｑ）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、有機溶媒抽出してから、濃縮する等の後処理操作を行うことにより、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。 (Production method 2)

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X ¹ , X ² and X ³ represent the same meaning as described above, m represents an integer of 0 to 2, Z represents a halogen atom, A methanesulfonyloxy group, a trifluoromethanesulfonyloxy group or a toluenesulfonyloxy group is represented. ]
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. 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 and 4-dimethylaminopyridine, 1,4-diazabicyclo [2.2. .2] organic bases such as octane and 1,8-diazabicyclo [5.4.0] -7-undecene.
The amount of the base used in the reaction is usually 1 to 10 moles relative to 1 mole of the compound (q).
The amount of the compound (r) used in the reaction is usually 1 to 10 moles per 1 mole of the compound (q).
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 the formula (I) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating. . 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、Ｒ³、Ｒ⁴、Ｘ¹、Ｘ²、Ｘ³及びＺは前記と同じ意味を表し、Ｒ^5-1はシアノ基、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５アルケニルオキシ基、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５アルキニルオキシ基、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、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、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５アルキニルチオ基又は−ＮＲ¹⁰Ｒ¹¹で示される基を表し、Ｒ¹⁰及びＲ¹¹は前記と同じ意味を表し、Ｍ¹はＮａ又はＫを表す。〕
該反応は通常溶媒中、塩基の存在下又は非存在下で行われる。
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。
該反応で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（Ｉ−ｂ）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Ｒ^5-1−ＨまたはＲ^5-1−Ｍ¹の量は、化合物（Ｉ−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、有機溶媒抽出してから、濃縮する等の後処理操作を行うことにより、化合物（Ｉ−ａ）を単離することができる。単離された化合物（Ｉ−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。 (Production method 3)
Among the compounds of the present invention, compound (Ia) can also be produced by the following method.

[Wherein R ¹ , R ² , R ³ , R ⁴ , X ¹ , X ² , X ³ and Z represent the same meaning as described above, and R ^5-1 may be substituted with a cyano group or a halogen atom. Good C1-C5 alkoxy group, C3-C5 alkenyloxy group optionally substituted with a halogen atom, C3-C5 alkynyloxy group optionally substituted with a halogen atom, C1-C1 optionally substituted with a halogen atom C5 alkylthio group, by C3~C5 may alkenylthio group substituted with a halogen atom, a group represented by or C3~C5 alkynylthio or -NR ¹⁰ R ¹¹ may be substituted by a halogen atom, R ¹⁰ And R ¹¹ represents the same meaning as described above, and M ¹ represents Na or K. ]
The reaction is usually performed in a solvent in the presence or absence 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. 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 and 4-dimethylaminopyridine, 1,4-diazabicyclo [2.2. .2] organic bases such as octane and 1,8-diazabicyclo [5.4.0] -7-undecene. The amount of the base used in the reaction is usually 1 to 10 moles relative to 1 mole of compound (Ib).
The amount of R ^5-1 -H or R ^5-1 -M ¹ used in the reaction is usually 1 to 10 moles per 1 mole of compound (Ib).
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 (Ia) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water, extraction with an organic solvent, and concentration. The isolated compound (Ia) 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し、ｍは０〜２の整数を表し、ＭはＭｇＩ、ＭｇＢｒ、ＭｇＣｌ、Ｌｉ、Ｋ、Ｎａ、ＺｎＲ²又はＣｕを表す。〕
工程（１−１）
化合物（ｄ）は化合物（ｃ）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（ｃ）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（ｃ）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、有機溶媒抽出してから、濃縮する等の後処理操作を行うことにより、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。 Compound (a) can be produced, for example, by the following 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, m represents an integer of 0 to 2, M represents MgI, MgBr, MgCl, Li, K , Na, ZnR ² or Cu. ]
Step (1-1)
Compound (d) can be produced by reacting compound (c) 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 carried out 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 for the reaction is usually 0.01 to 0.5 mol with respect to 1 mol of compound (c).
The amount of malononitrile used in the reaction is usually 1 to 10 moles per mole of compound (c).
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 (d) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating. The isolated compound (d) can be purified by chromatography, recrystallization or the like, if necessary.

Step (1-2)
(1) R ² is substituted by C1~C5 may be an alkyl group with a halogen atom, optionally substituted C2~C5 alkenyl group halogen atom, substituted C2~C5 may alkynyl with a halogen atom Compound (a) can be produced by reacting compound (d) with an organometallic compound (R ² -M).
The reaction is usually carried out in a solvent, if necessary, in the presence of a copper salt.
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 R ² -M used in the reaction include organic magnesium compounds such as methylmagnesium iodide, ethylmagnesium bromide, isopropylmagnesium bromide, vinylmagnesium bromide, ethynylmagnesium bromide, and dimethylmagnesium, and organic compounds such as methyllithium. Examples include lithium compounds, organic zinc compounds such as diethyl zinc, and organic copper compounds such as trifluoromethyl copper.
The amount of R ² —M used in the reaction is usually 1 to 10 moles per mole of compound (d).
Examples of the copper salt used in the reaction include copper (I) iodide and copper (I) bromide.
The amount of copper salt used in the reaction is usually 1 mol or less per 1 mol of compound (d).
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 performing post-treatment operations such as pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating. The isolated compound (a) can be purified by chromatography, recrystallization or the like, if necessary.

(2) When R ² represents a hydrogen atom Compound (a) can be produced by subjecting compound (d) to a reduction reaction.
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 (d).
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 performing post-treatment operations such as pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating. The isolated compound (a) can be purified by chromatography, recrystallization or the like, if necessary.

(3) When R ² represents a cyano group Compound (a) can be produced by reacting compound (d) with a metal 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 metal cyanide used in the reaction include sodium cyanide, potassium cyanide and copper cyanide.
The amount of metal cyanide used in the reaction is usually 1 to 10 moles per mole of compound (d).
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 performing post-treatment operations such as pouring the reaction mixture into water and extracting the mixture with an organic solvent, followed by concentration. The isolated compound (a) can be purified by chromatography, recrystallization or the like, if necessary.

〔式中、Ｒ¹、Ｒ⁵、Ｘ¹、Ｘ²、Ｘ³及びＭは前記と同じ意味を表し、ｍは０〜２の整数を表し、Ｒ²¹はメチル基又はエチル基を表す。〕
化合物（ｃ）は、例えば化合物（ｅ）を有機金属化合物（Ｒ¹−Ｍ）又は還元剤と反応させることにより製造することができる。
（１）Ｒ¹−Ｍと反応させる場合
反応に用いられるＲ¹−Ｍで示さ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及びメチルリチウム等の有機リチウム化合物が挙げられる。
反応に用いられるＲ¹−Ｍ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。
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、有機溶媒抽出してから、濃縮する等の後処理操作を行うことにより、化合物（ｃ）を単離することができる。単離された化合物（ｃ）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）還元剤と反応させる場合
反応に用いられる還元剤としては、水素化リチウムアルミニウム及び水素化ジイソブチルアルミニウム等が挙げられる。
該反応に用いられる還元剤の量は、化合物（ｅ）１モルに対して通常０．２５〜５モルの割合である。
該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。
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、有機溶媒抽出してから、濃縮する等の後処理操作を行うことにより、化合物（ｃ）を単離することができる。単離された化合物（ｃ）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)

[Wherein, R ¹ , R ⁵ , X ¹ , X ² , X ³ and M represent the same meaning as described above, m represents an integer of 0 to 2, and R ²¹ represents a methyl group or an ethyl group. ]
Compound (c) can be produced, for example, by reacting compound (e) with an organometallic compound (R ¹ -M) or a reducing agent.
(1) As the organometallic compound if represented by R ¹ -M used for the reaction is reacted with R ¹ -M, such as methyl magnesium iodide, magnesium bromide ethyl, isopropyl magnesium bromide, vinyl magnesium bromide, odor And organic magnesium compounds such as ethynylmagnesium and dimethylmagnesium and methyllithium.
The amount of R ¹ -M used in the reaction is usually 1 to 10 moles per 1 mole of compound (e).
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.
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 (c) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating. The isolated compound (c) can be purified by chromatography, recrystallization or the like, if necessary.
(2) When reacting with a reducing agent Examples of the reducing agent used in the reaction include lithium aluminum hydride and diisobutylaluminum hydride.
The amount of the reducing agent used in the reaction is usually in a ratio of 0.25 to 5 mol with respect to 1 mol of the compound (e).
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.
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 (c) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating. The isolated compound (c) can be purified by chromatography, recrystallization or the like, if necessary.

［式中、Ｒ²¹は前記と同じ意味を表し、Ｒ^5-1はヒドロキシル基、メルカプト基、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、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、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、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、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、−ＣＯＯＲ²¹で示される基又は水素原子を表し、Ｒ^5-2は各々、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、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、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、−ＣＯＯＲ²¹で示される基または水素原子を表す。但し、Ｒ^5-1及びＲ^5-2のいずれか１つは必ず−ＣＯＯＲ²¹で示される基である。Ｒ²²はメチル基、エチル基、Ｎａ又はＫを表す。］ (Reference production method 3)
Among the compounds (e), the compound (e-4) and the compound (e-5) are described in, for example, Synthesis, 2002, p. It can be produced according to the synthesis method of 5-pyrimidinecarboxylates described in 720-722.

[Wherein R ²¹ represents the same meaning as described above, and R ^5-1 represents a hydroxyl group, a mercapto group, a C1-C5 alkyl group optionally substituted with a halogen atom, or a C3 optionally substituted with a halogen atom. -C5 cycloalkyl group, C2-C5 alkenyl group optionally substituted with a halogen atom, C2-C5 alkynyl group optionally substituted with a halogen atom, C1-C5 alkoxy group optionally substituted with a halogen atom , substituted C1~C5 may alkylthio group with a halogen atom, a group or a hydrogen atom represented by -COOR ^21, each R ^5-2, are C1~C5 may have an alkyl group substituted with a halogen atom A C3-C5 cycloalkyl group optionally substituted with a halogen atom, a C2-C5 alkenyl group optionally substituted with a halogen atom, a halogen It may be substituted with child C2~C5 alkynyl group, an group or a hydrogen atom represented by -COOR ^21. However, one of R ^5-1 and R ^5-2 is always a group represented by —COOR ²¹ . R ²² represents a methyl group, an ethyl group, Na or K. ]

〔式中、Ｒ²¹は前記と同じ意味を表し、ｍは０〜２の整数を表し、Ｒ⁵²はハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基を表す。〕
工程（６−２）におけるエステル化の方法としては、例えば化合物（ｌ）をＲ²¹ＯＨで示されるアルコール（メタノール又はエタノール）に溶解し、酸（例えば硫酸が挙げられる）を加えて加熱還流する方法が挙げられる。 (Reference production method 4)
Among the compounds (e), the compound (e-7) is, for example, Eur. J. et al. Med. Chem, Vol. 15, p. The compound (1) obtained according to the method described in 157 to 163 can be produced by esterification.

[Wherein, R ²¹ represents the same meaning as described above, m represents an integer of 0 to 2, and R ⁵² represents a C1 to C5 alkyl group which may be substituted with a halogen atom. ]
As a method of esterification in the step (6-2), for example, the compound (l) is dissolved in an alcohol (methanol or ethanol) represented by R ²¹ OH, an acid (for example, sulfuric acid is added), and heated to reflux. A method is mentioned.

〔式中、Ｒ²¹は前記と同じ意味を表し、Ｒ^5-3はハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、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、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、Ｒ^5-4はハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、ハロゲン原子で置換されていてもよいＣ３〜Ｃ５シクロアルキル基、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、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、ヒドロキシル基又は水素原子を表す。〕 (Reference production method 5)
Among the compounds (e), the compound (e-8) can be produced, for example, by the following method.

[Wherein R ²¹ represents the same meaning as described above, and R ^5-3 represents a C1-C5 alkyl group optionally substituted with a halogen atom, a C3-C5 cycloalkyl group optionally substituted with a halogen atom, A C2-C5 alkenyl group which may be substituted with a halogen atom, a C2-C5 alkynyl group which may be substituted with a halogen atom or a hydrogen atom; R ^5-4 may be a C1 which may be substituted with a halogen atom; -C5 alkyl group, C3-C5 cycloalkyl group optionally substituted with a halogen atom, C2-C5 alkenyl group optionally substituted with a halogen atom, C2-C5 alkynyl group optionally substituted with a halogen atom Represents a hydroxyl group or a hydrogen atom. ]

〔式中、Ｒ²¹及びＲ⁵²は前記と同じ意味を表し、ｍは０〜２の整数を表す。〕 (Reference production method 6)
Among the compounds (e), the compound (e-9) is, for example, J. Med. Chem, Volume 30, p. It can manufacture according to the following method using the compound (n) manufactured according to the method of 239-249.

[Wherein R ²¹ and R ⁵² represent the same meaning as described above, and m represents an integer of 0 to 2. ]

〔式中、Ｒ^5-1、Ｒ^5-3及びＲ²¹は前記と同じ意味を表す。〕 (Reference production method 7)
Among the compounds (c), the compound (c-1) is exemplified by Chem. Ber. 97, p. It can be produced according to the method described in 3407-3417.

[Wherein R ^5-1 , R ^5-3 and R ²¹ represent the same meaning as described above. ]

〔式中、Ｒ³、Ｒ⁴及びＺ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挙げられる。
該反応で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（ｂ）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、有機溶媒抽出してから、濃縮する等の後処理操作を行うことにより、化合物（ｂ）を単離することができる。単離された化合物（ｂ）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。
化合物（ｑ）のうち、Ｒ³が水素原子を表し、Ｒ⁴がハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基、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アルキニル基を表す場合、該反応はＪ．Ｃｈｅｍ．Ｓｏｃ．ＰＥＲＫＩＮ．ＴＲＡＮＳ．Ｉ，１９９１，ｐ．２５８９〜２５９２に記載の方法に準じて製造することもできる。 (Reference production method 8)
Compound (q) can be produced, for example, by the following method.

[Wherein R ³ , R ⁴ and Z 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. 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 and 4-dimethylaminopyridine, 1,4-diazabicyclo [2.2. .2] organic bases such as octane and 1,8-diazabicyclo [5.4.0] -7-undecene.
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 used in the reaction is usually 1 to 10 moles per mole of 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 (b) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating. The isolated compound (b) can be purified by chromatography, recrystallization or the like, if necessary.
Among the compounds (q), R ³ represents a hydrogen atom, and R ⁴ is a C1-C5 alkyl group which may be substituted with a halogen atom, a C2-C5 alkenyl group which may be substituted with a halogen atom, or a halogen atom. In the case of a C2-C5 alkynyl group optionally substituted with Chem. Soc. PERKIN. TRANS. I, 1991, p. It can also be produced according to the method described in 2589-2592.

〔式中、Ｒ¹、Ｒ²、Ｒ⁵、Ｒ²¹、Ｍ、Ｘ¹、Ｘ²、Ｘ³及びＺは前記と同じ意味を表し、ｍは０〜２の整数を表す。〕 (Reference production method 9)
A compound (r) can be manufactured by making it react as follows using a compound (c) or a compound (e), for example. That is, the compound (c) or the compound (e) and an organometallic compound represented by R ² -M (for example, Grignard reagent and organolithium compound) or a reducing agent (for example, lithium aluminum hydride and hydrogenation) The compound (s) produced by reacting with diisopropylaluminum) is reacted with a halogenating agent (for example, thionyl chloride and phosphorus oxychloride), or the compound (s) is reacted with It can be produced by reacting trifluoromethanesulfonic acid anhydride, methanesulfonic acid chloride or toluenesulfonic acid chloride in the presence of a base.

[Wherein R ¹ , R ² , R ⁵ , R ²¹ , M, X ¹ , X ² , X ³ and Z represent the same meaning as described above, and m represents an integer of 0 to 2. ]

〔式中、Ｒ⁵、Ｘ¹、Ｘ²及びＸ³は前記と同じ意味を表し、ｍは０〜２の整数を表し、Ｒ^1-1及びＲ^2-1は各々、ハロゲン原子で置換されていてもよいＣ１〜Ｃ５アルキル基又は水素原子を表し、Ｚ¹は塩素原子又は臭素原子を表す。〕 (Reference production method 10)
Among the compounds (r), the compound (r-1) can also be produced by reacting the compound (t) with a halogenating agent. Examples of the halogenating agent used in the reaction include N-bromosuccinimide and N-chlorosuccinimide.

[Wherein R ⁵ , X ¹ , X ² and X ³ represent the same meaning as described above, m represents an integer of 0 to 2, and R ^1-1 and R ^2-1 are each substituted with a halogen atom. Represents a C1-C5 alkyl group or a hydrogen atom which may be present, and Z ¹ represents a chlorine atom or a bromine atom. ]

Examples of the pests for which the compound of the present invention exhibits a controlling effect include harmful arthropods such as harmful insects and harmful mites, and harmful nematodes. 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, Platia stali, Halyomorpha misarcs , Stink bugs such as Eysarcoris parvus, whitefly (Trialeurodes vaporariorum), whiteflies such as Bemisia argentifolii, Aonidiella aurantii, San Jose Scale insects such as scale insects (Comstockaspis perniciosa), citrus snow scale (Unaspis citri), ruby beetles (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 and other genus, Limantria and Euproctinis, etc., Suga such as Plutella xylostella, Pterinophora gossypiella and other species, Hyphantria cunea and other humans Common moths such as moths, tiger (Tinea translucens), moth (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), flies (Delia antiqua), flies Drosophila, butterflies, flyfish, abs, sand flies, leafhoppers, 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, horned beetle (Phyllotreta striolata), potato beetle (Leptinotarsa decemlineata) and other potato beetles, beetle, Epilachna vigintioctopunctata and other epilacunas Takikuimushi acids, Naga Shinkuimushi acids, Cerambycidae such, Aoba ants backlash Staphylinidae (Paederus fuscipes), and the like.

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

Thrips pests: Thrips palmi, Thrips tabaci, Frankliniella occidentalis, Frankliniella intonsa, etc.
Hymenoptera: bees such as ants, wasps, scallops, and Athalia japonica.

Straight-eyed pests: vignetting and grasshoppers
Lepidoptera: Cat fleas (Ctenocephalides felis), Fleas (Ctenocephalides canis), 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, Dust mites (Polyphagotarsonemus latus), Dustma mites (Haemaphysalis longicornis), Dick tick (Haemaphysalis flava), Dermacentor taxodes (Dermacentor taxodes) ), Tick such as Boophilus microplus, Mite such as Tyrophagus putrescentiae, Dermatophagoides farinae, Leopard mite such as Dermatophagoides ptrenyssnus Hosotsumedani (Cheyletus eruditus), Stag Tsumedani (Cheyletus malaccensis), Tsumedani such as Minami Tsumedani (Cheyletus moorei), chicken mites, and the like.
Spiders: Chiracanthium japonicum, Latrodectus hasseltii, etc.

Lip and limb class: Thereuonema hilgendorfi, Scolopendra subspinipes, etc.
Double-legged class: Japanese red millipede (Oxidus gracilis), Japanese red millipede (Nedyopus tambanus).
Isopods: Armadillidium vulgare, etc.
Gastropoda: Lix 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 may be the compound of the present invention itself, but it is usually mixed with a solid carrier, a liquid carrier and / or a gaseous carrier, and a surfactant or other formulation adjuvant is added if necessary. , Emulsion, oil, shampoo, flowable, powder, wettable powder, granule, paste preparation, microcapsule preparation, foam preparation, aerosol preparation, carbon dioxide preparation, tablet, resin preparation, etc. Is. These preparations may be used after being processed into poison baits, mosquito coils, electric mosquito mats, fumigants, fumigants, and sheets.
These preparations usually contain 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.), 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 further steps such as molding, cutting, It can be processed into resin preparations such as plates, films, tapes, nets, and strings. These resin preparations are processed, for example, as animal collars, animal ear tags, sheet preparations, attracting strings, or gardening supports.

  Examples of the bait base include cereal flour, vegetable oil, sugar, crystalline cellulose and the like, and if necessary, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, and preservatives such as dehydroacetic acid. Additives for preventing accidental eating by children and pets such as pepper powder, pests such as cheese flavor, onion flavor and peanut oil are added.

  The pest control agent of the present invention is used, for example, by applying it directly to pests and / or by applying it to habitats (plants, animals, soil, etc.)

  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 becomes 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, it is possible to control pests that live in the soil. In addition, these preparations can be applied to the nursery before planting, or they can be applied to 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 and the like are usually diluted with water so that the active ingredient concentration is 0.01 to 10000 ppm, and oils, aerosols, smoke agents, poison baits and the like are usually applied as they are.
When the pest control agent of the present invention is used for controlling ectoparasites of cattle, horses, pigs, sheep, goats, chickens, small animals such as dogs, cats, rats, mice, etc., a method known in veterinary medicine Can be used on animals. As a specific method of use, when systemic control is intended, for example, it is administered by tablet, feed mixing, suppository, injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.) When aiming at non-systemic control, for example, spraying an oil or aqueous solution, pour-on treatment or spot-on treatment, washing animals with a shampoo formulation Or it is used by the method of attaching a resin formulation to an animal using a collar or an ear tag. The amount of the compound of the present invention when administered to an animal body is usually in the range of 0.1 to 1000 mg per 1 kg 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 the active ingredient of such other insecticides and acaricides include allethrin, tetramethrin, praretrin, phenothrin, resmethrin, ciphenothrin, permethrin, cypermethrin, alpha cypermethrin, zetacypermethrin, deltamethrin, tralomethrin, cyfluthrin, beta Cyfluthrin, cyhalothrin, lambda cihalothrin, flamethrin, 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 active ingredients of such other fungicides include, for example, strobilurin compounds such as azoxystrobin, organophosphorus compounds such as triclofosmethyl, azole compounds such as triflumizole, pefrazoate, and difenoconazole, fusalide, flutolanil, validamycin, probenazole , Dichromedin, pencyclon, dazomet, kasugamycin, IBP, pyroxylone, oxolinic acid, tricyclazole, ferimzone, mepronil, EDDP, isoprothiolane, carpropamide, diclocimet, flametopir, fludioxonil, procymidone and dietofencarb.

  Hereinafter, the present invention will be described in more detail with reference to Production Examples, Formulation Examples, and Test Examples, but the present invention is not limited only to these examples. First, the manufacture example of this invention compound is shown.

Production Example 1
0.21 g of 2-t-butyl-5-chloromethylpyrimidine and 0.19 g of (3,3,3-trifluoropropyl) malononitrile are dissolved in 10 ml of N, N-dimethylformamide, and the mixture is stirred under ice-cooling. While adding 0.16 g of potassium carbonate, the mixture was stirred overnight at room temperature. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and [(2-t-butylpyrimidin-5-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (1)). 0.22 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 1.44 (9H, s), 2.28-2.32 (2H, m), 2.52-2.26 (2H, m) 3.24 (2H, s), 8.74 (2H, s)

Production Example 2
0.15 g of 2-t-butyl-5-chloromethylpyrazine and 0.13 g of (3,3,3-trifluoropropyl) malononitrile are dissolved in 5 ml of N, N-dimethylformamide, and the mixture is stirred under ice cooling. While adding 0.11 g of potassium carbonate, the mixture was stirred overnight at room temperature. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and [(2-t-butylpyrazin-5-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (2)). 0.13 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 1.45 (9H, s), 2.37-2.41 (2H, m), 2.55-2.64 (2H, m) 3.47 (2H, s), 8.55 (1H, s), 8.70 (1H, s)

Production Example 3
0.12 g of 3-t-butyl-6-chloromethylpyridazine and 0.10 g of (3,3,3-trifluoropropyl) malononitrile are dissolved in 5 ml of N, N-dimethylformamide, and the mixture is stirred under ice-cooling. While adding 0.087 g of potassium carbonate, the mixture was stirred overnight at room temperature. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and [(6-t-butylpyridazin-3-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (3)). 0.15 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 1.48 (1H, s), 2.37-2.41 (2H, m), 2.60-2.64 (2H, m) 3.65 (2H, s), 7.51 (1H, d), 7.61 (1H, d)

Production Example 4
100 mg of 5-chloromethyl-2-methylthiopyrimidine and 93 mg of (3,3,3-trifluoropropyl) malononitrile were dissolved in 3 ml of N, N-dimethylformamide. In addition, the mixture was stirred overnight at room temperature. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain [(2-methylthiopyrimidin-5-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (4)). 10 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 2.26-2.30 (2H, m), 2.51-2.63 (2H, m), 2.60 (3H, s) 3.20 (2H, s), 8.57 (2H, s)

Production Example 5
[(2-Methylthiopyrimidin-5-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (0.84 g) was dissolved in chloroform (30 ml), and the mixture was stirred under ice-cooling while adding metachloroperbenzoic acid. .97 g was added and stirred at room temperature for 6 hours. The reaction mixture was washed with 3% aqueous sodium thiosulfate and saturated aqueous sodium bicarbonate. The extract was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and described as [(2-methanesulfonylpyrimidin-5-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (5)). 0.76 g of a crude product of.
¹ H-NMR (DMSO-d ₆ , TMS), δ (ppm): 2.50-2.56 (2H, m), 2.61-2.72 (2H, m), 3.45 (3H, s), 3.77 (2H, s), 9.12 (2H, s)

Production Example 6
[(2-Methanesulfonylpyrimidin-5-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (0.50 g) was dissolved in dimethyl sulfoxide (5 ml), and potassium cyanide (0.10 g) was added to the mixture. Stir for 8 hours. Water was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain [(2-cyanopyrimidin-5-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (6)). 12 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 2.35-2.40 (2H, m), 2.55-2.64 (2H, m), 3.36 (2H, s) 8.95 (2H, s)

Production Example 7
70 mg of propargyl alcohol was dissolved in 10 ml of dry THF, and 50 mg of sodium hydride (60% oily) was added little by little while stirring the mixture at room temperature. Next, 400 mg of [(2-methanesulfonylpyrimidin-5-yl) methyl] (3,3,3-trifluoropropyl) malononitrile was added to the mixture stirred at room temperature for 1 hour. Then, it stirred at room temperature for 3 hours, saturated ammonium chloride aqueous solution was added to the reaction mixture, and it extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and described as {[2- (propargyloxy) pyrimidin-5-yl] methyl} (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (7)). 0.10 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 2.66-2.31 (2H, m), 2.50 (1H, t), 2.54-2.61 (2H, m) 3.23 (2H, s), 5.07 (2H, d), 8.61 (2H, s)

Production Example 8
50 mg of 2-butyn-1-ol was dissolved in 5 ml of dry THF, and 30 mg of sodium hydride (60% oily) was added little by little while stirring the mixture at room temperature. Next, 250 mg of [(2-methanesulfonylpyrimidin-5-yl) methyl] (3,3,3-trifluoropropyl) malononitrile was added to the reaction solution stirred at room temperature for 1 hour. Then, it stirred at room temperature for 3 hours, saturated ammonium chloride aqueous solution was added to the reaction mixture, and it extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and {[2- (2-butynyl-1-oxy) pyrimidin-5-yl] methyl} (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound ( 8) 0.10 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 1.87 (3H, t), 2.26-2.30 (2H, m), 2.54-2.61 (2H, m) 3.22 (2H, s), 5.03 (2H, q), 8.60 (2H, s)

Production Example 9
While stirring 0.24 g of 5-chloromethyl-2-methylpyrimidine and 0.27 g of (3,3,3-trifluoropropyl) malononitrile in 5 ml of N, N-dimethylformamide, the mixture was stirred under ice-cooling. 0.32 g of potassium carbonate was added and stirred overnight at room temperature. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain [(2-methylpyrimidin-5-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (9)). 11 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 2.27-2.31 (2H, m), 2.54-2.61 (2H, m), 2.80 (3H, s) 3.24 (2H, s), 8.71 (2H, s)

Production Example 10
1.0 g of 5-chloromethyl-2-isopropylpyrimidine and 0.95 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 15 ml of N, N-dimethylformamide, and the mixture was stirred under ice-cooling. 0.81 g of potassium carbonate was added, and the mixture was stirred overnight at room temperature. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain [(2-isopropylpyrimidin-5-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (10)). 40 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 1.38 (6H, d), 2.28-2.32 (2H, m), 2.55-2.61 (2H, m) 3.24 (2H, s), 3.28 (1H, m), 8.73 (2H, s)

Production Example 11
0.75 g of 5-bromomethyl-2-phenylpyrimidine and 0.49 g of (3,3,3-trifluoropropyl) malononitrile are dissolved in 15 ml of N, N-dimethylformamide, and the mixture is carbonated with stirring under ice cooling. 0.42 g of potassium was added and stirred overnight at room temperature. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain [(2-phenylpyrimidin-5-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (11)). 42 g were obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 2.30-2.34 (2H, m), 2.53-2.65 (2H, m), 3.31 (2H, s) 7.49-7.55 (3H, m), 8.47-8.50 (2H, m), 8.86 (2H, s)

Production Example 12
0.16 g of 5- (chloromethyl) pyrimidine and 0.15 g of (3,3,3-trifluoropropyl) malononitrile are dissolved in 5 ml of N, N-dimethylformamide, and the mixture is stirred with ice-cooling and potassium carbonate. 0.13 g was added and stirred overnight at room temperature. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.11 g of [(pyrimidin-5-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (12)). It was.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 2.30-2.34 (2H, m), 2.53-2.65 (2H, m), 3.29 (2H, s) , 8.84 (2H, s), 9.32 (1H, s)

Production Example 13
0.18 g of 4-t-butyl-2-chloromethylpyrimidine and 0.16 g of (3,3,3-trifluoropropyl) malononitrile are dissolved in 5 ml of N, N-dimethylformamide, and the mixture is stirred under ice cooling. While adding 0.14 g of potassium carbonate, the mixture was stirred overnight at room temperature. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and [(4-t-butylpyrimidin-2-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (13)). 0.08 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 1.39 (9H, s), 2.42-2.46 (2H, m), 2.59-2.70 (2H, m) 3.64 (2H, s), 7.29 (1H, d), 8.65 (1H, d)

Production Example 14
0.50 g of 5-bromomethyl-2-chloropyrimidine and 0.39 g of (3,3,3-trifluoropropyl) malononitrile are dissolved in 10 ml of N, N-dimethylformamide, and the mixture is stirred with ice-cooling and carbonic acid. 0.33 g of potassium was added and stirred overnight at room temperature. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography [(2-chloropyrimidin-5-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (14)) 0.21 g. Got.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 2.30-2.35 (2H, m), 2.53-2.65 (2H, m), 3.27 (2H, s) 8.71 (2H, s)

Production Example 15
80 mg of 4-bromomethyl-2-chloropyrimidine and 63 mg of (3,3,3-trifluoropropyl) malononitrile were dissolved in 3 ml of N, N-dimethylformamide, and 53 mg of potassium carbonate was added while stirring the mixture under ice cooling. Stir at room temperature overnight. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain [(2-chloropyrimidin-4-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (15)). 07 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 2.37-2.41 (2H, m), 2.55-2.67 (2H, m), 3.44 (2H, s) 7.36 (1H, d), 8.73 (1H, d)

Production Example 16
0.58 g of 5-bromomethyl-2-trifluoromethylpyrimidine and 0.39 g of (3,3,3-trifluoropropyl) malononitrile are dissolved in 10 ml of N, N-dimethylformamide, and the mixture is stirred under ice-cooling. While adding 0.33 g of potassium carbonate, the mixture was stirred overnight at room temperature. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and [(2-trifluoromethylpyrimidin-5-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (16)). 0.55 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 2.35-2.39 (2H, m), 2.55-2.65 (2H, m), 3.38 (2H, s) , 9.00 (2H, s)

Production Example 17
Dissolve 0.30 g of 5-bromomethyl-2-trifluoromethylpyrimidine and 0.13 g of allylmalononitrile in 5 ml of N, N-dimethylformamide, add 0.17 g of potassium carbonate while stirring the mixture under ice cooling, Stir at room temperature overnight. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.23 g of (allyl) [(2-trifluoromethylpyrimidin-5-yl) methyl] malononitrile (hereinafter referred to as the present compound (17)).
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 2.85 (2H, d), 3.30 (2H, s), 5.49-5.58 (2H, m), 5.97 (1H, m), 8.98 (2H, s)

Production Example 18
0.30 g of 5-bromomethyl-2-trifluoromethylpyrimidine and 0.15 g of (3-butenyl) malononitrile were dissolved in 5 ml of N, N-dimethylformamide, and 0.17 g of potassium carbonate was stirred while the mixture was stirred under ice cooling. And stirred at room temperature overnight. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed successively with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.21 g of (3-butenyl) [(2-trifluoromethylpyrimidin-5-yl) methyl] malononitrile (hereinafter referred to as the present compound (18)). .
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 2.14 to 2.18 (2H, m), 2.51 to 2.56 (2H, m), 3.33 (2H, s) 5.16-5.24 (2H, m), 5.83 (1H, m), 8.94 (2H, s)

Production Example 19
0.17 g of 5-chloromethyl-2-isopropylpyrimidine and 0.11 g of allylmalononitrile are dissolved in 3 ml of N, N-dimethylformamide, and 0.14 g of potassium carbonate is added to the mixture while stirring under ice-cooling. And stirred overnight. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.12 g of (allyl) [(2-isopropylpyrimidin-5-yl) methyl] malononitrile (hereinafter referred to as the present compound (19)).
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 1.37 (6H, d), 2.78 (2H, d), 3.17 (2H, s), 3.27 (1H, m ), 5.45-5.53 (2H, m), 5.95 (1H, m), 8.72 (2H, s)

Production Example 20
80 mg of 2- (bromomethyl) pyrazine and 100 mg of (3,3,3-trifluoropropyl) malononitrile were dissolved in 3 ml of N, N-dimethylformamide, and 86 mg of potassium carbonate was added while stirring the mixture under ice-cooling. Stir overnight. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.10 g of [(pyrazin-2-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (20)). It was.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 2.37-2.41 (2H, m), 2.55-2.64 (2H, m), 3.52 (2H, s) , 8.64-8.66 (3H, m)

Production Example 21
0.27 g of 3-bromomethyl-6-chloropyridazine and 0.21 g of (3,3,3-trifluoropropyl) malononitrile are dissolved in 5 ml of N, N-dimethylformamide, and the mixture is carbonated while stirring under ice-cooling. Potassium (0.18 g) was added, and the mixture was stirred overnight at room temperature. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain [(6-chloropyridazin-3-yl) methyl] (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (21)). 20 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 2.36-2.41 (2H, m), 2.54-2.65 (2H, m), 3.69 (2H, s) 7.59 (1H, d), 7.64 (1H, d)

Production Example 22
2-Bromomethylpyrimidine-5-carboxylic acid methyl ester (0.23 g) and (3,3,3-trifluoropropyl) malononitrile (0.16 g) were dissolved in N, N-dimethylformamide (5 ml), and the mixture was cooled with ice. While stirring, 0.14 g of potassium carbonate was added, and the mixture was stirred overnight at room temperature. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (2,2-dicyano-5,5,5-trifluoropentyl) pyrimidine-5-carboxylic acid methyl ester (hereinafter referred to as the present compound (22)). 0.21 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 2.42-2.46 (2H, m), 2.58-2.69 (2H, m), 3.73 (2H, s) 4.01 (3H, s), 9.31 (2H, s)

０．３４ｇ及び（３，３，３−トリフルオロプロピル）マロノニトリル０．３３ｇをＮ，Ｎ−ジメチルホルムアミド５ｍｌに溶解し、該混合液を氷冷下撹拌しながら炭酸カリウム０．２８ｇを加え、室温で一晩撹拌した。反応混合物に飽和食塩水を加え、ｔ−ブチルメチルエーテルで抽出した。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、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、［（６，７−ジヒドロ−５Ｈ−シクロペンタピリミジン−２−イル）メチル］（３，３，３−トリフルオロプロピル）マロノニトリル

（以下、本発明化合物（２３）と記す。）０．４４ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）、δ（ｐｐｍ）：２．１５−２．２３（２Ｈ、ｍ）、２．３９−２．４３（２Ｈ、ｍ）、２．５６−２．６８（２Ｈ、ｍ）、２．９７−３．０５（４Ｈ、ｍ）、３．５９（２Ｈ、ｓ）、８．５３（１Ｈ、ｓ） Production Example 23
2-Chloromethyl-6,7-dihydro-5H-cyclopentapyrimidine

0.34 g and 0.33 g of (3,3,3-trifluoropropyl) malononitrile were dissolved in 5 ml of N, N-dimethylformamide, and 0.28 g of potassium carbonate was added to the mixture while stirring under ice cooling. And stirred overnight. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain [(6,7-dihydro-5H-cyclopentapyrimidin-2-yl) methyl] (3,3,3-trifluoropropyl) malononitrile.

(Hereinafter referred to as the present compound (23).) 0.44 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 2.15-2.23 (2H, m), 2.39-2.43 (2H, m), 2.56-2.68 ( 2H, m), 2.97-3.05 (4H, m), 3.59 (2H, s), 8.53 (1H, s)

１３８ｍｇ及び（３，３，３−トリフルオロプロピル）マロノニトリル１１４ｍｇをＮ，Ｎ−ジメチルホルムアミド３ｍｌに溶解し、該混合液を氷冷下撹拌しながら炭酸カリウム９７ｍｇを加え、室温で一晩撹拌した。反応混合物に飽和食塩水を加え、ｔ−ブチルメチルエーテルで抽出した。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、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、［（７，７−ジメチル−６，７−ジヒドロ−５Ｈ−シクロペンタピリミジン−２−イル）メチル］（３，３，３−トリフルオロプロピル）マロノニトリル

（以下、本発明化合物（２４）と記す。）０．１９ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）、δ（ｐｐｍ）：１．３１（６Ｈ、ｓ）、２．０３（２Ｈ、ｔ）、２．４１−２．４５（２Ｈ、ｍ）、２．５９−２．６６（２Ｈ、ｍ）、２．９２（２Ｈ、ｔ）、３．６２（２Ｈ、ｓ）、８．５１（１Ｈ、ｓ） Production Example 24
2-Chloromethyl-7,7-dimethyl-6,7-dihydro-5H-cyclopentapyrimidine

138 mg and 114 mg of (3,3,3-trifluoropropyl) malononitrile were dissolved in 3 ml of N, N-dimethylformamide, and 97 mg of potassium carbonate was added while stirring the mixture under ice cooling, followed by stirring at room temperature overnight. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain [(7,7-dimethyl-6,7-dihydro-5H-cyclopentapyrimidin-2-yl) methyl] (3,3,3-trifluoropropyl) malononitrile.

(Hereinafter referred to as the present compound (24).) 0.19 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 1.31 (6H, s), 2.03 (2H, t), 2.41-2.45 (2H, m), 2.59 -2.66 (2H, m), 2.92 (2H, t), 3.62 (2H, s), 8.51 (1H, s)

Production Example 25
Dissolve 0.30 g of 5-bromomethyl-2-trifluoromethylpyrimidine and 0.13 g of propargylmalononitrile in 5 ml of N, N-dimethylformamide, add 0.17 g of potassium carbonate while stirring the mixture under ice cooling, Stir at room temperature overnight. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed successively with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.17 g of (propargyl) [(2-trifluoromethylpyrimidin-5-yl) methyl] malononitrile (hereinafter referred to as the present compound (25)).
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 2.59 (1H, t), 3.03 (2H, d), 3.50 (2H, s), 9.02 (2H, s )

Production Example 26
0.20 g of 5-bromomethyl-2-trifluoromethylpyrimidine and 0.30 g of (2,2,3,3-tetrafluoropropyl) malononitrile were dissolved in 5 ml of N, N-dimethylformamide, and the mixture was cooled with ice. While stirring, 0.23 g of potassium carbonate was added, and the mixture was stirred overnight at room temperature. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed successively with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and described as (2,2,3,3-tetrafluoropropyl) [(2-trifluoromethylpyrimidin-5-yl) methyl] malononitrile (hereinafter referred to as the present compound (26)). .) 0.24 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 3.00 (2H, t), 3.60 (2H, s), 5.96 (1H, tt), 9.06 (2H, s )

（以下、本発明化合物（２７）と記す。）０．３４ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）、δ（ｐｐｍ）：１．３１（６Ｈ、ｓ）、２．０２（２Ｈ、ｔ）、２．９０−２．９３（４Ｈ、ｍ）、３．５５（２Ｈ、ｓ）、５．４２−５．４７（２Ｈ、ｍ）、６．００（１Ｈ、ｍ）、８．５１（１Ｈ、ｓ） Production Example 27
2-Chloromethyl-7,7-dimethyl-6,7-dihydro-5H-cyclopentapyrimidine (0.40 g) and allylmalononitrile (0.22 g) are dissolved in 10 ml of N, N-dimethylformamide, and the mixture is cooled with ice. Under stirring, 0.28 g of potassium carbonate was added and stirred overnight at room temperature. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give (allyl) [(7,7-dimethyl-6,7-dihydro-5H-cyclopentapyrimidin-2-yl) methyl] malononitrile.

(Hereinafter referred to as the present compound (27).) 0.34 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 1.31 (6H, s), 2.02 (2H, t), 2.90-2.93 (4H, m), 3.55 (2H, s), 5.42-5.47 (2H, m), 6.00 (1H, m), 8.51 (1H, s)

（以下、本発明化合物（２８）と記す。）０．２９ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）、δ（ｐｐｍ）：１．３１（６Ｈ、ｓ）、２．０２（２Ｈ、ｔ）、２．１９−２．２３（２Ｈ、ｍ）、２．５２−２．５８（２Ｈ、ｍ）、２．９１（２Ｈ、ｔ）、３．５８（２Ｈ、ｓ）、５．１０−５．２１（２Ｈ、ｍ）、５．８４（１Ｈ、ｍ）、８．５１（１Ｈ、ｓ） Production Example 28
2-chloromethyl-7,7-dimethyl-6,7-dihydro-5H-cyclopentapyrimidine (0.40 g) and (3-butenyl) malononitrile (0.24 g) are dissolved in N, N-dimethylformamide (3 ml), and the mixture While stirring with ice, 0.28 g of potassium carbonate was added and stirred overnight at room temperature. Saturated brine was added to the reaction mixture, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain (3-butenyl) [(7,7-dimethyl-6,7-dihydro-5H-cyclopentapyrimidin-2-yl) methyl] malononitrile.

(Hereinafter referred to as the present compound (28).) 0.29 g was obtained.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 1.31 (6H, s), 2.02 (2H, t), 2.19-2.23 (2H, m), 2.52 -2.58 (2H, m), 2.91 (2H, t), 3.58 (2H, s), 5.10-5.21 (2H, m), 5.84 (1H, m), 8.51 (1H, s)

Specific examples of the compounds of the present invention are shown in (Table 1) to (Table 13) together with compound numbers.
A compound of formula (I);

なお、上記の（表１）〜（表１３）における表中の結合位置とは、Ｒ¹およびＲ²が結合している炭素原子が結合している環上の炭素原子の位置を意味する。また、(Ｒ)_mにおける空欄はｍ＝０であることを表し、”４，５−（ＣＨ₂）₃−”及び”４，５−Ｃ(ＣＨ₃)₂（ＣＨ₂）₂−”との記載は、それぞれ式（Ｉ）において、「４」で示される炭素原子の位置（左端）と「５」で示される炭素原子の位置（右端）に結合した基を示す

In addition, the bonding position in the table in the above (Table 1) to (Table 13) means the position of the carbon atom on the ring to which the carbon atom to which R ¹ and R ² are bonded is bonded. The blank in (R) _m represents m = 0, and “4,5- (CH ₂ ) ₃ —” and “4,5-C (CH ₃ ) ₂ (CH ₂ ) ₂ —” In the formula (I) represents a group bonded to the position (left end) of the carbon atom indicated by “4” and the position (right end) of the carbon atom indicated by “5”, respectively.

  Next, production examples of intermediate compounds are shown as reference production examples.

上記化合物はＳｙｎｔｈｅｓｉｓ，２００２、ｐ．７２０〜７２２に記載の方法にて製造することができる。 Reference production example 1
2-t-butyl-5-pyrimidinecarboxylic acid methyl ester (following formula)

Such compounds are described in Synthesis, 2002 , p. It can be produced by the method described in 720-722.

窒素雰囲気下、２−ｔ−ブチル−５−ピリミジンカルボン酸メチルエステル０．２７ｇを無水ＴＨＦ１０ｍｌ中に溶解し、氷冷下でジイソブチルアルミニウムヒドリドのトルエン溶液（１モル／Ｌ）３．０ｍｌを滴下し、１時間攪拌した。反応混合物を飽和食塩水中にあけ、酢酸エチルで抽出し、無水硫酸ナトリウムで乾燥した後、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、上式で示される（２−ｔ−ブチルピリミジン−５−イル）メタノール０．０９ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）、δ（ｐｐｍ）： １．４５（９Ｈ、ｓ）、４．７２（２Ｈ、ｂｒｓ）、８．６９（２Ｈ、ｓ） Reference production example 2
(2-t-Butylpyrimidin-5-yl) methanol (the following formula)

Under a nitrogen atmosphere, 0.27 g of 2-t-butyl-5-pyrimidinecarboxylic acid methyl ester was dissolved in 10 ml of anhydrous THF, and 3.0 ml of a toluene solution of diisobutylaluminum hydride (1 mol / L) was added dropwise under ice cooling. Stir for 1 hour. The reaction mixture was poured into saturated brine, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.09 g of (2-t-butylpyrimidin-5-yl) methanol represented by the above formula.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 1.45 (9H, s), 4.72 (2H, brs), 8.69 (2H, s)

（２−ｔ−ブチルピリミジン−５−イル）メタノール０．２５ｇをクロロホルム５ｍｌ中に溶解し、該混合液に塩化チオニル０．２ｇを加え、１時間加熱還流した。反応混合物を室温まで冷却し、減圧下濃縮した。残渣に水、飽和炭酸水素ナトリウム水溶液を加え、酢酸エチルで抽出し、無水硫酸ナトリウムで乾燥した後、減圧下濃縮することで２−ｔ−ブチル−５−クロロメチルピリミジン０．２１ｇを得た。 Reference production example 3
2-t-butyl-5-chloromethylpyrimidine (following formula)

0.25 g of (2-t-butylpyrimidin-5-yl) methanol was dissolved in 5 ml of chloroform, 0.2 g of thionyl chloride was added to the mixture, and the mixture was heated to reflux for 1 hour. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. Water and a saturated aqueous sodium hydrogen carbonate solution were added to the residue, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 0.21 g of 2-t-butyl-5-chloromethylpyrimidine.

上記化合物はＡｕｓｔ．Ｊ．Ｃｈｅｍ．，２６巻、ｐ．４４３〜４４７に記載の方法にて製造することができる。 Reference production example 4
2-Chloro-5-methylpyrimidine (following formula)

The above compounds are described in Aust. J. et al. Chem. 26, p. It can be manufactured by the method described in 443-447.

２−クロロ−５−メチルピリミジン０．４０ｇを四塩化炭素１５ｍｌに溶解し、該混合液にＮ−ブロモスクシンイミド０．８３ｇとアゾビスイソブチロニトリル０．０５ｇとを加え、８時間加熱還流した。反応混合物を室温まで冷却してから濾過し、得られた濾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、上式で示される５−ブロモメチル−２−クロロピリミジン０．２７ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）、δ（ｐｐｍ）： ４．４３（２Ｈ、ｓ）、８．６７（２Ｈ、ｓ） Reference production example 5
5-Bromomethyl-2-chloropyrimidine (following formula)

0.40 g of 2-chloro-5-methylpyrimidine was dissolved in 15 ml of carbon tetrachloride, 0.83 g of N-bromosuccinimide and 0.05 g of azobisisobutyronitrile were added to the mixture, and the mixture was heated to reflux for 8 hours. . The reaction mixture was cooled to room temperature and filtered, and the resulting filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.27 g of 5-bromomethyl-2-chloropyrimidine represented by the above formula.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 4.43 (2H, s), 8.67 (2H, s)

６−メチル−２Ｈ−ピリダジン−３−オン５．０ｇにオキシ塩化リン２８ｇを加え、２時間加熱還流した。反応混合物を室温まで冷却し、氷水に注いだ。酢酸エチルで抽出し、無水硫酸ナトリウムで乾燥した後、減圧下濃縮することで３−クロロ−６−メチルピリダジン１．６ｇを得た。 Reference production example 6
3-Chloro-6-methylpyridazine (following formula)

28 g of phosphorus oxychloride was added to 5.0 g of 6-methyl-2H-pyridazin-3-one, and the mixture was heated to reflux for 2 hours. The reaction mixture was cooled to room temperature and poured into ice water. After extraction with ethyl acetate, drying over anhydrous sodium sulfate, and concentration under reduced pressure, 1.6 g of 3-chloro-6-methylpyridazine was obtained.

３−クロロ−６−メチルピリダジン１．０ｇを四塩化炭素２０ｍｌに溶解し、Ｎ−ブロモスクシンイミド１．４ｇ及びアゾビスイソブチロニトリル０．１３ｇを加え、８時間加熱還流した。反応混合物を室温まで冷却し、生じた固体混合物を濾過し、得られた濾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、上式で示される３−ブロモメチル−６−クロロピリダジン０．２７ｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）、δ（ｐｐｍ）：４．５６（２Ｈ、ｓ）、７．３８（１Ｈ、ｄ）、７．４４（１Ｈ、ｄ） Reference production example 7
3-Bromomethyl-6-chloropyridazine (following formula)

1.0 g of 3-chloro-6-methylpyridazine was dissolved in 20 ml of carbon tetrachloride, 1.4 g of N-bromosuccinimide and 0.13 g of azobisisobutyronitrile were added, and the mixture was heated to reflux for 8 hours. The reaction mixture was cooled to room temperature, the resulting solid mixture was filtered, and the resulting filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.27 g of 3-bromomethyl-6-chloropyridazine represented by the above formula.
¹ H-NMR (CDCl ₃ , TMS), δ (ppm): 4.56 (2H, s), 7.38 (1H, d), 7.44 (1H, d)

  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 each of the compounds (1) to (28) of the present invention are dissolved in 37.5 parts of xylene and 37.5 parts of dimethylformamide, and 10 parts of polyoxyethylene styrylphenyl ether and 6 parts of calcium dodecylbenzenesulfonate are dissolved therein. And stirring well to obtain each emulsion.

Formulation Example 2
To 40 parts of each of the compounds (1) to (28) of the present invention, 5 parts of Solpol 5060 (registered trademark of Toho Chemical) is added and mixed well to prepare Carplex # 80 (registered trademark of Shionogi & Co., synthetic silicon hydroxide). Fine powder) 32 parts and 23 parts of 300 mesh diatomaceous earth are added and mixed with a juice mixer to obtain each wettable powder.

Formulation Example 3
To 3 parts of each of the compounds (1) to (28) of the present invention, 5 parts of synthetic silicon hydroxide fine powder, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 57 parts of clay are added, and mixed well with stirring. An appropriate amount of water is added to the mixture, and the mixture is further stirred, granulated with a granulator, and dried by ventilation to obtain each granule.

Formulation Example 4
4.5 parts of each of the compounds (1) to (28) of the present invention, 1 part of synthetic silicon hydroxide fine powder, 1 part of Doreles B (registered trademark, manufactured by Sankyo Co., Ltd.) as a flocculant and 7 parts of clay may be used in a mortar. After mixing, stir and mix with a juice mixer. 86.5 parts of cut clay is added to the obtained mixture and mixed thoroughly with stirring to obtain each powder.

Formulation Example 5
By mixing 10 parts of each of the compounds (1) to (28) of the present invention, 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt, and 55 parts of water, To obtain a formulation.

Formulation Example 6
0.5 parts of each of the compounds (1) to (28) of the present invention are dissolved in 10 parts of dichloromethane, and this is mixed with 89.5 parts of Isopar M (isoparaffin: Exxon Chemical Registration) to obtain each oil agent. .

Formulation Example 7
0.1 parts of each of the compounds (1) to (28) of the present invention and 49.9 parts of neothiozole (Chuo Kasei Co., Ltd.) are placed in an aerosol can and fitted with an aerosol valve, followed by 25 parts dimethyl ether and 25 parts LPG. Each oily aerosol is obtained by adding a shaker and mounting an actuator.

Formulation Example 8
0.6 parts of each of the compounds (1) to (28) of the present invention, 0.01 part of BHT, 5 parts of xylene, 3.39 parts of deodorized kerosene and 1 part of an emulsifier {Atmos 300 (registered trademark of Atmos Chemical)} The dissolved one 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 each aqueous aerosol.

  Next, test examples show that the compound of the present invention is useful 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 (1), (2), (3), (7), (8), (9), (10), (11), (13), (14), obtained by Formulation Example 5 (15), (16), (17), (18), (19), (24), (26) and (28) preparations are diluted for each active ingredient concentration to 500 ppm and used for testing. A drug solution was prepared.
On the other hand, 50g of soil bonsol 2 (manufactured by Sumitomo Chemical Co., Ltd.) is put in a polyethylene cup, seeded with 10 to 15 seeds, grown until the second true leaf develops, and then cut to a height of 5cm. The test chemical solution prepared as described above was sprayed at a rate of 20 ml / cup on the prepared rice. After the chemicals sprayed on rice were dried, they were put in a plastic cup to prevent the escape of the test insects, 30 first-instar larvae of the brown planthopper were released, covered, and then placed in a greenhouse at <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 (1), (2), (3), (7), (8), (9), (10), (11), (13), (14), (15), In the treatments (16), (17), (18), (19), (24), (26) and (28), the number of parasitic insects was 3 or less.

Test example 2
Each preparation of the present compound (1), (7), (8), (9), (10), (14), (16), (18) and (26) obtained by Preparation Example 5 It diluted with water so that an active ingredient density | concentration might be 500 ppm, and prepared the chemical | medical solution for a test.
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 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, in the treatments of the present compounds (1), (7), (8), (9), (10), (14), (16), (18) and (26), 6 days after the treatment, respectively. The number of parasitic insects was 3 or less.

Test example 3
The present compound (1), (2), (3), (7), (8), (9), (10), (11), (13), (14), obtained by Formulation Example 5 Each preparation of (16), (17), (18) and (19) was diluted with water so that the active ingredient concentration would be 500 ppm to prepare a test drug solution.
A filter paper of the same size 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 food. 10 female Musca domestica females were released into the polyethylene cup and capped. 24 hours later, the life-and-death of the house fly was investigated to determine the death rate.
As a result, the present compounds (1), (2), (3), (7), (8), (9), (10), (11), (13), (14), (16), In the treatments (17), (18) and (19), a death rate of 90% or more was shown.

Test example 4
The present compound (1), (6), (9), (10), (12), (13), (14), (16), (17), (18), obtained by Formulation Example 5 Each of the preparations (19) and (20) was diluted with water so that the active ingredient concentration was 500 ppm to prepare a test drug solution.
A filter paper of the same size 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 food. 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 (1), (6), (9), (10), (12), (13), (14), (16), (17), (18), (19) and In the treatment (20), the death rate was 100%.

Test Example 5
The present compound (1), (2), (3), (4), (6), (7), (8), (9), (10), (11), obtained by Formulation Example 5 (13), (14), (16), (17), (18), (19), (21), (22), (23), (25) and (26) preparations with active ingredient concentrations It diluted with water so that it might become 500 ppm, and the chemical | medical solution for a test 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 solution, and the survival rate was investigated one day later to determine the death rate.
As a result, the present compounds (1), (2), (3), (4), (6), (7), (8), (9), (10), (11), (13), In the processes of (14), (16), (17), (18), (19), (21), (22), (23), (25) and (26), the death rate is 95% or more. Indicated.

Claims (8)

Formula (I)

[Where,
R ¹ represents a hydrogen atom,
R ² represents a hydrogen atom,
R ³ represents a hydrogen atom,
R ⁴ represents a C1-C5 alkyl group which may be substituted with a halogen atom, a C2-C5 alkenyl group which may be substituted with a halogen atom, or a C2-C5 alkynyl group which may be substituted with a halogen atom. ,
X ¹ , X ² and X ³ each represent a nitrogen atom or CR ⁶ . However, of X ^1, X ² and X ^3, only two represents a nitrogen atom (wherein the position of the carbon atoms on the ring carbon atoms to which R ¹ and R ² are attached is attached is When X ¹ and X ² are nitrogen atoms, they are the positions of carbon atoms represented by 2, 4 or 5, and when X ¹ and X ³ are nitrogen atoms, the carbon atoms represented by 2 or 5 And when X ² and X ³ are nitrogen atoms, it is the position of the carbon atom represented by 5).
R ⁶ represents a hydrogen atom,
m represents an integer of 0 to 2,
R ⁵ may be a halogen atom, a cyano group, a C1-C5 alkyl group that may be substituted with a halogen atom, a C3-C6 alkynyloxy group that may be substituted with a halogen atom, or a halogen atom. A C1-C5 alkylthio group which may be substituted, a C1-C5 alkylsulfonyl group which may be substituted with a halogen atom, a C2-C5 alkoxycarbonyl group which may be substituted with a halogen atom, or a phenyl group;
However, when m is 2 and two carbon atoms to which two R ⁵ are bonded are adjacent to each other, the corresponding two R ⁵ may be combined to represent a C3-C6 alkanediyl group. ]
A malononitrile compound represented by: Formula (XI)

[Where,
R ¹ , R ² , R ³ and R ⁴ have the same meaning as defined in claim 1,
R ^5a is a hydrogen atom, a halogen atom, a cyano group, c androgenic substituted C1~C5 may be an alkyl group with atoms, c androgenic atoms optionally substituted C3~C6 alkynyloxy group, substituted with a halogen atom and each may be a C1~C5 alkylthio group, c androgenic atoms optionally substituted by C1~C5 alkylsulfonyl group, c androgenic C2~C5 alkoxycarbonyl group or which may be substituted with atoms represents a phenyl group. ]
The malononitrile compound of Claim 1 shown by these Formula (XII)

[Where,
R ¹ , R ² , R ³ and R ⁴ have the same meaning as defined in claim 1,
m represents an integer of 0 to 2,
Each R ⁵ is a halogen atom, a cyano group, c androgenic substituted C1~C5 may be an alkyl group with atoms, c androgenic atoms optionally substituted C3~C6 alkynyloxy group, substituted with a halogen atom may C1~C5 alkylsulfonyl group which may be substituted with may be C1~C5 alkylthio group or a c androgenic atom, C2-C5 alkoxycarbonyl group or which may be substituted with c androgenic atom represents a phenyl group. ]
A malononitrile compound represented by: Formula (XIII)

[Where,
R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meaning as defined in claim 1 ;
m represents an integer of 0 to 3. ]
The malononitrile compound of Claim 1 shown by these. Formula (XIV)

[Where,
^{R 1, R 2, R 3} , R 4 and R ⁵ Represents the same meaning as defined in claim 4,
m represents an integer of 0-2. ]
The malononitrile compound of Claim 1 shown by these. A malononitrile compound represented by the formula (XVI);

^{Wherein, R 1, R 2, R} 3, R 4 and R ⁵ Represents the same meaning as defined in claim 1,
m represents an integer of 0-2. ] A harmful arthropod control agent comprising the malononitrile compound according to any one of claims 1 to 6 as an active ingredient. Control of harmful arthropods characterized by applying an effective amount of the malononitrile compound according to any one of claims 1 to 6 to harmful arthropods or habitats of harmful arthropods (excluding the human body). Method.