JP2007031422A - Malononitrile compound and application of the same compound for controlling harmful organism - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound having excellent control effect on harmful organisms and to provide application of the compound for controlling harmful organisms. <P>SOLUTION: The malononitrile compound is represented by formula (I) (wherein R<SP>1</SP>is a 1-4C fluoroalkyl group; R<SP>2</SP>and R<SP>3</SP>are each a hydrogen atom or a 1-4C alkyl group; R<SP>4</SP>is a halogen atom, a 1-11C alkyl group which may be substituted with one or more halogen atoms, a 2-6C alkenyl group which may be substituted with one or more halogen atoms, a 2-6C alkynyl group which may be substituted with one or more halogen atoms or a 3-11C cycloalkyl group which may be substituted with one or more halogen atoms, with the proviso that at least one of R<SP>2</SP>and R<SP>3</SP>represents a 1-4C alkyl group). The malononitrile has excellent control effect on harmful organisms. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a malononitrile compound and its use for pest control.

  Conventionally, compounds aimed at controlling pests such as insects, ticks and nematodes, and methods for controlling them are provided. However, in some cases, these compounds may not show sufficient efficacy.

  An object of the present invention is to provide a compound having an excellent control effect against pests and a pest control use of the compound.

〔式中、Ｒ¹はＣ１−Ｃ４フルオロアルキル基を表し、Ｒ²及びＲ³は各々水素原子又はＣ１−Ｃ４アルキル基を表し、Ｒ⁴はハロゲン原子、１以上のハロゲン原子で置換されていてもよいＣ１−Ｃ１１アルキル基、１以上のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルケニル基、１以上のハロゲン原子で置換されていてもよいＣ２−Ｃ６アルキニル基又は１以上のハロゲン原子で置換されていてもよいＣ３−Ｃ１１シクロアルキル基を表す。但し、Ｒ²及びＲ³の少なくとも一方は必ずＣ１−Ｃ４アルキル基を表す。〕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若しく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 pest control effect, the present inventors have found that the malononitrile compound represented by the following formula (I) is an arthropod such as an insect and a tick, and a nematode. It has been found that it has excellent control activity against pests, and has led to the present invention.
That is, the present invention provides a compound of formula (I)

[Wherein R ¹ represents a C1-C4 fluoroalkyl group, R ² and R ³ each represent a hydrogen atom or a C1-C4 alkyl group, and R ⁴ is substituted with a halogen atom or one or more halogen atoms. A C1-C11 alkyl group which may be substituted with one or more halogen atoms, a C2-C6 alkenyl group which may be substituted with one or more halogen atoms, a C2-C6 alkynyl group which may be substituted with one or more halogen atoms, or one or more halogen atoms Represents an optionally substituted C3-C11 cycloalkyl group. However, at least one of R ² and R ³ always represents a C1-C4 alkyl group. ], A pest control agent characterized by containing the compound of the present invention as an active ingredient, and an effective amount of the compound of the present invention as a habitat for the pest or the pest Provided is a method for controlling pests, characterized by being applied to

  According to the present invention, pests such as insects, mites and nematodes can be effectively controlled.

In the present invention,
The halogen atom represents a fluorine atom, a chlorine atom and a bromine atom,
The expression “C1-C6 alkyl group” represents an alkyl group having 1 to 6 carbon atoms in total,
The expression “C1-C4 fluoroalkyl group” represents an alkyl group in which a hydrogen atom on one or more alkyl groups is substituted with a fluorine atom and the total number of carbon atoms is 1 to 4.

Examples of the C1-C4 fluoroalkyl group represented by R ¹ include a trifluoromethyl group, a 1-monofluoroethyl group, a 2-monofluoroethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 1,2,2,2-tetrafluoroethyl group, 1,1,2,2,2-pentafluoroethyl Group;
2-fluoropropyl group, 3-fluoropropyl group, 1,1-difluoropropyl group, 2,2-difluoropropyl group, 2,3-difluoropropyl group, 3,3-difluoropropyl group, 1,2,2- Trifluoropropyl group, 2,2,3-trifluoropropyl group, 3,3,3-trifluoropropyl group, 1,1,2,2-tetrafluoropropyl group, 2,2,3,3-tetrafluoro Propyl group, 2,3,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,3,3,3-hexafluoropropyl group, 1, 1,2,2,3,3,3-heptafluoropropyl group;
1-fluorobutyl group, 2-fluorobutyl group, 3-fluorobutyl group, 4-fluorobutyl group, 1,1-difluorobutyl group, 2,2-difluorobutyl group, 2,3-difluorobutyl group, 2, 4-difluorobutyl group, 3,3-difluorobutyl group, 4,4-difluorobutyl group, 1,2,2-trifluorobutyl group, 2,2,3-trifluorobutyl group, 3,3,4- Trifluorobutyl group, 3,4,4-trifluorobutyl group, 4,4,4-trifluorobutyl group, 1,1,2,2-tetrafluorobutyl group, 2,2,3,3-tetrafluoro Butyl group, 3,3,4,4-tetrafluorobutyl group, 3,4,4,4-tetrafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 2,2,3, 3,4,4-hexafluo Butyl, 1,1,2,2,3,3-hexafluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl and 1,1,2,2,3 , 3,4,4,4-nonafluorobutyl group.

Examples of the C1-C4 alkyl group represented by R ² and R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 1-methylpropyl group, and a 2-methylpropyl group.

Examples of the C1-C11 alkyl group optionally substituted with one or more halogen atoms represented by R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a 2-methylpropyl group, 1,1-dimethylethyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, isohexyl group, 3,3-dimethylbutyl group, heptyl group, octyl group, nonyl group, decyl group,

Monofluoromethyl group, difluoromethyl group, trifluoromethyl group, monochloromethyl group, dichloromethyl group, trichloromethyl group, monobromomethyl group, 1-monofluoroethyl group, 2-monofluoroethyl group, 1-monochloroethyl group 2-monochloroethyl group, 1-monobromoethyl group, 2-monobromoethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 1,2,2-trifluoroethyl group, 2, 2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 1,1,2,2,2-pentafluoroethyl group, 2-chloro-1-methylethyl group, 1-fluoro Propyl group, 2-fluoropropyl group, 3-fluoropropyl group, 3-chloropropyl group, 3-bromopropyl group, 1,1-difluoropropyl Pill group, 2,2-difluoropropyl group, 3,3-difluoropropyl group, 2,3,3-trifluoropropyl group, 3,3,3-trifluoropropyl group, 3-chloro-3,3-difluoro Propyl group, 3,3-dichloro-3-fluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,3 , 3,3-hexafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 2-chloro-3-bromo-2,3,3-trifluoropropyl group, 3- Bromo-2,2,3,3-tetrafluoropropyl group, 2- (trifluoromethyl) -2,3,3,3-tetrafluoropropyl group,

4-fluorobutyl group, 4-chlorobutyl group, 4-bromobutyl group, 2-fluorobutyl group, 2,2-difluorobutyl group, 3-fluorobutyl group, 3,3-difluorobutyl group, 4,4-difluorobutyl Group, 2,2,3-trifluorobutyl group, 2,2,3,3-tetrafluorobutyl group, 2,2,3,4-tetrafluorobutyl group, 3,3,4,4-tetrafluorobutyl Group, 3-chloro-3,4,4-trifluorobutyl group, 4-bromo-3-chloro-3,4,4-trifluorobutyl group, 3,4-dichloro-3,4,4-trifluoro Butyl group, 2,2,3,4,4-pentafluorobutyl group, 2,2,3,4,4,4-hexafluorobutyl group, 2,2,3,4,4-hexafluorobutyl Group, 3- (trifluoromethyl) 2,2,3,3,4,4,4-heptafluorobutyl group, 3,4,4,4-tetrafluorobutyl group, 1,1,2,2,3,3,4,4-octafluoro Butyl group, 1,1,2,2,3,3,4,4,4-nonafluorobutyl group,

5-fluoropentyl group, 5-chloropentyl group, 5-bromopentyl group, 2-fluoropentyl group, 2-chloropentyl group, 2,2-difluoropentyl group, 2,3-difluoropentyl group, 2,2- Dichloropentyl group, 2,3-dichloropentyl group, 3,4-difluoropentyl group, 3,4-dichloropentyl group, 2,2,3-trifluoropentyl group, 2,2,3,3-tetrafluoropentyl Group, 2,2,3,3,4-pentafluorofluoropentyl group, 2,2,3,3,4,4-hexafluoropentyl group, 2,2,3,3,4,4,5-hepta Fluoropentyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 3- A fluoropentyl group, - chloropentyl group, 3,3-difluoropentyl group, 3,3-dichloro-pentyl group, 3,3,4-trifluoro-pentyl group,

3,3,4,4-tetrafluoropentyl group, 3,3,4,4,5-pentafluoropentyl group, 3,4,5,5,5-pentafluoropentyl group, 3,4,4,5 , 5-pentafluoropentyl group, 3,3,4,4,5,5-hexafluoropentyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 4-fluoropentyl group, 4,4-difluoropentyl group, 4,4,5-trifluoropentyl group, 4,4,5,5-tetrafluoropentyl group, 4,4,5,5,5-pentafluoropentyl group, 5,5 -Difluoropentyl group, 5,5,5-trifluoropentyl group,

6-fluorohexyl group, 6-chlorohexyl group, 6-bromohexyl group, 2,2-difluorohexyl group, 3-fluorohexyl group, 3,3-difluorohexyl group, 4-fluorohexyl group, 4,4- Difluorohexyl group, 5,5-difluorohexyl group, 2,2,3-trifluorohexyl group, 2,2,3,3-tetrafluorohexyl group, 2,2,3,3,4-pentafluorofluorohexyl Group, 2,2,3,3,4,4-hexafluorohexyl group, 2,2,3,3,4,4,5-heptafluorohexyl group, 2,2,3,3,4,4, 5,5-octafluorohexyl group, 2,2,3,3,4,4,5,5,6-nonafluorohexyl group, 2,2,3,3,4,4,5,5,6 6-decafluorohexyl group, 2,2,3 , 4,4,5,5,6,6,6-undecafluorohexyl group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl group, 3,3-difluorohexyl group, 3,3,4-trifluorohexyl group, 3,3,4,4-tetrafluorohexyl group, 3,3,4,4,5-pentafluorohexyl group, 3,3 , 4,4,5,5-hexafluorohexyl group, 3,3,4,4,5,5,6-heptafluorohexyl group, 4,4-difluorohexyl group, 4,4,5-trifluorohexyl Group, 4,4,5,5-tetrafluorohexyl group, 4,4,5,5,6-pentafluorohexyl group, 4,4,5,5,6,6-hexafluorohexyl group, 4,4 , 5,5,6,6,6-heptafluorohexyl group, 5-fluorohexyl Group, 5,5-difluorohexyl group, 5,5,6-trifluorohexyl group, 5,5,6,6-tetrafluorohexyl group, 5,5,6,6,6-pentafluorohexyl group, Examples include 6,6-difluorohexyl group and 6,6,6-trifluorohexyl group.

Examples of the C2-C6 alkenyl group optionally substituted with one or more halogen atoms represented by R ⁴ include vinyl group, allyl group, 1-propenyl group, 2-methyl-1-propenyl group, 2-methyl- 2-propenyl group, 3-butenyl group, 2-butenyl group, 1-butenyl group, 3-methyl-2-butenyl group, 4-pentenyl group, 3-pentenyl group, 2-pentenyl group, 1-pentenyl group, 4 -Methyl-3-pentenyl group, 5-hexenyl group, 4-hexenyl group, 3-hexenyl group, 2-hexenyl group, 1-hexenyl group,

1-fluorovinyl group, 2-fluorovinyl group, 1-chlorovinyl group, 2-chlorovinyl group, 2,2-difluorovinyl group, 2,2-dichlorovinyl group, 2,2-dibromovinyl group, 2, 3,3-trifluoro-2-propenyl group, 3,3,3-trifluoro-1-propenyl group, 4,4-dibromo-3-butenyl group, 3,4,4-trifluoro-3-butenyl group 4,4,4-trifluoro-2-butenyl group, 5,5-difluoro-4-pentenyl group, 4,5,5-trifluoro-4-pentenyl group, 5,5,5-trifluoro-3 -Pentenyl group, 6,6-difluoro-5-hexenyl group, 5,6,6-trifluoro-5-hexenyl group and 6,6,6-trifluoro-4-hexenyl group.

Examples of the C2-C6 alkynyl group optionally substituted by one or more halogen atoms represented by R ⁴ include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3- Butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, 4, Examples include 4,4-trifluoro-2-butynyl group and 3-chloro-2-propynyl group.

Examples of the C3-C11 cycloalkyl group optionally substituted with one or more halogen atoms represented by R ⁴ include a cyclopropyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, and 2,2-dimethyl group. Cyclopropyl group, 2,3-dimethylcyclopropyl group, 2,2,3-trimethylcyclopropyl group, 2,2,3,3-tetramethylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group 1-fluorocyclopropyl group, 2-fluorocyclopropyl group, 2,2-difluorocyclopropyl group, 2,2,3-trifluorocyclopropyl group, 2,2,3,3-tetrafluorocyclopropyl group, 2,2-dichlorocyclopropyl group, 4- (trifluoromethyl) cyclohexyl group, 3- Fluoromethyl) cyclohexyl group, 2,2,3,3-tetrachloro-cyclopropyl,
Cyclopropylmethyl group, 2- (cyclopropyl) ethyl group, 3- (cyclopropyl) propyl group, (1-methylcyclopropyl) methyl group, 2- (1-methylcyclopropyl) ethyl group, 3- (1- Methylcyclopropyl) propyl group, cyclobutylmethyl group, 2- (cyclobutyl) ethyl group, 3- (cyclobutyl) propyl group, (2-fluorocyclopropyl) methyl group, 1- (2-fluorocyclopropyl) ethyl group, 2- (1-fluorocyclopropyl) ethyl group, 2- (2-fluorocyclopropyl) ethyl group, (2,2-difluorocyclopropyl) methyl group, 2- (2,2-difluorocyclopropyl) ethyl group, 1- (2,2-difluorocyclopropyl) ethyl group, (2,2,3,3-tetrafluorocyclopropyl) methyl Group, (2,2-dichlorocyclopropyl) methyl group, 2- (2,2-dichlorocyclopropyl) ethyl group, cyclopentylmethyl group, cyclohexylmethyl group, 1- (2,2,3-trifluorocyclopropyl ) Ethyl group, 1- (2,2,3,3-tetrafluorocyclopropyl) ethyl group, 4- (cyclopropyl) butyl group, 3- (cyclopropyl) butyl group, 2- (cyclopropyl) butyl group, 4- (1-fluorocyclopropyl) butyl group, 4- (2-fluorocyclopropyl) butyl group, 4- (2,2-difluorocyclopropyl) butyl group, 4- (2,2,3-trifluorocyclo) Propyl) butyl group and 4- (2,2,3,3-tetrafluorocyclopropyl) butyl group.

As an aspect of this invention compound, the following are mentioned, for example.
A malononitrile compound in which R ¹ is a C2-C4 fluoroalkyl group;
A malononitrile compound in which R ¹ is a C2-C4 fluoroalkyl group having 2 to 5 fluorine atoms;
A malononitrile compound in which R ¹ is a C 3 -C 4 fluoroalkyl group having 3 to 7 fluorine atoms;
A malononitrile compound in which R ¹ is a C4 fluoroalkyl group having 8 to 9 fluorine atoms;
A malononitrile compound in which R ² is a hydrogen atom and R ³ is a C1-C4 alkyl group;
A malononitrile compound in which R ² is a hydrogen atom and R ³ is a methyl group;
A malononitrile compound in which R ³ is a methyl group;
A malononitrile compound in which R ⁴ is a C1-C11 alkyl group optionally substituted by one or more halogen atoms;
A malononitrile compound in which R ⁴ is a C1-C11 alkyl group optionally substituted with one or more halogen atoms or a C3-C11 cycloalkyl group optionally substituted with one or more halogen atoms;
R ⁴ may be substituted with a C1-C11 alkyl group optionally substituted with one or more halogen atoms, a C2-C6 alkenyl group optionally substituted with one or more halogen atoms, or substituted with one or more halogen atoms. A malononitrile compound which is a good C2-C6 alkynyl group;
A malononitrile compound in which R ⁴ is a C1-C6 alkyl group optionally substituted by one or more halogen atoms;
R ⁴ may be a C1-C6 alkyl group optionally substituted with one or more halogen atoms, a C2-C6 alkenyl group optionally substituted with one or more halogen atoms, or a substituent substituted with one or more halogen atoms. A malononitrile compound which is a good C2-C6 alkynyl group;
A malononitrile compound in which R ⁴ is a C1-C11 alkyl group optionally substituted by one or more fluorine atoms;
A malononitrile compound in which R ⁴ is a C1-C11 alkyl group optionally substituted with one or more fluorine atoms or a C3-C11 cycloalkyl group optionally substituted with one or more fluorine atoms;
A malononitrile compound in which R ⁴ is a C1-C6 alkyl group optionally substituted by one or more fluorine atoms;
A malononitrile compound in which R ⁴ is a C2-C6 alkyl group optionally substituted by one or more fluorine atoms;

A malononitrile compound in which R ² is a hydrogen atom, R ³ is a C1-C4 alkyl group, and R ⁴ is a C1-C11 alkyl group optionally substituted by one or more halogen atoms;
R ² is a hydrogen atom, R ³ is a C1-C4 alkyl group, R ⁴ is a C1-C11 alkyl group optionally substituted with one or more halogen atoms, or substituted with one or more halogen atoms. A malononitrile compound which may be a C3-C11 cycloalkyl group;
R ² is a hydrogen atom, R ³ is a C1-C4 alkyl group, R ⁴ is a C1-C11 alkyl group optionally substituted with one or more halogen atoms, and is substituted with one or more halogen atoms. A malononitrile compound which may be a C2-C6 alkenyl group or a C2-C6 alkynyl group optionally substituted by one or more halogen atoms;
R ² is a hydrogen atom, R ³ is a C1-C4 alkyl group, R ⁴ is a C2-C11 alkyl group optionally substituted with one or more halogen atoms, and is substituted with one or more halogen atoms. A malononitrile compound which may be a C2-C6 alkenyl group or a C2-C6 alkynyl group optionally substituted by one or more halogen atoms;
A malononitrile compound in which R ² is a hydrogen atom, R ³ is a C1-C4 alkyl group, and R ⁴ is a C1-C6 alkyl group optionally substituted by one or more halogen atoms;
R ² is a hydrogen atom, R ³ is a C1-C4 alkyl group, R ⁴ is a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and is substituted with one or more halogen atoms. A malononitrile compound which may be a C2-C6 alkenyl group or a C2-C6 alkynyl group optionally substituted by one or more halogen atoms;
R ² is a hydrogen atom, R ³ is a C1-C4 alkyl group, R ⁴ is a C2-C6 alkyl group optionally substituted with one or more halogen atoms, and is substituted with one or more halogen atoms. A malononitrile compound which may be a C2-C6 alkenyl group or a C2-C6 alkynyl group optionally substituted by one or more halogen atoms;
A malononitrile compound in which R ² is a hydrogen atom, R ³ is a C1-C4 alkyl group, and R ⁴ is a C1-C11 alkyl group optionally substituted by one or more fluorine atoms;
R ² is a hydrogen atom, R ³ is a C1-C4 alkyl group, R ⁴ is a C1-C11 alkyl group optionally substituted with one or more fluorine atoms, or substituted with one or more fluorine atoms. A malononitrile compound which may be a C3-C11 cycloalkyl group;
A malononitrile compound in which R ² is a hydrogen atom, R ³ is a C1-C4 alkyl group, and R ⁴ is a C1-C6 alkyl group optionally substituted by one or more fluorine atoms;
A malononitrile compound in which R ² is a hydrogen atom, R ³ is a C1-C4 alkyl group, and R ⁴ is a C2-C6 alkyl group optionally substituted by one or more fluorine atoms.

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) or (Production Method 2).

〔式中、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は前記と同じ意味を表し、Ａ¹は臭素原子、ヨウ素原子、メタンスルホニルオキシ基、トルエンスルホニルオキシ基又はトリフルオロメタ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ヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素、トルエン、キシレン、メシチレン等の芳香族炭化水素、ジエチルエーテル、メチル ｔｅｒｔ−ブチルエーテル、テトラヒドロフラン、１，４−ジオキサン等のエーテル、Ｎ，Ｎ−ジメチルホルムアミド等の酸アミド、ジメチルスルホキシド等のジアルキルスルホキシド及びこれらの混合物が挙げられる。
反応に用いられる塩基としては例えば炭酸ナトリウム、炭酸カリウム等の炭酸塩、水素化ナトリウム等のアルカリ金属水素化物及びトリエチルアミン、ジイソプロピルエチルアミン等の第三級アミンが挙げられる。
反応に用いられる試剤の量は、化合物（ｂ）１モルに対して化合物（ａ）が通常１〜１０モルの割合であり、塩基が通常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０．１〜２４時間の範囲である。
反応終了後は、反応混合物を水に注加し、有機溶媒抽出して得られた有機層を、乾燥、濃縮する等の後処理操作を行うことにより、本発明化合物を単離することができる。単離された本発明化合物は必要に応じてクロマトグラフィー、再結晶等の操作により精製することもできる。 (Production method 1)
The compound of the present invention can be produced by reacting compound (a) with compound (b).

[Wherein, R ¹ , R ² , R ³ and R ⁴ represent the same meaning as described above, and A ¹ represents a bromine atom, an iodine atom, a methanesulfonyloxy group, a toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group. ]
The reaction is usually performed in a solvent in the presence of a base.
Examples of the solvent used in the reaction include aliphatic hydrocarbons such as hexane, heptane, octane, and cyclohexane, aromatic hydrocarbons such as toluene, xylene, and mesitylene, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 1,4-dioxane, and the like. Ethers, acid amides such as N, N-dimethylformamide, dialkyl sulfoxides such as dimethyl sulfoxide, and mixtures thereof.
Examples of the base used in the reaction include carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrides such as sodium hydride, and tertiary amines such as triethylamine and diisopropylethylamine.
The amount of the reagent used in the reaction is usually 1 to 10 mol of the compound (a) and 1 to 10 mol of the base, based on 1 mol of the compound (b).
The reaction temperature of the reaction is usually in the range of -20 to 100 ° C, and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound of the present invention can be isolated by performing post-treatment operations such as pouring the reaction mixture into water and extracting the organic layer obtained by organic solvent extraction, drying and concentrating. . The isolated compound of the present invention can be purified by operations such as chromatography, recrystallization and the like, if necessary.

〔式中、Ｒ²、Ｒ³及びＲ⁴は前記と同じ意味を表し、Ｒ⁵はＣ１−Ｃ２フルオロアルキル基を表し、Ａ²は臭素原子、ヨウ素原子、メタンスルホニルオキシ基、トルエンスルホニルオキシ基又はトリフルオロメタンスルホニルオキシ基を表す。〕
該反応は通常溶媒中、塩基及び触媒の存在下で行われる。
反応に用いられる溶媒としては例えばヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素、トルエン、キシレン、メシチレン等の芳香族炭化水素、ジエチルエーテル、メチル ｔｅｒｔ−ブチルエーテル、テトラヒドロフラン、１，４−ジオキサン等のエーテル、Ｎ，Ｎ−ジメチルホルムアミド等の酸アミド、ジメチルスルホキシド等のジアルキルスルホキシド及びこれらの混合物が挙げられる。
反応に用いられる塩基としては例えば炭酸ナトリウム、炭酸カリウム等の炭酸塩、水素化ナトリウム等のアルカリ金属水素化物及びトリエチルアミン、ジイソプロピルエチルアミン等の第三級アミンが挙げられる。
反応に用いられる触媒としては例えばテトラキス（トリフェニルホスフィン）パラジウム等の遷移金属錯体が挙げられる。
反応に用いられる試剤の量は、化合物（ｂ）１モルに対して化合物（ａ−１）が通常１〜１０モルの割合であり、塩基が通常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０．１〜２４時間の範囲である。
反応終了後は、反応混合物を水に注加し、有機溶媒抽出して得られた有機層を、乾燥、濃縮する等の後処理操作を行うことにより、式（Ｉ−１）で示されるマロノニトリル化合物を単離することができる。単離された式（Ｉ−１）で示されるマロノニトリル化合物は必要に応じてクロマトグラフィー、再結晶等の操作により精製することもできる。 (Production method 2)
Among the compounds of the present invention, the malononitrile compound represented by the formula (I-1) can also be produced by reacting the compound (a-1) with the compound (b).

[Wherein R ² , R ³ and R ⁴ represent the same meaning as described above, R ⁵ represents a C1-C2 fluoroalkyl group, A ² represents a bromine atom, an iodine atom, a methanesulfonyloxy group, a toluenesulfonyloxy group. Or represents a trifluoromethanesulfonyloxy group. ]
The reaction is usually performed in a solvent in the presence of a base and a catalyst.
Examples of the solvent used in the reaction include aliphatic hydrocarbons such as hexane, heptane, octane, and cyclohexane, aromatic hydrocarbons such as toluene, xylene, and mesitylene, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 1,4-dioxane, and the like. Ethers, acid amides such as N, N-dimethylformamide, dialkyl sulfoxides such as dimethyl sulfoxide, and mixtures thereof.
Examples of the base used in the reaction include carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrides such as sodium hydride, and tertiary amines such as triethylamine and diisopropylethylamine.
Examples of the catalyst used for the reaction include transition metal complexes such as tetrakis (triphenylphosphine) palladium.
The amount of the reagent used for the reaction is usually 1 to 10 moles of the compound (a-1) and 1 to 10 moles of the base to 1 mole of the compound (b).
The reaction temperature of the reaction is usually in the range of -20 to 100 ° C, and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the reaction mixture is poured into water, and the organic layer obtained by extraction with an organic solvent is subjected to post-treatment operations such as drying and concentration, thereby allowing malononitrile represented by the formula (I-1). The compound can be isolated. The isolated malononitrile compound represented by the formula (I-1) can be purified by an operation such as chromatography, recrystallization and the like, if necessary.

〔式中、Ｒ¹、Ｒ²及びＲ³は前記と同じ意味を表し、Ｒ⁴¹はオキソＣ１−Ｃ１１アルキル基、ヒドロキシＣ１−Ｃ１１アルキル基、オキソＣ３−Ｃ６アルケニル基、ヒドロキシＣ３−Ｃ６アルケニル基、オキソＣ４−Ｃ６アルキニル基、ヒドロキシＣ４−Ｃ６アルキニル基、オキソＣ３−Ｃ１１シクロアルキル基又はヒドロキシＣ３−Ｃ１１シクロアルキル基を表し、Ｒ^4-1はフルオロＣ１−Ｃ１１アルキル基、フルオロＣ３−Ｃ６アルケニル基、フルオロＣ４−Ｃ６アルキニル基又はフルオロＣ３−Ｃ１１アルキル基を表す。〕
該反応は溶媒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、例えばヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素、四塩化炭素、クロロホルム、ジクロロメタン等のハロゲン化炭化水素及びこれらの混合物が挙げられる。
反応に用いられるフッ素化剤としては例えば四フッ化硫黄、ジエチルアミノサルファトリフルオリド、ビス−（２−メトキシエチル）アミノサルファトリフルオリド、２−クロロ−１，１，２−トリフルオロエチル−ジエチルアミン及び２，２−ジフルオロ−１，３−ジメチルイミダゾリジンが挙げられる。
反応に用いられるフッ素化剤の量は、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−２０〜１００℃の範囲であり、反応時間は通常０．１〜３６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、有機溶媒抽出して得られた有機層を乾燥、濃縮する等の後処理操作を行うことにより、式（Ｉ−２）で示されるマロノニトリル化合物を単離することができる。単離された式（Ｉ−２）で示されるマロノニトリル化合物は必要に応じてクロマトグラフィー、再結晶等の操作により精製することもできる。 (Production method 3)
Among the compounds of the present invention, the malononitrile compound represented by the formula (I-2) can also be produced by reacting the compound (c) with a fluorinating agent.

[Wherein R ¹ , R ² and R ³ represent the same meaning as described above, and R ⁴¹ represents an oxo C1-C11 alkyl group, a hydroxy C1-C11 alkyl group, an oxo C3-C6 alkenyl group, a hydroxy C3-C6 alkenyl group. , oxo C4-C6 alkynyl group, hydroxy C4-C6 alkynyl group, oxo C3-C11 cycloalkyl group or a hydroxy C3-C11 cycloalkyl group, R ^4-1 fluoro C1-C11 alkyl group, fluoro C3-C6 alkenyl Represents a group, a fluoro C4-C6 alkynyl group or a fluoro C3-C11 alkyl group. ]
The reaction is performed in the presence or absence of a solvent.
Examples of the solvent used in the reaction include aliphatic hydrocarbons such as hexane, heptane, octane, and cyclohexane, halogenated hydrocarbons such as carbon tetrachloride, chloroform, and dichloromethane, and mixtures thereof.
Examples of the fluorinating agent used in the reaction include sulfur tetrafluoride, diethylaminosulfur trifluoride, bis- (2-methoxyethyl) aminosulfur trifluoride, 2-chloro-1,1,2-trifluoroethyl-diethylamine and 2 , 2-difluoro-1,3-dimethylimidazolidine.
The amount of the fluorinating agent used in the reaction is usually 1 to 10 moles per mole of the compound (c).
The reaction temperature of the reaction is usually in the range of -20 to 100 ° C, and the reaction time is usually in the range of 0.1 to 36 hours.
After completion of the reaction, the malononitrile compound represented by the formula (I-2) is obtained by performing post-treatment operations such as pouring the reaction mixture into water and extracting the organic layer obtained by organic solvent extraction and drying. Can be isolated. The isolated malononitrile compound represented by the formula (I-2) can be purified by operations such as chromatography, recrystallization and the like, if necessary.

〔式中、Ｒ³及びＲ⁴は前記と同じ意味を表し、Ａ³は臭素原子、ヨウ素原子、メタンスルホニルオキシ基、トルエンスルホニルオキシ基又はトリフルオロメタ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ヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素、トルエン、キシレン、メシチレン等の芳香族炭化水素、ジエチルエーテル、メチル ｔｅｒｔ−ブチルエーテル、テトラヒドロフラン、１，４−ジオキサン等のエーテル、Ｎ，Ｎ−ジメチルホルムアミド等の酸アミド及びこれらの混合物が挙げられる。
反応に用いられる塩基としては例えば炭酸ナトリウム、炭酸カリウム等の炭酸塩、水素化ナトリウム等のアルカリ金属水素化物及びトリエチルアミン、ジイソプロピルエチルアミン等の第三級アミンが挙げられる。
反応に用いられる試剤の量は、化合物（ｄ）１モルに対して、マロノニトリルが通常０．５〜１０モルであり、塩基が通常０．５〜５モルの割合である。
該反応の反応温度は通常−２０〜１００℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を水に注加し、有機溶媒抽出して得られた有機層を、乾燥、濃縮する等の後処理操作を行うことにより、化合物（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、再結晶等の操作により精製することもできる。 Next, production of the production intermediate of the compound of the present invention will be described.
Compound (b) can be produced, for example, by reacting compound (d) with malononitrile.

[Wherein, R ³ and R ⁴ represent the same meaning as described above, and A ³ represents a bromine atom, an iodine atom, a methanesulfonyloxy group, a toluenesulfonyloxy group, or a trifluoromethanesulfonyloxy group. ]
The reaction is usually performed in a solvent in the presence of a base.
Examples of the solvent used in the reaction include aliphatic hydrocarbons such as hexane, heptane, octane, and cyclohexane, aromatic hydrocarbons such as toluene, xylene, and mesitylene, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 1,4-dioxane, and the like. Ethers, acid amides such as N, N-dimethylformamide, and mixtures thereof.
Examples of the base used in the reaction include carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrides such as sodium hydride, and tertiary amines such as triethylamine and diisopropylethylamine.
The amount of the reagent used in the reaction is usually 0.5 to 10 moles of malononitrile and 0.5 to 5 moles of the base with respect to 1 mole of the compound (d).
The reaction temperature of the reaction is usually in the range of -20 to 100 ° C, and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (b) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water and extracting the organic layer obtained by organic solvent drying and concentration. it can. The isolated compound (b) can be purified by operations such as chromatography, recrystallization and the like, if necessary.

〔式中、Ｒ⁴は前記と同じ意味を表し、Ｒ^3-1はＣ１−Ｃ４アルキル基を表す。〕
該反応は通常溶媒中、必要に応じて銅塩の存在下で行われる。
反応に用いられる溶媒としては、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、トルエン、キシレン等の芳香族炭化水素及びこれらの混合物が挙げられる。
反応に用いられるアルキル化剤としては、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、ジメチルマグネシウム等のアルキルマグネシウム、メチルリチウム等のアルキルリチウム、及びジエチル亜鉛等のアルキル亜鉛などの有機金属化合物が挙げられ、銅塩としては例えばヨウ化銅（Ｉ）、臭化銅（Ｉ）等が挙げられる。
反応に用いられる試剤の量は、化合物（ｅ）１モルに対して、アルキル化剤が通常１〜１０モルの割合であり、銅塩が通常１モル以下である。
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、有機溶媒抽出して得られた有機層を、乾燥、濃縮する等の後処理操作を行うことにより、化合物（ｂ−１）を単離することができる。単離された化合物（ｂ−１）は必要に応じてクロマトグラフィー、再結晶等の操作により精製することもできる。 Compound (b-1) can be produced, for example, by reacting compound (e) with an alkylating agent.

[Wherein, R ⁴ represents the same meaning as described above, and R ^3-1 represents a C1-C4 alkyl group. ]
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 the alkylating agent used in the reaction include organic compounds such as alkylmagnesium such as methylmagnesium iodide, ethylmagnesium bromide, isopropylmagnesium bromide, dimethylmagnesium, alkyllithium such as methyllithium, and alkylzinc such as diethylzinc. Examples of the copper salt include copper iodide (I) and copper bromide (I).
The amount of the reagent used in the reaction is usually 1 to 10 mol of the alkylating agent and 1 mol or less of the copper salt with respect to 1 mol of the compound (e).
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-1) is isolated by performing post-treatment operations such as pouring the reaction mixture into water and extracting the organic layer obtained by organic solvent drying and concentration. be able to. The isolated compound (b-1) can be purified by procedures such as chromatography and recrystallization as necessary.

〔式中、Ｒ³及びＲ⁴は前記と同じ意味を表す。〕
該反応は通常溶媒中で行われる。
反応に用いられる溶媒としては、例えばジエチルエーテル、テトラヒドロフラン等のエーテル、トルエン、キシレン等の芳香族炭化水素、メタノール、エタノール等のアルコール、水及びこれらの混合物が挙げられる。
反応に用いられる還元剤としては、例えば水素化ホウ素ナトリウムが挙げられる。
反応に用いられる還元剤の量は、化合物（ｆ）１モルに対して通常０．２５〜２モルの割合である。
該反応の反応温度は通常０〜５０℃の範囲であり、反応時間は通常瞬時〜２４時間の範囲である。
反応終了後は、反応混合物を水に注加し、有機溶媒抽出して得られた有機層を、乾燥、濃縮する等の後処理操作を行うことにより、化合物（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、再結晶等の操作により精製することもできる。 Compound (b) can also be produced, for example, by reacting compound (f) with a reducing agent.

[Wherein R ³ and R ⁴ represent the same meaning as described above. ]
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, alcohols such as methanol and ethanol, water, and mixtures thereof.
Examples of the reducing agent used in the reaction include sodium borohydride.
The amount of the reducing agent used in the reaction is usually in a ratio of 0.25 to 2 mol with respect to 1 mol of the compound (f).
The reaction temperature of the reaction is usually in the range of 0 to 50 ° C., and the reaction time is usually in the range of instantaneous to 24 hours.
After completion of the reaction, the compound (b) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water and extracting the organic layer obtained by organic solvent drying and concentration. it can. The isolated compound (b) can be purified by operations such as chromatography, recrystallization and the like, if necessary.

〔式中、Ｒ³及びＲ⁴は前記と同じ意味を表す。〕
該反応は通常溶媒中、塩基の存在下で行われる。
反応に用いられる溶媒としては、例えばＮ，Ｎ−ジメチルホルムアミド等の酸アミド、ジエチルエーテル、テトラヒドロフラン等のエーテル、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、トルエン、キシレン等の芳香族炭化水素、メタノール、エタノール、イソプロパノ−ル等のアルコール及びこれらの混合物が挙げられる。
反応に用いられる塩基としては、例えば水酸化テトラブチルアンモニウム等が挙げられる。
反応に用いられる試剤の量は、化合物（ｇ）１モルに対して、マロノニトリルが通常１〜１０モルの割合であり、塩基が０．０１〜０．５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去し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、有機溶媒抽出して得られた有機層を、乾燥、濃縮する等の後処理操作を行うことにより、化合物（ｆ）を単離することができる。単離された化合物（ｆ）は必要に応じてクロマトグラフィー、再結晶等の操作により精製することもできる。 Compound (f) can be produced, for example, by reacting malononitrile with compound (g).

[Wherein R ³ and R ⁴ represent the same meaning as described above. ]
The reaction is usually performed in a solvent in the presence of a base.
Examples of the solvent used in the reaction include acid amides such as N, N-dimethylformamide, ethers such as diethyl ether and tetrahydrofuran, halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene, and aromatic carbonization such as toluene and xylene. Examples thereof include alcohols such as hydrogen, methanol, ethanol and isopropanol, and mixtures thereof.
Examples of the base used for the reaction include tetrabutylammonium hydroxide.
The amount of the reagent used in the reaction is usually 1 to 10 moles of malononitrile and 0.01 to 0.5 moles of base with respect to 1 mole of compound (g).
The reaction temperature of the reaction is usually in the range of −20 to 200 ° C., and the reaction time is usually in the range of 1 to 24 hours.
The reaction can be carried out while removing water generated by the reaction from the reaction system, if necessary.
After completion of the reaction, the compound (f) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water and extracting the organic layer obtained by organic solvent drying and concentration. it can. The isolated compound (f) can be purified by operations such as chromatography, recrystallization and the like, if necessary.

〔式中、Ｒ¹、Ｒ²及びＲ³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、例えばヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素、トルエン、キシレン、メシチレン等の芳香族炭化水素、ジエチルエーテル、メチル ｔｅｒｔ−ブチルエーテル、テトラヒドロフラン、１，４−ジオキサン等のエーテル、Ｎ，Ｎ−ジメチルホルムアミド等の酸アミド及びこれらの混合物が挙げられる。
反応に用いられる塩基としては、例えば炭酸ナトリウム、炭酸カリウム等の炭酸塩、水素化ナトリウム等のアルカリ金属水素化物、フッ化カリウム等のフッ化物塩及びトリエチルアミン、ジイソプロピルエチルアミン等の第三級アミンが挙げられる。
反応に用いられる試剤の量は、化合物（ｂ）１モルに対して、化合物（ｈ）が通常１〜１０モルの割合であり、塩基が通常０．５〜５モルの割合である。
該反応の反応温度は通常−２０〜１００℃の範囲であり、反応時間は通常０．１〜２４時間の範囲である。
反応終了後は、反応混合物を水に注加し、有機溶媒抽出して得られた有機層を乾燥、濃縮する等の後処理操作を行うことにより、化合物（ｃ−１）を単離することができる。単離された化合物（ｃ−１）は必要に応じてクロマトグラフィー、再結晶等の操作によりさらに精製することもできる。 Among the compounds (c), the compound (c-1) in which R ⁴¹ is a 2-oxoethyl group can produce, for example, the compound (b) and the compound (h).

[Wherein R ¹ , R ² and R ³ represent the same meaning as described above. ]
The reaction is usually performed in a solvent in the presence of a base.
Examples of the solvent used in the reaction include aliphatic hydrocarbons such as hexane, heptane, octane, and cyclohexane, aromatic hydrocarbons such as toluene, xylene, and mesitylene, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, and 1,4-dioxane. And ethers such as N, N-dimethylformamide, and mixtures thereof.
Examples of the base used in the reaction include carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrides such as sodium hydride, fluoride salts such as potassium fluoride, and tertiary amines such as triethylamine and diisopropylethylamine. It is done.
The amount of the reagent used in the reaction is usually 1 to 10 moles of the compound (h) and 1 to 5 moles of the base per 1 mole of the compound (b).
The reaction temperature of the reaction is usually in the range of -20 to 100 ° C, and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (c-1) is isolated by performing post-treatment operations such as pouring the reaction mixture into water and extracting the organic layer obtained by organic solvent extraction and drying. Can do. The isolated compound (c-1) can be further purified by operations such as chromatography, recrystallization and the like, if necessary.

  Examples of the pests for which the compound of the present invention exhibits a controlling effect include harmful arthropods such as insects and 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, Eysarcoris lewisi, Eysarcoris parvus (Eysarcoris parvus) Plautia stali), stink bugs such as Halyomorpha mista, whitefly (Trialeurodes vaporariorum), whiteflies such as Bemisia argentifolii, Aonidiella aurantii, Sanho Bed bugs such as scale insects such as Zephyllus (Comstockaspis perniciosa), citrus snow scale (Unaspis citri), ruby rot beetle (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, moths (Tinea translucens), moths (Tineola bisselliella), etc .;

Diptera: Culex pipiens pallens, Culex tritaeniorhynchus, Culex quinquefasciatus, etc., Aedes aegypti, Aedes albopics, etc. Anopheles, chironomids, Musca domestica, Muscina stabulans and other house flies, black flies, sphagnum flies, fly flies, fly flies such as fly flies (Delia platura), flies (Delia antiqua), flies Drosophila, fleas such as Megaselia spiracularis, Drosophila (Clogmia albipunctata) butterflies, flyfish, aphids, 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, Phyllotreta striolata, Colorado potato beetle (Leptinotarsa decemlineata) and other horn beetles, Dermestes maculates, etc. Epilacunas such as Epilachna vigintioctopunctata, slat beetles, moth beetles, leopard beetles, beetles, Paederus fuscipes, etc .;
Cockroach insects: German cockroach (Blattella germanica), Black cockroach (Periplaneta fuliginosa), American cockroach (Periplaneta americana), Great cockroach (Periplaneta brunnea), Great cockroach (Blatta orientalis), etc .;

Thrips eye pests: Thrips palmi, Thrips tabaci, Frankliniella occidentalis, Frankliniella intonsa, etc .;
Hymenopteran pests: Ants such as Monomorium pharaosis, Formica fusca japonica, Ruriari (Ochetellus glaber), Pristomyrmex pungens, Pheidole noda, hornet, Japanese hornet Athalia japonica)
Straight-eyed pests: keratoids, grasshoppers, etc .;
Lepidoptera: Cat fleas (Ctenocephalides felis), Fleas (Ctenocephalides canis), Fleas (Pulex irritans), Xenopsylla cheopis, etc.
Lice pests: white lice (Pediculus humanus corporis), white lice (Phthirus pubis), cattle lice (Haematopinus eurysternus), sheep lice (Dalmalinia ovis), etc .;
Termite pests: Yamato termite (Reticulitermes speratus), Japanese termite (Coptotermes formosanus), Eastern subterranian termite (Reticulitermes flavipes), Western subterranian termite (Reticulitermes hesperus), Dark southern subterranian termite (Reticulitermes virginite territhite) (Reticulitermes tibialis), Subteranian termites such as dessert subterranian termite (Heterotermes aureus), Drywood termites such as American termite minor (Incisitermes minor), and dumpwood termites such as Nevada dumpwood termite (Zootermopsis nevadensis) ;

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), Dust mites, Longiornis, Haemaphysalis longicornis, Haemaphysalis flava, American dog tics (Dermacentor variabiltus), Tick Iul ), Tick such as black-legged ticks (Ixodes scapularis), tick (Boophilus microplus), lone star tic (Amblyomma americanum), Rhipicephalus sanguineus, tyrophagus putrescen tiae and other mites, Dermatophagoides farinae, Dermatophagoides ptrenyssnus bacoti), winged spiders (Ornithonyssus sylvairum), duck spiders (Dermanyssus gallinae) and other tsutsugamushi (Leptotrombidium akamushi) and the like;

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

The pest control agent of the present invention may be the compound of the present invention itself. Usually, the compound of the present invention is mixed with a solid carrier, a liquid carrier and / or a gaseous carrier, and if necessary, a surfactant. It is formulated by adding other formulation adjuvants. That is, the pest control agent of the present invention usually contains the compound of the present invention and further contains an inert carrier. Examples of such preparations include emulsions, oils, shampoos, flowables, powders, wettable powders, granules, paste preparations, microcapsule preparations, foam preparations, aerosol preparations, carbon dioxide preparations, tablets, resin preparations, and paper preparations. Non-woven fabric preparations, knitted fabric preparations, and the like. These preparations may be used after being processed into poison baits, insecticides, electric insecticidal mats, fumigants, fumigants, sheets, and the like.
The preparation of the pest control agent of the present invention usually contains 0.01 to 98% 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 granules of chemical fertilizers (ammonium sulfate, phosphorous acid, ammonium nitrate, ammonium chloride, urea, etc.), sublimable substances that are solid at room temperature (2,4,6- Triisopropyl-1,3,5-trioxane, naphthalene, p-dichlorobenzene, camphor, adamantane, etc.), wool, silk, cotton, hemp, pulp, synthetic resin (eg, low density polyethylene, linear low density polyethylene) Polyethylene resins such as high-density polyethylene; ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymer; ethylene-methyl methacrylate copolymer Ethylene-methacrylic acid ester copolymers such as ethylene-ethyl methacrylate copolymer; ethylene-acrylic acid ester copolymers such as ethylene-methyl acrylate copolymer and ethylene-ethyl acrylate copolymer; ethylene -Ethylene-vinylcarboxylic acid copolymer such as acrylic acid copolymer; ethylene-tetracyclododecene copolymer; polypropylene resin such as propylene homopolymer and propylene-ethylene copolymer; poly-4-methylpentene -1, polybutene-1, polybutadiene, polystyrene; acrylonitrile-styrene resin; styrene-based elastomers such as acrylonitrile-butadiene-styrene resin, styrene-conjugated diene block copolymer, hydrogenated styrene-conjugated diene block copolymer; fluorine Resin; Polymeta Acrylic resins such as methyl laurate; Polyamide resins such as nylon 6 and nylon 66; Polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polycyclohexylene dimethylene terephthalate; Polycarbonate, polyacetal, poly Acrylic sulfone, polyarylate, hydroxybenzoic acid polyester, polyetherimide, polyester carbonate, polyphenylene ether resin, polyvinyl chloride, polyvinylidene chloride, polyurethane, foamed polyurethane, foamed polypropylene, foamed ethylene and other porous resins), glass, Felt, fiber, cloth, knitted fabric, sheet, paper, thread, foam, porous body and multifilament made of one or more of metals, ceramics, etc. It is below.

  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, benzyl alcohol, 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 (aceto , Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), sulfoxides (dimethyl sulfoxide, etc.), acid amides (N, N-dimethylformamide, N, N-dimethylacetamide, N -Methyl-pyrrolidone etc.), alkylidene carbonates (propylene carbonate etc.), vegetable oils (soybean oil, cottonseed oil etc.), plant essential oils (orange oil, hyssop oil, lemon oil etc.) and water.

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

  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 polyethylene resins such as low density polyethylene, linear low density polyethylene, and high density polyethylene; ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymers; Ethylene-methacrylic acid ester copolymer such as ethylene acid methyl copolymer and ethylene-ethyl methacrylate copolymer; ethylene-acrylic acid ester copolymer such as ethylene-methyl acrylate copolymer and ethylene-ethyl acrylate copolymer Polymers; ethylene-vinyl carboxylic acid copolymers such as ethylene-acrylic acid copolymers; ethylene-tetracyclododecene copolymers; polypropylene resins such as propylene copolymers and propylene-ethylene copolymers; 4-methylpentene-1, polybutene-1, polybutadiene, police Styrene, elastomers such as lenonitrile, acrylonitrile-styrene resin; acrylonitrile-butadiene-styrene resin, styrene-conjugated diene copolymer, styrene-conjugated diene block copolymer hydrogenated products; fluororesins; acrylic acid such as polymethyl methacrylate Resins; Polyamide resins such as nylon 6 and nylon 66; Polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene butarate, polycyclohexylene dimethylene terephthalate; Polycarbonate, polyacetal, polyacrylsulfone, polyarylate, hydroxy Examples include benzoic acid polyester, polyetherimide, polyester carbonate, polyphenylene ether resin, polyvinyl chloride, polyvinylidene chloride, and polyurethane. These base materials may be used alone or as a mixture of two or more kinds. These base materials may be phthalic acid esters (dimethyl phthalate, dioctyl phthalate, etc.), adipic acid esters if necessary. A plasticizer such as stearic acid may be added.

  The resin preparation can be obtained by kneading the compound of the present invention in the above-mentioned base material and then molding it by injection molding, extrusion molding, press molding or the like. The obtained resin preparation can be further processed into a plate shape, a film shape, a tape shape, a net shape, a string shape or the like through steps such as molding and cutting if necessary. 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 compound of the present invention is used to control pests by applying an effective amount of the compound of the present invention directly to the pests and / or to the habitat (plants, animals, soil, etc.) of the pests. can do.

When the pest control agent of the present invention is used for controlling agricultural and forestry pests, the application amount is usually 1 to 100,000 g / ha, preferably 10 to 1000 g / ha as the amount of the compound of the present invention. Emulsions, wettable powders, flowables, microcapsules and the like are diluted with water so that the active ingredient concentration is usually 0.01 to 1000 ppm, and oils, powders, granules and the like are usually used as they are.
These preparations are used by spraying the plants to be protected from pests as they are, or by spraying the water dilution of the preparations to the plants to be protected from pests. By treating these preparations in the soil, pests that live in the soil can be controlled, and these preparations can be treated in the nursery before planting, or they can be treated in planting holes and stocks at the time of planting. You can also Furthermore, the sheet preparation of the pest control agent of the present invention can be applied by a method such as wrapping around a plant, installing in the vicinity of the plant, or laying on the soil surface of the plant source.

When the pest control agent of the present invention is used for epidemics, the application amount is usually 0.001 to 100 mg / m ³ as the amount of the compound of the present invention when applied to a space, and is 0.00 when applied to a plane. 001 to 1000 mg / m ² . Emulsions, wettable powders, flowables and the like are usually applied by diluting with water so that the concentration of the compound of the present invention is usually 0.001 to 100000 ppm, preferably 0.01 to 1000 ppm, oils, aerosols, smoke agents, The poison bait is usually applied as it is. Insecticidal incense sticks, electric insecticidal mats, and the like are applied by volatilizing active ingredients by heating in accordance with the formulation form. Resin preparations, paper preparations, tablets, nonwoven fabric preparations, knitted fabric preparations, sheet preparations and the like can be used, for example, by leaving them as they are in the space to be applied and blowing them over the preparations.
Examples of the space to which the pest control agent of the present invention is applied for prevention of epidemics include closets, closets, Japanese dance, cupboards, toilets, bathhouses, storerooms, living rooms, canteens, warehouses, car interiors, and the like. It can also be applied in space.

  When the pesticidal agent of the present invention is used for controlling ectoparasites of domestic animals such as cattle, horses, pigs, sheep, goats and chickens, and small animals such as dogs, cats, rats and mice, a method known in veterinary medicine Can be used on animals. As a specific method of use, for the purpose of systemic control, for example, it is administered by tablet, feed mixing, suppository, injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.) For purposes of non-systemic control, for example, spraying oils or aqueous solutions, pour-on or spot-on treatment, washing animals with shampoo formulations or It is used by a method such as attaching a resin preparation to an animal using a collar or ear tag. The amount of the compound of the present invention when administered to an animal body is usually in the range of 0.01 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, for example, allethrin, tetramethrin, praretrin, phenothrin, resmethrin, ciphenothrin, permethrin, cypermethrin, alpha cypermethrin, zetacypermethrin, deltamethrin, tralomethrin, cyfluthrin, beta Cyfluthrin, cyhalothrin, lambda cihalothrin, frametrin, imiprotorin, etofenprox, fenvalerate, esfenvalerate, fenpropatoline, silafluophene, bifenthrin, transfluthrin, flucitrinate, taufulvalinate, acrinathrin, teflutrin, cyclo Protoline, 2,3,5,6-tetrafluoro-4- (methoxymethyl) benzyl (EZ)-(1RS, 3RS; 1RS, 3 R) -2,2-dimethyl-3-prop-1-enylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4-methylbenzyl (EZ)-(1RS, 3RS; 1RS, 3SR)- 2,2-dimethyl-3-prop-1-enylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4- (methoxymethyl) benzyl (1RS, 3RS; 1RS, 3SR) -2,2- Dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4- (methoxymethyl) benzyl 2,2,3,3-tetramethylcyclopropanecarboxylate , Pyrethroid compounds such as empensulin, dichlorvos, fenitrothion, cyanophos, profenofos, sulprophos, fentoate , Isoxathione, tetrachlorobinphos, fenthion, chlorpyrifos, diazinon, acephate, terbufos, folate, chlorethoxyphos, phosthiazate, etoprophos, kazusafos, methidathion and other organic phosphorus compounds, propoxer, carbaryl, methoxadiazone, fenocarb, thiodicarb Carbamate compounds such as benfuracarb, oxamyl, aldicarb, methiocarb, benzoylphenylurea compounds such as lufenuron, chlorfluazuron, hexaflumuron, diflubenzuron, triflumuron, teflubenzuron, flufenoxuron, fluazuron, novallon, triazuron, bistrifluron, Pyriproxyfen, methoprene, hydroprene, phenoxy Juvenile hormone-like substances such as Rub, neonicotinoid compounds such as acetamiprid, nitenpyram, thiacloprid, thiamethoxam and dinotefuran, N-phenylpyrazole compounds such as acetoprole and ethiprole, benzoylhydrazines such as tebufenozide, chromafenozide, methoxyphenozide and halofenozide Compound, diafenthiuron, pymetrozine, flonicamid, triazamate, buprofezin, spinosad, emamectin benzoate, chlorfenapyr, indoxacarb MP, pyridalyl, cyromazine, fenpyroximate, tebufenpyrad, tolfenpyrad, pyridaben, pyrimidifene, fluacripyrizexoxacin , Hexythiazox, clofentezine, phenoxide Tasuzu, dicofol, propargite, avermectin, milbemectin, amitraz, cartap, bensultap, thiocyclam, endosulfan, spirodiclofen, spiromesifen, include amidoflumet and azadirachtin.

  Examples of the active ingredient of such other bactericides include, for example, strobilurin compounds such as azoxystrobin, organophosphorus compounds such as triclofosmethyl, metconazole, hexaconazole, ipconazole, cipconazole, triflumizole, pefazoate, difenoconazole and the like. Azole compounds, iodopropargyl compounds such as IPBC, isothiazolone compounds such as OIT, MEC, fusalides, flutolanil, validamycin, probenazole, dichromedin, pencyclon, dazomet, kasugamycin, IBP, pyroxylone, oxolinic acid, tricyclazole, ferrimzone, mepronil, EDDP, isoprothiolane , Carpropamide, diclocimet, furametopir, fludioxonil, prosimidone and dietofencarb.

Hereinafter, although this invention is demonstrated in more detail by a manufacture example, a formulation example, and a test example, this invention is not limited only to these examples.
First, the manufacture example of this invention compound is shown.

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）δ（ｐｐｍ）：１．３９（３Ｈ，ｄ）、１．９６−２．５７（７Ｈ，ｍ）、５．８６−６．１６（１Ｈ，ｍ） Production Example 1
In 100 ml of acetone, 1.6 g of 2- (3,3,3-trifluoropropyl) malononitrile and 0.7 g of 2-butenal were dissolved, 1.5 g of potassium carbonate was added, and the mixture was stirred at room temperature for 3 hours. Dilute hydrochloric acid was added to the reaction mixture, and the mixture was extracted with methyl tert-butyl ether. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a residue.
The residue obtained by the above operation was added at 0 ° C. to a solution of 3.0 g of diethylaminosulfur trifluoride dissolved in 30 ml of 1,1,3,3,3-pentafluorobutane, followed by stirring at room temperature for 3 hours. Water was added to the reaction mixture, and the mixture was extracted with methyl tert-butyl ether. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (3,3-difluoro-1-methylpropyl) -2- (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (1). 0.09 g was obtained.
Compound (1) of the present invention

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.39 (3H, d), 1.96-2.57 (7H, m), 5.86-6.16 (1H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）δ（ｐｐｍ）：１．３９（３Ｈ，ｄ）、１．９４−２．１０（１Ｈ，ｍ）、２．１８−２．５３（６Ｈ，ｍ）、５．８６−６．１６（１Ｈ，ｍ） Production Example 2
Dissolve 2.1 g of 2- (3,3,4,4,4-tetrafluorobutyl) malononitrile and 0.6 g of 2-butenal in 30 ml of N, N-dimethylformamide, add 0.6 g of potassium fluoride, For 15 minutes. Dilute hydrochloric acid was added to the reaction mixture, and the mixture was extracted with methyl tert-butyl ether. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a residue.
The residue obtained by the above operation was added at 0 ° C. to a solution of 3.0 g of diethylaminosulfur trifluoride dissolved in 30 ml of 1,1,3,3,3-pentafluorobutane, followed by stirring at room temperature for 3 hours. Water was added to the reaction mixture, and the mixture was extracted with methyl tert-butyl ether. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (3,3-difluoro-1-methylpropyl) -2- (3,3,4,4,4-tetrafluorobutyl) malononitrile (hereinafter referred to as the present). 0.42 g was obtained.
Compound (2) of the present invention

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.39 (3H, d), 1.94-2.10 (1H, m), 2.18-2.53 (6H, m), 5.86-6.16 (1H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）δ（ｐｐｍ）：１．４３（３Ｈ，ｄ）、１．９７−２．１３（１Ｈ，ｍ）、２．２９−２．４３（１Ｈ，ｍ）、２．４９−２．５７（１Ｈ，ｍ）、２．６７−２．８５（２Ｈ，ｍ）、５．８８−６．２１（２Ｈ，ｍ） Production Example 3
In 20 ml of N, N-dimethylformamide, 2.0 g of 2- (2,2,3,3,4,4,5,5-octafluoropentyl) malononitrile and 0.4 g of 2-butenal are dissolved, and potassium fluoride 0 .4 g was added and stirred at room temperature for 30 minutes. Dilute hydrochloric acid was added to the reaction mixture, and the mixture was extracted with methyl tert-butyl ether. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a residue.
The residue obtained by the above operation was mixed with 10 ml of 1,1,3,3,3-pentafluorobutane, and 3.0 g of diethylaminosulfur trifluoride was added to 30 ml of 1,1,3,3,3-pentafluorobutane. The mixed solution was added to the dissolved solution at 0 ° C., followed by stirring at room temperature for 3 hours. Water was added to the reaction mixture, and the mixture was extracted with methyl tert-butyl ether. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (3,3-difluoro-1-methylpropyl) -2- (2,2,3,3,4,4,5,5-octafluoropentyl. ) 0.42 g of malononitrile (hereinafter referred to as the present compound (3)) was obtained.
Compound (3) of the present invention

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.43 (3H, d), 1.97-2.13 (1H, m), 2.29-2.43 (1H, m), 2.49-2.57 (1H, m), 2.67-2.85 (2H, m), 5.88-6.21 (2H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）δ（ｐｐｍ）：１．５３（３Ｈ，ｄ）、２．６２−２．８２（２Ｈ，ｍ）、３．０４−３．０９（１Ｈ，ｍ）、４．２７−４．３６（１Ｈ，ｍ）、６．０６（１Ｈ，ｔｔ） Production Example 4
To 20 ml of N, N-dimethylformamide, 16 g of 2- (2,2,3,3,4,4,5,5-octafluoropentyl) malononitrile and 14 g of 1,3-dibromo-1,1-difluorobutane were added, Next, 12 g of potassium carbonate was added and stirred at room temperature for 5 hours. Dilute hydrochloric acid was added to the reaction mixture, and the mixture was extracted with methyl tert-butyl ether. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel chromatography to give 2- (3,3-difluoro-1-methyl-2-propenyl) -2- (2,2,3,3,4,4,5,5-octafluoropentyl). 1.1 g of malononitrile (hereinafter referred to as the present compound (4)) was obtained.
The present compound (4)

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.53 (3H, d), 2.62-2.82 (2H, m), 3.04-3.09 (1H, m), 4.27-4.36 (1H, m), 6.06 (1H, tt)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）δ（ｐｐｍ）：１．５５（３Ｈ，ｄｄ）、２．６６−２．８５（１Ｈ，ｍ）、２．９２−３．１０（２Ｈ，ｍ）、４．８４−４．９０（１Ｈ，ｍ）、６．０８（１Ｈ，ｔｔ） Production Example 5
To 30 ml of 1,1,3,3,3-pentafluorobutane, 2- (4,4-difluoro-1-methyl-3-butenyl) -2- (2,2,3,3,4,4,5, 1.0 g of 5-octafluoropentyl) malononitrile was dissolved, 0.61 g of bromine was added, and the mixture was stirred at room temperature for 5 hours. Water was added to the reaction mixture, and the mixture was extracted with methyl tert-butyl ether. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel chromatography to give 2- (3,3-difluoro-2,3-dibromo-1-methylpropyl) -2- (2,2,3,3,4,4,5,5-octa 0.10 g of fluoropentyl) malononitrile (hereinafter referred to as the present compound (5)) was obtained.
Compound (5) of the present invention

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.55 (3H, dd), 2.66-2.85 (1H, m), 2.92-3.10 (2H, m), 4.84-4.90 (1H, m), 6.08 (1H, tt)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）δ（ｐｐｍ）：１．４６（３Ｈ，ｄ）、２．２６（１Ｈ，ｍ）、２．５４−２．８７（４Ｈ，ｍ）、６．０７（１Ｈ，ｔｔ） Production Example 6
5.6 g of 2- (2,2,3,3,4,4,5,5-octafluoropentyl) malononitrile and 3-iodo-1,1,1-difluorobutane in 20 ml of N, N-dimethylformamide 7 g was added, and then 2.7 g of potassium carbonate was added and stirred at 50 ° C. for 3 hours. Dilute hydrochloric acid was added to the reaction mixture, and the mixture was extracted with methyl tert-butyl ether. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel chromatography to give 2- (1-methyl-3,3,3-trifluoropropyl) -2- (2,2,3,3,4,4,5,5-octafluoropentyl). 0.2 g of malononitrile (hereinafter referred to as the present compound (6)) was obtained.
The present compound (6)

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.46 (3H, d), 2.26 (1H, m), 2.54-2.87 (4H, m), 6.07 ( 1H, tt)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）δ（ｐｐｍ）：１．４３（３Ｈ，d）、２．１６−２．３５（３Ｈ，m）、２．４１−２．６３（４Ｈ，m） Production Example 7
To 30 ml of N, N-dimethylformamide was added 4.9 g of 2- (3,3,3-trifluoropropyl) malononitrile and 7.1 g of 3-iodo-1,1,1-difluorobutane, and then 4.2 g of potassium carbonate. And stirred at 50 ° C. for 3 hours. Dilute hydrochloric acid was added to the reaction mixture, and the mixture was extracted with methyl tert-butyl ether. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel chromatography to give 2- (1-methyl-3,3,3-trifluoropropyl) -2- (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (7)). 0.18 g was obtained.
Compound (7) of the present invention

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.43 (3H, d), 2.16-2.35 (3H, m), 2.41-2.63 (4H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）δ（ｐｐｍ）：１．２８−１．４７（６Ｈ，ｍ）、１．８５−２．３９（３Ｈ，ｍ）、３．００−３．１０（１Ｈ，ｍ）、４．２３−４．３４（１Ｈ，ｍ）、５．８２−６．１５（１Ｈ、ｍ） Production Example 8
Dissolve 1.0 g of 2- (3,3-difluoro-1-methyl-3-butenyl) malononitrile and 0.37 g of 2-butenal in 20 ml of N, N-dimethylformamide, add 0.37 g of potassium fluoride, For 30 minutes. Dilute hydrochloric acid was added to the reaction mixture, and the mixture was extracted with methyl tert-butyl ether. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a residue.
The residue obtained by the above operation is mixed with 10 ml of 1,1,3,3,3-pentafluorobutane, and 1.7 g of diethylaminosulfur trifluoride is added to 30 ml of 1,1,3,3,3-pentafluorobutane. The mixed solution was added to the dissolved solution at 0 ° C., followed by stirring at room temperature for 30 minutes. Water was added to the reaction mixture, and the mixture was extracted with methyl tert-butyl ether. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (3,3-difluoro-1-methylpropenyl) -2- (3,3-difluoro-1-methylpropyl) malononitrile (hereinafter referred to as the present compound ( 8) 0.42 g was obtained.
Compound (8) of the present invention

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.28-1.47 (6H, m), 1.85-2.39 (3H, m), 3.00-3.10 (1H , M), 4.23-4.34 (1H, m), 5.82-6.15 (1H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）δ（ｐｐｍ）：１．５０（３Ｈ，ｄ）、２．１１−２．１５（２Ｈ，ｍ）、２．４８−２．５９（２Ｈ，ｍ）、２．８１−２．８９（１Ｈ，ｍ）、５．９１−６．００（１Ｈ，ｍ）、６．２９−６．３７（１Ｈ，ｍ） Production Example 9
Tetrakis (triphenylphosphine) palladium (0.3 g) and 2-methanesulfonyloxy-1,1,1-trifluoro-3-pentene (1.1 g) were added to tetrahydrofuran (20 ml), and the mixture was stirred at 0 ° C. for 10 minutes. A tetrahydrofuran solution of 0.97 g of 2- (3,3,3-trifluoropropyl) malononitrile and 0.24 g of sodium hydride was added dropwise and stirred at room temperature for 3 hours. Dilute hydrochloric acid was added to the reaction mixture, and the mixture was extracted with methyl tert-butyl ether. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 2- (1- 0.23 g of methyl-4,4,4-trifluoro-2-butenyl) -2- (3,3,3-trifluoropropyl) malononitrile (hereinafter referred to as the present compound (9)) was obtained.
Compound (9) of the present invention

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.50 (3H, d), 2.11-2.15 (2H, m), 2.48-2.59 (2H, m), 2.81-2.89 (1H, m), 5.91-6.00 (1H, m), 6.29-6.37 (1H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）δ（ｐｐｍ）：１．５５（３Ｈ，ｄ）、２．６４−２．７３（２Ｈ，ｍ）、２．９５−３．０３（１Ｈ，ｍ）、５．９２−６．０７（２Ｈ，ｍ）、６．３０−６．３８（１Ｈ，ｍ） Production Example 10
Tetrakis (triphenylphosphine) palladium (0.3 g) and 2-methanesulfonyloxy-1,1,1-trifluoro-3-pentene (1.1 g) were added to 10 ml of tetrahydrofuran and stirred at 0 ° C. for 10 minutes. A tetrahydrofuran solution of 2.1 g of 2- (2,2,3,3,4,4,5,5-octafluoropentyl) malononitrile and 0.32 g of sodium hydride was added dropwise and stirred at room temperature for 7 hours. Dilute hydrochloric acid was added to the reaction mixture, and the mixture was extracted with methyl tert-butyl ether. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 2- (1- Methyl-4,4,4-trifluoro-2-butenyl) -2- (2,2,3,3,4,4,5,5-octafluoropentyl) malononitrile (hereinafter referred to as the present compound (10)) .) 0.14 g was obtained.
Compound (10) of the present invention

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.55 (3H, d), 2.64-2.73 (2H, m), 2.95-3.03 (1H, m), 5.92-6.07 (2H, m), 6.30-6.38 (1H, m)

  Next, reference production examples of intermediates of the compound of the present invention are shown.

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）δ（ｐｐｍ）：２．３４〜２．４７（４Ｈ，ｍ）、３．９１（１Ｈ，ｔ） Reference production example 1
A solution prepared by dissolving 79.2 g of malononitrile in 100 ml of ethylene glycol dimethyl ether was added to a mixed solution obtained by adding 165.6 g of potassium carbonate to 500 ml of ethylene glycol dimethyl ether, followed by stirring at room temperature for 1 hour, and 1-iodo-3,3,4,4 , 4-pentafluorobutane 109.6 g in ethylene glycol dimethyl ether 200 ml was added and stirred at room temperature for 10 hours. The reaction mixture was then poured into water and extracted with methyl tert-butyl ether. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel chromatography to obtain 48.4 g of 2- (3,3,4,4,4-pentafluorobutyl) malononitrile.
2- (3,3,4,4,4-pentafluorobutyl) malononitrile

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 2.34 to 2.47 (4H, m), 3.91 (1H, t)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）δ（ｐｐｍ）：４．８２（２Ｈ，ｍ）、６．０４（１Ｈ，ｔｔ） Reference production example 2
100 ml of trifluoromethanesulfonic anhydride was added to 139 g of 2,2,3,3,4,4,5,5-octafluoropentanol at 0 ° C., and the mixture was stirred at room temperature for 1 hour and then at 60 ° C. for 3 hours. The reaction mixture was then poured into ice water and extracted with methyl tert-butyl ether. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and (2,2,3,3,4,4,5,5-octafluoropentyl) trifluoromethanesulfone. 187 g of acid ester was obtained.
(2,2,3,3,4,4,5,5-octafluoropentyl) trifluoromethanesulfonic acid ester

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 4.82 (2H, m), 6.04 (1H, tt)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）δ（ｐｐｍ）：２．９０（２Ｈ，ｄｔ）、４．１５（１Ｈ，ｔ）、６．０６（１Ｈ，ｔｔ） Reference production example 3
To 20 ml of dimethyl sulfoxide, 15 g of (2,2,3,3,4,4,5,5-octafluoropentyl) trifluoromethanesulfonate ester and 2.6 g of malononitrile were added, and then 5.5 g of potassium carbonate was added to the water bath. Stir in for 3 hours. Dilute hydrochloric acid was added to the reaction mixture, and the mixture was extracted with methyl tert-butyl ether. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel chromatography to obtain 2.0 g of 2- (2,2,3,3,4,4,5,5-octafluoropentyl) malononitrile.
2- (2,2,3,3,4,4,5,5-octafluoropentyl) malononitrile

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 2.90 (2H, dt), 4.15 (1H, t), 6.06 (1H, tt)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）δ（ｐｐｍ）：１．４０（３Ｈ，ｄ）、３．１０−３．１９（１Ｈ，ｍ）、３．７１（１Ｈ，ｄ）、４．２５−４．３４（１Ｈ，ｍ） Reference production example 4
To 30 ml of N, N-dimethylformamide, 10 g of 1,3-dibromo-1,1-difluorobutane and 2.6 g of malononitrile were added, and then 5.5 g of potassium carbonate was added and stirred at room temperature for 5 hours. Dilute hydrochloric acid was added to the reaction mixture, and the mixture was extracted with methyl tert-butyl ether. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel chromatography to obtain 1.1 g of 2- (3,3-difluoro-1-methyl-3-butenyl) malononitrile.
2- (3,3-Difluoro-1-methyl-2-propenyl) malononitrile

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.40 (3H, d), 3.10-3.19 (1H, m), 3.71 (1H, d), 4.25- 4.34 (1H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）δ（ｐｐｍ）：１．４３（３Ｈ，ｄ）、２．２５−２．５０（２Ｈ，ｍ）、２．５７−２．６７（１Ｈ，ｍ）、３．８９（１Ｈ，ｄ） Reference production example 5
To 30 ml of N, N-dimethylformamide, 10 g of 3-iodo-1,1,1-trifluorobutane and 2.6 g of malononitrile were added, and then 5.5 g of potassium carbonate was added and stirred at room temperature for 5 hours. Dilute hydrochloric acid was added to the reaction mixture, and the mixture was extracted with methyl tert-butyl ether. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel chromatography to obtain 1.5 g of 2- (1-methyl-3,3,3-trifluoropropyl) malononitrile.
2- (1-Methyl-3,3,3-trifluoropropyl) malononitrile

¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.43 (3H, d), 2.25-2.50 (2H, m), 2.57-2.67 (1H, m), 3.89 (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
Nine parts of each of the compounds (1) to (10) of the present invention are dissolved in 37.5 parts of xylene and 37.5 parts of N, N-dimethylformamide, and 10 parts of polyoxyethylene styryl phenyl ether and dodecylbenzenesulfone are dissolved therein. Add 6 parts of calcium acid and mix well with stirring to obtain an emulsion.

Formulation Example 2
To 40 parts of each of the compounds (1) to (10) 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 a wettable powder.

Formulation Example 3
Add 3 parts of each of the compounds (1) to (10) 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, and mix well with stirring. An appropriate amount of water is added to the mixture, further stirred, granulated with a granulator, and dried by ventilation to obtain granules.

Formulation Example 4
Juice after thoroughly mixing 4.5 parts of each of the compounds (1) to (10) of the present invention, 1 part of synthetic hydrous silicon fine powder, 1 part of Doreles B (manufactured by Sankyo) as a flocculant and 7 parts of clay in a mortar Stir and mix with a mixer. 86.5 parts of cut clay is added to the resulting mixture and mixed thoroughly with stirring to obtain a powder.

Formulation Example 5
Formulation by mixing 10 parts of each of the compounds (1) to (10) of the present invention, 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt and 55 parts of water, and finely pulverizing them by a wet pulverization method. Get.

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

Formulation Example 7
0.1 parts of each of the compounds (1) to (10) of the present invention and 49.9 parts of Neothiozole (Chuo Kasei Co., Ltd.) are put into an aerosol can, and after mounting an aerosol valve, 25 parts of dimethyl ether and 25 parts of LPG Is added, shaken, and an actuator is attached to obtain an oily aerosol.

Formulation Example 8
A mixture of 0.6 parts of each of the compounds (1) to (10) 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 name of Atmos Chemical)} Then, 50 parts of distilled water is filled in an aerosol container, a valve part is attached, and 40 parts of propellant (LPG) is pressurized and filled through the valve to obtain an aqueous aerosol.

Formulation Example 9
A paperwork piece having a honeycomb structure of 0.5 cm (thickness) × 69 cm (length) × 0.2 cm (width) is wound from one end to produce a carrier having a diameter of 5.5 cm and a width of 0.2 cm ( (See FIGS. 1 and 2). An appropriate amount of a solution prepared by dissolving 5 parts of each of the compounds (1) to (10) of the present invention in 95 parts of acetone is uniformly applied to the carrier, and then acetone is air-dried to obtain a preparation.

Formulation Example 10
Three-dimensional knitted fabric (trade name: Fusion, model number: AKE69440, Publisher: Asahi Kasei Fibers Corporation, thickness: 4.3mm, basis weight: 321g / m ^2, made of polyamide) is cut into a circle with a diameter of 5cm. An appropriate amount of a solution prepared by dissolving 5 parts of each of the compounds (1) to (10) of the present invention in 95 parts of acetone is uniformly applied to the three-dimensional knitted fabric, and then acetone is air-dried to obtain a preparation.

Formulation Example 11
98 parts by weight of ethylene-methyl methacrylate copolymer (methyl methacrylate content: 10% by weight, MFR = 2 [g / 10 min]) and 2 parts by weight of each of the compounds (1) to (10) of the present invention, It is melt-kneaded at 130 ° C. with a 45 mmφ co-directional twin-screw extruder, melt-kneaded at 150 ° C. with a 40 mmφ extruder, extruded into a sheet form from a T-die, and cooled with a cooling roll to obtain a resin formulation.

Formulation Example 12
An ethylene-vinyl acetate copolymer (vinyl acetate content: 10% by weight, MFR = 2 [g / 10 min]) of 98 parts by weight and 2 parts by weight of each of the compounds (1) to (10) of the present invention were each 45 mm in diameter. Melting and kneading at 130 ° C. with a directional twin screw extruder, melting and kneading at 150 ° C. with a 40 mmφ extruder, extruding into a sheet from a T die, and cooling with a cooling roll to obtain a resin formulation.

Formulation Example 13
5 parts of each of the compounds (1) to (10) of the present invention are dissolved in 95 parts of acetone. An appropriate amount of this solution is applied to paper (2000 cm ² ) having a foldable structure shown in FIG. 3, and acetone is air-dried to obtain a preparation.

Formulation Example 14
5 parts of each of the compounds (1) to (10) of the present invention are dissolved in 95 parts of acetone. An appropriate amount of this solution is applied to paper (2000 cm ² ) having a foldable structure shown in FIG. 4, and acetone is air-dried to obtain a preparation.

Formulation Example 15
A solution is obtained by mixing 3.6 parts of each of the present compounds (1) to (10) and 14.3 parts of acetone. To this, 0.2 part of zinc oxide, 1.0 part of α-starch and 42.8 parts of azodicarbonamide are added, 38.1 parts of water is added, and the mixture is kneaded and formed into granules by an extruder and dried. A granule containing the compound of the present invention is placed in the upper space of a container whose central part is divided by an aluminum partition, and 50 g of calcium oxide is accommodated in the lower space of the container to obtain a smoke agent.

Formulation Example 16
Mix 0.5 parts of zinc oxide, 2 parts of α-starch and 97.5 parts of azodicarbonamide, add water to knead, form the kneaded product into granules with an extruder, and dry to form granules. obtain. 2 g of the granules are uniformly impregnated with an acetone solution containing 0.58 g of each of the compounds (1) to (10) of the present invention and then dried to contain each of the compounds (1) to (10) of the present invention. Obtain granules. A granule containing the compound of the present invention is placed in the upper space of a container whose central part is divided by an aluminum partition, and 50 g of calcium oxide is accommodated in the lower space of the container to obtain a smoke agent.

Formulation Example 17
0.5 g of each of the compounds (1) to (10) of the present invention is dissolved in 20 ml of acetone, and 99.4 g of a carrier for mosquito coils (mixed in a weight ratio of 4: 3: 3 with tab powder: straw powder: wood powder) and After stirring and mixing uniformly with 0.3 g of green pigment, 120 ml of water is added, and the kneaded mixture is molded and dried to obtain a mosquito coil.

Formulation Example 18
A solution obtained by mixing 10 parts of each of the compounds (1) to (10) of the present invention, 40 parts of acetyltributyl citrate, 40 parts of isononyl adipate, 5 parts of a blue pigment, and 5 parts of a fragrance is 3.4 cm × 2. An electric mosquito-removing mat is obtained by uniformly impregnating a substrate for an electric mat having a thickness of 1 cm and a thickness of 0.22 cm (a fibril of a mixture of cotton linter and pulp hardened into a plate shape).

Formulation Example 19
Liquid absorbent core (inorganic powder) in which 0.1 part of each of the compounds (1) to (10) of the present invention was dissolved in 99.9 parts of deodorized kerosene, placed in a vinyl chloride container, and the upper part could be heated with a heater. The body is solidified with a binder and sintered) to obtain a liquid-absorbing core type heat-transpiration insecticide part.

Formulation Example 20
0.2 parts of each of the compounds (1) to (10) of the present invention and 49.8 parts of Neothiozole (Chuo Kasei Co., Ltd.) are put into an aerosol can, and after mounting an aerosol valve, 25 parts of dimethyl ether and 25 parts of LPG are filled. The aerosol agent is obtained by adding a shake and mounting a full-volume injection type aerosol actuator.

Formulation Example 21
A spot-on agent is obtained by adding 99.8 parts of diethylene glycol monoethyl ether to 0.2 parts of each of the compounds (1) to (10) of the present invention and mixing well with stirring.

Formulation Example 22
The compound of the present invention (3 cm in diameter and 3 mm in thickness) was added to a disc-shaped solid (diameter 3 cm, thickness 3 mm) obtained by pressure-molding (4 t / cm ² ) of 4000 mg of 2,4,6-triisopropyl-1,3,5-trioxane. A tablet is obtained by uniformly applying 1 mL of a solution consisting of 3.3 parts of each of 1) to (10) and 96.7 parts of acetone and then drying.

Formulation Example 23
A homogeneous mixture of 200 mg of each of the compounds (1) to (10) of the present invention and 4000 mg of 2,4,6-triisopropyl-1,3,5-trioxane was pressure-molded (4 t / cm ² ) to form a disc-like shape. By making the diameter (3 cm, thickness 3 mm), a tablet is obtained.

Formulation Example 24
200 mg of each of the compounds (1) to (10) of the present invention and 4000 mg of 2,4,6-triisopropyl-1,3,5-trioxane are put in a 50 mL screw tube and melted by heating, and then cooled to room temperature to form tablets. Get.

  Next, test examples show that the compound of the present invention is effective as an active ingredient of a pest control agent.

Test example 1
A 1% (w / v) acetone solution of the compounds (1) to (10) of the present invention was prepared. 1 μl of the acetone solution was dropped onto the ventral side of the chest of a female German cockroach (Blattella germanica), then transferred to a plastic cup having a diameter of about 9 cm and a height of about 4.5 cm, and left at 25 ° C. with food and water. Seven days later, the dead cockroach was observed to determine the death rate. Three cockroaches were used per cup, and the test was repeated three times.
As a result, the mortality rate was 90% or more in the treatments of the compounds (1) to (10) of the present invention.

Test example 2
The preparation of the compound (1) of the present invention obtained in Formulation Example 5 was diluted so that the active ingredient concentration was 500 ppm to prepare a test drug solution.
On the other hand, 50 g of soil bonsol 2 (manufactured by Sumitomo Chemical Co., Ltd.) was put in a polyethylene cup, seeded with 10 to 15 seeds, grown until the second true leaf developed, and then the height was cut to 5 cm. The test chemical solution prepared as described above was sprayed on rice at a rate of 20 ml / cup. After the chemical sprayed on the rice has dried, put it in a plastic cup to prevent escape of the test insects, release 30 first-instar larvae of the brown planthopper, cover them, and then leave them in a greenhouse (25 ° C) did. Six days after releasing the green planthopper larvae, the number of the green planthopper parasitic on the rice was investigated.
As a result, in the treatment with the compound (1) of the present invention, the number of parasitic insects was 3 or less.

Test example 3
The preparation of the compound (1) of the present invention obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 500 ppm to prepare a test drug solution.
A 5.5 cm diameter filter paper was placed on the bottom of a 5.5 cm diameter polyethylene cup, 0.7 ml of the test chemical solution was dropped on the filter paper, and 30 mg of sucrose was uniformly added as a bait. 10 female Musca domestica females were released into the polyethylene cup and capped. After 24 hours, the life-and-death of the house fly was investigated to determine the death rate.
As a result, the treatment with the compound (1) of the present invention showed a death rate of 90% or more.

Test example 4
The preparation of the compound (1) of the present invention obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 500 ppm to prepare a test drug solution.
A 5.5 cm diameter filter paper was placed on the bottom of a 5.5 cm diameter polyethylene cup, 0.7 ml of the test chemical solution was dropped on the filter paper, and 30 mg of sucrose was uniformly added as a bait. 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 treatment with the compound (1) of the present invention showed a mortality rate of 100%.

Test Example 5
The preparation of the compound (1) of the present invention obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 500 ppm to prepare a test drug solution.
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 after 1 day, the viability was investigated to determine the mortality rate.
As a result, the treatment with the compound (1) of the present invention showed a death rate of 90% or more.

10 is a top view of a solid carrier of Preparation Example 9. FIG.

10 is a perspective view of a solid carrier of Formulation Example 9. FIG.

It is explanatory drawing which shows the paper which has the foldable structure of the formulation example 13. The paper folded as shown in (a) swings about one side of the planar member as an axis, so that, for example, as shown in (b), the cylindrical material spreads through 180 ° and becomes one form at the time of use.

It is explanatory drawing which shows the paper which has the foldable structure of the formulation example 14. In the paper folded as shown in (a), the cylindrical material can be expanded as shown in (b) by separating the opposing planar members from each other.

Claims (7)

Formula (I)

[Where,
R ¹ represents a C1-C4 fluoroalkyl group,
R ² and R ³ each represent a hydrogen atom or a C1-C4 alkyl group,
R ⁴ is a halogen atom, a C1-C11 alkyl group optionally substituted with one or more halogen atoms, a C2-C6 alkenyl group optionally substituted with one or more halogen atoms, and substituted with one or more halogen atoms. Represents a C2-C6 alkynyl group which may be optionally substituted or a C3-C11 cycloalkyl group optionally substituted by one or more halogen atoms.
However, at least one of R ² and R ³ always represents a C1-C4 alkyl group. ]
A malononitrile compound represented by: R ⁴ may be substituted with a C1-C11 alkyl group optionally substituted with one or more halogen atoms, a C2-C6 alkenyl group optionally substituted with one or more halogen atoms, or substituted with one or more halogen atoms. The malononitrile compound according to claim 1, which is a good C2-C6 alkynyl group. The malononitrile compound according to claim 1, wherein R ⁴ is a C1-C11 alkyl group which may be substituted with one or more halogen atoms or a C3-C11 cycloalkyl group which may be substituted with one or more halogen atoms. The malononitrile compound according to claim 1, wherein R ⁴ is a C1-C6 alkyl group which may be substituted with one or more halogen atoms. The malononitrile compound according to any one of claims 1 to 4, wherein R ² is a hydrogen atom, and R ³ is a C1-C4 alkyl group.   A pest control agent comprising the malononitrile compound according to any one of claims 1 to 5 as an active ingredient. A method for controlling pests, which comprises applying an effective amount of the malononitrile compound according to any one of claims 1 to 5 to pests or habitats of pests.

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