JP4433788B2 - Benzyl sulfide derivatives and their use for controlling harmful arthropods - Google Patents

Description

  The present invention relates to a benzyl sulfide derivative and its use for controlling harmful arthropods.

  Conventionally, many harmful arthropod control agents have been developed and put into practical use for controlling harmful arthropods.

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

〔式中、Ｒ¹はハロゲン原子で置換されていてもよいＣ１〜Ｃ４アルキル基、ハロゲン原子で置換されていてもよいＣ２〜３アルケニル基、ハロゲン原子で置換されていてもよいＣ２〜Ｃ３アルキニル基、シアノ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〜Ｃ４アルキル基又は水素原子を表し、Ｒ³はＣ１〜Ｃ３フルオロアルキル基、Ｃ２〜Ｃ３フルオロアルケニル基またはＣ２〜Ｃ３フルオロアルキニル基を表し、Ｒ⁴はハロゲン原子、シアノ基、ニトロ基、Ｃ１〜Ｃ４ハロアルキル基、ハロゲン原子で置換されていてもよいＣ２〜Ｃ４アルケニル基、ハロゲン原子で置換されていてもよいＣ２〜Ｃ４アルキニル基、ハロゲン原子で置換されていてもよいＣ１〜Ｃ４アルコキシ基、ハロゲン原子で置換されていてもよいＣ１〜Ｃ４アルキルチオ基、ハロゲン原子で置換されていてもよいＣ１〜Ｃ４アルキルスルフィニル基又はハロゲン原子で置換されていてもよいＣ１〜Ｃ４アルキルスルホニル基を表し、Ｒ⁵は同一又は相異なり、水素原子又はフッ素原子を表し、ｍは１〜３の任意の整数を表し、ｎは０〜２の任意の整数を表す。但し、ｍが２又は３である場合には、Ｒ⁴は同一でも相異なっていてもよい。〕で表されるベンジルスルフィド、ベンジルスルホキシド及びベンジルスルホン化合物（以下、例えばベンジルスルフィド誘導体あるいは本発明化合物と記す場合がある。）、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本発明の有害節足動物防除剤及び本発明化合物の有効量を有害節足動物又は有害節足動物の生息場所に施用することを特徴とする有害節足動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 harmful arthropods, the present inventors have found that the benzyl sulfide derivative represented by the following formula (I) is harmful to harmful insects and harmful mites. It has been found that it has excellent efficacy against arthropods, and the present invention has been completed.
That is, the present invention provides the following formula (I)

[Wherein, R ¹ is a C1 to C4 alkyl group optionally substituted with a halogen atom, a C2 to alkenyl group optionally substituted with a halogen atom, or a C2 to C3 alkynyl optionally substituted with a halogen atom. Represents a group, a cyano group or a hydrogen atom,
R ² represents a C1-C4 alkyl group which may be substituted with a halogen atom or a hydrogen atom, R ³ represents a C1-C3 fluoroalkyl group, a C2-C3 fluoroalkenyl group or a C2-C3 fluoroalkynyl group, R ⁴ is a halogen atom, a cyano group, a nitro group, a C1-C4 haloalkyl group, a C2-C4 alkenyl group optionally substituted with a halogen atom, a C2-C4 alkynyl group optionally substituted with a halogen atom, or a halogen atom. An optionally substituted C1-C4 alkoxy group, a C1-C4 alkylthio group optionally substituted with a halogen atom, a C1-C4 alkylsulfinyl group optionally substituted with a halogen atom, or a halogen atom; represents may also be C1~C4 alkylsulfonyl group, R ⁵ may be the same or different, a hydrogen atom or It represents Tsu atom, m represents an arbitrary integer of 1 to 3, n represents any integer of 0 to 2. However, when m is 2 or 3, R ⁴ may be the same or different. Benzyl sulfide, benzyl sulfoxide and benzyl sulfone compounds represented by the following formulas (hereinafter sometimes referred to as benzyl sulfide derivatives or compounds of the present invention), the compounds of the present invention comprising the compounds of the present invention as active ingredients Provided is a method for controlling harmful arthropods, which comprises applying an effective amount of the harmful arthropod control agent and the compound of the present invention to the harmful arthropods or the habitat of the harmful arthropods.

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

  In the present invention, the description such as C1 to C4 means the total number of carbon atoms constituting each substituent. In the present invention, the term “fluoroalkyl group” represents an alkyl group formed by bonding one or more fluorine atoms to a carbon atom.

In the formula (I), examples of the C1-C4 alkyl group optionally substituted with the halogen atom represented by R ¹ include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, and 1,1-dimethylethyl. Group, chloromethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group and 1,1,2,2-tetrafluoroethyl group,
Examples of the C2-C3 alkenyl group optionally substituted with a halogen atom include a vinyl group, a 2,2-difluorovinyl group, a 1,2,2-trifluorovinyl group, a 1-propenyl group, and a 2-propenyl group. You can
Examples of the C2 to C3 alkynyl group optionally substituted with a halogen atom include a 1-propynyl group and a 3,3,3-trifluoro-1-propynyl group.

Examples of the C1-C4 alkyl group optionally substituted with a halogen atom represented by R ² include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, a 1,1-dimethylethyl group, a chloromethyl group, Examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and a 1,1,2,2-tetrafluoroethyl group.

Examples of the C1-C3 fluoroalkyl group represented by R ³ include a trifluoromethyl group, a 1,1,2,2,2-pentafluoroethyl group, a 1,1-difluoroethyl group, or a 1,1,2,2 , 3,3,3-heptafluoropropyl group,
Examples of the C2-C3 fluoroalkenyl group include a 1,2,2-trifluorovinyl group or a 2,2-difluorovinyl group,
Examples of the C2-C3 fluoroalkynyl group include a 2-fluoroethynyl group and a 3,3,3-trifluoro-1-propynyl group.

Examples of the halogen atom represented by R ⁴ include a fluorine atom, a chlorine atom and a bromine atom,
Examples of the C1-C4 haloalkyl group include C1 such as a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1,1,2,2,2-pentafluoroethyl group, and a 2,2,2-trifluoroethyl group. A -C2 fluoroalkyl group;
1,1,2,2,3,3,3-heptafluoropropyl group, 1-trifluoromethyl-2,2,2-trifluoroethyl group and 1-fluoro-1-trifluoromethyl-2,2, 2-trifluoroethyl group,
Examples of the C2-C4 alkenyl group optionally substituted with a halogen atom include a vinyl group, a 1-propenyl group and a 2,2-difluorovinyl group,
Examples of the C2-C4 alkynyl group optionally substituted with a halogen atom include ethynyl group, 1-propynyl group, and 3,3,3-trifluoro-1-propynyl group,
Examples of the C1-C4 alkoxy group optionally substituted with a halogen atom include a trifluoromethoxy group, a bromodifluoromethoxy group, a difluoromethoxy group, a chlorodifluoromethoxy group, a pentafluoroethoxy group, and 2,2,2-trifluoro. An ethoxy group and a 1,1,2,2-tetrafluoroethoxy group,
Examples of the C1-C4 alkylthio group optionally substituted with a halogen atom include a methylthio group, an ethylthio group, a trifluoromethylthio group, and a 2,2,2-trifluoroethylthio group,
Examples of the C1-C4 alkylsulfinyl group optionally substituted with a halogen atom include a methylsulfinyl group, an ethylsulfinyl group, and a trifluoromethylsulfinyl group.
Examples of the C1-C4 alkylsulfonyl group that may be substituted with a halogen atom include a methylsulfonyl group, an ethylsulfonyl group, and a trifluoromethylsulfonyl group.

As an aspect of this invention compound, the following compounds are mentioned, for example.
In the formula (I), compounds wherein R ¹ is a hydrogen atom;
In the formula (I), compounds wherein R ¹ is a C1 to C4 alkyl group optionally substituted with a halogen atom;
In the formula (I), compounds wherein R ¹ is a cyano group;
In the formula (I), compounds wherein R ¹ is a methyl group;
In the formula (I), compounds wherein R ² is a hydrogen atom;
In the formula (I), compounds wherein R ² is a hydrogen atom or a methyl group;
In the formula (I), compounds wherein R ² is a C1 to C4 alkyl group optionally substituted with a halogen atom;
In the formula (I), compounds wherein R ¹ and R ² are hydrogen atoms;
In the formula (I), compounds in which R ¹ and R ² are C1-C4 alkyl groups optionally substituted with a halogen atom;
In the formula (I), compounds wherein R ¹ and R ² are methyl groups;
In the formula (I), a compound wherein R ¹ is a C1-C4 alkyl group optionally substituted with a halogen atom, and R ² is a hydrogen atom;
In the formula (I), compounds wherein R ³ is a C1 to C2 fluoroalkyl group;
In the formula (I), compounds wherein R ³ is a fluoromethyl group;
In the formula (I), compounds wherein R ³ is a trifluoromethyl group;
In the formula (I), compounds wherein R ³ is a 2,2,2-trifluoroethyl group;
In the formula (I), compounds wherein R ³ is a 1,1,2,2,2-pentafluoroethyl group;
In the formula (I), compounds wherein m is 1;
In the formula (I), a compound wherein m is 1 and R ⁴ is a chlorine atom substituted at the 4-position;
In the formula (I), a compound wherein m is 1 and R ⁴ is a halogen atom substituted at the 4-position;
In the formula (I), compounds wherein m is 1 and R ⁴ is a trifluoromethyl group;
In the formula (I), compounds wherein m is 2;
In the formula (I), a compound wherein m is 2 and one of R ⁴ is a halogen atom substituted at the 4-position;
In the formula (I), compounds wherein m is 3;
In the formula (I), compounds wherein m is 3 and R ⁴ substituted in the 4 position is a halogen atom;
In the formula (I), compounds wherein m is 3 and R ⁴ are both halogen atoms;
In the formula (I), compounds wherein m is 3 and R ⁴ substituted at the 3-position and 5-position is a fluorine atom;
In the formula (I), compounds wherein R ⁵ are all hydrogen atoms;
In the formula (I), a compound wherein one of R ⁵ is a hydrogen atom and the other is a fluorine atom;
In the formula (I), compounds wherein all R ⁵ are fluorine atoms;

In the formula (I), compounds each having R ⁵ as a hydrogen atom and m being 1;
In the formula (I), a compound wherein one of R ⁵ is a hydrogen atom, the other is a fluorine atom, and m is 1;
In the formula (I), R ⁵ is a hydrogen atom, m is 1, and R ⁴ is a chlorine atom substituted at the 4-position;
In formula (I), a compound wherein one of R ⁵ is a hydrogen atom, the other is a fluorine atom, m is 1, and R ⁴ is a chlorine atom substituted at the 4-position;
In the formula (I), a compound in which R ⁵ is a hydrogen atom, m is 1, and R ⁴ is a halogen atom substituted at the 4-position;
In the formula (I), a compound wherein one of R ⁵ is a hydrogen atom, the other is a fluorine atom, m is 1, and R ⁴ is a halogen atom substituted at the 4-position;
In the formula (I), R ⁵ is a hydrogen atom, m is 1, and R ⁴ is a trifluoromethyl group;
In the formula (I), compounds each having R ⁵ as a hydrogen atom and m being 2;
In the formula (I), a compound in which R ⁵ is a hydrogen atom, m is 2, and one of R ⁴ is a halogen atom substituted at the 4-position;
In the formula (I), compounds each having R ⁵ as a hydrogen atom and m being 3;
In the formula (I), compounds in which R ⁵ is a hydrogen atom, m is 3, and R ⁴ substituted at the 4-position is a halogen atom;
In the formula (I), R ⁵ is a hydrogen atom, m is 3, and R ⁴ is a halogen atom;
In formula (I), a compound in which R ⁵ is a hydrogen atom, m is 3, and R ⁴ substituted at the 3-position and 5-position is a fluorine atom;
In the formula (I), a compound in which R ⁵ is a fluorine atom, m is 3, and R ⁴ substituted at the 3-position and 5-position is a fluorine atom;

A compound in which n is 0 in formula (I);
In the formula (I), compounds wherein R ² is a hydrogen atom or a methyl group, and n is 0;
In the formula (I), compounds wherein R ³ is a C1 to C3 fluoroalkyl group and n is 0;
In the formula (I), compounds wherein R ¹ is a hydrogen atom, R ² is a hydrogen atom or a methyl group, and n is 0;
In the formula (I), a compound wherein R ² is a hydrogen atom or a methyl group, and R ³ is a C1-C3 fluoroalkyl group;
In the formula (I), a compound in which R ¹ is a hydrogen atom, R ² is a hydrogen atom or a methyl group, and R ³ is a C1-C3 fluoroalkyl group;

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

  Among the compounds of the present invention represented by the formula (I), the compound represented by the formula (Ia) in which n is 0 can be produced, for example, by the following (Production Method 1) to (Production Method 4). .

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びｍは前記と同じ意味を表し、Ｚ¹は塩素原子、臭素原子、ヨウ素原子、メタンスルホニル基等の脱離基を表す。］
該反応は、通常塩基の存在下、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばジエチルエーテル、テトラヒドロフラン、ジメトキシエタン等のエーテル類、Ｎ，Ｎ−ジメチルホルムアミド等の酸アミド類、ジメチルスルホキシド、スルホラン等の有機硫黄類、ヘキサン、ヘプタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、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、水及びそれらの混合物があげられる。
該反応に用いられる塩基としては、例えば水素化ナトリウム、水酸化ナトリウム、水酸化カリウム、炭酸カリウム等の無機塩基、ナトリウムメトキシド、カリウムｔｅｒｔ−ブトキシド等のアルカリ金属アルコキシド及びトリエチルアミン、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あげられる。反応に用いられる塩基の量は、化合物（ａ）１モルに対して、通常１〜１０モルの割合である。
反応に用いられる化合物（ｂ）の量は、化合物（ａ）１モルに対して、通常１〜１０モルの割合である。
該反応の反応温度は通常−５０〜１００℃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。単離した化合物（Ｉ−ａ）は必要に応じてクロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 1)
The compound represented by the formula (Ia) can be produced, for example, by reacting the following compound (a) and compound (b).

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and m represent the same meaning as described above, and Z ¹ represents a leaving group such as a chlorine atom, a bromine atom, an iodine atom or a methanesulfonyl group. . ]
The reaction is usually performed in the presence of a base and usually in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as diethyl ether, tetrahydrofuran and dimethoxyethane, acid amides such as N, N-dimethylformamide, organic sulfurs such as dimethyl sulfoxide and sulfolane, and aliphatics such as hexane and heptane. Examples thereof include hydrocarbons, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene, water, and mixtures thereof.
Examples of the base used in the reaction include inorganic bases such as sodium hydride, sodium hydroxide, potassium hydroxide and potassium carbonate, alkali metal alkoxides such as sodium methoxide and potassium tert-butoxide, and triethylamine, 1,4-diazabicyclo And organic bases such as [2.2.2] 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 per 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 −50 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 pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating. The isolated compound (Ia) can be further purified by chromatography, recrystallization or the like, if necessary.

〔式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びｍは前記と同じ意味を表し、Ｚ²は塩素原子、臭素原子、ヨウ素原子、メタンスルホニル基等の脱離基を表す。〕
該反応は、通常塩基の存在下、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばジエチルエーテル、テトラヒドロフラン、ジメトキシエタン等のエーテル類、Ｎ，Ｎ−ジメチルホルムアミド等の酸アミド類、ジメチルスルホキシド、スルホラン等の有機硫黄類、ヘキサン、ヘプタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、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、水及びそれらの混合物があげられる。
該反応に用いられる塩基としては、例えば水素化ナトリウム、水酸化ナトリウム、水酸化カリウム、炭酸カリウム等の無機塩基、ナトリウムメトキシド、カリウムｔｅｒｔ−ブトキシド等のアルカリ金属アルコキシド及びトリエチルアミン、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あげられる。反応に用いられる塩基の量は、化合物（ｄ）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（ｃ）の量は、化合物（ｄ）１モルに対して、通常１〜１０モルの割合である。
該反応の反応温度は通常−５０〜１００℃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。単離した化合物（Ｉ−ａ）は必要に応じてクロマトグラフィー、再結晶等でさらに精製することもできる。 (Production method 2)
The compound represented by the formula (Ia) can also be produced, for example, by reacting the following compound (c) and compound (d).

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and m represent the same meaning as described above, and Z ² represents a leaving group such as a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyl group, etc. . ]
The reaction is usually performed in the presence of a base and usually in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as diethyl ether, tetrahydrofuran and dimethoxyethane, acid amides such as N, N-dimethylformamide, organic sulfurs such as dimethyl sulfoxide and sulfolane, and aliphatics such as hexane and heptane. Examples thereof include hydrocarbons, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene, water, and mixtures thereof.
Examples of the base used in the reaction include inorganic bases such as sodium hydride, sodium hydroxide, potassium hydroxide and potassium carbonate, alkali metal alkoxides such as sodium methoxide and potassium tert-butoxide, and triethylamine, 1,4-diazabicyclo And organic bases such as [2.2.2] 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 (d).
The amount of the compound (c) used in the reaction is usually 1 to 10 moles relative to 1 mole of the compound (d).
The reaction temperature of the reaction is usually in the range of −50 to 100 ° C., and the reaction time is usually in the range of 1 to 24 hours.
After completion of the reaction, the compound (Ia) can be isolated by pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating. The isolated compound (Ia) can be further purified by chromatography, recrystallization or the like, if necessary.

  In addition, the said compound (a) and a compound (d) are The Journal of Organic Chemistry, 27 (1), p.93-95 (1962), HETEROCYCLES, 24 (5), p.1331-1346 (1986), for example. Can be produced according to the method described in 1. above.

〔式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、ｍ、Ｚ¹及びＺ²は前記と同じ意味を表し、Ｒ¹¹はメチル基又はアミノ基を表す。〕
工程（３−１）
化合物（ｆ）は、化合物（ｃ）と化合物（ｅ）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、例えばジクロロメタン、クロロホルム等のハロゲン化炭化水素類、メタノール、エタノール等のアルコール類及びそれらの混合物があげられる。
反応に用いられる化合物（ｅ）の量は、化合物（ｃ）１モルに対して、通常１〜３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０．５〜２４０時間の範囲である。
反応終了後は、反応混合物を濃縮する等の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）はそのまま工程（３−２）に用いることができるが、必要により再結晶等によりさらに精製することもできる。
工程（３−２）
式（Ｉ−ａ）で示される化合物は、化合物（ｆ）と化合物（ｂ）とを塩基の存在下で反応させることにより製造することができる。
該反応は、通常溶媒の存在下、通常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、例えばジエチルエーテル、テトラヒドロフラン、ジメトキシエタン等のエーテル類、Ｎ，Ｎ−ジメチルホルムアミド等の酸アミド類、ジメチルスルホキシド、スルホラン等の有機硫黄類、ヘキサン、ヘプタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、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、水及びそれらの混合物があげられる。
反応に用いられる塩基としては、例えば水酸化ナトリウム、水酸化カリウム等の無機塩基及びナトリウムメトキシド、カリウムｔｅｒｔ−ブトキシド等のアルカリ金属アルコキシドあげられる。
反応に用いられる塩基の量は、化合物（ｆ）１モルに対して通常１〜５０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（ｆ）１モルに対して、通常１〜１０モルの割合である。
該反応は必要に応じて、臭化テトラｎ−ブチルアンモニウム等の相間移動触媒を用いて行うことができる。その場合に用いられる相間移動触媒の量は、化合物（ｆ）1モルに対して、通常０．０５〜１．０モルの割合である。
該反応の反応温度は、通常−５０〜１００℃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。単離した化合物（Ｉ−ａ）は必要に応じてクロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production method 3)
The compound represented by the formula (Ia) can also be produced from the compound (c) by the following method.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , m, Z ¹ and Z ² represent the same meaning as described above, and R ¹¹ represents a methyl group or an amino group. ]
Step (3-1)
Compound (f) can be produced by reacting compound (c) with compound (e).
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, and mixtures thereof.
The amount of the compound (e) used in the reaction is usually 1 to 3 moles relative to 1 mole of the compound (c).
The reaction temperature is usually in the range of 20 to 200 ° C., and the reaction time is usually in the range of 0.5 to 240 hours.
After completion of the reaction, the compound (f) can be isolated by performing an operation such as concentrating the reaction mixture. The isolated compound (f) can be used as it is in the step (3-2), but can be further purified by recrystallization or the like, if necessary.
Step (3-2)
The compound represented by the formula (Ia) can be produced by reacting the compound (f) and the compound (b) in the presence of a base.
The reaction is usually performed in the presence of a solvent and usually in the presence of a base.
Examples of the solvent used in the reaction include ethers such as diethyl ether, tetrahydrofuran and dimethoxyethane, acid amides such as N, N-dimethylformamide, organic sulfurs such as dimethyl sulfoxide and sulfolane, and aliphatics such as hexane and heptane. Examples thereof include hydrocarbons, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene, water, and mixtures thereof.
Examples of the base used in the reaction include inorganic bases such as sodium hydroxide and potassium hydroxide, and alkali metal alkoxides such as sodium methoxide and potassium tert-butoxide.
The amount of the base used for the reaction is usually 1 to 50 mol per 1 mol of the compound (f).
The amount of compound (b) used in the reaction is usually 1 to 10 moles per mole of compound (f).
The reaction can be carried out using a phase transfer catalyst such as tetra n-butylammonium bromide as necessary. The amount of the phase transfer catalyst used in that case is usually 0.05 to 1.0 mol with respect to 1 mol of the compound (f).
The reaction temperature of the reaction is usually in the range of −50 to 100 ° C., and the reaction time is usually in the range of 1 to 24 hours.
After completion of the reaction, the compound (Ia) can be isolated by pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating. The isolated compound (Ia) can be further purified by chromatography, recrystallization or the like, if necessary.

〔式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、ｍ、Ｚ¹及びＺ²は前記と同じ意味を表し、Ｒ¹²はメチル基又はフェニル基を表す。〕
工程（４−１）
化合物（ｈ）は、化合物（ｂ）と化合物（ｇ）とを、塩基の存在下で反応させることにより製造することができる。
該反応は通常溶媒の存在下、通常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、例えばジエチルエーテル、テトラヒドロフラン、ジメトキシエタン等のエーテル類、Ｎ，Ｎ−ジメチルホルムアミド等の酸アミド類、ジメチルスルホキシド、スルホラン等の有機硫黄類、ヘキサン、ヘプタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、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及びそれらの混合物があげられる。
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、炭酸カリウム等の無機塩基及びトリエチルアミン、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。
反応に用いられる化合物（ｇ）の量は、化合物（ｂ）１モルに対して、通常１〜５モルの割合である。
該反応の反応温度は通常−２０〜８０℃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、反応混合物を酸性水（希塩酸等）に注加し、有機溶媒抽出してから、濃縮する等の操作を行うことにより、化合物（ｈ）を単離することができる。単離した化合物（ｈ）は必要に応じてクロマトグラフィー、再結晶等でさらに精製することもできる。
工程（４−２）
式（Ｉ−ａ）で示される化合物は、化合物（ｃ）と化合物（ｈ）とを塩基の存在下で反応させることにより製造することができる。
該反応は通常溶媒の存在下、通常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、例えばジエチルエーテル、テトラヒドロフラン、ジメトキシエタン等のエーテル類、Ｎ，Ｎ−ジメチルホルムアミド等の酸アミド類、ジメチルスルホキシド、スルホラン等の有機硫黄類、ヘキサン、ヘプタン等の脂肪族炭化水素類、トルエン、キシレン等の芳香族炭化水素類、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、水及びそれらの混合物があげられる。
該反応に用いられる塩基としては、例えば水酸化ナトリウム、水酸化カリウム等の無機塩基、ナトリウムメトキシド、ナトリウムエトキシド、カリウムｔｅｒｔ−ブトキシド等のアルカリ金属アルコキシドがあげられる。反応に用いられる塩基の量は、化合物（ｈ）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（ｃ）の量は、化合物（ｈ）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−５０〜１００℃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。単離した化合物（Ｉ−ａ）は必要に応じてクロマトグラフィー、再結晶等によりさらに精製することもできる。 (Production Method 4)
The compound represented by the formula (Ia) can also be produced from the compound (b) by the following method.

[Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , m, Z ¹ and Z ² represent the same meaning as described above, and R ¹² represents a methyl group or a phenyl group. ]
Step (4-1)
Compound (h) can be produced by reacting compound (b) and compound (g) in the presence of a base.
The reaction is usually performed in the presence of a solvent, usually in the presence of a base.
Examples of the solvent used in the reaction include ethers such as diethyl ether, tetrahydrofuran and dimethoxyethane, acid amides such as N, N-dimethylformamide, organic sulfurs such as dimethyl sulfoxide and sulfolane, and aliphatics such as hexane and heptane. Examples thereof include hydrocarbons, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene, and mixtures thereof.
Examples of the base used in the reaction include inorganic bases such as sodium hydride and potassium carbonate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7. -Organic bases such as 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 the compound (g) used in the reaction is usually 1 to 5 mol relative to 1 mol of the compound (b).
The reaction temperature of the reaction is usually in the range of -20 to 80 ° C, and the reaction time is usually in the range of 1 to 24 hours.
After completion of the reaction, the compound (h) can be isolated by performing an operation such as pouring the reaction mixture into acidic water (diluted hydrochloric acid or the like), extraction with an organic solvent, and concentration. The isolated compound (h) can be further purified by chromatography, recrystallization or the like, if necessary.
Step (4-2)
The compound represented by the formula (Ia) can be produced by reacting the compound (c) and the compound (h) in the presence of a base.
The reaction is usually performed in the presence of a solvent, usually in the presence of a base.
Examples of the solvent used in the reaction include ethers such as diethyl ether, tetrahydrofuran and dimethoxyethane, acid amides such as N, N-dimethylformamide, organic sulfurs such as dimethyl sulfoxide and sulfolane, and aliphatics such as hexane and heptane. Examples thereof include hydrocarbons, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene, water, and mixtures thereof.
Examples of the base used in the reaction include inorganic bases such as sodium hydroxide and potassium hydroxide, and alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide. The amount of the base used for the reaction is usually 1 to 10 moles relative to 1 mole of the compound (h).
The amount of compound (c) used in the reaction is usually 1 to 10 moles per mole of compound (h).
The reaction temperature of the reaction is in the range of −50 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 pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating. The isolated compound (Ia) can be further purified by chromatography, recrystallization or the like, if necessary.

〔式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びｍは前記と同じ意味を表し、ｒは１又は２を表す。〕
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えばメタノール、エタノール等のアルコール類、ジクロロメタン、クロロホルム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、酢酸、トリフルオロ酢酸等の脂肪族カルボン酸類、水及びそれらの混合物があげられる。
該反応に用いられる酸化剤としては、例えば過酢酸、トリフルオロ過酢酸、ｍ−クロロ過安息香酸類等の有機過酸化物類、塩素、臭素のハロゲン分子、Ｎ−クロロコハク酸イミド等の含ハロゲンイミド類、過塩素酸（若しくはその塩）、過ヨウ素酸（若しくはその塩）等のハロゲン化物類、過マンガン酸カリウム等の過マンガン酸塩類、クロム酸カリウム等のクロム酸塩類及び過酸化水素があげられる。反応に用いられる酸化剤の量は、化合物（Ｉ−ａ）１モルに対して通常１〜１０モルの割合である。
該反応の反応温度は通常−５０〜２００℃の範囲であり、反応時間は通常１〜７２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、濃縮する等の操作を行うことにより、化合物（Ｉ−ｂ）を単離することができる。単離した有機溶媒抽出してから、濃縮する等の操作を行うことにより、スルフィド誘導体（Ｉ−ｂ）を単離することができる。単離したスルフィド誘導体（Ｉ−ｂ）は、必要に応じてクロマトグラフィー、再結晶等でさらに精製することもできる。 (Production method 5)
Among the compounds of the present invention represented by the formula (I), the compound represented by the formula (Ib) wherein n is 1 or 2 is produced by oxidizing the compound represented by the formula (Ia). Can do.

[Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and m represent the same meaning as described above, and r represents 1 or 2. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include alcohols such as methanol and ethanol, halogenated hydrocarbons such as dichloromethane and chloroform, aromatic hydrocarbons such as toluene and xylene, and aliphatic carboxylic acids such as acetic acid and trifluoroacetic acid. , Water and mixtures thereof.
Examples of the oxidizing agent used in the reaction include organic peroxides such as peracetic acid, trifluoroperacetic acid, and m-chloroperbenzoic acid, halogen molecules of chlorine and bromine, and halogen-containing imides such as N-chlorosuccinimide. , Halides such as perchloric acid (or its salt), periodic acid (or its salt), permanganates such as potassium permanganate, chromates such as potassium chromate and hydrogen peroxide It is done. The amount of the oxidizing agent used in the reaction is usually 1 to 10 moles per mole of the compound (Ia).
The reaction temperature of the reaction is usually in the range of −50 to 200 ° C., and the reaction time is usually in the range of 1 to 72 hours.
After completion of the reaction, the compound (Ib) can be isolated by performing an operation such as pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating. The sulfide derivative (Ib) can be isolated by performing an operation such as concentration after extracting the isolated organic solvent. The isolated sulfide derivative (Ib) can be further purified by chromatography, recrystallization or the like, if necessary.

  Examples of harmful arthropods for which the compounds of the present invention represented by formula (I) are effective include harmful insects and harmful mites. More specifically, the following are mentioned.

Hemiptera: Laodelphax striatellus, Japanese green planthopper (Nilaparvata lugens), Japanese green planthoppers (Sogatella furcifera) and other leafhoppers (Nephotettix cincticeps), Nephotettixvis , Aphids such as Myzus persicae, Nezara antennata, Riptortus clavetus, Eysarcoris lewisi, Eysarcoris parvus (Eysarcoris parvus) Plautia stali), Halyomorpha mista, Stenotus rubrovittatus, Trichonotylus ruficornis, etc., Trialeurodes vaporariorum, Silver leaf whitefly Whiteflies such as Bemisia argentifolii, Aonidiella aurantii, Sanho scale insect (Comstockaspis perniciosa), Citrus snow scale (Unaspis citri), Ruby beetle (Ceroplastes rubens), Icerya purchasi and Icerya purchasi , Lice, etc.

Lepidopterous insects: Chilo suppressalis, Cnaphalocrocis medinalis, Notarcha derogata, Plodia interpunctella, etc., Spodoptera litura, Psedia, Psedia, Heliotis genus, Helicobelpa genus moths, white butterflies (Pieris rapae), white butterflies, Adoxofies genus, Nashihime shinshin oyster (Grapholita molesta), codling moth (Cydia pomonella) scallop moth, Carposina niponensis, etc Anemone such as genus Anatolia, Limantria genus, Euprocutis genus, etc., Suga, such as Plutella xylostella, Pterinophora gossypiella, etc., Higan, such as Hyphantria cunea 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 (Delia antiqua), flies, etc. Liriomyza trifolii) and other leafhoppers, fruit flies, fruit flies, butterflies, flyfish, abs, and fly flies.

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: keratoids, grasshoppers, crickets, etc.
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), pig lice (Haematopinus suis), 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 lycopers), citrus spider mite (Aculops lycopers) Mites (Aculus schlechtendali), mites (Polyphagotarsonemus latus), mites, mite, mite (Haemaphysalis longicornis), Ima tick (Haemaphysalis longicornis), Ms. ), Tick such as Ixodes persulcatus, Boophilus microplus, tick such as Tyrophagus putrescentiae, Dermatophagoides farinae, Dermatophagoide s ptrenyssnus) and other tick mites, such as thorn ticks (Cheyletus eruditus), stag beetles (Cheyletus malaccensis), and tick ticks (Cheyletus moorei).
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.
Gastropods: Limax marginatus, Limax flavus, etc.

The harmful arthropod 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. Into emulsions, oils, shampoos, flowables, powders, wettable powders, granules, pastes, microcapsules, foams, aerosols, carbon dioxide, tablets, resin formulations, etc. It has been done. 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 present compound.

  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 gas, liquefied petroleum gas (LPG), dimethyl ether, carbon dioxide gas, and the like.

  Examples of surfactants include alkyl sulfate salts, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyethylene glycol ethers, polyhydric alcohol esters, and sugar alcohol derivatives. It is done.

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

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

  When the harmful arthropod control agent of the present invention is used for controlling agricultural and forestry pests, the application amount is usually 1 to 10,000 g / ha, preferably 10 to 500 g / ha as the amount of active ingredient. Emulsions, wettable powders, flowables, microcapsule preparations, etc. are usually diluted with water so that the active ingredient concentration is 1-1000 ppm, and powders, granules, etc. are usually used as they are. These preparations may be applied directly to plants to be protected from harmful arthropods. By treating these preparations in the soil, harmful arthropods that inhabit the soil can be controlled, and these preparations can be treated on the nursery before planting, It can also be processed. Furthermore, the sheet preparation of the harmful arthropod 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 harmful arthropod 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 space, and 0 when applied to a plane. 0.001 to 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 harmful arthropod control agent of the present invention is used to control ectoparasites of cattle, horses, pigs, sheep, goats, chickens, small animals such as dogs, cats, rats, mice, etc., it is well known in veterinary medicine. Can be used on animals. As a specific method of use, for the purpose of systemic suppression, for example, administration by tablet, feed mixing, suppository, injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.) is intended for non-systemic suppression. In this case, for example, an oil agent or an aqueous liquid is sprayed, a pour-on treatment or a spot-on treatment is performed, the animal is washed with a shampoo preparation, or a resin preparation is attached to the animal with 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 0.1 to 1000 mg per 1 kg body weight of the animal.

  The harmful arthropod control agent of the present invention includes other insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil improvers, animal feeds and the like. They can be mixed or used together.

  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, furamethrin, imiprothrin, etofenprox, fenvalerate, esfenvalerate, fenpropatoline, silafluophene, bifenthrin, transfluthrin, flucitrinate, taufluvalinate, acrinatrin, teflutrin, methfluthrin, dimefluthrin, Pyrethroid compounds such as profluthrin, dichlorvos, fenitrothion, cyanophos, profenofos Sulprophos, phentoate, isoxathione, tetrachlorobinphos, fenthion, chlorpyrifos, diazinon, acephate, terbufos, folate, chlorethoxyphos, phosthiazate, etoprophos, kazusafos, methidathion, etc. Carbamate compounds such as thiodicarb, alaniccarb, benfuracarb, oxamil, aldicarb, methiocarb, benzoylphenylurea compounds such as lufenuron, chlorfluazuron, hexaflumuron, diflubenzuron, triflumuron, teflubenzuron, flufenoxuron, fluazuron, novallon, triazuron, Proxyfen, metoprene, hydroprene, Juvenile hormone-like substances such as enoxycarb, acetamiprid, nitenpyram, thiacloprid, neonicotinoid compounds such as thiamethoxam, dinotefuran, clothianidin, N-phenylpyrazole compounds such as acetoprole and ethiprole, tebufenozide, chromafenozide, methoxyphenozide, halofenodid, etc. Benzoylhydrazine compounds, diafenthiuron, pymetrozine, flonicamid, triazamate, buprofezin, spinosad, emamectin benzoate, chlorfenapyr, indoxacarb, pyridalyl, cyromazine, fenpyroximate, bifenazate, tefenfenpyrad, tolfenpyrazole, pyridabento, pyrimidazole, pyrimidazole, pyrimidazole Phenazaquin, acequinosyl, hex Azokusu, clofentezine, fenbutatin oxide, dicofol, propargite, avermectin, milbemectin, amitraz, cartap, bensultap, thiocyclam, endosulfan, spirodiclofen, spiromesifen and azadirachtin the like.

  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, Framethopil, Fludioxonil, Prosimidone and Dietofencarb.

  Hereinafter, although this invention is demonstrated in more detail by a manufacture example, a formulation example, a test example, etc., this invention is not limited only to these examples. In addition, the compound number in a manufacture example is a number as described in a postscript (Table 1)-(Table 7).

  First, the manufacture example of this invention compound is shown.

Production Example 1
Dissolve 0.78 g of 4-chlorobenzyl mercaptan and 0.87 g of 1-bromo-3,3,3-trifluoropropane in 10 ml of N, N-dimethylformamide, add 0.68 g of potassium carbonate at room temperature and stir for 6 hours. did. Thereafter, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 1.17 g of 4-chlorobenzyl = 3,3,3-trifluoropropyl sulfide (the present compound (1)). Yield 93%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.31 (d, 2H), 7.23 (d, 2H), 3.70 (s, 2H), 2.55 to 2.59 ( m, 2H), 2.24-2.36 (m, 2H)

Production Example 2
1.5 g of 3-chlorobenzyl bromide was dissolved in 20 ml of chloroform, 0.55 g of thioacetamide was added thereto, and the mixture was heated to reflux for 2 days. Thereafter, the reaction mixture was allowed to cool to near room temperature and then concentrated under reduced pressure. To the obtained concentrate was added 1.29 g of 1-bromo-3,3,3-trifluoropropane, 0.07 g of tetra-n-butylammonium bromide, 11.0 g of sodium hydroxide, 20 ml of toluene and 10 ml of water, Stir vigorously at room temperature for 1 hour. Thereafter, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 1.47 g of 3-chlorobenzyl = 3,3,3-trifluoropropyl sulfide (the present compound (2)). Yield 79%
_{^{1 H-NMR (CDCl 3,}} TMS): δ (ppm) 7.32-7.39 (m, 2H), 7.19-7.29 (m, 2H), 3.86 (s, 2H), 2.62-2.66 (m, 2H), 2.28-2.40 (m, 2H)

Production Example 3
Dissolve 1.5 g of 4-fluorobenzyl chloride and 0.30 g of S- (3,3,3-trifluoropropyl) = benzenethioate in 10 ml of methanol and add 0.3 ml of sodium methoxide (28% methanol solution) at room temperature. Was dripped. After stirring at the same temperature for 12 hours, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.27 g of 4-fluorobenzyl = 3,3,3-trifluoropropyl sulfide (the present compound (3)). Yield 88%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.27 (dd, 2H), 7.02 (dd, 2H), 3.71 (s, 2H), 2.55 to 2.59 ( m, 2H), 2.24-2.36 (m, 2H)

Production Example 4
3-Bromobenzyl bromide (3.0 g) was dissolved in chloroform (20 ml), and thioacetamide (0.90 g) was added thereto, followed by heating under reflux for 10 hours. Thereafter, the reaction mixture was allowed to cool to near room temperature and then concentrated under reduced pressure. To the resulting concentrate was added 2.12 g of 1-bromo-3,3,3-trifluoropropane, 0.12 g of tetra-n-butylammonium bromide, 18.0 g of sodium hydroxide, 20 ml of toluene and 20 ml of water, Stir vigorously at room temperature for 3 hours. Thereafter, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 2.84 g of 4-bromobenzyl = 3,3,3-trifluoropropyl sulfide (present compound (4)). Yield 79%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.45 (d, 2H), 7.16 (d, 2H), 3.68 (dd, 2H), 2.54 to 2.58 ( m, 2H), 2.24-2.38 (m, 2H)

Production Example 5
Production Example using 20 ml of methanol, 0.70 g of 4-iodobenzyl bromide, 0.55 g of S- (3,3,3-trifluoropropyl) = benzenethioate and 0.5 ml of sodium methoxide (28% methanol solution) According to the method described in 3, 4-iodobenzyl = 3,3,3-trifluoropropyl sulfide (present compound (5)) (0.75 g) was obtained. Yield 92%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.65 (d, 2H), 7.06 (d, 2H), 3.68 (s, 2H), 2.54 to 2.58 ( m, 2H), 2.24-2.36 (m, 2H)

Production Example 6
In 20 ml of chloroform, 2.0 g of 4-cyanobenzyl bromide was dissolved, 0.77 g of thioacetamide was added thereto, and then the mixture was heated to reflux for 6 hours. Thereafter, the reaction mixture was allowed to cool to near room temperature and then concentrated under reduced pressure. To the resulting concentrate was added 1.81 g of 1-bromo-3,3,3-trifluoropropane, 0.10 g of tetra-n-butylammonium bromide, 15.3 g of sodium hydroxide, 20 ml of toluene and 20 ml of water, Stir vigorously at room temperature for 2 hours. Thereafter, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 1.88 g of 4-cyanobenzyl = 3,3,3-trifluoropropyl sulfide (present compound (6)). Yield 75%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.63 (d, 2H), 7.43 (d, 2H), 3.73 (s, 2H), 2.56-2.60 ( m, 2H), 2.25-2.40 (m, 2H)

Production Example 7
Reaction time using 5 ml of methanol, 0.20 g of 4-nitrobenzyl bromide, 0.18 g of S- (3,3,3-trifluoropropyl) = benzenethioate and 0.2 ml of sodium methoxide (28% methanol solution) In accordance with the method described in Production Example 3 except that 0.5 hour was used, 0.19 g of 4-nitrobenzyl = 3,3,3-trifluoropropyl sulfide (the present compound (7)) was obtained. Yield 84%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 8.22 (d, 2H), 7.48 (d, 2H), 3.81 (s, 2H), 2.57-2.61 ( m, 2H), 2.28-2.39 (m, 2H)

Production Example 8
5 ml of methanol, 0.10 g of 4- (trifluoromethyl) benzyl bromide, 0.10 g of S- (3,3,3-trifluoropropyl) = benzenethioate and 0.1 ml of sodium methoxide (28% methanol solution) And (4-trifluoromethyl) benzyl = 3,3,3-trifluoropropyl sulfide (present compound (8)) according to the method described in Preparation Example 3 except that the reaction time was 10 hours. 09 g was obtained. Yield 78%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.59 (d, 2H), 7.43 (d, 2H), 3.77 (s, 2H), 2.56-2.60 ( m, 2H), 2.26-2.40 (m, 2H)

Production Example 9
Using 10 ml of N, N-dimethylformamide, 0.50 g of (3-trifluoromethyl) benzyl mercaptan, 0.46 g of 1-bromo-3,3,3-trifluoropropane and 0.36 g of potassium carbonate, the reaction time was 2 Except for the time, according to the method described in Preparation Example 1, 0.60 g of (3-trifluoromethyl) benzyl = 3,3,3-trifluoropropyl sulfide (present compound (9)) was obtained. Yield 80%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.42-7.64 (m, 4H), 3.78 (s, 2H), 2.57-2.64 (m, 2H), 2.26-2.37 (m, 2H)

Production Example 10
10 ml of methanol, 0.30 g of 4- (1,1,2,2,2-pentafluoroethyl) benzyl bromide, 0.24 g of S- (3,3,3-trifluoropropyl) = benzenethioate and sodium methoxide (28% methanol solution) Using 0.2 ml, according to the method described in Production Example 3, 4- (1,1,2,2,2-pentafluoroethyl) benzyl = 3,3,3-trifluoropropyl = 0.24 g of sulfide (the present compound (10)) was obtained. Yield 68%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.59 (d, 2H), 7.44 (d, 2H), 3.78 (s, 2H), 2.58-2.62 ( m, 2H), 2.21-2.37 (m, 2H)

Production Example 11
4-Ethynylbenzyl bromide (0.50 g) was dissolved in chloroform (5 ml), and thioacetamide (0.19 g) was added thereto, followed by heating under reflux for 1 hour. Thereafter, the reaction mixture was allowed to cool to near room temperature and then concentrated under reduced pressure. To the obtained concentrate was added 0.45 g of 1-bromo-3,3,3-trifluoropropane, 0.02 g of tetra-n-butylammonium bromide, 3.84 g of sodium hydroxide, 10 ml of toluene and 5 ml of water, Stir vigorously at room temperature for 3 hours. Thereafter, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.41 g of 4-ethynylbenzyl = 3,3,3-trifluoropropyl sulfide (present compound (11)). Yield 65%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.45 (d, 2H), 7.25 (d, 2H), 3.72 (s, 2H), 3.08 (s, 1H) 2.54-2.58 (m, 2H), 2.23-2.35 (m, 2H)

Production Example 12
10 ml of methanol, 0.33 g of 4- (trifluoromethoxy) benzyl bromide, 0.30 g of S- (3,3,3-trifluoropropyl) = benzenethioate and 0.3 ml of sodium methoxide (28% methanol solution) In accordance with the method described in Production Example 3, 4- (trifluoromethoxy) benzyl = 3,3,3-trifluoropropyl = sulfide (present compound (12)) (0.37 g) was obtained. Yield 95%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.34 (d, 2H), 7.18 (d, 2H), 3.73 (s, 2H), 2.57-2.61 ( m, 2H), 2.25-2.37 (m, 2H)

Production Example 13
Using 10 ml of methanol, 0.30 g of 4- (methylthio) benzyl chloride, 0.41 g of S- (3,3,3-trifluoropropyl) = benzenethioate and 0.4 ml of sodium methoxide (28% methanol solution) Except that the reaction time was 3 days, 0.39 g of 4- (methylthio) benzyl = 3,3,3-trifluoropropyl sulfide (present compound (13)) was obtained according to the method described in Preparation Example 3. . Yield 84%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.18-7.25 (m, 4H), 3.70 (s, 2H), 2.55 to 2.59 (m, 2H), 2.50 (s, 3H), 2.24-2.46 (m, 2H)

Production Example 14
10 ml of methanol, 0.20 g of 4- (trifluoromethylthio) benzyl bromide, 0.17 g of S- (3,3,3-trifluoropropyl) = benzenethioate and 0.2 ml of sodium methoxide (28% methanol solution) 4- (trifluoromethylthio) benzyl = 3,3,3-trifluoropropyl = sulfide (present compound (14)) according to the method described in Preparation Example 3 except that the reaction time was 10 hours. 22 g was obtained. Yield 93%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.62 (d, 2H), 7.37 (d, 2H), 3.75 (s, 2H), 2.57-2.61 ( m, 2H), 2.24-2.36 (m, 2H)

Production Example 15
10 ml of methanol, 0.26 g of 4- (methylsulfonyl) benzyl chloride, 0.30 g of S- (3,3,3-trifluoropropyl) = benzenethioate and 0.3 ml of sodium methoxide (28% methanol solution) were used. According to the method described in Production Example 3 except that the reaction time was 1 hour, 0.37 g of 4- (methylsulfonyl) benzyl = 3,3,3-trifluoropropyl sulfide (the present compound (15)) was added. Obtained. Yield 97%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.92 (d, 2H), 7.52 (d, 2H), 3.80 (s, 2H), 3.07 (s, 3H) 2.58-2.62 (m, 2H), 2.28-2.40 (m, 2H)

Production Example 16
1.20 g of 4-chloro-3-fluorobenzyl chloride was dissolved in 10 ml of ethanol, and 0.56 g of thiourea was added thereto, followed by heating under reflux for 6 hours. Thereafter, the reaction mixture was allowed to cool to near room temperature and then concentrated under reduced pressure. To the resulting concentrate was added 1.19 g of 1-bromo-3,3,3-trifluoropropane, 0.06 g of tetra-n-butylammonium bromide, 4.89 g of potassium hydroxide, 10 ml of toluene and 10 ml of water, Stir vigorously at room temperature for 1 hour. Thereafter, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 1.24 g of 4-chloro-3-fluorobenzyl = 3,3,3-trifluoropropyl sulfide (present compound (16)). Yield 68%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.34 (dd, 1H), 7.14 (d, 1H), 7.04 (d, 1H), 3.72 (s, 2H) 2.56-2.60 (m, 2H), 2.26-2.38 (m, 2H)

Production Example 17
10 ml of methanol, 0.29 g of 4-chloro-2-fluorobenzyl bromide, 0.30 g of S- (3,3,3-trifluoropropyl) = benzenethioate and 0.3 ml of sodium methoxide (28% methanol solution) 4-chloro-2-fluorobenzyl = 3,3,3-trifluoropropyl = sulfide (present compound (17)) according to the method described in Preparation Example 3 except that the reaction time was 1 hour. 25 g was obtained. Yield 72%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.25-7.27 (m, 1H), 7.09-7.14 (m, 2H), 3.73 (s, 2H), 2.60-2.64 (m, 2H), 2.29-2.41 (m, 2H)

Production Example 18
In 10 ml of ethanol, 0.50 g of 4-chloro-3,5-difluorobenzyl chloride was dissolved, 0.21 g of thiourea was added thereto, and the mixture was heated to reflux for 6 hours. Thereafter, the reaction mixture was allowed to cool to near room temperature and then concentrated under reduced pressure. To the obtained concentrate was added 0.45 g of 1-bromo-3,3,3-trifluoropropane, 0.02 g of tetra-n-butylammonium bromide, 1.87 g of potassium hydroxide, 10 ml of toluene and 5 ml of water, Stir vigorously at room temperature for 3 hours. Thereafter, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.42 g of 4-chloro-3,5-difluorobenzyl = 3,3,3-trifluoropropyl sulfide (the present compound (18)). Yield 56%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 6.97 (d, 2H), 3.68 (s, 2H), 2.57-2.65 (m, 2H), 2.28- 2.40 (m, 2H)

Production Example 19
1.00 g of 3,4-dichlorobenzyl chloride was dissolved in 10 ml of ethanol, and 0.43 g of thiourea was added thereto, followed by heating under reflux for 4 hours. Thereafter, the reaction mixture was allowed to cool to near room temperature and then concentrated under reduced pressure. To the obtained concentrate was added 0.91 g of 1-bromo-3,3,3-trifluoropropane, 0.05 g of tetra-n-butylammonium bromide, 3.13 g of potassium hydroxide, 10 ml of toluene and 15 ml of water, Stir vigorously at room temperature for 6 hours. Thereafter, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 1.14 g of 3,4-dichlorobenzyl = 3,3,3-trifluoropropyl sulfide (present compound (19)). Yield 77%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.39-7.42 (m, 2H), 7.14 (dd, 1H), 3.68 (s, 2H), 2.56- 2.60 (m, 2H), 2.29-2.39 (m, 2H)

Production Example 20
In 10 ml of ethanol, 0.62 g of 4-chloro-3- (trifluoromethyl) benzyl bromide was dissolved, 0.19 g of thiourea was added thereto, and then the mixture was heated to reflux for 6 hours. Thereafter, the reaction mixture was allowed to cool to near room temperature and then concentrated under reduced pressure. To the obtained concentrate was added 0.40 g of 1-bromo-3,3,3-trifluoropropane, 0.02 g of tetra-n-butylammonium bromide, 1.66 g of potassium hydroxide, 10 ml of toluene and 10 ml of water, Stir vigorously at room temperature for 3 hours. Thereafter, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.42 g of 4-chloro-3- (trifluoromethyl) benzyl = 3,3,3-trifluoropropyl sulfide (present compound (20)). Yield 57%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.63 (s, 1H), 7.41-7.48 (m, 2H), 3.74 (s, 2H), 2.57- 2.61 (m, 2H), 2.28-2.40 (m, 2H)

Production Example 21
0.50 g of 3,4-difluorobenzyl bromide was dissolved in 5 ml of chloroform, and 0.18 g of thioacetamide was added thereto, followed by heating under reflux for 10 hours. Thereafter, the reaction mixture was allowed to cool to near room temperature and then concentrated under reduced pressure. To the obtained concentrate was added 0.43 g of 1-bromo-3,3,3-trifluoropropane, 0.02 g of tetra-n-butylammonium bromide, 3.60 g of sodium hydroxide, 20 ml of toluene and 10 ml of water, Stir vigorously at room temperature for 6 hours. Thereafter, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.46 g of 3,4-difluorobenzyl = 3,3,3-trifluoropropyl sulfide (present compound (21)). Yield 75%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.00-7.18 (m, 3H), 3.66 (dd, 2H), 2.56-2.60 (m, 2H), 2.27-2.35 (m, 2H)

Production Example 22
In 10 ml of ethanol, 0.41 g of 3-chloro-4-fluorobenzyl chloride was dissolved, and 0.19 g of thiourea was added thereto, followed by heating under reflux for 10 hours. Thereafter, the reaction mixture was allowed to cool to near room temperature and then concentrated under reduced pressure. To the obtained concentrate was added 0.40 g of 1-bromo-3,3,3-trifluoropropane, 0.02 g of tetra-n-butylammonium bromide, 1.66 g of potassium hydroxide, 10 ml of toluene and 10 ml of water, Stir vigorously at room temperature for 6 hours. Thereafter, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.45 g of 3-chloro-4-fluorobenzyl = 3,3,3-trifluoropropyl sulfide (present compound (22)). Yield 72%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.37 (dd, 1H), 7.07-7.19 (m, 2H), 3.68 (s, 2H), 2.56- 2.60 (m, 2H), 2.26-2.38 (m, 2H)

Production Example 23
1.54 g of 3,4,5-trifluorobenzyl bromide was dissolved in 10 ml of chloroform, and 0.45 g of thioacetamide was added thereto, followed by heating under reflux for 14 hours. Thereafter, the reaction mixture was allowed to cool to near room temperature and then concentrated under reduced pressure. To the resulting concentrate was added 1.07 g of 1-bromo-3,3,3-trifluoropropane, 0.06 g of tetra-n-butylammonium bromide, 9.04 g of sodium hydroxide, 10 ml of toluene and 10 ml of water, Stir vigorously at room temperature for 6 hours. Thereafter, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 1.66 g of 3,4,5-trifluorobenzyl = 3,3,3-trifluoropropyl sulfide (present compound (23)). Yield 74%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 6.97 (ddd, 2H), 3.66 (s, 2H), 2.57-2.61 (m, 2H), 2.27- 2.39 (m, 2H)

Production Example 24
10 ml of methanol, 0.28 g of 2,3,4,5,6-pentafluorobenzyl bromide, 0.25 g of S- (3,3,3-trifluoropropyl) = benzenethioate and sodium methoxide (28% methanol solution) ) 0.2 ml, and 2,3,4,5,6-pentafluorobenzyl = 3,3,3-trifluoropropyl sulfide (present compound (24)) 0 according to the method described in Production Example 3 .29 g was obtained. Yield 88%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 3.79 (d, 2H), 2.68-2.72 (m, 2H), 2.35-2.53 (m, 2H)

Production Example 25
4-Bromo-3-fluorobenzyl bromide (1.96 g) was dissolved in 20 ml of chloroform, and 0.55 g of thioacetamide was added thereto, followed by heating under reflux for 2 days. Thereafter, the reaction mixture was allowed to cool to near room temperature and then concentrated under reduced pressure. To the resulting concentrate was added 1.29 g of 1-bromo-3,3,3-trifluoropropane, 0.07 g of tetra-n-butylammonium bromide, 11.0 g of sodium hydroxide, 20 ml of toluene and 10 ml of water, Stir vigorously at room temperature for 6 hours. Thereafter, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 1.88 g of 4-bromo-3-fluorobenzyl = 3,3,3-trifluoropropyl sulfide (present compound (25)). Yield 81%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.50 (dd, 1H), 7.12 (dd, 1H), 6.97 (dd, 1H), 3.68 (s, 2H) 2.56-2.60 (m, 2H), 2.23-2.38 (m, 2H)

Production Example 26
4-Bromo-3-fluorobenzyl = 3,3,3-trifluoropropyl = sulfide 0.34 g was dissolved in 10 ml of 1-methyl-2-pyrrolidinone, and 0.13 g of cuprous cyanide was dissolved in the resulting concentrate. Then, the mixture was heated and stirred at 160 ° C. for 6 hours and then at 180 ° C. for 2 days. Thereafter, the reaction mixture was allowed to cool to near room temperature, 10% hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.07 g of 4-cyano-3-fluorobenzyl = 3,3,3-trifluoropropyl sulfide (present compound (26)). Yield 25%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.60 (dd, 1H), 7.21-7.26 (m, 2H), 3.76 (s, 2H), 2.58- 2.65 (m, 2H), 2.28-2.40 (m, 2H)

Production Example 27
0.45 g of diethylaminosulfur trifluoride was dissolved in 10 ml of dichloromethane, 0.50 g of 3- (4-chlorobenzylthio) -1-propanol was added thereto at −78 ° C., and the mixture was stirred at the same temperature for 1 hour. Thereafter, the reaction mixture was warmed to room temperature and further stirred for 1 hour. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.12 g of 4-chlorobenzyl = 3-fluoropropyl = sulfide (the present compound (27)). Yield 24%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.28 (d, 2H), 7.25 (d, 2H), 4.49 (dt, 2H), 3.68 (s, 2H) , 2.52 (t, 2H), 1.85-2.01 (m, 2H)

Production Example 28
0.08 g of diethylaminosulfur trifluoride was dissolved in 5 ml of dichloromethane, and 0.10 g of 3- (4-chlorobenzylthio) propionaldehyde dissolved in 5 ml of dichloromethane was added thereto at room temperature, followed by stirring at the same temperature for 2 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.10 g of 4-chlorobenzyl = 3,3-difluoropropyl = sulfide (the present compound (28)). Yield 91%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.29 (d, 2H), 7.24 (d, 2H), 5.88 (ddt, 1H), 3.69 (s, 2H) , 2.52 (t, 2H), 2.00-2.12 (m, 2H)

Production Example 29
Other than using 5 ml of N, N-dimethylformamide, 0.20 g of 4-chlorobenzyl mercaptan, 0.30 g of 1-iodo-4,4,4-trifluorobutane and 0.17 g of potassium carbonate, and setting the reaction time to 10 hours. In accordance with the method described in Production Example 1, 0.31 g of 4-chlorobenzyl = 4,4,4-trifluorobutyl sulfide (the present compound (29)) was obtained. Yield 92%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.30 (d, 2H), 7.25 (d, 2H), 3.67 (s, 2H), 2.45 (t, 2H) 2.10-2.22 (m, 2H), 1.76-1.83 (m, 2H)

Production Example 30
Using 10 ml of N, N-dimethylformamide, 0.30 g of 4-chlorobenzyl mercaptan, 0.52 g of 1-iodo-3,3,4,4,4-pentafluorobutane and 0.22 g of potassium carbonate, the reaction time was 2 According to the method described in Preparation Example 1 except that the period was set to 0.4 days, 0.45 g of 4-chlorobenzyl = 3,3,4,4,4-pentafluorobutyl sulfide (the present compound (30)) was obtained. Yield 78%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.29 (d, 2H), 7.27 (d, 2H), 3.71 (s, 2H), 2.53-2.63 ( m, 2H), 2.25 (ddt, 2H)

Production Example 31
Using 10 ml of N, N-dimethylformamide, 0.17 g of 4-chlorobenzyl mercaptan, 0.20 g of 1-bromo-3,4,4-trifluoro-3-butene and 0.15 g of potassium carbonate, the reaction time was 10 hours. Except that, 4-chlorobenzyl = 3,4,4-trifluoro-3-butenyl = sulfide (present compound (31)) 0.26 g was obtained according to the method described in Production Example 1. Yield 92%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.30 (d, 2H), 7.26 (d, 2H), 3.69 (s, 2H), 2.58 (t, 2H) 2.44-2.54 (m, 2H)

Production Example 32
Using 5 ml of N, N-dimethylformamide, 0.10 g of 1- (4-chlorophenyl) ethyl mercaptan, 0.10 g of 1-bromo-3,3,3-trifluoropropane and 0.08 g of potassium carbonate, the reaction time was 12 0.12 g of 1- (4-chlorophenyl) ethyl = 3,3,3-trifluoropropyl sulfide (present compound (32)) was obtained according to the method described in Preparation Example 1 except that the time was used. Yield 75%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.31 (d, 2H), 7.26 (d, 2H), 3.93 (q, 1H), 2.44-2.50 ( m, 2H), 2.17-2.30 (m, 2H), 1.56 (dd, 3H)

Production Example 33
0.50 g of 1- (3,4,5-trifluorophenyl) ethyl chloride was dissolved in 10 ml of ethanol, 0.22 g of thiourea was added thereto, and then the mixture was heated to reflux for 6 hours. Thereafter, the reaction mixture was allowed to cool to near room temperature and then concentrated under reduced pressure. To the obtained concentrate was added 0.45 g of 1-bromo-3,3,3-trifluoropropane, 0.02 g of tetra-n-butylammonium bromide, 3.85 g of sodium hydroxide, 10 ml of toluene and 5 ml of water, Stir vigorously at room temperature for 6 hours. Thereafter, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.40 g of 1- (3,4,5-trifluorophenyl) ethyl = 3,3,3-trifluoropropyl sulfide (the present compound (33)). . Yield 54%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 6.94-7.02 (m, 2H), 3.87 (q, 1H), 2.49 (t, 2H), 2.20- 2.33 (m, 2H), 1.50 (d, 3H)

Production Example 34
0.53 g of 1- (4-chlorophenyl) propyl bromide was dissolved in 10 ml of ethanol, and 0.19 g of thiourea was added thereto, followed by heating under reflux for 20 hours. Thereafter, the reaction mixture was allowed to cool to near room temperature and then concentrated under reduced pressure. To the obtained concentrate was added 0.40 g of 1-bromo-3,3,3-trifluoropropane, 0.02 g of tetra-n-butylammonium bromide, 1.66 g of potassium hydroxide, 10 ml of toluene and 10 ml of water, Stir vigorously at room temperature for 3 hours. Thereafter, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.25 g of 1- (4-chlorophenyl) propyl = 3,3,3-trifluoropropyl sulfide (present compound (34)). Yield 39%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.30 (d, 2H), 7.23 (d, 2H), 3.65 (t, 1H), 2.39-2.45 ( m, 2H), 2.14-2.27 (m, 2H), 1.76-1.94 (m, 2H), 0.89 (t, 3H)

Production Example 35
Dissolve 0.30 g of 4-chlorobenzyl = 3,3,3-trifluoropropyl sulfide in 10 ml of tetrahydrofuran, and add 0.6 ml of lithium diisopropylamide (2M-tetrahydrofuran / n-heptane solution) at −78 ° C. It was dripped. After stirring at the same temperature for 10 minutes, 0.20 g of 1-iodopropane was added and the reaction mixture was warmed to room temperature. After further stirring for 3 hours, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.10 g of 1- (4-chlorophenyl) butyl = 3,3,3-trifluoropropyl sulfide (the present compound (35)). Yield 29%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.31 (d, 2H), 7.24 (d, 2H), 3.74 (dd, 1H), 2.19-2.44 ( m, 4H), 1.78-1.82 (m, 2H), 1.21-1.41 (m, 2H), 0.88 (t, 3H)

Production Example 36
10 ml of tetrahydrofuran, 0.30 g of 4-chlorobenzyl = 3,3,3-trifluoropropyl sulfide, 0.6 ml of lithium diisopropylamide (2M-tetrahydrofuran / n-heptane solution) and 0.20 g of 2-iodopropane were used. (1- (4-chlorophenyl) -2-methyl) propyl = 3,3,3-trifluoropropyl sulfide (the compound of the present invention) according to the method described in Preparation Example 35 except that the reaction time was changed to 4 hours. 36)) 0.12 g was obtained. Yield 34%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.31 (d, 2H), 7.23 (d, 2H), 3.51 (d, 1H), 2.01-2.39 ( m, 5H), 1.07 (d, 3H), 0.81 (d, 3H)

Production Example 37
Dissolve 0.30 g of bromo (4-chlorophenyl) acetonitrile and 0.30 g of S- (3,3,3-trifluoropropyl) = benzenethioate in 10 ml of methanol, and add sodium methoxide (28% methanol solution) at -78 ° C. ) 0.3 ml was added dropwise. After stirring at the same temperature for 3 hours, the mixture was warmed to room temperature and further stirred for 1 hour. 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.04 g of (4-chlorophenyl) -3,3,3-trifluoropropylthioacetonitrile (present compound (37)). Yield 11%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.44 (d, 2H), 7.42 (d, 2H), 4.82 (s, 1H), 2.79-2.95 ( m, 2H), 2.39-2.47 (m, 2H)

Production Example 38
10 ml of N, N-dimethylformamide, 0.28 g of (1- (4-chlorophenyl) -1-methyl) ethyl mercaptan, 0.26 g of 1-bromo-3,3,3-trifluoropropane and 0.06 g of potassium carbonate. (1- (4-chlorophenyl) -1-methyl) ethyl = 3,3,3-trifluoropropyl sulfide (the compound of the present invention) according to the method described in Production Example 1 except that the reaction time was 10 hours. (38)) 0.20 g was obtained. Yield 48%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.45 (d, 2H), 7.30 (d, 2H), 2.36-2.40 (m, 2H), 2.04- 2.13 (m, 2H), 1.73 (s, 6H)

Production Example 39
Dissolve 0.70 g of 4-chlorobenzyl = 3,3,3-trifluoropropyl sulfide in 20 ml of acetonitrile, and add 1.19 g of tetra-n-butylammonium periodate and 0.18 g of aluminum chloride at room temperature. And then heated to reflux for 10 hours. The reaction mixture was allowed to cool to near room temperature, poured into water, and extracted with ethyl acetate. The organic layer was washed successively with saturated aqueous sodium thiosulfate solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.25 g of 4-chlorobenzyl = 3,3,3-trifluoropropyl = sulfoxide (the present compound (39)). Yield 34%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.40 (d, 2H), 7.24 (d, 2H), 3.98 (dd, 2H), 2.52-2.84 ( m, 4H)

Production Example 40
In 10 ml of acetic acid, 0.50 g of 4-chlorobenzyl = 3,3,3-trifluoropropyl = sulfide was dissolved, and 10 ml of a peracetic acid solution was added thereto at room temperature, followed by stirring at 90 ° C. for 2 hours. The reaction mixture was allowed to cool to near room temperature and poured into water, and the precipitated crystals were filtered. The crystals were further washed with water and dried under reduced pressure for 1 day to obtain 0.55 g of 4-chlorobenzyl = 3,3,3-trifluoropropylsulfone (compound (40)). Yield 98%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.42 (d, 2H), 7.35 (d, 2H), 4.26 (s, 2H), 3.04-3.08 ( m, 2H), 2.53-2.65 (m, 2H)

Production Example 41
Acetic acid 5 ml, 4- (trifluoromethyl) benzyl = 3,3,3-trifluoropropyl = sulfide 0.10 g and peracetic acid solution 5 ml were used according to the method described in Production Example 40 and 4- (trifluoromethyl) 0.11 g of benzyl = 3,3,3-trifluoropropyl = sulfone (the present compound (41)) was obtained. Yield 98%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.71 (d, 2H), 7.55 (d, 2H), 4.35 (s, 2H), 3.08-3.12 ( m, 2H), 2.59-2.66 (m, 2H)

で示される化合物。 Next, specific examples of the compound of the present invention are shown in (Table 1) to (Table 7) together with compound numbers. However, the description such as (F, H) of R ^{5 in} the table indicates that (R ⁵ located at the 2-position is F and R ⁵ located at the 6-position is H).
Formula (I)

A compound represented by

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

６．９０ｇを得た。収率 ８１％
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．９７（ｄ，２Ｈ）、７．５８−７．６２（ｍ，１Ｈ）、７．４７（ｄｄ，２Ｈ）、３．２４（ｔ，２Ｈ）、２．４４−２．５６（ｍ，２Ｈ） Reference production example 1
9.6 g of 1-bromo-3,3,3-trifluoropropane and 5 g of thiobenzoic acid were dissolved in 30 ml of N, N-dimethylformamide, and 1.45 g of sodium hydride (60% oily) was added under ice cooling. The reaction mixture was then warmed to room temperature. After stirring at the same temperature for 12 hours, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and S- (3,3,3-trifluoropropyl) = benzenethioate represented by the following formula:

6.90 g was obtained. Yield 81%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.97 (d, 2H), 7.58-7.62 (m, 1H), 7.47 (dd, 2H), 3.24 ( t, 2H), 2.44-2.56 (m, 2H)

０．７９ｇを得た。収率 ９８％
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．５９（ｄ，２Ｈ）、７．５０（ｄ，２Ｈ）、４．７９（ｓ，２Ｈ） Reference production example 2
To 0.13 g of lithium aluminum hydride in 20 ml of diethyl ether, 0.95 g of ethyl 4- (1,1,2,2,2-pentafluoroethyl) benzoate was added at 0 ° C. and stirred for 2 hours. Thereafter, a small amount of ice was added to the reaction mixture, and the mixture was further stirred until the gray portion disappeared, and then the mixture was filtered through Celite. The filtrate was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 4- (1,1,2,2,2-pentafluoroethyl) benzyl alcohol represented by the following formula:

0.79 g was obtained. Yield 98%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.59 (d, 2H), 7.50 (d, 2H), 4.79 (s, 2H)

２．２８ｇを得た。収率 ８９％
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）：δ（ｐｐｍ）７．６０（ｄ，２Ｈ）、７．５２（ｄ，２Ｈ）、４．５０（ｓ，２Ｈ） Reference production example 3
Dissolve 2.00 g of 4- (1,1,2,2,2-pentafluoroethyl) benzyl alcohol and 2.78 g of triphenylphosphine in 20 ml of dichloromethane, and gradually add 4.40 g of carbon tetrabromide under ice cooling. added. After the addition, the reaction mixture was warmed to room temperature and further stirred for 0.5 hour. Thereafter, the reaction mixture was concentrated under reduced pressure, the residue was subjected to silica gel column chromatography, and 4- (1,1,2,2,2-pentafluoroethyl) benzyl bromide represented by the following formula:

2.28 g was obtained. Yield 89%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.60 (d, 2H), 7.52 (d, 2H), 4.50 (s, 2H)

１．６８ｇを得た。収率 ８７％
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．４５（ｄ，２Ｈ）、７．３４（ｄ，２Ｈ）、４．５０（ｓ，２Ｈ）、３．１０（ｓ，１Ｈ） Reference production example 4
In 10 ml of methanol, 2.0 g of 4-((2-trimethylsilyl) ethynyl) benzaldehyde was dissolved, and 0.19 g of sodium borohydride was added at room temperature. After stirring at the same temperature for 2 hours, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. This was dissolved in 10 ml of tetrahydrofuran without purification, and 10 ml of tetra-n-butylammonium fluoride (1M-tetrahydrofuran solution) was added at room temperature. After stirring at the same temperature for 0.5 hour, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained concentrate was dissolved in 30 ml of dichloromethane, and 3.11 g of triphenylphosphine was added. To this, 4.92 g of carbon tetrabromide was added little by little under ice cooling, and the mixture was stirred at the same temperature for 2 hours. After warming to room temperature and stirring for another 10 hours, the reaction mixture was concentrated under reduced pressure, the residue was subjected to silica gel column chromatography, and 4- (ethynyl) benzyl bromide represented by the following formula:

1.68 g was obtained. Yield 87%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.45 (d, 2H), 7.34 (d, 2H), 4.50 (s, 2H), 3.10 (s, 1H)

１．１３ｇを得た。収率 ６５％
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．０３（ｄｄ，２Ｈ）、４．５１（ｓ，２Ｈ） Reference production example 5
2.0 g of 5-bromo-2-chloro-1,3-difluorobenzene was dissolved in 30 ml of diethyl ether, and 6.6 ml of n-butyllithium (1.6M n-hexane solution) was added dropwise at -78 ° C. The mixture was stirred at the same temperature for 15 minutes, 0.7 ml of N, N-dimethylformamide was added, and after further stirring for 15 minutes, the reaction mixture was warmed to room temperature. 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained concentrate was dissolved in 30 ml of methanol, and 0.32 g of sodium borohydride was added under ice cooling. After stirring at the same temperature for 0.5 hour, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained concentrate was dissolved in 20 ml of carbon tetrachloride, 2.77 g of triphenylphosphine was added, and the mixture was heated to reflux for 10 hours. Thereafter, the reaction mixture was allowed to cool to near room temperature, the reaction mixture was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography to give 4-chloro-3,5-difluorobenzyl chloride represented by the following formula.

1.13 g was obtained. Yield 65%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.03 (dd, 2H), 4.51 (s, 2H)

０．１０ｇを得た。収率 ４９％
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）９．７２（ｓ，１Ｈ）、７．２９（ｄ，２Ｈ）、７．２５（ｄ，２Ｈ）、３．７０（ｓ，２Ｈ）、２．６５−２．７２（ｍ，４Ｈ）
参考製造例７
３，４，５−トリフルオロベンズアルデヒド２．０ｇをテトラヒドロフラン５０ｍｌに溶解し、０℃で臭化メチルマグネシウム（０．９３Ｍ−テトラヒドロフラン溶液）１３．４ｍｌを加えた。同温で１時間攪拌した後、反応混合物を室温まで昇温した。反応混合物に１０％塩酸を加え、酢酸エチルで抽出した。有機層を１０％塩酸および飽和食塩水で順次洗浄し、無水硫酸マグネシウムで乾燥した後、減圧下濃縮した。これを精製することなく四塩化炭素３０ｍｌに溶解し、トリフェニルホスフィン３．７５ｇを加え、６時間加熱還流した。その後室温付近まで放冷した反応混合物を減圧下濃縮し、残渣をシリカゲルカラムクロマトグラフィーに付し、下式で示される１−（３，４，５−トリフルオロフェニル）エチルクロライド

１．８５ｇを得た。収率 ７６％
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）６．９７−７．１０（ｍ，２Ｈ）、４．９６（ｑ，１Ｈ）、１．８０（ｄ，３Ｈ） Reference production example 6
In 5 ml of dimethyl sulfoxide, 0.21 g of 3- (4-chlorobenzylthio) -1-propanol and 1.3 ml of triethylamine were dissolved, and 1.2 g of sulfur trioxide pyridine complex was added at room temperature. After stirring at the same temperature for 2 days, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 3- (4-chlorobenzylthio) propionaldehyde represented by the following formula:

0.10 g was obtained. Yield 49%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 9.72 (s, 1H), 7.29 (d, 2H), 7.25 (d, 2H), 3.70 (s, 2H) 2.65-2.72 (m, 4H)
Reference production example 7
2.0 g of 3,4,5-trifluorobenzaldehyde was dissolved in 50 ml of tetrahydrofuran, and 13.4 ml of methylmagnesium bromide (0.93 M-tetrahydrofuran solution) was added at 0 ° C. After stirring at the same temperature for 1 hour, the reaction mixture was warmed to room temperature. 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 10% hydrochloric acid and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. This was dissolved in 30 ml of carbon tetrachloride without purification, added with 3.75 g of triphenylphosphine, and heated to reflux for 6 hours. Thereafter, the reaction mixture was allowed to cool to near room temperature and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 1- (3,4,5-trifluorophenyl) ethyl chloride represented by the following formula:

1.85 g was obtained. Yield 76%
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 6.97-7.10 (m, 2H), 4.96 (q, 1H), 1.80 (d, 3H)

  Next, formulation examples are shown. In addition, a part shows a weight part. However, this invention compound is represented by the said compound number.

Formulation Example 1
9 parts of the compounds (1) to (41) 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 calcium dodecylbenzenesulfonate are dissolved therein. Add 6 parts and mix well to obtain an emulsion.

Formulation Example 2
To 40 parts of the present compounds (1) to (41), 5 parts of Solpol 5060 (registered trademark of Toho Chemical Co., Ltd.) is added and mixed well. Carplex # 80 (registered trademark of Shionogi & Co., synthetic silicon hydroxide fine powder) ) Add 32 parts, 23 parts of 300 mesh diatomaceous earth and mix with a juice mixer to obtain a wettable powder.

Formulation Example 3
Add 3 parts of the compounds (1) to (41) of the present invention, 5 parts of fine powder of hydrous silicon oxide, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 57 parts of clay, and mix well with stirring. An appropriate amount of water is added, further stirred, granulated with a granulator, and dried by ventilation to obtain granules.

Formulation Example 4
After thoroughly mixing 4.5 parts of the present compounds (1) to (41), 1 part of synthetic silicon hydroxide fine powder, 1 part of Doreles B (Sankyo Co., Ltd.) as a flocculant and 7 parts of clay in a mortar, Stir and mix. 86.5 parts of cut clay is added to the resulting mixture and mixed thoroughly with stirring to obtain a powder.

Formulation Example 5
The compound of the present invention (1) to (41) 10 parts; 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt; and 55 parts of water are mixed and pulverized by a wet pulverization method to prepare a preparation. obtain.

Formulation Example 6
0.5 parts of the compounds (1) to (41) of the present invention are dissolved in 10 parts of dichloromethane and mixed with 89.5 parts of Isopar M (isoparaffin: Exxon Chemical Registration) to obtain an oil.

Formulation Example 7
This invention compound (1)-(41) 0.1 part and neothiozole (Chuo Kasei Co., Ltd.) 49.9 part are put into an aerosol can, and after mounting an aerosol valve, it is filled with 25 parts dimethyl ether and 25 parts LPG. Then, an oily aerosol is obtained by mounting the actuator.

Formulation Example 8
Compound (1)-(41) 0.6 part, BHT 0.01 part, xylene 5 part, deodorized kerosene 3.39 part and emulsifier {Atmos 300 (registered trademark name of Atmos Chemical)} 1 part were mixed and 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 an aqueous aerosol.

  Next, test examples show that the compounds of the present invention are effective as active ingredients for harmful arthropod control agents.

Test example 1
The preparation of the test compound obtained in Formulation Example 5 was diluted so that the active ingredient concentration was 55.6 ppm to prepare a test drug solution.
On the other hand, until the second true leaf develops, 50 g of soil soil bonsol 2 (manufactured by Sumitomo Chemical Co., Ltd.) is put in a polyethylene cup having 5 holes with a diameter of 5 mm on the bottom and 10 to 15 seeds are sown. The grown rice was treated by absorbing 45 ml of the test chemical prepared as described above from the bottom of the cup. Then, after leaving still in the greenhouse <25 degreeC> for 6 days, the height of the rice was cut into 5 cm, 30 first-instar larvae of the brown planthopper were released, and left still in the greenhouse <25 degreeC>. Six days after releasing the green planthopper larvae, the number of the green planthopper parasitic on the rice was investigated.
Compound (4), (8), (9), (10), (11), (12), (16), (17), (18), (19), (20), (22) , (23), (24), (25), (26), (30), (33), (39), (41), the number of insects parasitic after 6 days of treatment is 3 or less. there were.

Test example 2
The preparation of the test compound 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 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. Ten female fly (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.
Compound (1), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14) , (15), (16), (17), (18), (19), (20), (21), (22), (23), (24), (25), (26), ( 27), (28), (30), (31), (32), (33), (34), (36), (37), (41) showed a death rate of 70% or more. It was.

Test example 3
The preparation of the test compound 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 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 German cockroaches (Blattala germanica) were released into the polyethylene cup and capped. Six days later, the death and death of German cockroaches were investigated to determine the death rate.
Compound (1), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14) , (16), (17), (18), (19), (20), (21), (22), (23), (24), (25), (26), (30), ( 32), (33), (34), (36), and (37) showed 100% mortality.

Claims (6)

Formula (I)

Wherein, R ¹ is a halogen atom substituted by C1~C4 may alkyl group, shea anode group or a hydrogen atoms,
R ² represents a C1-C4 alkyl group which may be substituted with a halogen atom or a hydrogen atom,
R ³ represents C1~C3 fluoroalkyl group or C2~C3 fluoroalkenyl group,
R ⁴ is a halogen atom, a cyano group, a nitro group, C1 -C4 haloalkyl group, c androgenic substituted C2~C4 may alkynyl in atom, a substituted C1 -C4 may be alkoxy groups with a halogen atom, a halogen may C1~C4 alkylthio group or which may be substituted with atoms represents a substituted C1~C4 may alkylsulfonyl group with a halogen atom,
R ⁵ is the same or different and represents a hydrogen atom or a fluorine atom;
m represents an arbitrary integer of 1 to 3, and n represents an arbitrary integer of 0 to 2.
However, when m is 2 or 3, R ⁴ may be the same or different. ]
A benzyl sulfide derivative represented by The benzyl sulfide derivative according to claim 1, wherein R ² is a hydrogen atom or a methyl group.   The benzyl sulfide derivative according to claim 1 or 2, wherein n is 0. The benzyl sulfide derivative according to any one of claims 1 to 3, wherein R ³ is a C1 to C3 fluoroalkyl group.   A harmful arthropod control agent comprising the benzyl sulfide derivative represented by the formula (I) according to any one of claims 1 to 4 as an active ingredient.   An effective amount of a benzyl sulfide compound represented by the formula (I) according to any one of claims 1 to 4 is applied to a harmful arthropod or a place where the harmful arthropod grows. Control method.