JP2010150156A - Noxious organism-controlling composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition exhibiting excellent controlling efficacy on a noxious organism. <P>SOLUTION: The noxious organism-controlling composition comprises an organic sulfur compound represented by formula (I): Cy-(CH<SB>2</SB>)<SB>m</SB>-CR<SP>1</SP>R<SP>2</SP>-S(O)<SB>n</SB>-CH<SB>2</SB>CH<SB>2</SB>-R<SP>3</SP>[wherein R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>, R<SP>6</SP>, m and n each represents a specific meaning] and a neonicotinoid compound selected from the group consisting of imidacloprid, thiacloprid, acetamiprid, nitenpyram, clothianidin and thiamethoxam. The controlling method of a noxious organism comprises applying the composition to the noxious organism or a habitat of the noxious organism. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a pest control composition containing an organic sulfur compound represented by the following formula (I) and a neonicotinoid compound.

It is known that a composition containing a neonicotinoid compound such as imidacloprid or clothianidin has a controlling effect against domestic pests (for example, Patent Document 1).
Depending on the control target, a better control effect may be required.

Special table 2007-518737 gazette

  This invention makes it a subject to provide the composition which has the outstanding control effect suitable for control of a pest.

〔式中、
Ｃｙは群Ｅ１〜Ｅ２より選ばれる基で置換されていてもよいフェニル基、群Ｅ１〜Ｅ２より選ばれる基で置換されていてもよい５〜６員のヘテロアリール基、群Ｅ１〜Ｅ３より選ばれる基で置換されていてもよい３〜７員のシクロアルキル基又は群Ｅ１〜Ｅ３より選ばれる基で置換されていてもよい５〜７員のシクロアルケニル基を表し、
Ｒ¹はハロゲン原子で置換されていてもよいＣ１〜Ｃ４鎖式炭化水素基、ハロゲン原子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鎖式炭化水素基、-Ｃ(=Ｇ)Ｒ⁴、シアノ基、ハロゲン原子又は水素原子を表し、
Ｒ³は少なくとも１つのフッ素原子を含むＣ１〜Ｃ５ハロアルキル基又はフッ素原子を表し、
Ｇは酸素原子又は硫黄原子を表し、
Ｒ⁴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Ｃ３〜Ｃ６アルケニルオキシ基、ハロゲン原子で置換されていてもよいＣ３〜Ｃ６アルキニルオキシ基、ハロゲン原子で置換されていてもよいＣ１〜Ｃ４アルキルアミノ基、ハロゲン原子で置換されていてもよいジ（Ｃ１〜Ｃ４アルキル）アミノ基、ヒドロキシル基、アミノ基、Ｃ２〜Ｃ５環状アミノ基又は水素原子を表し、
ｍは０又は１を表し、ｎは０、１又は２を表し、
群Ｅ１は、群Ｌから選ばれる基で置換されていてもよいＣ１〜Ｃ６鎖式炭化水素基、ハロゲン原子で置換されていてもよいＣ３〜Ｃ６シクロアルキル基、-ＯＲ⁵、-ＳＲ⁵、-Ｓ(=Ｏ)Ｒ⁵、-Ｓ(=Ｏ)₂Ｒ⁵、-Ｃ(=Ｏ)Ｒ⁶、-ＯＣ(=Ｏ)Ｒ⁷、シアノ基、ニトロ基、ヒドロキシル基及びハロゲン原子からなる一価基の群を表し、
群Ｅ２は、群Ｌから選ばれる基で置換されていてもよいＣ２−Ｃ６アルカンジイル基、群Ｌから選ばれる基で置換されていてもよい１，３−ブタジエン−１，４−ジイル基、-Ｇ-Ｔ-Ｇ-及び-Ｔ-Ｇ-Ｔ-からなる二価基の群を表し、
群Ｅ３は、=Ｏ、=ＮＯ-Ｒ⁵、=Ｃ=ＣＨ₂及び=Ｃ(Ｒ⁸)Ｒ⁹からなる二価基の群を表し、
Ｔはメチレン基又はエチレン基を表し、
Ｒ⁵は群Ｌから選ばれる基で置換されていてもよいＣ１〜Ｃ４鎖式炭化水素基又は群Ｌから選ばれる基で置換されていてもよいＣ３〜Ｃ６シクロアルキル基を表し、
Ｒ⁶は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Ｃ３〜Ｃ６アルケニルオキシ基、ハロゲン原子で置換されていてもよいＣ３〜Ｃ６アルキニルオキシ基、ハロゲン原子で置換されていてもよいＣ１〜Ｃ４アルキルアミノ基、ハロゲン原子で置換されていてもよいジ（Ｃ１〜Ｃ４アルキル）アミノ基、ハロゲン原子で置換されていてもよいＣ１〜Ｃ４アルキル基、ヒドロキシル基、アミノ基、Ｃ２〜Ｃ５環状アミノ基又は水素原子を表し、
Ｒ⁷は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Ｃ３〜Ｃ６アルケニルオキシ基、ハロゲン原子で置換されていてもよいＣ３〜Ｃ６アルキニルオキシ基、ハロゲン原子で置換されていてもよいＣ１〜Ｃ４アルキルアミノ基、ハロゲン原子で置換されていてもよいジ（Ｃ１〜Ｃ４アルキル）アミノ基、ハロゲン原子で置換されていてもよいＣ１〜Ｃ４アルキル基、アミノ基、Ｃ２〜Ｃ５環状アミノ基又は水素原子を表し、
Ｒ⁸およびＲ⁹は同一または相異なり、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鎖式炭化水素基、ハロゲン原子又は水素原子を表し、
群Ｌは、ヒドロキシル基、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Ｃ３〜Ｃ６アルケニルオキシ基、ハロゲン原子で置換されていてもよいＣ３〜Ｃ６アルキニルオキシ基、アミノ基、ハロゲン原子で置換されていてもよいＣ１〜Ｃ４アルキルアミノ基、ハロゲン原子で置換されていてもよいジ（Ｃ１〜Ｃ４アルキル）アミノ基、Ｃ２〜Ｃ５環状アミノ基、-Ｃ(=Ｏ)Ｒ⁶、-ＯＣ(=Ｏ)Ｒ⁷及びハロゲン原子からなる群を表す。〕
で示される有機硫黄化合物と、
イミダクロプリド、チアクロプリド、アセタミプリド、ニテンピラム、クロチアニジン及びチアメトキサムからなる群より選ばれるネオニコチノイド系化合物とを含有する組成物が、有害生物に対して優れた防除効力を有することを見出し、本発明に到った。 As a result of intensive studies to find a composition having an excellent control effect, the present inventor has found that the following formula (I)

[Where,
Cy is a phenyl group which may be substituted with a group selected from groups E1 to E2, a 5- to 6-membered heteroaryl group which may be substituted with a group selected from groups E1 to E2, and a group E1 to E3. A 3- to 7-membered cycloalkyl group optionally substituted with a group or a 5- to 7-membered cycloalkenyl group optionally substituted with a group selected from the groups E1 to E3,
R ¹ represents a C1-C4 chain hydrocarbon group optionally substituted with a halogen atom, a halogen atom or a hydrogen atom,
R ² represents a C1-C4 chain hydrocarbon group optionally substituted with a halogen atom, —C (═G) R ⁴ , a cyano group, a halogen atom or a hydrogen atom;
R ³ represents a C1-C5 haloalkyl group containing at least one fluorine atom or a fluorine atom,
G represents an oxygen atom or a sulfur atom,
R ⁴ is a C1-C4 alkyl group which may be substituted with a halogen atom, a C1-C4 alkoxy group which may be substituted with a halogen atom, a C3-C6 alkenyloxy group which may be substituted with a halogen atom, halogen A C3-C6 alkynyloxy group optionally substituted with an atom, a C1-C4 alkylamino group optionally substituted with a halogen atom, a di (C1-C4 alkyl) amino group optionally substituted with a halogen atom, Represents a hydroxyl group, an amino group, a C2-C5 cyclic amino group or a hydrogen atom;
m represents 0 or 1, n represents 0, 1 or 2,
Group E1 is group substituted by C1~C6 may chain hydrocarbon group selected from the group L, optionally substituted C3~C6 cycloalkyl group with a halogen atom, -OR ^5, -SR ^5, -S (= O) R ⁵ , -S (= O) ₂ R ⁵ , -C (= O) R ⁶ , -OC (= O) R ⁷ , cyano group, nitro group, hydroxyl group and halogen atom Represents a group of monovalent groups,
Group E2 is a C2-C6 alkanediyl group optionally substituted with a group selected from Group L, a 1,3-butadiene-1,4-diyl group optionally substituted with a group selected from Group L; Represents a group of divalent groups consisting of -G-T-G- and -T-G-T-;
Group E3 represents a group of divalent groups consisting of ═O, ═NO—R ⁵ , ═C═CH ₂ and ═C (R ⁸ ) R ⁹ ;
T represents a methylene group or an ethylene group,
R ⁵ represents a C1-C4 chain hydrocarbon group which may be substituted with a group selected from Group L or a C3-C6 cycloalkyl group which may be substituted with a group selected from Group L;
R ⁶ is a C1-C4 alkoxy group which may be substituted with a halogen atom, a C3-C6 alkenyloxy group which may be substituted with a halogen atom, a C3-C6 alkynyloxy group which may be substituted with a halogen atom, A C1-C4 alkylamino group optionally substituted with a halogen atom, a di (C1-C4 alkyl) amino group optionally substituted with a halogen atom, a C1-C4 alkyl group optionally substituted with a halogen atom, Represents a hydroxyl group, an amino group, a C2-C5 cyclic amino group or a hydrogen atom;
R ⁷ is a C1-C4 alkoxy group which may be substituted with a halogen atom, a C3-C6 alkenyloxy group which may be substituted with a halogen atom, a C3-C6 alkynyloxy group which may be substituted with a halogen atom, A C1-C4 alkylamino group optionally substituted with a halogen atom, a di (C1-C4 alkyl) amino group optionally substituted with a halogen atom, a C1-C4 alkyl group optionally substituted with a halogen atom, Represents an amino group, a C2-C5 cyclic amino group or a hydrogen atom,
R ⁸ and R ⁹ are the same or different and represent a C1-C4 alkoxy group which may be substituted with a halogen atom, a C1-C4 chain hydrocarbon group which may be substituted with a halogen atom, a halogen atom or a hydrogen atom. Represent,
Group L is a hydroxyl group, a C1-C4 alkoxy group optionally substituted with a halogen atom, a C3-C6 alkenyloxy group optionally substituted with a halogen atom, or a C3-C6 optionally substituted with a halogen atom. An alkynyloxy group, an amino group, a C1-C4 alkylamino group optionally substituted with a halogen atom, a di (C1-C4 alkyl) amino group optionally substituted with a halogen atom, a C2-C5 cyclic amino group,- It represents a group consisting of C (═O) R ⁶ , —OC (═O) R ⁷ and a halogen atom. ]
An organic sulfur compound represented by
The present inventors have found that a composition containing a neonicotinoid compound selected from the group consisting of imidacloprid, thiacloprid, acetamiprid, nitenpyram, clothianidin and thiamethoxam has an excellent control effect against pests. It was.

That is, the present invention includes the following inventions.
[Invention 1]
A pest control composition comprising an organic sulfur compound represented by the formula (I) and a neonicotinoid compound selected from the group consisting of imidacloprid, thiacloprid, acetamiprid, nitenpyram, clothianidin and thiamethoxam.
[Invention 2]
The composition according to invention 1, wherein in formula (I), Cy is a phenyl group which may be substituted with a group selected from groups E1 to E2.
[Invention 3]
The composition according to invention 1, wherein in formula (I), Cy is a 5- to 6-membered heteroaryl group optionally substituted with a group selected from groups E1 to E2.
[Invention 4]
The composition according to invention 1, wherein in formula (I), Cy is a pyridyl group optionally substituted with a group selected from groups E1 to E2.
[Invention 5]
In formula (I), Cy may be substituted with a group selected from 3 to 7-membered cycloalkyl groups or groups selected from groups E1 to E3 which may be substituted with groups selected from groups E1 to E3. The composition of claim 1 which is a membered cycloalkenyl group.
[Invention 6]
According to the invention 1, wherein in the formula (I), Cy is a cyclohexyl group which may be substituted with a group selected from the groups E1 to E3 or a cyclohexenyl group which may be substituted with a group selected from the groups E1 to E3 Composition.
[Invention 7]
The composition according to any one of Inventions 1 to 6, wherein the neonicotinoid compound is a compound selected from the group consisting of clothianidin and thiamethoxam.
[Invention 8]
The composition according to any one of claims 1 to 6, wherein the neonicotinoid compound is clothianidin.
[Invention 9]
In formula (I), Cy is a phenyl group which may be substituted with a group selected from groups E1 to E2,
The composition according to invention 1, wherein the neonicotinoid compound is a compound selected from the group consisting of clothianidin and thiamethoxam.
[Invention 10]
In formula (I), Cy is a 5- to 6-membered heteroaryl group optionally substituted with a group selected from groups E1 to E2.
The composition according to invention 1, wherein the neonicotinoid compound is a compound selected from the group consisting of clothianidin and thiamethoxam.
[Invention 11]
In formula (I), Cy is a pyridyl group optionally substituted with a group selected from the groups E1 to E2.
The composition according to invention 1, wherein the neonicotinoid compound is a compound selected from the group consisting of clothianidin and thiamethoxam.
[Invention 12]
In formula (I), Cy may be substituted with a group selected from 3 to 7-membered cycloalkyl group or group E1 to E3 optionally substituted with a group selected from groups E1 to E3. A membered cycloalkenyl group,
The composition according to invention 1, wherein the neonicotinoid compound is a compound selected from the group consisting of clothianidin and thiamethoxam.
[Invention 13]
In formula (I), Cy is a cyclohexyl group optionally substituted with a group selected from groups E1 to E3 or a cyclohexenyl group optionally substituted with a group selected from groups E1 to E3.
The composition according to invention 1, wherein the neonicotinoid compound is a compound selected from the group consisting of clothianidin and thiamethoxam.
[Invention 14]
In formula (I), Cy is a phenyl group which may be substituted with a group selected from groups E1 to E2,
The composition according to invention 1, wherein the neonicotinoid compound is clothianidin.
[Invention 15]
In formula (I), Cy is a 5- to 6-membered heteroaryl group optionally substituted with a group selected from groups E1 to E2.
The composition according to invention 1, wherein the neonicotinoid compound is clothianidin.
[Invention 16]
In formula (I), Cy is a pyridyl group optionally substituted with a group selected from the groups E1 to E2.
The composition according to invention 1, wherein the neonicotinoid compound is clothianidin.
[Invention 17]
In formula (I), Cy may be substituted with a group selected from 3 to 7-membered cycloalkyl group or group E1 to E3 optionally substituted with a group selected from groups E1 to E3. A membered cycloalkenyl group,
The composition according to invention 1, wherein the neonicotinoid compound is clothianidin.
[Invention 18]
In formula (I), Cy is a cyclohexyl group optionally substituted with a group selected from groups E1 to E3 or a cyclohexenyl group optionally substituted with a group selected from groups E1 to E3.
The composition according to invention 1, wherein the neonicotinoid compound is clothianidin.
[Invention 19]
A pest control method comprising applying the composition according to any one of the inventions 1 to 18 to a pest or a habitat of the pest.
[Invention 20]
Use of the composition according to any one of Inventions 1 to 18 for controlling pests.

  The control composition of the present invention has excellent efficacy in controlling pests.

  In the control composition of the present invention, an organic sulfur compound represented by the formula (I) (hereinafter referred to as the present organic sulfur compound) and neonicochi selected from the group consisting of imidacloprid, thiacloprid, acetamiprid, nitenpyram, clothianidin and thiamethoxam. The weight ratio with respect to the noid compound (hereinafter referred to as the present neonicotinoid compound) is preferably 1000: 1 to 1: 1000, more preferably 500: 1 to 1: 500, 100: 1 to 1: 100, It is in the range of 10: 1 to 1:10.

  In the present specification, the “halogen atom” means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of the “phenyl group optionally substituted with a group selected from the groups E1 to E2” include a phenyl group, 4-fluorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 4- An iodophenyl group,
3,4-difluorophenyl group, 3-chloro-4-fluorophenyl group, 4-chloro-3-fluorophenyl group, 4-chloro-2-fluorophenyl group, 3,4-dichlorophenyl group, 4-bromo-3 A fluorophenyl group,
3,4,5-trifluorophenyl group, 4-chloro-3,5-difluorophenyl group,
2,3,4,5,6-pentafluorophenyl group,
3-cyanophenyl group, 4-cyanophenyl group,
3-nitrophenyl group, 4-nitrophenyl group,
3-methylphenyl group, 4-methylphenyl group, 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 4-chloro-3- (tri Fluoromethyl) phenyl group, 4- (1,1,2,2,2-pentafluoroethyl) phenyl group,
4-ethynylphenyl group, 4-ethynyl-3-fluorophenyl group,
3-methoxyphenyl group, 4-methoxyphenyl group, 4- (trifluoromethoxy) phenyl group,
3- (methylthio) phenyl group, 4- (methylthio) phenyl group, 4- (trifluoromethylthio) phenyl group,
4- (methylsulfonyl) phenyl group is mentioned.

Examples of the 5- to 6-membered heteroaryl group in the “5- to 6-membered heteroaryl group optionally substituted with a group selected from the groups E1 to E3” include a 2-pyridyl group, a 3-pyridyl group, and 4- Pyridyl group of pyridyl group; pyridazinyl group of 3-pyridazinyl group and 4-pyridazinyl group; pyrimidinyl group of 2-pyrimidinyl group, 4-pyrimidinyl group and 5-pyrimidinyl group; pyrazinyl group of 2-pyrazinyl group; 1,2,4 -1,2,4-triazinyl group of triazin-3-yl group, 1,2,4-triazin-5-yl group and 1,2,4-triazin-6-yl group; -2-yl group 1,2,4-triazinyl group; 1-pyrrolyl group, 2-pyrrolyl group, pyrrolyl group of 3-pyrrolyl group; Group: 2-thienyl group, thienyl group of 3-thienyl group; 1-pyrazolyl group, 3-pyrazolyl group, pyrazolyl group of 4-pyrazolyl group; 3-isoxazolyl group, 4-isoxazolyl group, isoxazolyl group of 5-isoxazolyl group 3-isothiazolyl group, 4-isothiazolyl group, isothiazolyl group of 5-isothiazolyl group; 1-imidazolyl group, 2-imidazolyl group, imidazolyl group of 4-imidazolyl group; 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group; Oxazolyl group; 2-thiazolyl group, 4-thiazolyl group, thiazolyl group of 5-thiazolyl group; 1 of 1,2,4-triazol-1-yl group, 1,2,4-triazol-3-yl group , 2,4-triazolyl group; 1,3,4-oxadiazol-2-yl group oxa Azolyl group; 1,3,4-thiadiazolyl group of 1,3,4-thiadiazol-2-yl group; 1,2,4-oxadiazol-3-yl group, 1,2,4-oxadiazole- 1,2-4-diadiazolyl group of 5-yl group; 1,2,4-thiadiazolyl group of 1,2,4-thiadiazol-3-yl group, 1,2,4-thiadiazol-5-yl group It is done.
Specific examples of the “5- to 6-membered heteroaryl group optionally substituted with a group selected from groups E1 to E2” include, for example, 3-pyridyl group, 6-chloro-3-pyridyl group, 6- (tri Fluoromethyl) -3-pyridyl group, 2-pyridyl group, 5-chloro-2-pyridyl group, 5- (trifluoromethyl) -2-pyridyl group,
5-pyrimidyl group, 2-chloro-5-pyrimidyl group, 2-methoxy-5-pyrimidyl group, 2- (trifluoromethyl) -5-pyrimidyl group, 2-pyrazinyl group,
2-pyrrolyl group, 2-furanyl group, 2-thienyl group, 5-chloro-2-thienyl group, 1-pyrazolyl group, 3-isoxazolyl group, 5-tert-butyl-3-isoxazolyl group, 4-thiazolyl group, Examples include 1-imidazolyl group, 4- (trifluoromethyl) -1-imidazolyl group, 4-imidazolyl group, and 1-tert-butyl-4-imidazolyl group.

The 3- to 7-membered cycloalkyl group in the “3- to 7-membered cycloalkyl group optionally substituted with a group selected from the groups E1 to E3” is a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, A cycloheptyl group and a cyclooctyl group.
Specific examples of the “3- to 7-membered cycloalkyl group optionally substituted with a group selected from groups E1 to E3” include, for example, a cyclopropyl group, a 2,2-dimethylcyclopropyl group, and 2,2-dichloro group. A cyclopropyl group,
Cyclobutyl group, cyclopentyl group,
Cyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 4- (hydroxymethyl) cyclohexyl group, 4-cyanocyclohexyl group, 4-formylcyclohexyl group, 4- (2,2-dibromoethenyl) cyclohexyl group, 4-ethynylcyclohexyl group, 4- (4-methoxycarbonyl-1-butynyl) cyclohexyl group,
4,4-difluorocyclohexyl group, 4,4-dimethylcyclohexyl group, 4-ethynyl-4-hydroxycyclohexyl group, 4-ethynyl-4-fluorocyclohexyl group,
4,4- (1,1-dichloroethylene) cyclohexyl group, 4,4- (1,1-dibromoethylene) cyclohexyl group, 4,4-ethylenedioxycyclohexyl group, 4,4-ethylenedithiocyclohexyl group,
3-oxocyclohexyl group, 4-oxocyclohexyl group, 4-methylenecyclohexyl group, 4- (hydroxyimino) cyclohexyl group, 4- (methoxyimino) cyclohexyl group, 4- (ethoxyimino) cyclohexyl group, 4- (tert- A butoxyimino) cyclohexyl group, a 4- (allyloxyimino) cyclohexyl group, and a 4- (benzyloxyimino) cyclohexyl group.

Examples of the 5- to 7-membered cycloalkenyl group in the “5- to 7-membered cycloalkenyl group optionally substituted with a group selected from the groups E1 to E3” include 1-cyclopentyl, 2-cyclopentyl, and 3-cyclopentyl. 1-cyclohexenyl group, 2-cyclohexenyl group, cyclohexenyl group of 3-cyclohexenyl group; 1-cycloheptyl group, cycloheptyl group of 2-cycloheptyl group.
Specific examples of the “5- to 7-membered cycloalkenyl group optionally substituted with a group selected from the groups E1 to E3” include, for example, a 1-cyclopentyl group, 1-cyclohexyl group, 4-cyclohexenyl group, 1- Examples include a fluoro-4-cyclohexenyl group and a 1-ethynyl-4-cyclohexenyl group.

  Examples of the “C1-C4 chain hydrocarbon group optionally substituted with a halogen atom” include a methyl group, an ethyl group, a propyl group, and a 1-methylethyl group (sometimes referred to as an isopropyl group), 2 , 2-dimethylpropyl group, chloromethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 1, C1-C4 alkyl optionally substituted by a halogen atom such as 1,2,2,2-pentafluoroethyl group, 1,1-dimethylethyl group (hereinafter sometimes referred to as t-butyl group). Group: vinyl group, 2,2-difluorovinyl group, 1,2,2-trifluorovinyl group, 1-propenyl group, 2-propenyl group, 3,3-difluoro-2-propenyl group, 1 -C2-C4 alkenyl group optionally substituted with a halogen atom such as methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-butenyl group, 2-butenyl group; ethynyl group, 1-propynyl group 3,3,3-trifluoro-1-propynyl group, 2-propynyl group, 1-methyl-2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, etc. C2-C4 alkynyl group which may be included is mentioned.

The group represented by “—C (═G) R ⁴ ” is, for example, a C1-C4 alkyl group in which G is an oxygen atom and R ⁴ is optionally substituted with a halogen atom, such as an acetyl group or a propionyl group. A group; G such as a methoxycarbonyl group and an ethoxycarbonyl group is an oxygen atom, and R ⁴ is a C1-C4 alkoxy group optionally substituted with a halogen atom; G such as an allyloxycarbonyl group is an oxygen atom; A group in which R ⁴ is a C1-C4 alkenyloxy group optionally substituted with a halogen atom; G, such as a propargyloxycarbonyl group, is an oxygen atom, and C ⁴ -C4 alkynyl in which R ⁴ is optionally substituted with a halogen atom an oxy group; N- methylcarbamoyl group, N- in G is an oxygen atom ethylcarbamoyl group, R ⁴ is is C1~C4 may be alkyl substituted by a halogen atom Group is an amino group; N, N-in G is an oxygen atom dimethylcarbamoyl group etc., radical R ⁴ is optionally substituted di (C1 -C4 alkyl) amino group by a halogen atom; a carboxyl group; a carbamoyl Group; a group such as piperidinocarbonyl group where G is an oxygen atom and R ⁴ is a C2 to C5 cyclic amino group; a formyl group and the like.

  Examples of the “C1-C5 haloalkyl group containing at least one fluorine atom” include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1,1,2,2,2-pentafluoroethyl group, 2,2, 2-trifluoroethyl group, 1,1-difluoroethyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 1,1-difluoropropyl group, 2,2-difluoropropyl group, 3,3,3-trifluoropropyl group, 1,1,2,2,3,3,4,4,4-nonafluorobutyl group, 1,1-difluorobutyl group, 2,2-difluorobutyl group, Substituted only with fluorine atoms such as 1,1,2,2,3,3,4,4,5,5,5-undecafluoropentyl, 1,1-difluoropentyl and 2,2-difluoropentyl Is C1-C5 alkyl group; chlorodifluoromethyl group, 1,2-dichloro-1,2,2-trifluoroethyl group, 1,1-dichloro-2,2,2-trifluoroethyl group, 1-chloro-1 , 3,3,3-tetrafluoropropyl group, 2,3-dichloro-2,3,3-trifluoropropyl group and 2,2-dichloro-3,3,3-trifluoropropyl group, C1-C5 alkyl group substituted with a chlorine atom; 2,2-dibromo-3,3,3-trifluoropropyl group, 2-bromo-3,3,3-trifluoropropyl group, 2,3-dibromo -3,3-difluoropropyl group, 3-bromo-3,3-difluoropropyl group, 1-bromo-1,3,3,3-tetrafluoropropyl group, 1-bromo-2,2,3,3 3-pentafluo Propyl group, 1,3-dibromo-2,2,3,3-tetrafluoropropyl group, 3-bromo-2,3,3-trifluoropropyl group, 3-bromo-2,2,3,3-tetra A C1-C5 alkyl group substituted with a fluorine atom and a bromine atom, such as a fluoropropyl group, a 2,3-dibromo-2,3,3-trifluoropropyl group and a 3-bromo-3,3-difluoropropyl group; Can be mentioned.

  Examples of the “C1-C4 alkoxy group optionally substituted with a halogen atom” include a methoxy group, an ethoxy group, and a trifluoromethoxy group. Examples of the “C3-C6 alkenyloxy group optionally substituted with a halogen atom” include an allyloxy group. Examples of the “C3-C6 alkynyloxy group optionally substituted with a halogen atom” include a propargyloxy group. Examples of the “C1-C4 alkylamino group optionally substituted with a halogen atom” include a methylamino group and an ethylamino group. Examples of the “di (C1-C4 alkyl) amino group optionally substituted with a halogen atom” include a dimethylamino group and a diethylamino group.

Examples of the “C1-C6 chain hydrocarbon group optionally substituted with a group selected from Group L” include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group, a 2,2-dimethylpropyl group, Chloromethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 1,1,2,2,2 -Pentafluoroethyl group, 1,1-dimethylethyl group, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, trifluoromethoxymethyl, (1-propenyloxy) methyl group, (2 -Propenyloxy) methyl group, (1-methyl-2-propenyloxy) methyl group, (1,1-dimethyl-2-propenyloxy) methyl group, (2,2 Difluoro-2-propenyloxy) methyl group, 1- (1-propenyloxy) ethyl group, 1- (2-propenyloxy) ethyl group, 1- (1-methyl-2-propenyloxy) ethyl group, 1- ( 1,1-dimethyl-2-propenyloxy) ethyl group, 1- (2,2-difluoro-2-propenyloxy) ethyl group, 2- (1-propenyloxy) ethyl group, 2- (2-propenyloxy) Ethyl group, 2- (1-methyl-2-propenyloxy) ethyl group, 2- (1,1-dimethyl-2-propenyloxy) ethyl group, 2- (2,2-difluoro-2-propenyloxy) ethyl Group, (2-propynyloxy) methyl group, (1-methyl-2-propynyloxy) methyl group, (1,1-dimethyl-2-propynyloxy) methyl group, Nyloxy) methyl group, (1-methyl-2-butynyloxy) methyl group, (1,1-dimethyl-2-butynyloxy) methyl group, (3,3,3-trifluoro-1-propynyloxy) methyl group, 1 -(2-propynyloxy) ethyl group, 1- (1-methyl-2-propynyloxy) ethyl group, 1- (1,1-dimethyl-2-propynyloxy) ethyl group, 1- (2-butynyloxy) ethyl Group, 1- (1-methyl-2-butynyloxy) ethyl group, 1- (1,1-dimethyl-2-butynyloxy) ethyl group, 1- (3,3,3-trifluoro-1-propynyloxy) ethyl Group, 2- (2-propynyloxy) ethyl group, 2- (1-methyl-2-propynyloxy) ethyl group, 2- (1,1-dimethyl-2-propynyloxy) ethyl group, 2- (2-butynyloxy) ethyl group, 2- (1-methyl-2-butynyloxy) ethyl group, 2- (1,1-dimethyl-2-butynyloxy) ethyl group, 2- (3,3,3-tri From group L such as fluoro-1-propynyloxy) ethyl group, hydroxymethyl group, 1-hydroxyethyl group, 1-hydroxy-1-methylethyl group, 2-hydroxyethyl group, 2-hydroxy-1-methylethyl group A C1-C6 alkyl group optionally substituted with a selected group;
Vinyl group, 2,2-difluorovinyl group, 1,2,2-trifluorovinyl group, 1-propenyl group, 2-propenyl group, 3,3-difluoro-2-propenyl group, 1-methyl-2-propenyl group A C2-C6 alkenyl group optionally substituted with a group selected from group L such as a group;
1-ethynyl group, 2-bromoethynyl group, 2-iodoethynyl group and 2- (methoxycarbonyl) ethynyl group, 1-propynyl group, 3-fluoro-1-propynyl group, 3,3-difluoro-1-propynyl group 3- (dimethylamino) -1-propynyl group, 3,3,3-trifluoro-1-propynyl group, 3-methoxy-1-propynyl group, 3- (methoxycarbonyl) -1-propynyl group, 2- Propynyl, 1-fluoro-2-propynyl, 1,1-difluoro-2-propynyl, 1-butynyl, 4-fluoro-1-butynyl, 4-methoxy-1-butynyl, 4- (dimethyl Amino) -1-butynyl group, 4- (methoxycarbonyl) -1-butynyl group, 2-butynyl group, 4-fluoro-2-butynyl group, 4-methoxy-2-butynyl group Nyl group, 4- (dimethylamino) -2-butynyl group, 4- (methoxycarbonyl) -2-butynyl group, 3-butynyl group, 1,1-difluoro-3-butynyl group, 1-pentynyl group, 5- Fluoro-1-pentynyl group, 5-methoxy-1-pentynyl group, 5- (dimethylamino) -1-pentynyl group, 5- (methoxycarbonyl) -1-pentynyl group, 2-pentynyl group, 5-fluoro-2 -Substituted with a group selected from the group L such as a pentynyl group, 5-methoxy-2-pentynyl group, 5- (dimethylamino) -2-pentynyl group, 5- (methoxycarbonyl) -2-pentynyl group Good C2-C5 alkenyl groups are mentioned.

Examples of the “C3-C6 cycloalkyl group optionally substituted with a halogen atom” include a cyclopropyl group, a cyclohexyl group, a 4-chlorocyclohexyl group, and the like. Examples of the group represented by “—OR ⁵ ” include a methoxy group, an allyloxy group, a cyclohexyloxy group, and the like. Examples of the group represented by “—SR ⁵ ” include a methylthio group and an allylthio group. Examples of the group represented by “—S (═O) R ⁵ ” include a methylsulfenyl group. Examples of a group represented by "-S (= O) ₂ R ^5", for example, methylsulfonyl group and the like. Examples of the group represented by “—C (═O) R ⁶ ” include a formyl group, an acetyl group, a methoxycarbonyl group, a carbamoyl group, and the like. Examples of the group represented by “—OC (═O) R ⁷ ” include an acetyloxy group.

Examples of the “C2-C6 alkanediyl group optionally substituted with a group selected from group L” include ethane-1,2-diyl group, butane-1,2-diyl group and the like. Examples of the “1,3-butadiene-1,4-diyl group optionally substituted with a group selected from Group L” include 1,3-butadiene-1,4-diyl group, 2-chloro-1, Examples include 3-butadiene-1,4-diyl group, 2,3-dichloro-1,3-butadiene-1,4-diyl group, and the like. Examples of the group represented by “—G-T-G-” include a methylenedioxy group and an ethylenedioxy group. Examples of the group represented by “—T-G-T—” include —CH ₂ —O—CH ₂ — and the like. Examples of the group represented by “═NO—R ⁵ ” include a methoxyimino group and a hydroxyimino group. Examples of the group represented by “═C (R ⁸ ) R ⁹ ” include a vinylidene group.

As this organic sulfur compound, for example, in the formula (I), an organic sulfur compound in which Cy is a phenyl group optionally substituted by a group selected from the groups E1 to E2;
In formula (I), an organic sulfur compound in which Cy is a pyridyl group optionally substituted with a group selected from groups E1 to E2 or a pyrimidyl group optionally substituted with a group selected from groups E1 to E2;
In formula (I), Cy is selected from thienyl group optionally substituted with a group selected from groups E1 to E2, isoxazolyl group optionally substituted with a group selected from groups E1 to E2, and selected from groups E1 to E2. An organic sulfur compound which is an imidazolyl group optionally substituted with a group selected from the above, or a pyrazolyl group optionally substituted with a group selected from the group E1 to E2;
In formula (I), an organic sulfur compound in which Cy is a cyclohexyl group optionally substituted with a group selected from groups E1 to E2 or a cyclohexenyl group optionally substituted with a group selected from groups E1 to E2 Is mentioned.

In the present organic sulfur compound, when R ¹ and R ² are different from each other, a stereoisomer exists based on the asymmetric carbon to which R ¹ and R ² are bonded. What contains in arbitrary ratios can be used.
Subsequently, the manufacturing method of this organic sulfur compound is demonstrated.

［式中、Ｃｙ、Ｒ¹、Ｒ²、Ｒ³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。 Among the organic sulfur compounds, the compound represented by the formula (Ia) in which n is 0 in the formula (I) can be produced by, for example, the following (Production Method 1) to (Production Method 4).
(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, Cy, R ¹ , R ² , R ³ 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 in the reaction is usually 1 to 10 moles relative to 1 mole of the compound (a).
The amount of the compound (b) used in the reaction is usually 1 to 10 moles relative to 1 mole of the compound (a).
The reaction temperature of the reaction is usually in the range of −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 performing an operation such as 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、Ｃｙ、Ｒ¹、Ｒ²、Ｒ³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, Cy, R ¹ , R ² , R ³ 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 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 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 performing an operation such as 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、Ｃｙ、Ｒ¹、Ｒ²、Ｒ³、ｍ、Ｚ¹及びＺ²は前記と同じ意味を表し、Ｒ²⁰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。 (Production method 3)
The compound represented by the formula (Ia) can also be produced from the compound (c) by the following method.

[Wherein, Cy, R ¹ , R ² , R ³ , m, Z ¹ and Z ² represent the same meaning as described above, and R ²⁰ 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 for 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 in the reaction is usually 1 to 50 mol per 1 mol of compound (f).
The amount of the compound (b) used in the reaction is usually 1 to 10 moles relative to 1 mole of the 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 performing an operation such as 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、Ｃｙ、Ｒ¹、Ｒ²、Ｒ³、ｍ、Ｚ¹及びＺ²は前記と同じ意味を表し、Ｒ²¹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（c）１モルに対して通常１〜１０モルの割合である。
反応に用いられる化合物（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。 (Production Method 4)
The compound represented by the formula (Ia) can also be produced from the compound (c) by the following method.

[Wherein, Cy, R ¹ , R ² , R ³ , m, Z ¹ and Z ² represent the same meaning as described above, and R ²¹ represents a methyl group or a phenyl group. ]
Step (4-1)
Compound (h) can be produced by reacting compound (b) with 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 for the reaction is usually 1 to 10 moles relative to 1 mole of the compound (c).
The amount of the compound (g) used in the reaction is usually 1 to 5 moles relative to 1 mole 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 the compound (c) used in the reaction is usually 1 to 10 mol with respect to 1 mol of the 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 performing an operation such as 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、Ｃｙ、Ｒ¹、Ｒ²、Ｒ³、Ｒ²¹、ｍ、Ｚ¹及びＺ²は前記と同じ意味を表す。〕
工程（５−１）
化合物（ｉ）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。 (Production method 5)
The compound represented by the formula (Ia) can also be produced from the compound (b) by the following method.

[Wherein, Cy, R ¹ , R ² , R ³ , R ²¹ , m, Z ¹ and Z ² represent the same meaning as described above. ]
Step (5-1)
Compound (i) can be produced by reacting compound (b) with 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 moles relative to 1 mole 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 (5-2)
The compound represented by the formula (Ia) can be produced by reacting the compound (c) with the compound (i) 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 in the reaction is usually 1 to 10 moles per mole of compound (i).
The amount of the compound (c) used in the reaction is usually 1 to 10 moles relative to 1 mole of the compound (i).
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 performing an operation such as 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、Ｃｙ、Ｒ³、ｎ及びｍは前記と同じ意味を表し、Ｚ³及びＺ⁴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し、Ｒ^1aはハロゲン原子で置換されていてもよいＣ１〜Ｃ４鎖式炭化水素基を表し、Ｒ^2aは-Ｃ(＝Ｏ)Ｒ⁵またはシアノ基を表す。］
工程（６−１）
式（I-b）で示される化合物は、化合物（ｋ）と化合物（ｊ）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（ｊ）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（ｋ）の量は、化合物（ｊ）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-b）を単離することができる。単離した化合物（I-b）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 6)
Among the present organic sulfur compounds represented by formula (I), R ¹ is a C1-C4 chain hydrocarbon group or hydrogen atom optionally substituted with a halogen atom, and R ² is —C (═O) R. Compounds (Ib) and (Ic) which are ⁵ or a cyano group can also be produced from compound (j) by the following method.

[Wherein, Cy, R ³ , n and m represent the same meaning as described above, Z ³ and Z ⁴ represent a leaving group such as a chlorine atom, a bromine atom, an iodine atom and a methanesulfonyl group, and R ^1a represents a halogen atom. A C1-C4 chain hydrocarbon group which may be substituted with an atom is represented, and R ^2a represents —C (═O) R ⁵ or a cyano group. ]
Step (6-1)
The compound represented by the formula (Ib) can be produced by reacting the compound (k) and the compound (j) in the presence of a base.
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 (j).
The amount of the compound (k) used in the reaction is usually 1 to 10 moles relative to 1 mole of the compound (j).
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 (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 isolated compound (Ib) can be further purified by chromatography, recrystallization or the like, if necessary.

Step (6-2)
The compound represented by the formula (Ic) can be produced by reacting the compound (l) with the compound (Ib) in the presence of a base.
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 in the reaction is usually 1 to 10 moles per 1 mole of compound (Ib).
The amount of the compound (l) used in the reaction is usually 1 to 10 moles relative to 1 mole of the compound (Ib).
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 (Ic) can be isolated by performing an operation such as pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating. The isolated compound (Ic) can be further purified by chromatography, recrystallization or the like, if necessary.

［式中、Ｃｙ、Ｒ^1a、Ｒ^2a、Ｒ³、ｎ、ｍ、Ｚ³及びＺ⁴は前記と同じ意味を表す。］
工程（７−１）
化合物（ｑ）は、化合物（ｋ）と化合物（ｊ）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（ｊ）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（ｋ）の量は、化合物（ｊ）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（ｑ）を単離することができる。単離した化合物（ｑ）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 7)
Among the present organic sulfur compounds represented by the formula (I), R ¹ is a C1-C4 chain hydrocarbon group or hydrogen atom optionally substituted with a halogen atom, and R ² is —C (═O) R. Compound (Ic) which is ⁵ or a cyano group can also be produced from compound (j) by the following method.

[Wherein, Cy, R ^1a , R ^2a , R ³ , n, m, Z ³ and Z ⁴ represent the same meaning as described above. ]
Step (7-1)
Compound (q) can be produced by reacting compound (k) with compound (j) in the presence of a base.
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 (j).
The amount of the compound (k) used in the reaction is usually 1 to 10 moles relative to 1 mole of the compound (j).
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 (q) can be isolated by performing an operation such as pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating. The isolated compound (q) can be further purified by chromatography, recrystallization or the like, if necessary.

Step (7-2)
The compound represented by the formula (Ic) can be produced by reacting the compound (l) and the compound (q) in the presence of a base.
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 in the reaction is usually 1 to 10 moles per 1 mole of compound (Ib).
The amount of compound (l) used in the reaction is usually 1 to 10 moles per mole of compound (q).
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 (Ic) can be isolated by performing an operation such as pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating. The isolated compound (Ic) can be further purified by chromatography, recrystallization or the like, if necessary.

［式中、Ｃｙ、Ｒ^2a、Ｒ³、ｎ及びｍは前記と同じ意味を表し、Ｒ^1bはハロゲン原子を表す。］
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Ｎ，Ｎ−ジメチルホルムアミド等の酸アミド類、ジエチルエーテル、テトラヒドロフラン等のエーテル類、ジメチルスルホキシド、スルホラン等の有機硫黄、クロロホルム、四塩化炭素、１，２−ジクロロエタン、ジクロロメタン、ジクロロベンゼン等のハロゲン化炭化水素類、アセトニトリル、プロピオニトリル等の脂肪族ニトリル類、トルエン、キシレン等の芳香族炭化水素類、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、リチウムジイソプロピルアミド等のアルカリ金属アミド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（I-a）１モルに対して、通常１〜１０モルの割合である。
該反応に用いられるハロゲン化剤Ａとしては、例えば四塩化炭素、ヘキサクロロエタン等のハロゲン化炭化水素、フッ素、塩素、臭素、ヨウ素のハロゲン、Ｎ−クロロコハク酸イミド、Ｎ−ブロモコハク酸イミド、Ｎ−ヨードコハク酸イミド等のＮ−ハロゲン化コハク酸イミド、１−フルオロ−２，４，６−トリメチルピリジニウム トリフルオロメタンスルホナート、１，１’−ジフルオロ−２，２’−ビピリジニウム ビステトラフルオロボレート等のＮ−フルオロピリジニウム塩、塩化銅(ＩＩ)、臭化銅(ＩＩ)等の無機塩があげられる。反応に用いられるハロゲン化剤の量は、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−１００〜１００℃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-ｄ）を単離することができる。単離した化合物（I-ｄ）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 8)
Among the present organic sulfur compounds represented by formula (I), a compound in which R ¹ is a halogen atom and R ² is —C (═O) R ⁵ or a cyano group is obtained from compound (Ib) by the following method. Can be manufactured.

[Wherein, Cy, R ^2a , R ³ , n and m represent the same meaning as described above, and R ^1b represents a halogen atom. ]
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 acid amides such as N, N-dimethylformamide, ethers such as diethyl ether and tetrahydrofuran, organic sulfur such as dimethyl sulfoxide and sulfolane, chloroform, carbon tetrachloride, and 1,2-dichloroethane. Halogenated hydrocarbons such as dichloromethane and dichlorobenzene, aliphatic nitriles such as acetonitrile and propionitrile, aromatic hydrocarbons such as toluene and xylene, 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 alkali metals such as lithium diisopropylamide. And organic bases such as amide and triethylamine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene. The amount of the base used in the reaction is usually 1 to 10 moles per 1 mole of compound (Ia).
Examples of the halogenating agent A used in the reaction include halogenated hydrocarbons such as carbon tetrachloride and hexachloroethane, halogens of fluorine, chlorine, bromine and iodine, N-chlorosuccinimide, N-bromosuccinimide, N- N such as N-halogenated succinimide such as iodosuccinimide, 1-fluoro-2,4,6-trimethylpyridinium trifluoromethanesulfonate, 1,1′-difluoro-2,2′-bipyridinium bistetrafluoroborate -Inorganic salts such as fluoropyridinium salts, copper (II) chloride, copper (II) bromide. The amount of the halogenating agent used in the reaction is usually 1 to 10 moles per mole of compound (Ia).
The reaction temperature of the reaction is usually in the range of −100 to 100 ° C., and the reaction time is usually in the range of 1 to 24 hours.
After completion of the reaction, the compound (Id) can be isolated by pouring the reaction mixture into water, extracting the mixture with an organic solvent, and concentrating the mixture. The isolated compound (Id) can be further purified by chromatography, recrystallization or the like, if necessary.

［式中、Ｃｙ、Ｒ^1b、Ｒ^2a、Ｒ⁴、ｎ及びｍは前記と同じ意味を表す。］
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、例えばクロロホルム、四塩化炭素、１，２−ジクロロエタン、ジクロロメタン、ジクロロベンゼン等のハロゲン化炭化水素類、アセトニトリル、プロピオニトリル等の脂肪族ニトリル類、トルエン、キシレン等の芳香族炭化水素類、酢酸等の脂肪族カルボン酸類、二硫化炭素、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ハロゲン化剤Ｂとしては、例えばフッ素、塩素、臭素、ヨウ素のハロゲン、フッ化水素、塩化水素、臭化水素、ヨウ化水素のハロゲン化水素、塩化チオニル、臭化チオニル、塩化スルフリル等のハロゲン化硫黄化合物、三塩化リン、三臭化リン、五塩化リン、オキシ塩化リン等のハロゲン化リン化合物があげられる。反応に用いられるハロゲン化剤の量は、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−１００〜２００℃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-ｄ）を単離することができる。単離した化合物（I-ｄ）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 9)
Among the present organic sulfur compounds represented by formula (I), a compound in which R ¹ is a halogen atom and R ² is —C (═O) R ⁵ or a cyano group is obtained from compound (Ib) by the following method. Can be manufactured.

[Wherein, Cy, R ^1b , R ^2a , R ⁴ , n and m represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include halogenated hydrocarbons such as chloroform, carbon tetrachloride, 1,2-dichloroethane, dichloromethane and dichlorobenzene, aliphatic nitriles such as acetonitrile and propionitrile, toluene, xylene and the like. Examples thereof include aromatic hydrocarbons, aliphatic carboxylic acids such as acetic acid, carbon disulfide, water, and mixtures thereof.
Examples of the halogenating agent B used in the reaction include fluorine, chlorine, bromine, iodine halogen, hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide hydrogen halide, thionyl chloride, thionyl bromide, chloride. Examples thereof include sulfur halide compounds such as sulfuryl, and phosphorus halide compounds such as phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, and phosphorus oxychloride. The amount of the halogenating agent used in the reaction is usually 1 to 10 moles per mole of compound (Ia).
The reaction temperature is usually in the range of −100 to 200 ° C., and the reaction time is usually in the range of 1 to 24 hours.
After completion of the reaction, the compound (Id) can be isolated by pouring the reaction mixture into water, extracting the mixture with an organic solvent, and concentrating the mixture. The isolated compound (Id) can be further purified by chromatography, recrystallization or the like, if necessary.

〔式中、Ｃｙ、Ｒ¹、Ｒ²、Ｒ³及びｍは前記と同じ意味を表し、ｎ'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、ペルオキシ硫酸カリウム等のペルオキシ硫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-ｅ）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-ｅ）を単離することができる。単離したスルフィド誘導体（I-ｅ）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。
化合物（I-a）は公知の製造方法に準じて製造することができる。 (Production method 10)
Among the present organic sulfur compounds represented by the formula (I), the compound represented by the formula (Ie) in which n is 1 or 2 can be produced by oxidizing the compound represented by the formula (Ia). it can.

[Wherein, Cy, R ¹ , R ² , R ³ and m represent the same meaning as described above, and n ′ 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 acids, halogen molecules such as 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, potassium peroxysulfate, etc. Examples include peroxysulfates and hydrogen peroxide. The amount of the oxidizing agent used for the reaction is usually 1 to 10 moles relative to 1 mole of 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 (Ie) can be isolated by pouring the reaction mixture into water, extracting the mixture with an organic solvent, and concentrating the mixture. The sulfide derivative (I-e) can be isolated by performing an operation such as extraction after concentration of the isolated organic solvent and concentration. The isolated sulfide derivative (Ie) can be further purified by chromatography, recrystallization or the like, if necessary.
Compound (Ia) can be produced according to a known production method.

The neonicotinoid compound is a compound selected from the group consisting of imidacloprid, thiacloprid, acetamiprid, nitenpyram, clothianidin and thiamethoxam, imidacloprid is a compound represented by the following formula (IIa), and thiacloprid is represented by the following formula (IIb) Acetamiprid is a compound represented by the following formula (IIc),
Nitenpyram is a compound represented by the following formula (IId), clothianidin is a compound represented by the following formula (IIe), and thiamethoxam is a compound represented by the following formula (IIf).

  This neonicotinoid compound is described in, for example, JP-A-7-278094, JP-A-2-209868, JP-A-1-70467, JP-A-3-218354, JP-A-4-273863, and the like. Can be manufactured by the method described above. Commercially available compounds can also be used.

  Examples of pests for which the pest control composition of the present invention is effective include harmful insects and harmful mites. More specifically, the following are mentioned.

Hemiptera: Insects such as Laodelphax striatellus, Nilaparvata lugens, Sogatella furcifera, Nephotettix cincticeps, Nephotettimpca Leafhoppers, cotton aphids (Aphis gossypii), peach aphids (Myzus persicae), radish aphids (Brevicoryne brassicae), snowy aphids (Aphis spiraecola), tulip beetles (Macrosiphum euphorbiae), aphid sols Aphids (Rhopalosiphum padi), citrus aphids (Toxoptera citricidus), peach beetles (Hyalopterus pruni) chinensis), stink bugs (Eysarcoris parvus), stink bugs (Halyomorpha mista), stink bugs (Trialeurodes vaporariorum), tobacco whitefly (Bemisia tabaci), citrus whitefly (Dialeurodes citri), Dialeurodes citri Whitefly, Aonidiella aurantii, Sanchez scale insect (Comstockaspis perniciosa), Citrus snow scale (Unaspis citri), Ruby beetle (Ceroplastes rubens), Icerya purchasi, Fujikonae scale krak Scale insects such as Pseudoococcus longispinis and Pseudaulacaspis pentagona, bedbugs such as Cimex lectularius, bed bugs, etc.

Lepidoptera: Chilo suppressalis, Tryporyza incertulas, Cnaphalocrocis medinalis, Notarcha derogata, Plodia interpunctella, Ostrinia furiscal (Ostrinia furiscalis) Common moths such as Pediasia teterrellus, Spodoptera litura, Spodoptera exigua, Pseudaletia separata, Mamestra brassicae, Agrotis ipsilon, Agrotis ipsilon, Agrotis ipsilon, Heliotis, Helicoberpa, etc., White butterflies, such as Pieris rapae, Adoxofies, Grapholita molesta, Leguminivora glycinivorella, Azuki beetle (Matsumuraeses azukivora), Apple coca (Adoxophyes orana fasciata), Chanokokumonmonaki (Adoxophyes honmai.), Chamonaki (Homona magnanima), Midlekakumonamaki (Archips fuscocupreanus), Codling moth (Cydia pomonella), etc. ringoneella, Carposina niponensis, etc., Rionetia genus, Scots moth, Limantria, Euplottis, etc., Plutella xylostella, etc., Pectinophora gossypiella Potatoes such as potato moth (Phthorimaea operculella), hitoragers such as Hyphantria cunea, Hirosukoga such as tiger (Tinea translucens), moth (Tineola bisselliella) and the like.

Thrips of the order of thrips: Frankliniella occidentalis, Thrips parmi, Scirtothrips dorsalis, Thrips tabaci, etc.

Diptera: Culex pipiens pallens, Culex tritaeniorhynchus, Culex quinquefasciatus, etc., Aedes aegypti, Aedes albopictus, etc. Genus Anopheles, Chironomidae, Musca domestica, Muscina stabulans, and other houseflies, fly flies, fungi, flies, fly flies such as Delia platura, Delia antiqua, flies (Agromyza oryzae), rice leaf fly (Hydrellia griseola), tomato leaf fly, (Liriomyza sativae), bean leaf fly (Liriomyza trifolii), leafhopper (Chromatomyia horticola) and other leafhoppers (Chromatomyia horticola), Dacus cucurbitae) Fruit flies such as fruit flies (Ceratitis capitata), fruit flies, fruit flies such as Megaselia spiracularis, butterflies such as Clogmia albipunctata, flies such as flies, Tabanus trigonus Etc.

Coleoptera: Western corn root worms (Diabrotica virgifera virgifera), corn root worms such as Southern corn root worms (Diabrotica undecimpunctata howardi), Douganebubui (Anomala cuprea), Japanese beetle (Anomala rufocuprea), Japanese beetle (Popillia japonica) Genus, maize weevil (Sitophilus zeamais), water weevil (Lissorhoptrus oryzophilus), azuki beetle (Callosobruchuys chienensis), weevil (Echinocnemus squameus), cotton weevil (Anthonomus grandis), sweet weevil Grub beetles such as Tenebrio molitor, Tribolium castaneum,
Rice beetles (Oulema oryzae), leaf beetle (Aulacophora femoralis), leaf beetle (Phyllotreta striolata), leaf beetle (Leptinotarsa decemlineata), leaf beetle, Anthrenus verbasci (Lasioderma serricorne) and other species, Epilachna vigintioctopunctata and other epilacunas, Lyctus brunneus, pine beetle (Tomicus piniperda) and other species, and Longhorn beetles such as Anoplophora malasiaca), click beetles (Agriotes spp.), And long-horned beetle (Paederus fuscipes).

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

Lepidoptera: Cat fleas (Ctenocephalides felis), dog fleas (Ctenocephalides canis), human fleas (Pulex irritans), keops rat fleas (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.

Hymenoptera: Monomorium pharaosis, Black ants (Formica fusca japonica), Rugliari (Ochetellus glaber), Amphidia (Pristomyrmex pungens), Giant ants (Pheidole noda), Hachiriari (Acromyrmex spp.), Firesis p Such as ants, wasps, scallops, bees (Athalia rosae), Japanese bees (Athalia japonica), etc.

Cockroaches: cockroaches (Blattella germanica), black cockroach (Periplaneta fuliginosa), cockroach (Periplaneta americana), cockroach (Periplaneta brunnea), cockroaches such as cockroach (Blatta orientalis), ants (Coptotermes formosanus), American ant termite (Incisitermes minor), Daikoku termite (Cryptotermes domesticus), Taiwan termite (Odontotermes formosanus), Koshun termite (Neotermes koshunensis), Satsuma termite (Glyptotermes snakatanto) Termites (Glyptotermes fuscus), white termites (Glyptotermes kodamai), white termites (Glyptotermes kushimensis), termites (Hodotermopsis japonica), white-tailed termites (Coptotermes guangzhoensis), Rami termite Termites (Reticulitermes flaviceps amamianus), Kang Mont termites (Reticulitermes sp.), Takasago termite (Nasutitermes takasagoensis), Nitobe termites (Pericapritermes nitobei), warrior termite (Sinocapritermes mushae) termites such as such.

Acarid pests: Spider spider mites (Tetranychus urticae), Spider spider mites (Tetranychus kanzawai), Spider spider mites (Panonychus citri) Ripe spider mites (Panonychus ulmi), Spider mites (Aculops pelekassi), Rick mite Citrus (Aculops) Tomato rustic mites (Aculops lycopersici), Chinese radish mites (Calacarus carinatus), Chinese radish mites (Acaphylla theavagrans), Green rustic mites (Eriophyes chibaensis), apple rustic mites (Aculus schlechtendali), mussels moth, Scarlet mites (Brevipalpus phoenicis) and other spider mites, mosquito spider mites (Haemaphysalis longicornis), Scarlet tick (Haemaphysalis flava), Dermacentor taiwanicus, American dock tick (Dermacentorx varieties) tick such as odes ovatus), shredded tick (Ixodes persulcatus), black legged tick (Ixodes scapularis), lone star tick (Amblyomma americanum), oxid tick (Boophilus microplus), rhipicephalus sanguineus Mushroom mites such as Octodectes cynotis, mite mites such as Sacroptes scabiei, mite mites such as Demodex canis, Tyrophagus putrescentiae, mite mite such as tyrophagus similimato farinae), leopard mites such as Dermatophagoides ptrenyssnus, thorn mites such as Cheyletus malaccensis, tick mites such as nit bait, nits airum), cucumbers such as Dermanyssus gallinae, tsutsugamushi such as Leptotrombidium akamushi, spiders such as Chiracanthium japonicum and Latrodectus hasseltii.

Lip and leg class: Gezi (Thereuonema hilgendorfi), Tobismkade (Scolopendra subspinipes), etc.
Double-legged class: zelkova (Oxidus gracilis), red scallop (Nedyopus tambanus), etc.
Isopods: Armadillidium vulgare, etc.
Gastropoda: Limax marginatus, Limax flavus, etc.

The pest control composition of the present invention may be only the present organic sulfur compound and the present neonicotinoid compound, but is usually mixed with a solid carrier, a liquid carrier and / or a gaseous carrier, and if necessary, a surfactant or the like. Emulsions, oils, shampoos, flowables, powders, wettable powders, granules, pastes, microcapsules, foams, aerosols, carbon dioxide, tablets, resins It is formulated into a form such as a preparation. 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 in the total amount of the present organic sulfur compound and the present neonicotinoid 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.), pyrrolidone (N-methyl-2-pyrrolidone, N-octyl-2-pyrrolidone, etc.), propylene carbonate, ethyl lactate, 1,3-dimethyl-2-imidazolidinone, vegetable oil (soybean oil, cottonseed oil, etc.), plant essential oil ( 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.), adipic acid esters as necessary. Further, a plasticizer such as stearic acid may be added. The resin formulation is obtained by kneading the compound in the base material using a normal kneading apparatus, and then molding by injection molding, extrusion molding, press molding, etc., and if necessary, through further steps such as molding, cutting, It can be processed into resin preparations such as 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, peanut oil and the like are added.

  The pest control composition of the present invention is used, for example, by being applied directly to harmful arthropods and / or by applying to harmful habitats (plants, animal bodies, soil, etc.).

  When the pest control composition 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 in terms of the total amount of the organic sulfur compound and the neonicotinoid compound. It is. Emulsions, wettable powders, flowables, microcapsule preparations, etc. are usually diluted with water so that the total of the present organic sulfur compound and the present neonicotinoid compound is 1 to 1000 ppm, and powders, granules, etc. are usually used. Use as is. These formulations may be applied directly to plants that are 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.

  The harmful arthropod control agent of the present invention can be used in farmland such as fields, paddy fields, lawns, orchards, and without causing phytotoxicity to crops cultivated in the farmland. It may be possible to control harmful arthropods on the ground.

Specific examples of such crops include the following crops.
Agricultural crops: corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, sugar beet, rapeseed, sunflower, sugarcane, tobacco, etc.
Vegetables: Solanum vegetables (eggplants, tomatoes, peppers, peppers, potatoes, etc.), Cucurbitaceae vegetables (cucumbers, pumpkins, zucchini, watermelons, melons, etc.), cruciferous vegetables (radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage) , Mustard, broccoli, cauliflower, etc.), asteraceae vegetables (burdock, shungiku, artichoke, lettuce, etc.), liliaceae vegetables (leek, onion, garlic, asparagus), celeryaceae vegetables (carrot, parsley, celery, American scallop, etc.) ), Red crustacean vegetables (spinach, chard, etc.), perilla vegetables (perilla, mint, basil, etc.), strawberries, sweet potatoes, yam, taro, etc.
Bridegroom,
Foliage plant,
Fruit trees; pears (apples, pears, Japanese pears, quince, quince, etc.), nuclear fruits (peaches, plums, nectarines, umes, sweet cherry, apricots, prunes, etc.), citrus (satsuma mandarin, orange, lemon, lime, grapefruit) ), Nuts (chestnut, walnut, hazel, almond, pistachio, cashew nut, macadamia nut, etc.), berries (blueberry, cranberry, blackberry, raspberry, etc.), grape, oyster, olive, loquat, banana, coffee, Date palm, coconut palm, etc.
Trees other than fruit trees: Cha, mulberry, flowering trees, street trees (ash, birch, dogwood, eucalyptus, ginkgo, lilac, maple, oak, poplar, redwood, fu, sycamore, zelkova, black bean, peach tree, Tsuga, rat, pine, Spruce, yew) etc.

The above crops include HPPD inhibitors such as isoxaflutol, ALS inhibitors such as imazetapyr and thifensulfuron methyl, EPSP synthase inhibitors, glutamine synthase inhibitors, acetyl CoA carboxylase inhibitors, herbicides such as bromoxynil Also included are crops that have been rendered resistant to resistance by classical breeding methods or genetic engineering techniques.
Examples of crops to which tolerance has been imparted by classical breeding methods include, for example, imidazolinone herbicide-resistant Clearfield (registered trademark) sulfonylurea-based ALS-inhibiting types such as canola and thifensulfuron-methyl Examples include herbicide-resistant STS soybeans. Similarly, SR corn and the like are examples of crops to which tolerance has been imparted to acetyl CoA carboxylase inhibitors such as trion oxime and aryloxyphenoxypropionic acid herbicides by classical breeding methods. Crops that have been rendered tolerant to acetyl CoA carboxylase inhibitors are Proceedings of the National Academy of Sciences of the United States of America (Proc. Natl. Acad. Sci. USA) 87, 7175-7179 (1990). A mutant acetyl CoA carboxylase resistant to an acetyl CoA carboxylase inhibitor has been reported in Weed Science 53, 728-746 (2005), and the like. By introducing a mutation related to imparting resistance into a crop acetyl-CoA carboxylase, a crop resistant to the acetyl-CoA carboxylase inhibitor can be produced. Furthermore, nucleic acid introduced with a base substitution mutation represented by chimera plastic technology (Gura T. 1999. Repairing the Genome's Spelling Mistakes. Science 285: 316-318.) Is introduced into a crop cell (acetyl CoA carboxylase). By generating site-specific amino acid substitution mutations in the (herbicide target) gene, crops resistant to (acetyl CoA carboxylase inhibitor / herbicide) can be created.

  Examples of crops to which tolerance is imparted by genetic recombination technology include glyphosate and glufosinate-resistant corn varieties, such as Roundup Ready (registered trademark) and Liberty Link (registered trademark). Already sold by name.

Examples of the crops include crops that can synthesize selective toxins known in the genus Bacillus using genetic recombination techniques.
Examples of insecticidal toxins expressed in such genetically modified plants include insecticidal proteins derived from Bacillus cereus and Bacillus popillie; Cry1Ab derived from Bacillus thuringiensis , Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, etc., insecticidal proteins such as VIP1, VIP2, VIP3 or VIP3A; nematode-derived insecticidal proteins; Toxins produced by animals such as insect-specific neurotoxins; filamentous fungi toxins; plant lectins; agglutinins; trypsin inhibitors, serine protease inhibitors Agents, protease inhibitors such as patatin, cystatin, papain inhibitor; ribosome inactivating protein (RIP) such as lysine, corn-RIP, abrin, saporin, bryodin; 3-hydroxysteroid oxidase, ecdysteroid-UDP-glucosyl Steroid metabolic enzymes such as transferase and cholesterol oxidase; ecdysone inhibitor; HMG-CoA reductase; ion channel inhibitors such as sodium channel inhibitor and calcium channel inhibitor; juvenile hormone esterase; diuretic hormone receptor; stilbene synthase; Synthase; chitinase; glucanase and the like.
Further, as toxins expressed in such genetically modified crops, insecticidal proteins such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, and other insecticidal proteins such as VIP1, VIP2, VIP3 or VIP3A Also included are hybrid toxins, partially defective toxins, and modified toxins. Hybrid toxins are produced by new combinations of different domains of these proteins using recombinant technology. As a toxin lacking a part, Cry1Ab lacking a part of the amino acid sequence is known. In the modified toxin, one or more amino acids of the natural toxin are substituted.
Examples of these toxins and recombinant plants capable of synthesizing these toxins are disclosed in, for example, EP-A-0374753, WO93 / 07278, WO95 / 34656, EP-A-0427529, EP-A-451878, WO03 / 052073, etc. Are listed.
The toxins contained in these recombinant plants particularly confer resistance to Coleoptera pests, Diptera pests, and Lepidoptera pests.

  In addition, genetically modified plants that contain one or more insecticidal pest resistance genes and express one or more toxins are already known and some are commercially available. Examples of these genetically modified plants include YieldGuard (registered trademark) (a corn variety expressing Cry1Ab toxin), YieldGuard Rootworm (registered trademark) (a corn variety expressing Cry3Bb1 toxin), YieldGuard Plus (registered trademark) (maize variety expressing Cry1Ab and Cry3Bb1 toxin), Herculex I (registered trademark) (phosphino to confer resistance to Cry1Fa2 toxin and glufosinate Corn varieties expressing tricine N-acetyltransferase (PAT)), NuCOTN33B <(registered trademark)> (cotton varieties expressing Cry1Ac toxin), Volgaard I (Bollg) rd I) <registered trademark> (cotton variety expressing Cry1Ac toxin), Volgard II (registered trademark) (cotton variety expressing Cry1Ac and Cry2Ab toxin), VIPCOT <registered trademark> (expressing VIP toxin) Cotton cultivars), NewLeaf <registered trademark> (potato cultivar expressing Cry3A toxin), Natureguard Agurisure GT Advantage (NatureGuard <Agriure <registered trademark> GT Advantage> (GA21 glyphosate resistant trait), Aggresure CB Advantage (Agriure <(R)> CB Advantage) (Bt11 corn borer (CB) trait), Protector (<Trademark>), and the like.

The crops include those given the ability to produce an anti-pathogenic substance having a selective action using genetic recombination technology.
Examples of anti-pathogenic substances include PR proteins (described in PRPs, EP-A-0392225); sodium channel inhibitors, calcium channel inhibitors (virus-produced KP1, KP4, KP6 toxins, etc.) Stilbene synthase; bibenzyl synthase; chitinase; glucanase; peptide antibiotics, heterocyclic antibiotics, protein factors involved in plant disease resistance (called plant disease resistance genes) , Described in WO03 / 000906), and the like. Such anti-pathogenic substances and genetically modified plants that produce them are described in EP-A-0392225, WO95 / 33818, EP-A-0353191, and the like.

When the pest control composition of the present invention is used for prevention of epidemics, the application rate is usually 0.001 to 10 mg / m ³ in total for the present organic sulfur compound and the present neonicotinoid compound when applied to space. When applied to a plane, it is 0.001 to 100 mg / m ² . Emulsions, wettable powders, flowables, etc. are usually diluted with water so that the total concentration of the organic sulfur compound and the neonicotinoid compound is 0.01 to 10000 ppm. Agents, poison baits, etc. are usually applied as they are.

When the pest control composition 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. It can be used for animals by oral or parenteral administration. Specifically, for the purpose of systemic suppression, for example, tablets (including sugar-coated tablets and film-coated tablets), pills, capsules, granules, fine granules, powders, emulsions, suspensions , Oral preparations such as films; and injections (eg, subcutaneous injections, intravenous injections, intramuscular injections, intraperitoneal injections, drops, sustained-release injections), suppositories (eg, rectal seats) Agents, vaginal suppositories), implants (embedded tablets, molded with biodegradable polymers as base materials, encapsulated in capsules of biocompatible metals such as titanium and releasing active ingredients at a constant rate And the like) and the like. In the case of oral administration, the above preparation can be used by mixing with feed.
In the case of non-systemic suppression, for example, spraying an oil or aqueous solution, applying external preparations (eg, transdermal preparations, ointments), pour-on treatment or spot-on treatment, It is used by a method such as washing the animal or attaching the resin preparation to the animal with a collar or ear tag. The total amount of the present organic sulfur compound and the present neonicotinoid compound 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.

In the pharmaceutical dosage forms used in the above veterinary administration methods, various organic or inorganic carrier substances commonly used as pharmaceutical materials are used, and excipients, lubricants, binders, disintegrants in solid preparations; It is blended as a solvent, a solubilizing agent, a suspending agent, a tonicity agent, a buffering agent, a soothing agent and the like in a liquid preparation. If necessary, preparation additives such as preservatives, antioxidants, colorants, sweeteners and the like can also be used. Preferable examples of the excipient include lactose, sucrose, D-mannitol, D-sorbitol, starch, pregelatinized starch, dextrin, crystalline cellulose, low-substituted hydroxypropylcellulose, sodium carboxymethylcellulose, gum arabic, dextrin, pullulan , Light anhydrous silicic acid, synthetic aluminum silicate, magnesium aluminate metasilicate and the like. Preferable examples of the lubricant include magnesium stearate, calcium stearate, talc, colloidal silica and the like. Preferable examples of the binder include pregelatinized starch, sucrose, gelatin, gum arabic, methylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, sucrose, D-mannitol, trehalose, dextrin, pullulan, hydroxypropylcellulose, hydroxy Examples thereof include propylmethylcellulose and polyvinylpyrrolidone. Preferable examples of the disintegrant include lactose, sucrose, starch, carboxymethylcellulose, carboxymethylcellulose calcium, croscarmellose sodium, carboxymethylstarch sodium, light anhydrous silicic acid, low substituted hydroxypropylcellulose and the like. Preferable examples of the solvent include water for injection, physiological saline, Ringer's solution, alcohol, propylene glycol, polyethylene glycol, sesame oil, corn oil, olive oil, cottonseed oil and the like. Preferable examples of the solubilizer include polyethylene glycol, propylene glycol, D-mannitol, trehalose, benzyl benzoate, ethanol, trisaminomethane, cholesterol, triethanolamine, sodium carbonate, sodium citrate, sodium salicylate, sodium acetate. Etc. Suitable examples of the suspending agent include surfactants such as stearyltriethanolamine, sodium lauryl sulfate, laurylaminopropionic acid, lecithin, benzalkonium chloride, benzethonium chloride, glyceryl monostearate; for example, polyvinyl alcohol, polyvinyl Examples include hydrophilic polymers such as pyrrolidone, sodium carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose; polysorbates, polyoxyethylene hydrogenated castor oil, and the like. Preferable examples of the tonicity agent include sodium chloride, glycerin, D-mannitol, D-sorbitol, glucose and the like. Preferable examples of the buffer include buffers such as phosphate, acetate, carbonate and citrate. Preferable examples of the soothing agent include benzyl alcohol. Preferable examples of the preservative include p-hydroxybenzoates, chlorobutanol, benzyl alcohol, phenethyl alcohol, dehydroacetic acid, sorbic acid and the like. Preferable examples of the antioxidant include sulfite and ascorbate. Suitable examples of the coloring agent include water-soluble edible tar dyes (eg, edible dyes such as edible red Nos. 2 and 3, edible yellows 4 and 5, edible blue Nos. 1 and 2, and water-insoluble lake dyes ( Examples thereof include aluminum salts of the water-soluble edible tar pigments, natural pigments (eg, β-carotene, chlorophyll, bengara, etc.).
Injectables contain active ingredients as dispersants (eg, polysorbate 80, polyoxyethylene hydrogenated castor oil 60, polyethylene glycol, carboxymethyl cellulose, sodium alginate, etc.), preservatives (eg, methyl paraben, propyl paraben, benzyl alcohol, Chlorobutanol, phenol, etc.), isotonic agents (eg, sodium chloride, glycerin, D-mannitol, D-sorbitol, glucose, etc.) and other aqueous solvents (eg, distilled water, physiological saline, Ringer's solution, etc.) or oily It is produced by dissolving, suspending or emulsifying in a solvent (eg, olive oil, sesame oil, cottonseed oil, vegetable oil such as corn oil, propylene glycol, etc.). At this time, additives such as a solubilizing agent (eg, sodium salicylate, sodium acetate, etc.), a stabilizer (eg, human serum albumin), a soothing agent (eg, benzyl alcohol, etc.) may be used as desired. The injection solution is usually filled in a suitable ampoule.
The pest control composition of the present invention can also be used as a sustained-release preparation. Examples of the sustained-release preparation include microcapsules (for example, microspheres) produced by an underwater drying method (o / w method, w / o / w method, etc.), a phase separation method, a spray drying method, or a method equivalent thereto. -Microcapsules, microparticles, etc.), and those molded with biocompatible polymers.

  The pest control composition of the present invention is mixed with other insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil improvers, animal feeds, etc. Or it can also use together.

Hereinafter, the present invention will be described in more detail by reference production examples of the present organic sulfur compound, examples of the chain organic sulfur compound, formulation examples and test examples of the pest control composition of the present invention. It is not limited to.
The abbreviations used in this specification have the following meanings.
Me: methyl group, Et: ethyl group, Bn: benzyl group, Ph: phenyl group, Ts: p-toluenesulfonyl group, Ac: acetyl group.
First, the manufacture example of this organic sulfur compound is shown in a reference manufacture example.

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．３１（ｄ，２Ｈ）、７．２３（ｄ，２Ｈ）、３．７０（ｓ，２Ｈ）、２．５５−２．５９（ｍ，２Ｈ）、２．２４−２．３６（ｍ，２Ｈ） Reference 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 (hereinafter referred to as the present organic sulfur compound (1)) represented by the following formula. It was.
This organic sulfur compound (1)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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 (hereinafter referred to as the present organic sulfur compound (2)) represented by the following formula. It was.
This organic sulfur compound (2)

_{^{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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．２７（ｄｄ，２Ｈ）、７．０２（ｄｄ，２Ｈ）、３．７１（ｓ，２Ｈ）、２．５５−２．５９（ｍ，２Ｈ）、２．２４−２．３６（ｍ，２Ｈ） Reference 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 (hereinafter referred to as the present organic sulfur compound (3)) represented by the following formula. It was.
This organic sulfur compound (3)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．４５（ｄ，２Ｈ）、７．１６（ｄ，２Ｈ）、３．６８（ｄｄ，２Ｈ）、２．５４−２．５８（ｍ，２Ｈ）、２．２４−２．３８（ｍ，２Ｈ） Reference 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 (hereinafter referred to as the present organic sulfur compound (4)) represented by the following formula. It was.
This organic sulfur compound (4)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．６５（ｄ，２Ｈ）、７．０６（ｄ，２Ｈ）、３．６８（ｓ，２Ｈ）、２．５４−２．５８（ｍ，２Ｈ）、２．２４−２．３６（ｍ，２Ｈ） Reference production example 5
Reference production 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 Example 3, 0.75 g of 4-iodobenzyl = 3,3,3-trifluoropropyl sulfide (hereinafter referred to as the present organic sulfur compound (5)) represented by the following formula was obtained. .
This organic sulfur compound (5)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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 (hereinafter referred to as the present organic sulfur compound (6)) represented by the following formula. It was.
This organic sulfur compound (6)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference production example 7
Reaction time with 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 Reference Production Example 3, except that the time was 0.5 hours, 4-nitrobenzyl = 3,3,3-trifluoropropyl sulfide (hereinafter referred to as the present organic sulfur compound (7 ) 0.19 g was obtained.
This organic sulfur compound (7)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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) (4-trifluoromethyl) benzyl = 3,3,3-trifluoropropyl sulfide (hereinafter referred to as the following formula) according to the method described in Reference Production Example 3 except that the reaction time was 10 hours. 0.09 g of the organic sulfur compound (8) is obtained.
This organic sulfur compound (8)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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, (3-trifluoromethyl) benzyl = 3,3,3-trifluoropropyl = sulfide (hereinafter referred to as the present organic sulfur compound (9 ) 0.60 g was obtained.
This organic sulfur compound (9)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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 4- (1,1,2,2,2-pentafluoroethyl) benzyl represented by the following formula according to the method described in Reference Production Example 3 using 0.2 ml of (28% methanol solution) , 3-trifluoropropyl sulfide (0.24 g) (hereinafter referred to as the present organic sulfur compound (10)) was obtained.
This organic sulfur compound (10)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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 (hereinafter referred to as the present organic sulfur compound (11)) represented by the following formula. It was.
This organic sulfur compound (11)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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 Reference Production Example 3, 4- (trifluoromethoxy) benzyl = 3,3,3-trifluoropropyl sulfide represented by the following formula (hereinafter referred to as the present organic sulfur compound (12)) .) 0.37 g was obtained.
This organic sulfur compound (12)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．１８−７．２５（ｍ，４Ｈ）、３．７０（ｓ，２Ｈ）、２．５５−２．５９（ｍ，２Ｈ）、２．５０（ｓ，３Ｈ）、２．２４−２．４６（ｍ，２Ｈ） Reference 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) According to the method described in Reference Production Example 3 except that the reaction time was 3 days, 4- (methylthio) benzyl = 3,3,3-trifluoropropyl sulfide (hereinafter referred to as the present organic sulfur compound) represented by the following formula: (Described as (13).) 0.39 g was obtained.
This organic sulfur compound (13)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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) In accordance with the method described in Reference Production Example 3 except that the reaction time was 10 hours, 4- (trifluoromethylthio) benzyl = 3,3,3-trifluoropropyl sulfide (hereinafter referred to as the following formula) This organic sulfur compound (14) is described.) 0.22 g was obtained.
This organic sulfur compound (14)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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 Reference Production Example 3 except that the reaction time was set to 1 hour, 4- (methylsulfonyl) benzyl = 3,3,3-trifluoropropyl sulfide (hereinafter referred to as this organic compound) represented by the following formula: 0.37 g of the sulfur compound (15) was obtained.
This organic sulfur compound (15)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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, and 4-chloro-3-fluorobenzyl = 3,3,3-trifluoropropyl sulfide (hereinafter referred to as the present organic sulfur compound (16)) represented by the following formula 1 .24 g was obtained.
This organic sulfur compound (16)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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) In accordance with the method described in Reference Production Example 3 except that the reaction time was 1 hour, 4-chloro-2-fluorobenzyl = 3,3,3-trifluoropropyl sulfide (hereinafter referred to as the following formula). 0.25 g of this organic sulfur compound (17) is obtained.
This organic sulfur compound (17)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）６．９７（ｄ，２Ｈ）、３．６８（ｓ，２Ｈ）、２．５７−２．６５（ｍ，２Ｈ）、２．２８−２．４０（ｍ，２Ｈ） Reference 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, and 4-chloro-3,5-difluorobenzyl = 3,3,3-trifluoropropyl sulfide (hereinafter referred to as the present organic sulfur compound (18)) represented by the following formula. ) 0.42 g was obtained.
This organic sulfur compound (18)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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, and 3,4-dichlorobenzyl = 3,3,3-trifluoropropyl sulfide (hereinafter referred to as the present organic sulfur compound (19)) represented by the following formula: 1.14 g Got.
This organic sulfur compound (19)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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, and 4-chloro-3- (trifluoromethyl) benzyl = 3,3,3-trifluoropropyl sulfide (hereinafter referred to as the present organic sulfur compound (20)) represented by the following formula: 0.42 g was obtained.
This organic sulfur compound (20)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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, and 3,4-difluorobenzyl = 3,3,3-trifluoropropyl sulfide (hereinafter referred to as the present organic sulfur compound (21)) represented by the following formula: 0.46 g Got.
This organic sulfur compound (21)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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, and 3-chloro-4-fluorobenzyl = 3,3,3-trifluoropropyl sulfide (hereinafter referred to as the present organic sulfur compound (22)) represented by the following formula: 0 .45 g was obtained.
This organic sulfur compound (22)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）６．９７（ｄｄｄ，２Ｈ）、３．６６（ｓ，２Ｈ）、２．５７−２．６１（ｍ，２Ｈ）、２．２７−２．３９（ｍ，２Ｈ） Reference 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, and 3,4,5-trifluorobenzyl = 3,3,3-trifluoropropyl sulfide represented by the following formula (hereinafter referred to as the present organic sulfur compound (23)). 1.66 g was obtained.
This organic sulfur compound (23)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）３．７９（ｄ，２Ｈ）、２．６８−２．７２（ｍ，２Ｈ）、２．３５−２．５３（ｍ，２Ｈ） Reference 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 (hereinafter referred to as the following formula) according to the method described in Reference Production Example 3. This is referred to as the present organic sulfur compound (24).) 0.29 g was obtained.
This organic sulfur compound (24)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 3.79 (d, 2H), 2.68-2.72 (m, 2H), 2.35-2.53 (m, 2H)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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, and 4-bromo-3-fluorobenzyl = 3,3,3-trifluoropropyl = sulfide (hereinafter referred to as the present organic sulfur compound (25)) represented by the following formula 1 .88 g was obtained.
This organic sulfur compound (25)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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, and 4-cyano-3-fluorobenzyl = 3,3,3-trifluoropropyl sulfide (hereinafter referred to as the present organic sulfur compound (26)) represented by the following formula: 0 0.07 g was obtained.
This organic sulfur compound (26)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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 (hereinafter referred to as the present organic sulfur compound (27)) represented by the following formula.
This organic sulfur compound (27)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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 (hereinafter referred to as the present organic sulfur compound (28)) represented by the following formula.
This organic sulfur compound (28)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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. According to the method described in Reference Production Example 1, 4-chlorobenzyl = 4,4,4-trifluorobutyl = sulfide (hereinafter referred to as the present organic sulfur compound (29)) represented by the following formula: 0.31 g Got.
This organic sulfur compound (29)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference 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 Reference Production Example 1 except that the period was set to 1 day, 4-chlorobenzyl = 3,3,4,4,4-pentafluorobutyl = sulfide (hereinafter referred to as the present organic sulfur compound (30 ) 0.45 g was obtained.
This organic sulfur compound (30)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference production example 31
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 Except for the time, 1- (4-chlorophenyl) ethyl = 3,3,3-trifluoropropyl sulfide represented by the following formula (hereinafter referred to as the present organic sulfur compound (31) is used in accordance with the method described in Reference Production Example 1. ) 0.12 g was obtained.
This organic sulfur compound (31)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference Production Example 32
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, and 1- (3,4,5-trifluorophenyl) ethyl = 3,3,3-trifluoropropyl sulfide (hereinafter referred to as the present organic sulfur compound (32 ) 0.40 g was obtained.
This organic sulfur compound (32)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference Production Example 33
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, and 1- (4-chlorophenyl) propyl = 3,3,3-trifluoropropyl sulfide (hereinafter referred to as the present organic sulfur compound (33)) represented by the following formula: 0 .25 g was obtained.
This organic sulfur compound (33)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference Production Example 34
4-Chlorobenzyl = 3,3,3-trifluoropropyl sulfide 0.30 g was dissolved in 10 ml of tetrahydrofuran, and 0.6 ml of lithium diisopropylamide (2M-tetrahydrofuran / n-heptane solution) was added thereto 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, and 1- (4-chlorophenyl) butyl = 3,3,3-trifluoropropyl sulfide (hereinafter referred to as the present organic sulfur compound (34)) represented by the following formula: 0 .10 g was obtained.
This organic sulfur compound (34)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference Production Example 35
Using 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 (1- (4-chlorophenyl) -2-methyl) propyl = 3,3,3-trifluoropropyl represented by the following formula in accordance with the method described in Reference Production Example 35 except that the reaction time was changed to 4 hours. = 0.12 g of sulfide (hereinafter referred to as the present organic sulfur compound (35)) was obtained.
This organic sulfur compound (35)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference Production Example 36
Dissolve 0.30 g of 2-bromo-2- (4-chlorophenyl) acetonitrile and 0.30 g of S- (3,3,3-trifluoropropyl) = benzenethioate in 10 ml of methanol, and add sodium methoxide at -78 ° C. (28% methanol solution) 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, and 2- (4-chlorophenyl) -2- (3,3,3-trifluoropropylthio) acetonitrile (hereinafter referred to as the present organic sulfur compound (36)) represented by the following formula: .) 0.04 g was obtained.
This organic sulfur compound (36)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference Production Example 37
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-trifluoro represented by the following formula according to the method described in Reference Production Example 1 except that the reaction time was 10 hours. 0.20 g of propyl sulfide (hereinafter referred to as the present organic sulfur compound (37)) was obtained.
This organic sulfur compound (37)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．４０（ｄ，２Ｈ）、７．２４（ｄ，２Ｈ）、３．９８（ｄｄ，２Ｈ）、２．５２−２．８４（ｍ，４Ｈ） Reference Production Example 38
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 (hereinafter referred to as the present organic sulfur compound (38)) represented by the following formula. It was.
This organic sulfur compound (38)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference Production Example 39
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. Further, the crystals were washed with water, dried under reduced pressure for 1 day, and 4-chlorobenzyl = 3,3,3-trifluoropropylsulfone (hereinafter referred to as the present organic sulfur compound (39)) represented by the following formula. ) 0.55 g was obtained.
This organic sulfur compound (39)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，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） Reference Production Example 40
According to the method described in Reference Production Example 40, 5 ml of acetic acid, 0.10 g of 4- (trifluoromethyl) benzyl = 3,3,3-trifluoropropyl = sulfide and 5 ml of peracetic acid solution are used. 0.11 g of 4- (trifluoromethyl) benzyl = 3,3,3-trifluoropropyl = sulfone (hereinafter referred to as the present organic sulfur compound (40)) was obtained.
This organic sulfur compound (40)

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)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．５６−７．６５（２H，ｍ）、６．５７（１H，ｂｓ）、５．９１（１H，ｂｓ）、３．５６−３．７３（２H，ｍ）、３．２３−３．４８（２H，ｍ） Reference Production Example 41
Dissolve 0.5 g of methyl 2-fluoro-2- (3,4,5-trifluorophenyl) -2- (3,3,3-trifluoropropylsulfonyl) acetate in 20 ml of methanol and add ammonia (7M- (Methanol solution) 0.6 mL was added and stirred at the same temperature for 14 hours. The reaction mixture was concentrated under reduced pressure, and the resulting residue was subjected to column chromatography to give 2-fluoro-2- (3,3,3-trifluoropropylsulfonyl) -2- (3,4) represented by the following formula. , 5-trifluorophenyl) acetamide (hereinafter referred to as the present organic sulfur compound (41)) 0.35 g was obtained.
This organic sulfur compound (41)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.56-7.65 (2H, m), 6.57 (1H, bs), 5.91 (1H, bs), 3.56- 3.73 (2H, m), 3.23-3.48 (2H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．３６（２H，ｄｄ）、６．４１（１H，ｂｓ）、６．１５（１H，ｂｓ）、３．２６−３．５８（２H，ｍ）、２．５０−２．７４（２H，ｍ）２．０８（３H，ｓ） Reference Production Example 42
Dissolve 1.0 g of methyl 2- (3,4,5-trifluorophenyl) -2- (3,3,3-trifluoropropylsulfonyl) propanoate in 2.0 ml of methanol and add ammonia (7M-methanol at room temperature). Solution) 8.0 mL was added and stirred at the same temperature for 48 hours. The reaction mixture was concentrated under reduced pressure, and the resulting residue was subjected to column chromatography to give 2- (3,4,5-trifluorophenyl) -2- (3,3,3-trifluoro represented by the following formula. 0.20 g of propylsulfonyl) propanamide (hereinafter referred to as the present organic sulfur compound (42)) was obtained.
This organic sulfur compound (42)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.36 (2H, dd), 6.41 (1H, bs), 6.15 (1H, bs), 3.26-3.58 ( 2H, m), 2.50-2.74 (2H, m) 2.08 (3H, s)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．７４（１H，ｄｄ）、７．６４（１H，ｄｄ）、７．５５（１H，ｄｄ）、６．６０（１H、ｂｓ）、６．０２（１H，ｂｓ）、３．２１−３．４６（２H，ｍ）、２．４９−２．６９（２H，ｍ） Reference Production Example 43
Dissolve 0.8 g of methyl 2- (4-chloro-3-fluorophenyl) -2-fluoro-2- (3,3,3-trifluoropropylsulfonyl) acetate in 20 ml of methanol and add ammonia (7M-methanol at room temperature). Solution) 1.5 mL was added and stirred at the same temperature for 16 hours. The reaction mixture was concentrated under reduced pressure, and the obtained residue was subjected to column chromatography to give 2- (4-chloro-3-fluorophenyl) -2-fluoro-2- (3, 3, 3 -Trifluoropropylsulfonyl) acetamide (hereinafter referred to as the present organic sulfur compound (43)) 0.60 g was obtained.
This organic sulfur compound (43)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.74 (1H, dd), 7.64 (1H, dd), 7.55 (1H, dd), 6.60 (1H, bs) 6.02 (1H, bs), 3.21-3.46 (2H, m), 2.49-2.69 (2H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．８６（２H，ｄ）、７．４９（２H，ｄ）、６．５７（１H，ｂｓ）、５．９２（１H，ｂｓ）、３．２０−３．４５（２H，ｍ）、２．４３−２．６８（２H，ｍ） Reference Production Example 44
Dissolve 0.6 g of methyl 2- (4-chlorophenyl) -2-fluoro-2- (3,3,3-trifluoropropylsulfonyl) acetate in 30 ml of methanol, and add 0.7 ml of ammonia (7 M methanol solution) at room temperature. And stirred at the same temperature for 10 hours. The reaction mixture was concentrated under reduced pressure, and the resulting residue was subjected to column chromatography to give 2- (4-chlorophenyl) -2-fluoro-2- (3,3,3-trifluoropropylsulfonyl) represented by the following formula. ) Acetamide (hereinafter referred to as the present organic sulfur compound (44)) 0.40 g was obtained.
This organic sulfur compound (44)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.86 (2H, d), 7.49 (2H, d), 6.57 (1H, bs), 5.92 (1H, bs) 3.20-3.45 (2H, m), 2.43-2.68 (2H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）８．０６（２H，ｄ）、７．７８（２H，ｄ）６．５８（１H，ｂｓ）、５．９２（１H，ｂｓ）、３．２２−３．４８（２H，ｍ）、２．５２−２．６８（２H，ｍ） Reference Production Example 45
Dissolve 0.4 g of methyl 2-fluoro-2- (4-trifluoromethylphenyl) -2- (3,3,3-trifluoropropylsulfonyl) acetate in 30 ml of methanol and add ammonia (7M methanol solution) at room temperature. 0.4 mL was added and stirred at the same temperature for 4 days. The reaction mixture was concentrated under reduced pressure, and the resulting residue was subjected to column chromatography to give 2-fluoro-2- (3,3,3-trifluoropropylsulfonyl) -2- (4-trimethyl) represented by the following formula. 0.25 g of fluoromethylphenyl) acetamide (hereinafter referred to as the present organic sulfur compound (45)) was obtained.
This organic sulfur compound (45)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 8.06 (2H, d), 7.78 (2H, d) 6.58 (1H, bs), 5.92 (1H, bs), 3.22-3.48 (2H, m), 2.52-2.68 (2H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．３６−７．３４ （４H，ｍ）， ６．３０ （１H， bｓ）， ５．８９ （１H， bｓ）, ４．５４ （１H，ｓ），２．８１−２．６９ （２H，ｍ），２．４６−２．３１ （２H， m）. Reference Production Example 46
1.69 g of 2- (4-chlorophenyl) -2- (3,3,3-trifluoropropylsulfanyl) acetic acid and 0.81 g of thionyl chloride are dissolved in 15 mL of toluene, and one drop of N, N-dimethylformamide is added at room temperature. After the addition, the mixture was stirred at 80 ° C. for 1 hour. After concentrating the reaction mixture, the residue was dissolved in 10 mL of tetrahydrofuran, and 4.0 mL of ammonia (28% aqueous solution) was added at room temperature. After stirring at the same temperature for 0.5 hour, the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure, and the obtained residue was subjected to silica gel column chromatography to give 2- (4-chlorophenyl) -2- (3, 3, 3 -Trifluoropropylsulfanyl) acetamide (hereinafter referred to as the present organic sulfur compound (46)) 1.52 g was obtained.
This organic sulfur compound (46)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.36-7.34 (4H, m), 6.30 (1H, bs), 5.89 (1H, bs), 4.54 ( 1H, s), 2.81-2.69 (2H, m), 2.46-2.31 (2H, m).

¹Ｈ−ＮＭＲ（DMSO−D₆，ＴＭＳ）：δ（ｐｐｍ）７．７６ （１H， ｂｓ）， ７．６４−７．６１ （２H，ｍ）， ７．５６−７．５３ （２H，ｍ）， ５．４２ （１H，ｓ）， ３．５７−３．５４ （１H，ｍ）， ３．３３−３．２９ （１H，ｍ），２．８１−２．５６ （２H， m）． Reference Production Example 47
0.40 g of 2- (4-chlorophenyl) -2- (3,3,3-trifluoropropylsulfanyl) acetamide is dissolved in 10 mL of chloroform, and 0.76 g of meta-chloroperbenzoic acid (67%) is added at room temperature. . The mixture was stirred at room temperature for 3 hours and then refluxed for 10 hours. The resulting reaction mixture was washed successively with aqueous sodium sulfite solution and saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography, and 2- (4-chlorophenyl) -2- (3,3,3-trifluoropropylsulfonyl) acetamide (hereinafter referred to as the present organic sulfur compound (47) represented by the following formula: ) 0.30 g was obtained.
This organic sulfur compound (47)

¹ H-NMR (DMSO-D ₆ , TMS): δ (ppm) 7.76 (1H, bs), 7.64-7.61 (2H, m), 7.56-7.53 (2H, m ), 5.42 (1H, s), 3.57-3.54 (1H, m), 3.33-3.29 (1H, m), 2.81-2.56 (2H, m).

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．６１ （２H， d）， ７．４４ （２H， d）， ６．６７ （１H， ｂｓ）， ５．７７ （１H， ｂｓ）， ４．１３ （１H， d）， ３．９３−３．８５ （１H，ｍ）， ３．５６−３．４８ （１H，ｍ）， ３．４１ （１H， d），２．８３−２．７６ （２H， m） Reference production example 48
Dissolve 0.33 g of methyl 2-chloro-3- (4-trifluoromethylphenyl) -2- (3,3,3-trifluoropropylsulfonyl) propanoate in 3.0 ml of methanol and add ammonia (7M- Methanol solution) 1.0 mL was added and stirred at the same temperature for 28 hours. The reaction mixture was concentrated under reduced pressure, and the resulting residue was subjected to column chromatography to give 2-chloro-3- (4-trifluoromethylphenyl) -2- (3,3,3-trimethyl represented by the following formula. 0.20 g of fluoropropylsulfonyl) propanamide (hereinafter referred to as the present organic sulfur compound (48)) was obtained.
This organic sulfur compound (48)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.61 (2H, d), 7.44 (2H, d), 6.67 (1H, bs), 5.77 (1H, bs) 4.13 (1H, d), 3.93-3.85 (1H, m), 3.56-3.48 (1H, m), 3.41 (1H, d), 2.83-2 .76 (2H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．６１−７．５９ （２H，ｍ）， ７．５２−７．４５ （２H，ｍ）， ６．６７ （１H， ｂｓ）， ５．８９ （１H， ｂｓ）， ４．１３ （１H， ｄ）， ３．９１−３．８７ （１H，ｍ）， ３．５６−３．４８ （１H，ｍ）， ３．４１ （１H， ｄ），２．８１−２．７７ （２H， m） Reference Production Example 49
0.23 g of methyl 2-chloro-3- (3-trifluoromethylphenyl) -2- (3,3,3-trifluoropropylsulfonyl) propanoate is dissolved in 3.0 ml of methanol, and ammonia (7M- (Methanol solution) 0.8 mL was added and stirred at the same temperature for 2 hours. The reaction mixture was concentrated under reduced pressure, and the resulting residue was subjected to column chromatography to give 2-chloro-3- (3-trifluoromethylphenyl) -2- (3,3,3-trimethyl represented by the following formula. 0.13 g of fluoropropylsulfonyl) propanamide (hereinafter referred to as the present organic sulfur compound (49)) was obtained.
This organic sulfur compound (49)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.61-7.59 (2H, m), 7.52-7.45 (2H, m), 6.67 (1H, bs), 5.89 (1H, bs), 4.13 (1H, d), 3.91-3.87 (1H, m), 3.56-3.48 (1H, m), 3.41 (1H, d), 2.81-2.77 (2H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．７２ （１H， ｄ）， ７．５２−７．５０ （１H，ｍ）， ７．４５−７．４３ （２H，ｍ）， ６．９５ （１H， ｂｓ）， ６．４１ （１H， ｂｓ）， ４．２８ （１H， ｄ）， ３．８７−３．８０ （２H，ｍ）， ３．５８−３．５０ （１H，ｍ），２．８２−２．７６ （２H， m） Reference production example 50
0.61 g of methyl 2-chloro-3- (2-trifluoromethylphenyl) -2- (3,3,3-trifluoropropylsulfonyl) propanoate is dissolved in 3.0 ml of methanol, and ammonia (7M- (Methanol solution) 5.2 mL was added and stirred at the same temperature for 2 hours. The reaction mixture was concentrated under reduced pressure, and the resulting residue was subjected to column chromatography to give 2-chloro-3- (2-trifluoromethylphenyl) -2- (3,3,3-trimethyl represented by the following formula. 0.20 g of fluoropropylsulfonyl) propanamide (hereinafter referred to as the present organic sulfur compound (50)) was obtained.
This organic sulfur compound (50)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.72 (1H, d), 7.52-7.50 (1H, m), 7.45-7.43 (2H, m), 6.95 (1H, bs), 6.41 (1H, bs), 4.28 (1H, d), 3.87-3.80 (2H, m), 3.58-3.50 (1H, m), 2.82-2.76 (2H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）８．６６（１Ｈ，ｄ），７．８５（１Ｈ，ｄｄ），７．６７（１Ｈ，ｄ），３．８０（２Ｈ，ｓ），２．６０−２．６４（２Ｈ，ｍ），２，３１−２．４３（２Ｈ，ｍ） Reference Production Example 51
In 10 mL of methanol, 200 mg of 5-chloromethyl-2-trifluoromethylpyridine and 240 mg of S- (3,3,3-trifluoropropyl) benzenethioate were dissolved, and sodium methoxide (28% methanol solution) 0. 2 mL was added dropwise. 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 dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to column chromatography, and 2-trifluoromethyl-5- (3,3,3-trifluoropropylsulfanylmethyl) pyridine (hereinafter referred to as the present organic sulfur compound (51)) represented by the following formula: 230 mg was obtained.
This organic sulfur compound (51)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 8.66 (1H, d), 7.85 (1H, dd), 7.67 (1H, d), 3.80 (2H, s) 2.60-2.64 (2H, m), 2, 31-2.43 (2H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）８．７５（１Ｈ，ｄ），８．０３（１Ｈ，ｄｄ），７．７９（１Ｈ，ｄ），４．３８（２Ｈ，ｓ），３．１７−３．２１（２Ｈ，ｍ），２，６４−２．７６（２Ｈ，ｍ） Reference Production Example 52
In 20 mL of methanol, 300 mg of 5-chloromethyl-2-trifluoromethylpyridine and 359 mg of S- (3,3,3-trifluoropropyl) benzenethioate were dissolved, and sodium methoxide (28% methanol solution) 0. 3 mL was added dropwise. After stirring for 18 hours at the same temperature, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with chloroform. The organic layer was concentrated under reduced pressure, and the resulting residue was dissolved in 10 mL of chloroform, and 5 mL of peracetic acid (30% acetic acid solution) was added dropwise at room temperature. After stirring at the same temperature for 4 hours, saturated sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to column chromatography, and 2-trifluoromethyl-5- (3,3,3-trifluoropropanesulfonylmethyl) pyridine (hereinafter referred to as the present organic sulfur compound (52)) represented by the following formula: 180 mg was obtained.
This organic sulfur compound (52)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 8.75 (1H, d), 8.03 (1H, dd), 7.79 (1H, d), 4.38 (2H, s) 3.17-3.21 (2H, m), 2,64-2.76 (2H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）８．６８（１Ｈ，ｓ），７．８９（１Ｈ，ｄ），７．６８（１Ｈ，ｄ），４．０６（１Ｈ，ｑ），２．５２（２Ｈ，ｔ），２．２３−２．３７（２Ｈ，ｍ），１．６３（３Ｈ，ｄ） Reference Production Example 53
In 50 mL of methanol, 1.12 g of 5- (1-bromoethyl) -2-trifluoromethylpyridine and 1.03 g of S- (3,3,3-trifluoropropyl) benzenethioate are dissolved, and sodium methoxide ( 28% methanol solution) 0.87 mL was added dropwise. After stirring at the same temperature for 10 hours, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to column chromatography, and 2-trifluoromethyl-5- [1- (3,3,3-trifluoropropylsulfanyl) ethyl] pyridine (hereinafter referred to as the present organic sulfur compound) represented by the following formula: (Indicated as (53).) 1.00 g was obtained.
This organic sulfur compound (53)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 8.68 (1H, s), 7.89 (1H, d), 7.68 (1H, d), 4.06 (1H, q) , 2.52 (2H, t), 2.23-2.37 (2H, m), 1.63 (3H, d)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）８．７５（１Ｈ，ｓ），８．０６（１Ｈ，ｄｄ），７．７８（１Ｈ，ｄ），４．３５（１Ｈ，ｑ），２．９６−３．１３（２Ｈ，ｍ），２．５５−２．７３（２Ｈ，ｍ），１．８８（３Ｈ，ｄ） Reference production example 54
0.8 g of the organic sulfur compound (3) was dissolved in 30 mL of chloroform, and 5 mL of peracetic acid (30% acetic acid solution) was added dropwise at room temperature. After stirring at the same temperature for 10 hours, a saturated sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to column chromatography, and 2-trifluoromethyl-5- [1- (3,3,3-trifluoropropanesulfonyl) ethyl] pyridine (hereinafter referred to as the present organic sulfur compound) represented by the following formula: (Described as (54).) 0.64 g was obtained.
This organic sulfur compound (54)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 8.75 (1H, s), 8.06 (1H, dd), 7.78 (1H, d), 4.35 (1H, q) 2.96-3.13 (2H, m), 2.55-2.73 (2H, m), 1.88 (3H, d)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）８．４９（１Ｈ，ｄ），７．６６（１Ｈ，ｄｄ），７．３２（１Ｈ，ｄ），３．８３（２Ｈ，ｓ），２．６３−２．６６（２Ｈ，ｍ），２，３２−２．４３（２Ｈ，ｍ） Reference production example 55
In 20 mL of methanol, 500 mg of 2-bromomethyl-5-chloropyridine and 567 mg of S- (3,3,3-trifluoropropyl) benzenethioate are dissolved, and 0.5 mL of sodium methoxide (28% methanol solution) is added dropwise at room temperature. did. After stirring at the same temperature for 24 hours, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue is subjected to column chromatography and described as 5-chloro-2- (3,3,3-trifluoropropylsulfanylmethyl) pyridine (hereinafter referred to as the present organic sulfur compound (55)) represented by the following formula. ) 500 mg was obtained.
This organic sulfur compound (55)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 8.49 (1H, d), 7.66 (1H, dd), 7.32 (1H, d), 3.83 (2H, s) 2.6-2.66 (2H, m), 2, 32-2.43 (2H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）８．４８（１Ｈ，ｄ），７．６７（１Ｈ，ｄｄ），７．３５（１Ｈ，ｄ），４．０９（１Ｈ，ｑ），２．５１−２．５７（２Ｈ，ｍ），２．１９−２．４０（２Ｈ，ｍ），１．６１（３Ｈ，ｄ） Reference production example 56
In 20 mL of methanol, 435 mg of 2- (1-bromoethyl) -5-chloropyridine and 462 mg of S- (3,3,3-trifluoropropyl) benzenethioate were dissolved, and sodium methoxide (28% methanol solution) was added at room temperature. 4 mL was added dropwise. After stirring at the same temperature for 10 hours, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to column chromatography, and 5-chloro-2- [1- (3,3,3-trifluoropropylsulfanyl) ethyl] pyridine represented by the following formula (hereinafter, this organic sulfur compound (56 ) 300 mg was obtained.
This organic sulfur compound (56)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 8.48 (1H, d), 7.67 (1H, dd), 7.35 (1H, d), 4.09 (1H, q) 2.51-2.57 (2H, m), 2.19-2.40 (2H, m), 1.61 (3H, d)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）８．８０（１Ｈ，ｓ），７．９２（１Ｈ，ｄｄ），７．５０（１Ｈ，ｄ），３．９１（２Ｈ，ｓ），２．６５−２．６９（２Ｈ，ｍ），２，３４−２．４６（２Ｈ，ｍ） Reference Production Example 57
Dissolve 500 mg of 2-bromomethyl-5-trifluoromethylpyridine and 488 mg of S- (3,3,3-trifluoropropyl) benzenethioate in 20 mL of methanol, and add 0.4 mL of sodium methoxide (28% methanol solution) at room temperature. Was dripped. After stirring at the same temperature for 10 minutes, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to column chromatography, and 5-trifluoromethyl-2- (3,3,3-trifluoropropylsulfanylmethyl) pyridine (hereinafter referred to as the present organic sulfur compound (57)) represented by the following formula: 400 mg was obtained.
This organic sulfur compound (57)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 8.80 (1H, s), 7.92 (1H, dd), 7.50 (1H, d), 3.91 (2H, s) , 2.65-2.69 (2H, m), 2, 34-2.46 (2H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）８．７９（１Ｈ，ｄ），７．９３（１Ｈ，ｄｄ），７．５４（１Ｈ，ｄ），４．１７（１Ｈ，ｑ），２．５５−２．５９（２Ｈ，ｍ），２．３１−２．３９（２Ｈ，ｍ），１．６５（３Ｈ，ｄ） Reference Production Example 58
Dissolve 452 mg of 2- (1-bromoethyl) -5-trifluoromethylpyridine and 417 mg of S- (3,3,3-trifluoropropyl) benzenethioate in 20 mL of methanol, and add sodium methoxide (28% methanol solution) at room temperature. ) 0.4 mL was added dropwise. After stirring at the same temperature for 1 hour, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to column chromatography, and 5-trifluoromethyl-2- [1- (3,3,3-trifluoropropylsulfanyl) ethyl] pyridine (hereinafter referred to as the present organic sulfur compound) represented by the following formula: (Indicated as (58).) 760 mg was obtained.
This organic sulfur compound (58)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 8.79 (1H, d), 7.93 (1H, dd), 7.54 (1H, d), 4.17 (1H, q) 2.55-2.59 (2H, m), 2.31-2.39 (2H, m), 1.65 (3H, d)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）８．８８（１Ｈ，ｓ），８．０２（１Ｈ，ｄｄ），７．６４（１Ｈ，ｄ），４．５２（１Ｈ，ｑ），３．１１−３．２４（２Ｈ，ｍ），２．５４−２．７０（２Ｈ，ｍ），１．９０（３Ｈ，ｄ） Reference Production Example 59
680 mg of this organic sulfur compound (58) was dissolved in 30 mL of chloroform, and 851 mg of meta-chloroperbenzoic acid was added at room temperature. After stirring at the same temperature for 20 hours, a saturated sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to column chromatography, and 5-trifluoromethyl-2- [1- (3,3,3-trifluoropropanesulfonyl) ethyl] pyridine (hereinafter referred to as the present organic sulfur compound) represented by the following formula: (Indicated as (59).) 580 mg was obtained.
This organic sulfur compound (59)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 8.88 (1H, s), 8.02 (1H, dd), 7.64 (1H, d), 4.52 (1H, q) 3.11-3.24 (2H, m), 2.54-2.70 (2H, m), 1.90 (3H, d)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）８．８６（２Ｈ，ｓ），３．８０（２Ｈ，ｓ），２．６５−２．６９（２Ｈ，ｍ），２，３４−２．４６（２Ｈ，ｍ） Reference Production Example 60
Dissolve 1.03 g of 5-bromomethyl-2-trifluoromethylpyrimidine and 1.00 g of S- (3,3,3-trifluoropropyl) benzenethioate in 30 mL of methanol, and add sodium methoxide (28% methanol solution) at room temperature. ) 0.8 mL was added dropwise. After stirring for 6 hours at the same temperature, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to column chromatography, and 2-trifluoromethyl-5- (3,3,3-trifluoropropylsulfanylmethyl) pyrimidine (hereinafter referred to as the present organic sulfur compound (60)) represented by the following formula: ) 330 mg was obtained.
This organic sulfur compound (60)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 8.86 (2H, s), 3.80 (2H, s), 2.65-2.69 (2H, m), 2,34- 2.46 (2H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）８．６０（２Ｈ，ｓ），３．７０（２Ｈ，ｓ），２．６３−２．６７（２Ｈ，ｍ），２，３２−２．４４（２Ｈ，ｍ）
本有機硫黄化合物（６２）

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）８．４７（２Ｈ，ｓ），４．０３（３Ｈ，ｓ），３．６７（２Ｈ，ｓ），２．６１−２．６５（２Ｈ，ｍ），２，３１−２．４３（２Ｈ，ｍ） Reference Production Example 61
Dissolve 1.10 g of 2-chloro-5-bromomethylpyrimidine and 1.24 g of S- (3,3,3-trifluoropropyl) benzenethioate in 50 mL of methanol, and add sodium methoxide (28% methanol solution) at room temperature. 1.0 mL was added dropwise. After stirring at the same temperature for 4 hours, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue is subjected to column chromatography and described as 2-chloro-5- (3,3,3-trifluoropropylsulfanylmethyl) pyrimidine (hereinafter referred to as the present organic sulfur compound (61)) represented by the following formula. ) 90 mg, and 260 mg of 2-methoxy-5- (3,3,3-trifluoropropylsulfanylmethyl) pyrimidine (hereinafter referred to as the present organic sulfur compound (62)) represented by the following formula was obtained.
This organic sulfur compound (61)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 8.60 (2H, s), 3.70 (2H, s), 2.63-2.67 (2H, m), 2, 32- 2.44 (2H, m)
This organic sulfur compound (62)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 8.47 (2H, s), 4.03 (3H, s), 3.67 (2H, s), 2.61-2.65 ( 2H, m), 2, 31-2.43 (2H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）８．９０（１Ｈ，ｍ），８．０７（１Ｈ，ｄｄ），７，８５（１Ｈ，ｄ），５，３４（１Ｈ，ｓ），３．８７（３Ｈ，ｓ），３．７７（１Ｈ，ｄｄｄ），３．４６（１Ｈ，ｄｄｄ），２．７９−２．５４（２Ｈ，ｍ） Reference Production Example 62
635 mg of 2-chloro-5-trifluoromethylpyridine and 703 g of methyl (3,3,3-trifluoropropylsulfonyl) acetate are dissolved in 20 mL of dimethyl sulfoxide, 1.14 g of cesium carbonate is added at room temperature, and the mixture is stirred at 110 ° C. for 10 hours. Stir. After adding 10% hydrochloric acid to the reaction mixture and extracting with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography, and methyl 2- (5-trifluoromethylpyridin-2-yl) -2- (3,3,3-trifluoropropylsulfonyl) acetate represented by the following formula ( Hereinafter, this organic sulfur compound (63) is described.) 360 mg was obtained.
This organic sulfur compound (63)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 8.90 (1H, m), 8.07 (1H, dd), 7, 85 (1H, d), 5, 34 (1H, s) , 3.87 (3H, s), 3.77 (1H, ddd), 3.46 (1H, ddd), 2.79-2.54 (2H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）８．８８（１Ｈ，ｍ），８．１５−８．１２（２Ｈ，ｍ），３．９９（１Ｈ，ｄｄｄ），３．９４（３Ｈ，ｓ），３．５８（１Ｈ，ｄｄｄ），２．８５−２．５５（２Ｈ，ｍ） Reference Production Example 63
472 mg of this organic sulfur compound (63) was dissolved in 5.0 mL of N, N-dimethylformamide, and 244 mg of N-chlorosuccinimide was added at room temperature. After stirring at the same temperature for 1 hour, the reaction mixture was subjected to silica gel column chromatography, and 2-chloro-2- (5-trifluoromethylpyridin-2-yl) -2- (3,3 , 3-trifluoropropylsulfonyl) methyl acetate (hereinafter referred to as the present organic sulfur compound (64)) (410 mg) was obtained.
This organic sulfur compound (64)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 8.88 (1H, m), 8.15-8.12 (2H, m), 3.99 (1H, ddd), 3.94 ( 3H, s), 3.58 (1H, ddd), 2.85-2.55 (2H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）８．９４（１Ｈ，ｓ），８．１０（１Ｈ，ｄｄ），７．８６（１Ｈ，ｄ），５．８６（１Ｈ，ｓ），３．６３−３．５５（２Ｈ，ｍ），２．８４−２．６４（２Ｈ，ｍ） Reference production example 64
This organic sulfur compound (64) was dissolved in 5.0 mL of methanol, and 2.0 mL of aqueous ammonia (28% aqueous solution) was added at room temperature. After stirring at the same temperature for 2 hours, the mixture was concentrated under reduced pressure, and the resulting residue was subjected to silica gel column chromatography to give 2- [chloro- (3,3,3-trifluoropropanesulfonyl) methyl represented by the following formula. 352 mg of -5-trifluoromethylpyridine (hereinafter referred to as the present organic sulfur compound (65)) was obtained.
This organic sulfur compound (65)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 8.94 (1H, s), 8.10 (1H, dd), 7.86 (1H, d), 5.86 (1H, s) , 3.63-3.55 (2H, m), 2.84-2.64 (2H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）６．６９−６．７２（２Ｈ，ｍ），４．１３（１Ｈ，ｑ），２．５７−２．６４（２Ｈ，ｍ），２．２６−２．３８（２Ｈ，ｍ），１．６２（３Ｈ，ｄ） Reference Production Example 65
236 mg of sodium borohydride was dissolved in 20 mL of methanol, and 1.00 g of 2-acetyl-5-chlorothiophene 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 chloroform. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was dissolved in 20 mL of chloroform, and 0.9 mL of thionyl chloride was added at room temperature. After stirring at the same temperature for 1 hour, the reaction mixture was concentrated under reduced pressure. The obtained residue was dissolved in 20 mL of tetrahydrofuran, and 1.46 g of S- (3,3,3-trifluoropropyl) benzenethioate was added at room temperature. To this solution, 1.2 mL of sodium methoxide (28% methanol solution) was added dropwise at room temperature. After stirring at the same temperature for 1 hour, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to column chromatography, and 2-chloro-5- [1- (3,3,3-trifluoropropylsulfanyl) ethyl] thiophene (hereinafter referred to as the present organic sulfur compound (66) represented by the following formula: ) 300 mg was obtained.
This organic sulfur compound (66)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 6.69-6.72 (2H, m), 4.13 (1H, q), 2.57-2.64 (2H, m), 2.26-2.38 (2H, m), 1.62 (3H, d)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）５．９６（１Ｈ，ｓ），３．７０（２Ｈ，ｓ），２．６３−２．６７（２Ｈ，ｍ），２．２９−２．４１（２Ｈ，ｍ），１．３４（９Ｈ，ｄ） Reference production example 66
In 20 mL of methanol, 500 mg of 3-chloromethyl-5-tert-butylisoxazole and 537 mg of S- (3,3,3-trifluoropropyl) benzenethioate were dissolved, and sodium methoxide (28% methanol solution) 0 was dissolved at room temperature. .5 mL was added dropwise. 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 dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to column chromatography, and 5-tert-butyl-3-[(3,3,3-trifluoropropylsulfanyl) methyl] isoxazole represented by the following formula (hereinafter referred to as the present organic sulfur compound ( 67).) 440 mg was obtained.
This organic sulfur compound (67)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 5.96 (1H, s), 3.70 (2H, s), 2.63-2.67 (2H, m), 2.29- 2.41 (2H, m), 1.34 (9H, d)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）：δ（ｐｐｍ）７．６５（１Ｈ，ｓ），７．４３（１Ｈ，ｓ），５．０１（２Ｈ，ｓ），２．６７−２．７１（２Ｈ，ｍ），２．２７−２．３８１（２Ｈ，ｍ） Reference Production Example 67
To 10 mL of tetrahydrofuran was dissolved 1.00 g of 4-trifluoromethylimidazole and 0.4 mL of tetra-n-butylammonium hydroxide solution (10%), and 10 mL of formaldehyde (36% aqueous solution) was added at room temperature. After stirring at the same temperature for 14 hours, the reaction mixture was concentrated under reduced pressure, and the resulting residue was subjected to column chromatography to obtain crude 4-trifluoromethylimidazol-1-ylmethanol. This was dissolved in 20 mL of chloroform, and 0.8 mL of thionyl chloride was added at room temperature. After stirring for 16 hours under reflux conditions, the reaction mixture was returned to room temperature and concentrated under reduced pressure. The obtained residue was dissolved in 20 mL of tetrahydrofuran, and 940 mg of S- (3,3,3-trifluoropropyl) benzenethioate was added. To this solution, 2.4 mL of sodium methoxide (28% methanol solution) was added dropwise at room temperature. After stirring at the same temperature for 10 hours, 10% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to column chromatography, and 4-trifluoromethyl-1-[(3,3,3-trifluoropropylsulfanyl) methyl] -1H-imidazole (hereinafter referred to as the present organic sulfur) represented by the following formula: Compound (68).) 800 mg was obtained.
This organic sulfur compound (68)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.65 (1H, s), 7.43 (1H, s), 5.01 (2H, s), 2.67-2.71 ( 2H, m), 2.27-2.381 (2H, m)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）：δ（ｐｐｍ）７．４６（１Ｈ，ｓ），７．４５（１Ｈ，ｓ），３．６５（２Ｈ，ｓ），２．６１−２．６５（２Ｈ，ｍ），２．２６−２．３８（２Ｈ，ｍ），１．５４（９Ｈ，ｓ） Reference production example 68
To 26 ml of methanol were added 1.68 g of potassium thioacetate and 2.32 g of 1-tert-butyl-4- (chloromethyl) -1H-pyrazole, and the mixture was heated at 50 ° C. for 4 hours. After cooling to room temperature, 2.78 g of 28% sodium methoxide methanol solution and 3.54 g of 1-iodo-3,3,3-trifluoropropane were added and heated at 50 ° C. for 4 hours. After cooling to room temperature, 50 ml of water was added, and the mixture was concentrated to 50 ml under reduced pressure. After extraction with ethyl acetate, the organic layer was washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The obtained residue was subjected to column chromatography, and 1-tert-butyl-4-[(3,3,3-trifluoropropylsulfanyl) methyl] -1H-pyrazole (hereinafter referred to as the present organic sulfur) represented by the following formula: 2.73 g of compound (69) was obtained.
This organic sulfur compound (69)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.46 (1H, s), 7.45 (1H, s), 3.65 (2H, s), 2.61-2.65 ( 2H, m), 2.26-2.38 (2H, m), 1.54 (9H, s)

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃、ＴＭＳ）：δ（ｐｐｍ）７．６６（１Ｈ，ｓ），７．５６（１Ｈ，ｓ），４．２０（２Ｈ，ｓ），３．０５−３．０９（２Ｈ，ｍ），２．５１−２．６３（２Ｈ，ｍ），１．６０（９Ｈ，ｓ） Reference Production Example 69
In 40 mL of water, 24.59 g of potassium hydrogen persulfate (Oxone (registered trademark), manufactured by DuPont) was dissolved, and 2.40 g of the organic sulfur compound (4) dissolved in 40 mL of methanol was added. The mixture was heated to 50 ° C., stirred for 5 hours, and then cooled to room temperature. A 10% aqueous sodium sulfite solution was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The obtained residue was subjected to column chromatography, and 1-tert-butyl-4-[(3,3,3-trifluoropropylsulfonyl) methyl] -1H-pyrazole (hereinafter referred to as the present organic sulfur) represented by the following formula: Compound (70).) 2.61 g was obtained.
This organic sulfur compound (70)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.66 (1H, s), 7.56 (1H, s), 4.20 (2H, s), 3.05-3.09 ( 2H, m), 2.51-2.63 (2H, m), 1.60 (9H, s)

Reference production example 70
[Step 1]
4.06 g of methyl bromo- (4-bromophenyl) acetate was dissolved in 6.0 mL of tetrahydrofuran, and 1.79 g of potassium thioacetate and 2.0 mL of water were added at room temperature, followed by stirring at the same temperature for 3 hours. The organic layer was separated by separating the reaction mixture, and the aqueous layer was extracted with MTBE. The organic layers were combined, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 4.21 g of methyl acetylsulfanyl- (4-bromophenyl) acetate.
Methyl acetylsulfanyl- (4-bromophenyl) acetate
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.48-7.45 (2H, m), 7.28-7.26 (2H, m), 5.27 (1H, s), 3.74 (3H, s), 2.35 (3H, s)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）７．５０−７．４９(２Ｈ，ｍ)、７．３４−７．３３(２Ｈ，ｍ)、４．５５(１Ｈ，ｓ)、３．７５(３Ｈ，ｓ)、 ２．７５−２．６２(２Ｈ，ｍ)、２．３９−２．２７(２Ｈ，ｍ) [Step 2]
In 25 mL of methanol, 4.21 g of methyl acetylsulfanyl- (4-chlorophenyl) acetate and 4.12 g of 3-iodo-1,1,1-trifluoropropane were dissolved, and 28% sodium methoxide (methanol solution) 3 at room temperature. .54 g was added dropwise over 30 minutes. The reaction mixture was stirred at the same temperature for 12 hours, neutralized with 12% aqueous hydrochloric acid solution, and concentrated under reduced pressure. The concentrate was dissolved in 30 mL of ethyl acetate and washed with 10 mL of water and 10 mL of saturated brine. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. 1. The residue was subjected to column chromatography to obtain methyl 2- (4-bromophenyl) -2- (3,3,3-trifluoropropylsulfanyl) acetate (hereinafter referred to as the present organic sulfur compound (71)). 05 g was obtained.
This organic sulfur compound (71)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.50-7.49 (2H, m), 7.34-7.33 (2H, m), 4.55 (1H, s), 3.75 (3H, s), 2.75-2.62 (2H, m), 2.39-2.27 (2H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）７．６２−７．５９(２Ｈ，ｍ)、７．４７−７．４５(２Ｈ，ｍ)、５．０１(１Ｈ，ｓ)、 ３．８８ (３Ｈ， ｓ)、 ３．５０ (１Ｈ， ｔｄ， Ｊ ＝ １２．９， ４．５ Ｈｚ)、 ３．１９ (１Ｈ， ｔｄ， Ｊ ＝ １２．９， ４．５ Ｈｚ)、 ２．７２−２．４１ (２Ｈ， ｍ) Reference production example 71
984 mg of methyl 2- (4-bromophenyl) -2- (3,3,3-trifluoropropylsulfanyl) acetate was dissolved in 10 mL of chloroform, and 1.70 g of m-chloroperbenzoic acid (67%) was added at 40 ° C. Slowly added and stirred at the same temperature for 4 hours. The reaction mixture was washed with a saturated sodium bicarbonate solution, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to column chromatography to obtain 723 mg of methyl 2- (4-bromophenyl) -2- (3,3,3-trifluoropropylsulfonyl) acetate (hereinafter referred to as the present organic sulfur compound (72)). Obtained.
This organic sulfur compound (72)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.62-7.59 (2H, m), 7.47-7.45 (2H, m), 5.01 (1H, s), 3.88 (3H, s), 3.50 (1H, td, J = 12.9, 4.5 Hz), 3.19 (1H, td, J = 12.9, 4.5 Hz), 2 .72-2.41 (2H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）７．６３−７．６０ (４Ｈ， ｍ)、 ７．５６−７．５３ (４Ｈ， ｍ)、 ３．９５ (３Ｈ， ｓ)、 ３．８０−３．６４ (２Ｈ， ｍ)、 ２．７２−２．６７ (２Ｈ， ｍ) Reference production example 72
A solution of 91 mg of sodium hydride (55% oily) in 15 mL of tetrahydrofuran and 723 mg of methyl 2- (4-bromophenyl) -2- (3,3,3-trifluoropropylsulfonyl) acetate in 5 mL of tetrahydrofuran at room temperature. Was dripped. After stirring at the same temperature for 30 minutes, 279 mg of N-chlorosuccinimide was added. The reaction mixture was stirred for 5 hours and then neutralized with 12% aqueous hydrochloric acid. The aqueous layer was extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to column chromatography, and methyl 2-chloro-2- (4-bromophenyl) -2- (3,3,3-trifluoropropylsulfonyl) acetate (hereinafter referred to as the present organic sulfur compound (73)). 134 mg was obtained.
This organic sulfur compound (73)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.63-7.60 (4H, m), 7.56-7.53 (4H, m), 3.95 (3H, s), 3.80-3.64 (2H, m), 2.72-2.67 (2H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）７．６２−７．６０ (２Ｈ， ｍ)、 ７．４８−７．４６ (２Ｈ， ｍ)、 ５．６２ (１Ｈ， ｓ)、 ３．５１−３．３５ (２Ｈ， ｍ)、 ２．７３−２．６７ (２Ｈ， ｍ) Reference production example 73
Dissolve 631 mg of methyl 2-chloro-2- (4-bromophenyl) -2- (3,3,3-trifluoropropylsulfonyl) acetate in 5 mL of methanol, and add 3.0 mL of aqueous ammonia (28% aqueous solution) at room temperature. Was added. After stirring at the same temperature for 2 hours, the mixture was concentrated under reduced pressure, the residue was subjected to column chromatography, and 4-bromo-α-chlorobenzyl = 3,3,3-trifluoropropylsulfone (hereinafter referred to as the present organic sulfur compound ( 74).) 447 mg was obtained.
This organic sulfur compound (74)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 7.62-7.60 (2H, m), 7.48-7.46 (2H, m), 5.62 (1H, s), 3.51-3.35 (2H, m), 2.73-2.67 (2H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、ＴＭＳ、δ（ｐｐｍ））：２．７５−２．８０（２Ｈ，ｍ）、３．４７−３．５１（２Ｈ，ｍ）、５．０５（１Ｈ、ｓ）、７．２５−７．２８（２Ｈ、ｄ） Reference production example 74
(3,3,3-trifluoropropylsulfonyl) acetonitrile (3.72 g) and 1,4-dioxane (100 ml) were dissolved, and 60% sodium hydride (1.71 g) was added at 0 ° C. in a nitrogen atmosphere. After stirring the solution for 30 minutes, 3.04 g of 3,4,5-trifluorobromobenzene, 447.6 mg of phenylphosphine and 294.4 mg of tris (dibenzylideneacetone) dipalladium (0) chloroform complex were added, and the mixture was heated at 80 ° C. Stir for 6 hours. The reaction mixture was cooled to room temperature, 1N aqueous hydrochloric acid solution was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and filtered, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (3,4,5-trifluorobenzyl) -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound (75)) 1.20 g was obtained.
This organic sulfur compound (75)

¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.75-2.80 (2H, m), 3.47-3.51 (2H, m), 5.05 (1H, s) 7.25-7.28 (2H, d)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、ＴＭＳ、δ（ｐｐｍ））：２．７７−２．９３（２Ｈ，ｍ）、３．６７−３．７５（２Ｈ，ｍ）、７．３７−７．４０（２Ｈ、ｄ） Reference production example 75
500 mg of 2- (3,4,5-trifluorobenzyl) -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile was dissolved in 20 ml of tetrahydrofuran, and 60% sodium hydride 60 at 60C under a nitrogen atmosphere. .4 mg was added. After stirring the solution for 15 minutes, 0.50 g of N-fluorobenzenesulfonimide was added, and the mixture was stirred at room temperature for 2 hours. 1N aqueous hydrochloric acid solution was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and filtered, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography, and 2-fluoro-2- (3,4,5-trifluorobenzyl) -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound). (Described as (76).) 360 mg was obtained.
This organic sulfur compound (76)

¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.77-2.93 (2H, m), 3.67-3.75 (2H, m), 7.37-7.40 ( 2H, d)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、ＴＭＳ、δ（ｐｐｍ））：２．６４−２．７６（２Ｈ，ｍ）、３．４２−３．５０（１Ｈ，ｍ）、３．５６−３．６３（１Ｈ，ｍ）、５．２８（１Ｈ、ｓ）、７．５６（１Ｈ、ｄ）、７．８７（１Ｈ、ｄｄ）、８．６８（１Ｈ、ｄ） Reference production example 76
Dissolved in 2.67 g of (3,3,3-trifluoropropylsulfonyl) acetonitrile and 26 ml of 1,2-dimethoxyethane, 0.58 g of 60% sodium hydride was added at 0 ° C. under a nitrogen atmosphere. After stirring the solution for 30 minutes, 2.55 g of 2-bromo-5-chloropyridine and 1.50 g of tetrakistriphenylphosphine palladium were added, and the mixture was stirred for 15 hours under reflux conditions. The reaction mixture was cooled to 0 ° C., added with 50 ml of water, stirred for 15 minutes, and extracted three times with 50 ml of ethyl acetate. The organic layers were combined, dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. The residue was subjected to silica gel column chromatography and described as 2- (5-chloropyridin-2-yl) -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound (77)). .) 0.51 g was obtained.
This organic sulfur compound (77)

¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.64-2.76 (2H, m), 3.42-3.50 (1H, m), 3.56-3.63 ( 1H, m), 5.28 (1H, s), 7.56 (1H, d), 7.87 (1H, dd), 8.68 (1H, d)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３、ＴＭＳ、δ（ｐｐｍ））：２．２５（３Ｈ、ｓ）、２．５０−２．６６（１Ｈ，ｍ）、２．６９−２．８４（１Ｈ，ｍ）、３．２９−３．３７（１Ｈ，ｍ）、３．５４−３．６２（１Ｈ，ｍ）、７．６１（１Ｈ、ｄ）、７．８５（１Ｈ、ｄｄ）、８．６８（１Ｈ、ｄ） Reference Production Example 77
0.41 g of 2- (5-chloropyridin-2-yl) -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile is dissolved in 4 ml of N, N-dimethylformamide, 0.32 g of potassium carbonate, iodine 0.28 g of methyl chloride was added, and the mixture was stirred overnight at room temperature under a nitrogen atmosphere. To the reaction mixture was added 50 ml of saturated brine, and the mixture was extracted 3 times with 30 ml of ethyl acetate. The organic layers were combined, dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. The residue was subjected to silica gel column chromatography to give 2- (5-chloropyridin-2-yl) -2- (3,3,3-trifluoropropylsulfonyl) propionitrile (hereinafter referred to as the present organic sulfur compound (78)). 0.32 g was obtained.
This organic sulfur compound (78)

¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 2.25 (3H, s), 2.50-2.66 (1H, m), 2.69-2.84 (1H, m) 3.29-3.37 (1H, m), 3.54-3.62 (1H, m), 7.61 (1H, d), 7.85 (1H, dd), 8.68 (1H) D)

Reference production example 78
[Step 1]
1,4-Dioxaspiro [4.5] decane-8-methanol (5.45 g) was dissolved in 30 ml of pyridine, and 6.64 g of p-toluenesulfonyl chloride was added thereto, followed by stirring at room temperature for 6 hours. 100 ml of water was added to the reaction mixture, and the mixture was extracted twice with 100 ml of ethyl acetate. The organic layer was washed successively with 100 ml of 1N aqueous hydrochloric acid twice, then once with 100 ml of saturated aqueous sodium hydrogen carbonate solution and once with 100 ml of saturated brine. The organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 9.86 g of 1,4-dioxaspiro [4.5] dec-8-ylmethyl = p-toluenesulfonate.

[Step 2]
1.86 g of 1,4-dioxaspiro [4.5] dec-8-ylmethyl = p-toluenesulfonate was dissolved in 40 ml of dimethyl sulfoxide, 4.00 g of potassium thioacetate was added thereto, and the mixture was stirred at 70 ° C. for 8 hours. . After cooling to room temperature, 100 ml of water was added to the reaction mixture, and the mixture was extracted twice with 100 ml of ethyl acetate. The organic layer was washed with 100 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 5.41 g of 1,4-dioxaspiro [4.5] dec-8-ylmethyl = thioacetate.

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．２５−１．３５（２Ｈ，ｍ），１．４８−１．５８（３Ｈ，ｍ），１．７３−１．７９（２Ｈ，ｍ），１．８４−１．８８（２Ｈ，ｍ），２．３３−２．４３（２Ｈ，ｍ），２．４６（２Ｈ，ｄ），２．６５−２．６９（２Ｈ，ｍ），３．９４（４Ｈ，ｓ） [Step 3]
Dissolve 5.41 g of 1,4-dioxaspiro [4.5] dec-8-ylmethyl thioacetate in 20 ml of methanol and add 6.75 g of 28% sodium methoxide / methanol solution to this at 0 ° C. in a nitrogen atmosphere. It was. To the mixture, 7.81 g of 3,3,3-trifluoro-1-iodopropane was added, stirred at room temperature for 1 hour, and then stirred at 70 ° C. for 1 hour. The reaction mixture was cooled to room temperature, 100 ml of water was added, the mixture was concentrated under reduced pressure, and the aqueous layer was extracted twice with 100 ml of ethyl acetate. The organic layer was washed with 100 ml of saturated brine, and the organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 8- (3,3,3-trifluoropropylthiomethyl) -1,4-dioxaspiro [4.5] decane (hereinafter referred to as the present organic sulfur compound ( 101).) 3.69 g was obtained.
This organic sulfur compound (101)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.25-1.35 (2H, m), 1.48-1.58 (3H, m), 1.73-1.79 (2H , M), 1.84-1.88 (2H, m), 2.33-2.43 (2H, m), 2.46 (2H, d), 2.65-2.69 (2H, m ), 3.94 (4H, s)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．４３−１．５３（２Ｈ，ｍ），１．５８−１．６６（２Ｈ，ｍ），１．７３−１．７９（２Ｈ，ｍ），１．９７−２．０１（２Ｈ，ｍ），２．１５−２．１７（１Ｈ，ｍ），２．６４−２．７４（２Ｈ，ｍ），２．９５（２Ｈ，ｄ），３．１６−３．２０（２Ｈ，ｍ），３．９２−３．９７（４Ｈ，ｍ） Reference Production Example 79
The organic sulfur compound (101) (3.69 g) was dissolved in chloroform (60 ml). Under a nitrogen atmosphere, m-chloroperbenzoic acid (6.56 g) was added thereto at 0 ° C., and the mixture was stirred at room temperature for 1 hour. Stir for hours. The reaction mixture was cooled to 0 ° C., 50 ml of 5% aqueous sodium sulfite solution was added and stirred for 1 hour, and then the organic layer was separated. The aqueous layer was extracted with 50 ml of chloroform, and the organic layers were combined, washed twice with 50 ml of saturated aqueous sodium hydrogen carbonate solution, and washed with 100 ml of saturated brine. The obtained organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 8- (3,3,3-trifluoropropylsulfonylmethyl) -1,4-dioxaspiro [4.5] decane (hereinafter referred to as the present organic sulfur compound ( 102).) 4.10 g was obtained.
This organic sulfur compound (102)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.43-1.53 (2H, m), 1.58-1.66 (2H, m), 1.73-1.79 (2H M), 1.97-2.01 (2H, m), 2.15-2.17 (1H, m), 2.64-2.74 (2H, m), 2.95 (2H, d). ), 3.16-3.20 (2H, m), 3.92-3.97 (4H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．５９−１．７０（２Ｈ，ｍ），２．３３−２．３６（２Ｈ，ｍ），２．４３−２．４６（４Ｈ，ｍ），２．５８−２．６７（１Ｈ，ｍ），２．２．６９−２．７３（２Ｈ，ｍ），３．０３（２Ｈ，ｄ），３．２０−３．２５（２Ｈ，ｍ） Reference production example 80
4.00 g of this organic sulfur compound (102) was dissolved in 30 ml of acetone, 0.43 g of toluenesulfonic acid was added thereto, and the mixture was stirred at 50 ° C. for 8 hours in a nitrogen atmosphere. The reaction solution was concentrated under reduced pressure, the residue was subjected to silica gel column chromatography, and 4- (3,3,3-trifluoropropylsulfonylmethyl) cyclohexanone (hereinafter referred to as the present organic sulfur compound (103)) represented by the following formula: 3.35 g was obtained.
This organic sulfur compound (103)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.59-1.70 (2H, m), 2.33-2.36 (2H, m), 2.43-2.46 (4H M), 2.58-2.67 (1H, m), 2.2.69-2.73 (2H, m), 3.03 (2H, d), 3.20-3.25 (2H) , M)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．４５−１．５６（２Ｈ，ｍ），１．７２−１．８８（２Ｈ，ｍ），２．０５−２．２３（５Ｈ，ｍ），２．６３−２．７５（２Ｈ，ｍ），２．９７（２Ｈ，ｄ），３．０２−３．２２（２Ｈ，ｍ）
本有機硫黄化合物（１０５）

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．６５−１．７３（１Ｈ，ｍ），１．９９−２．１０（２Ｈ，ｍ），２．１９−２．２５（１Ｈ，ｍ），２．３３−２．４３（３Ｈ，ｍ），２．６３−２．７５（２Ｈ，ｍ），３．０２（２Ｈ，ｄ），３．１８−３．２２（２Ｈ，ｍ），５．１１−５．１９（１Ｈ，ｍ） Reference production example 81
0.82 g of this organic sulfur compound (103) was dissolved in 6 ml of chloroform, and 1.06 g of diethylaminosulfur trifluoride was added thereto at 0 ° C. in a nitrogen atmosphere, followed by stirring at room temperature for 5 hours. The reaction solution was diluted with 30 ml of chloroform, 30 ml of water was added, and the organic layer was separated. The aqueous layer was extracted twice with 30 ml of chloroform, and the organic layers were combined and washed with 50 ml of saturated brine. The obtained organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue is subjected to silica gel column chromatography and described as 1,1-difluoro-4- (3,3,3-trifluoropropylsulfonylmethyl) cyclohexane (hereinafter referred to as the present organic sulfur compound (104)) represented by the following formula. ) 0.30 g and 1-fluoro-4- (3,3,3-trifluoropropylsulfonyl) methyl] cyclohexene (hereinafter referred to as the present organic sulfur compound (105)) represented by the following formula: 0.27 g. It was.
This organic sulfur compound (104)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.45-1.56 (2H, m), 1.72-1.88 (2H, m), 2.05-2.23 (5H) M), 2.62-2.75 (2H, m), 2.97 (2H, d), 3.02-3.22 (2H, m)
This organic sulfur compound (105)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.65-1.73 (1H, m), 1.99-2.10 (2H, m), 2.19-2.25 (1H , M), 2.33-2.43 (3H, m), 2.63-2.75 (2H, m), 3.02 (2H, d), 3.18-3.22 (2H, m ), 5.11-5.19 (1H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．５０−１．５９（４Ｈ，ｍ），２．０３−２．１１（６Ｈ，ｍ），２．５３（１Ｈ，ｓ），２．６３−２．７４（２Ｈ，ｍ），２．９７（２Ｈ，ｄ），３．１６−３．２０（２Ｈ，ｍ） Reference production example 82
0.83 g of the organic sulfur compound (103) was dissolved in 10 ml of tetrahydrofuran, and 7.2 ml of a 0.5 M ethynylmagnesium bromide / tetrahydrofuran solution was added thereto at 0 ° C. in a nitrogen atmosphere, followed by stirring at 0 ° C. for 5 hours. To the reaction solution was added 30 ml of 1N aqueous hydrochloric acid solution, and the mixture was extracted twice with 30 ml of ethyl acetate. The organic layers were combined and washed with 30 ml of saturated aqueous sodium hydrogen carbonate solution and 30 ml of saturated brine. The obtained organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 1-ethynyl-4- (3,3,3-trifluoropropylsulfonylmethyl) cyclohexanol represented by the following formula (hereinafter referred to as the present organic sulfur compound (106)). 0.43 g was obtained.
This organic sulfur compound (106)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.50-1.59 (4H, m), 2.03-2.11 (6H, m), 2.53 (1H, s), 2.63-2.74 (2H, m), 2.97 (2H, d), 3.16-3.20 (2H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．５２−１．５９（２Ｈ，ｍ），１．７２−１．９４（４Ｈ，ｍ），２．１７−２．２８（３Ｈ，ｍ），２．６２−２．７２（３Ｈ，ｍ），２．９５（２Ｈ，ｄ），３．１７−３．２２（２Ｈ，ｍ） Reference production example 83
0.29 g of this organic sulfur compound (106) was dissolved in 2 ml of chloroform, 0.32 g of diethylaminosulfur trifluoride was added thereto at 0 ° C. under a nitrogen atmosphere, and the mixture was stirred at room temperature for 5 hours. The reaction solution was diluted with 20 ml of chloroform, 20 ml of water was added, and then the organic layer was separated. The aqueous layer was extracted twice with 20 ml of chloroform. The organic layers were combined and washed with 50 ml of saturated brine. The obtained organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 1-ethynyl-1-fluoro-4- (3,3,3-trifluoropropylsulfonylmethyl) cyclohexane (hereinafter referred to as the present organic sulfur compound (107)) represented by the following formula: 0.14 g was obtained.
This organic sulfur compound (107)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.52-1.59 (2H, m), 1.72-1.94 (4H, m), 2.17-2.28 (3H M), 2.62-2.72 (3H, m), 2.95 (2H, d), 3.17-3.22 (2H, m)

Reference production example 84
[Step 1]
4.86 g of diisopropylamine was dissolved in 50 ml of tetrahydrofuran and cooled to −50 ° C. under a nitrogen atmosphere. 30 ml of 1.6M n-butyllithium / n-hexane solution was added to the solution and stirred at −50 ° C. for 30 minutes. Further, 9.28 g of methyl 2- (1,4-dioxaspiro [4,5] dec-8-yl) acetate dissolved in 40 ml of tetrahydrofuran was added dropwise to the mixture over 15 minutes, followed by stirring at 0 ° C. for 30 minutes. The mixture was cooled to −50 ° C., 8.54 g of N-bromosuccinimide dissolved in 30 ml of tetrahydrofuran was added, and the mixture was stirred at 0 ° C. for 2 hours and at room temperature for 5 hours. 100 ml of water was added to the reaction mixture, and the organic layer was separated. The aqueous layer was extracted twice with 100 ml of ethyl acetate. The organic layers were combined, washed twice with 100 ml of 1N aqueous hydrochloric acid, and washed with 100 ml of saturated aqueous sodium bicarbonate and 100 ml of saturated brine. The organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was dissolved in 50 ml of dimethyl sulfoxide, 5.04 g of potassium thioacetate was added, and the mixture was stirred at 50 ° C. for 4 hours. After cooling to room temperature, 100 ml of water was added to the reaction mixture, and the mixture was extracted twice with 100 l of ethyl acetate. The combined organic layers were washed with 100 ml of 1N aqueous hydrochloric acid solution, 100 ml of saturated aqueous sodium hydrogen carbonate solution and 100 ml of saturated brine. The organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 4.27 g of methyl 2- (acetylthio) -2- (1,4-dioxaspiro [4,5] dec-8-yl) acetate.

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．３１−１．８１（８Ｈ，ｍ），２．１１−２．１６（１Ｈ，ｍ），２．３４−２．４１（２Ｈ，ｍ），２．７１−２．７８（２Ｈ，ｍ），３．０４（１Ｈ，ｄ），３．７５（３Ｈ，ｓ），４．９１−４．９６（４Ｈ，ｍ） [Step 2]
Dissolve 4.27 g of methyl 2- (acetylthio) -2- (1,4-dioxaspiro [4,5] dec-8-yl) acetate in 30 ml of methanol and add it to 28% sodium methoxy at 0 ° C. in a nitrogen atmosphere. 3.14 g of methanol / methanol solution was added. Further, 4.33 g of 3,3,3-trifluoro-1-iodopropane was added to the mixture, and the mixture was stirred at room temperature for 1 hour and then stirred at 70 ° C. for 1 hour. The reaction mixture was cooled to room temperature, 100 ml of water was added to the reaction mixture, concentrated under reduced pressure until the total amount was about 100 ml, and extracted twice with 100 ml of ethyl acetate. The organic layers were combined, washed with 100 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (1,4-dioxaspiro [4,5] dec-8-yl) -2- (3,3,3-trifluoropropylthio) acetic acid represented by the following formula: 3.60 g of methyl (hereinafter referred to as the present organic sulfur compound (108)) was obtained.
This organic sulfur compound (108)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.31-1.81 (8H, m), 2.11-2.16 (1H, m), 2.34-2.41 (2H) M), 2.71-2.78 (2H, m), 3.04 (1H, d), 3.75 (3H, s), 4.91-4.96 (4H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．５０−１．８３（７Ｈ，ｍ），２．１４−２．１７（１Ｈ，ｍ），２．２６−２．２９（１Ｈ，ｍ），２．６６−２．７４（２Ｈ，ｍ），３．１９−３．２７（１Ｈ，ｍ），３．４８−３．５３（１Ｈ，ｍ），３．７５（１Ｈ，ｄ），３．８４（３Ｈ，ｓ），３．９１−３．９６（４Ｈ，ｍ） Reference production example 85
3.60 g of the organic sulfur compound (108) was dissolved in 20 ml of chloroform, and 4.75 g of m-chloroperbenzoic acid was added thereto at 0 ° C. in a nitrogen atmosphere. The mixture was stirred at room temperature for 1 hour and then stirred at 50 ° C. for 3 hours. The reaction mixture was cooled to 0 ° C., 50 ml of 5% aqueous sodium sulfite solution was added and stirred for 1 hour, and then the organic layer was separated. The aqueous layer was extracted with 50 ml of chloroform, and the organic layers were combined, washed twice with 50 ml of saturated aqueous sodium hydrogen carbonate solution, and washed with 100 ml of saturated brine. The obtained organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (1,4-dioxaspiro [4,5] dec-8-yl) -2- (3,3,3-trifluoropropylsulfonyl) acetic acid represented by the following formula: 2.41 g of methyl (hereinafter referred to as the present organic sulfur compound (109)) was obtained.
This organic sulfur compound (109)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.50-1.83 (7H, m), 2.14-2.17 (1H, m), 2.6-2.29 (1H) M), 2.66-2.74 (2H, m), 3.19-3.27 (1H, m), 3.48-3.53 (1H, m), 3.75 (1H, d). ), 3.84 (3H, s), 3.91-3.96 (4H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．７３−１．８６（２Ｈ，ｍ），２．１０−２．１３（１Ｈ，ｍ），２．４０−２．４９（５Ｈ，ｍ），２．６８−２．７７（３Ｈ，ｍ），３．２８−３．３５（１Ｈ，ｍ），３．４７−３．５３（１Ｈ，ｍ），３．８５（２Ｈ，ｄ），３．８７（３Ｈ，ｓ） Reference production example 86
2.41 g of the organic sulfur compound (109) was dissolved in 25 ml of acetone, 0.11 g of toluenesulfonic acid was added thereto, and the mixture was stirred at 50 ° C. for 8 hours in a nitrogen atmosphere. The reaction solution was concentrated under reduced pressure, the residue was subjected to silica gel column chromatography, and methyl 2- (4-oxocyclohexyl) -2- (3,3,3-trifluoropropylsulfonyl) acetate represented by the following formula ( Hereinafter referred to as the present organic sulfur compound (110).) 1.24 g was obtained.
This organic sulfur compound (110)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.73-1.86 (2H, m), 2.10-2.13 (1H, m), 2.40-2.49 (5H M), 2.68-2.77 (3H, m), 3.28-3.35 (1H, m), 3.47-3.53 (1H, m), 3.85 (2H, d) ), 3.87 (3H, s)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．６７−１．８３（６Ｈ，ｍ），２．１４−２．３７（３Ｈ，ｍ），２．６６−２．７４（２Ｈ，ｍ），３．２２−３．２９（１Ｈ，ｍ），３．４５−３．５２（１Ｈ，ｍ），３．７７（１Ｈ，ｄ），３．８６（３Ｈ，ｓ） Reference production example 87
1.24 g of this organic sulfur compound (109) was dissolved in 17 ml of chloroform, and 1.37 g of diethylaminosulfur trifluoride was added thereto at 0 ° C. in a nitrogen atmosphere, followed by stirring at room temperature for 5 hours. The reaction solution was diluted with 40 ml of chloroform, 30 ml of water was added, and then the organic layer was separated. The aqueous layer was extracted twice with 30 ml of chloroform, and the organic layers were combined and washed with 50 ml of saturated brine. The obtained organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and methyl 2- (4,4-difluorocyclohexyl) -2- (3,3,3-trifluoropropylsulfonyl) acetate represented by the following formula (hereinafter referred to as the present organic sulfur compound ( 111)) 0.87 g was obtained.
This organic sulfur compound (111)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.67-1.83 (6H, m), 2.14-2.37 (3H, m), 2.66-2.74 (2H) M), 3.22-3.29 (1H, m), 3.45-3.52 (1H, m), 3.77 (1H, d), 3.86 (3H, s)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．６７−１．８９（５Ｈ，ｍ），２．１２−２．４３（３Ｈ，ｍ），２．５５−２．７４（３Ｈ，ｍ），３．２１−３．４０（２Ｈ，ｍ），３．９８（３Ｈ，ｓ） Reference production example 88
This organic sulfur compound (111) (0.50 g) is dissolved in tetrahydrofuran (5 ml), and after adding 0.07 g of 60% sodium hydride to this at 0 ° C. in a nitrogen atmosphere, N-fluorobenzenesulfonimide (0.50 g) is further added. And stirred at room temperature for 5 hours. 30 ml of water was added to the reaction solution, and the organic layer was separated. The aqueous layer was extracted twice with 30 ml of ethyl acetate, and the organic layers were combined and washed with 50 ml of saturated brine. The obtained organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and methyl 2- (4,4-difluorocyclohexyl) -2-fluoro-2- (3,3,3-trifluoropropylsulfonyl) acetate (hereinafter referred to as the present compound) represented by the following formula: 0.43 g of organic sulfur compound (112) is obtained.
This organic sulfur compound (112)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.67-1.89 (5H, m), 2.12-2.43 (3H, m), 2.55-2.74 (3H) , M), 3.21-3.40 (2H, m), 3.98 (3H, s)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．７３−１．８８（４Ｈ，ｍ），２．２１−２．６１（４Ｈ，ｍ），２．６１−２．７７（３Ｈ，ｍ），３．２８−３．３５（１Ｈ，ｍ），３．４０−３．４８（１Ｈ，ｍ），５．９０（１Ｈ，ｓ），６．５３（１Ｈ，ｓ） Reference production example 89
The organic sulfur compound (112) (0.33 g) was dissolved in 3 ml of methanol, and 3 ml of a 2.0 M ammonia / methanol solution was added thereto at 0 ° C., followed by stirring at room temperature for 18 hours. 30 ml of water was added to the reaction solution, extracted twice with 30 ml of ethyl acetate, the organic layers were combined and washed with 50 ml of saturated brine. The obtained organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (4,4-difluorocyclohexyl) -2-fluoro-2- (3,3,3-trifluoropropylsulfonyl) acetamide (hereinafter referred to as this organic compound) represented by the following formula: 0.43 g of the sulfur compound (113) was obtained.
This organic sulfur compound (113)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.73-1.88 (4H, m), 2.21-2.61 (4H, m), 2.61-2.77 (3H M), 3.28-3.35 (1H, m), 3.40-3.48 (1H, m), 5.90 (1H, s), 6.53 (1H, s)

ｔｒａｎｓ体
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）０．９６−１．０１（４Ｈ，ｍ），１．４０−１．４７（４Ｈ，ｍ），１．５８−１．８３（１Ｈ，ｍ），１．９２−１．９４（１Ｈ，ｍ），２．３４−２．４０（２Ｈ，ｍ），２．４３（２Ｈ，ｄ），２．６４−２．６８（２Ｈ，ｍ）３．４５（２Ｈ，ｄｄ）
ｃｉｓ体
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．２２−１．２７（４Ｈ，ｍ），１．４０−１．６２（６Ｈ，ｍ），２．３４−２．４０（２Ｈ，ｍ），２．５２（２Ｈ，ｄ），２．６４−２．６８（２Ｈ，ｍ）３．５３（２Ｈ，ｄｄ） Reference production example 90
To 22.8 g of cyclohexane-1,4-dimethanol monotosylate (trans / cis = 6/4) and 100 ml of dimethyl sulfoxide were added 8.68 g of potassium thioacetate, and the mixture was stirred at room temperature for 1 hour and at 60 ° C. for 6 hours. . The mixture was cooled to room temperature, 100 ml of saturated brine was added, and the mixture was extracted twice with 200 ml of t-butyl methyl ether. The organic layers were combined, washed with 100 ml of saturated brine and 100 ml of water, dried over sodium sulfate, filtered, and concentrated under reduced pressure. To the residue, 100 ml of methanol was added, and while cooling in an ice bath, 15.43 g of 28% sodium methoxide was added dropwise to a diluted solution of 50 ml of methanol over 30 minutes, followed by stirring for 30 minutes. Thereafter, 17.92 g of 3,3,3-trifluoro-1-iodopropane was added to the mixture, and the mixture was stirred at 60 ° C. for 6 hours. The reaction mixture was cooled to room temperature, 150 ml of saturated brine was added, and methanol was distilled off under reduced pressure. The obtained concentrate was extracted twice with 200 ml of t-butyl methyl ether, subjected to silica gel column chromatography, and 4- (3,3,3-trifluoropropylthiomethyl) cyclohexanemethanol (hereinafter referred to as the following formula). And this organic sulfur compound (114).) 8.46 g was obtained.
This organic sulfur compound (114): mixture of trans isomer / cis isomer = 6/4

trans body
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 0.96-1.01 (4H, m), 1.40-1.47 (4H, m), 1.58-1.83 (1H M), 1.92-1.94 (1H, m), 2.34-2.40 (2H, m), 2.43 (2H, d), 2.64-2.68 (2H, m). 3.45 (2H, dd)
cis body
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.22-1.27 (4H, m), 1.40-1.62 (6H, m), 2.34-2.40 (2H , M), 2.52 (2H, d), 2.64-2.68 (2H, m) 3.53 (2H, dd)

本有機硫黄化合物（１１５ｔ）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．０４−１．１９（４Ｈ，ｍ），１．３０（１Ｈ，ｔ），１．４５−１．４９（１Ｈ，ｍ），１．８４−１．８９（２Ｈ，ｍ），２．０４−２．１０（３Ｈ，ｍ），２．６２−２．７４（２Ｈ，ｍ），２．９３（２Ｈ，ｄ），３．１５−３．１９（２Ｈ，ｍ），３．４５（２Ｈ，ｄｄ）
本有機硫黄化合物（１１５ｃ）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．０４−１．１９（４Ｈ，ｍ），１．３０（１Ｈ，ｔ），１．４５−１．４９（１Ｈ，ｍ），１．８４−１．８９（２Ｈ，ｍ），２．０４−２．１０（３Ｈ，ｍ），２．６２−２．７４（２Ｈ，ｍ），２．９３（２Ｈ，ｄ），３．１５−３．１９（２Ｈ，ｍ），３．４５（２Ｈ，ｄｄ） Reference production example 91
7.4 g of the present organic sulfur compound (114) (where trans form / cis form = 6/4) is dissolved in 60 ml of chloroform, and 10.85 g of m-chloroperbenzoic acid is added thereto at 0 ° C. in a nitrogen atmosphere. The mixture was stirred at room temperature for 1 hour and at 50 ° C. for 3 hours. The reaction mixture was cooled to 0 ° C., 50 ml of 5% aqueous sodium sulfite solution was added, and the mixture was stirred for 1 hour. The organic layer was separated and the aqueous layer was extracted twice with 50 ml of chloroform. The organic layers were combined, washed twice with 50 ml of saturated aqueous sodium hydrogen carbonate solution, and washed with 100 ml of saturated brine. The obtained organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, crystallized with t-butyl methyl ether, and 4- (3,3,3-trifluoropropylsulfonylmethyl) cyclohexanemethanol (hereinafter referred to as the present organic sulfur compound ( 115).) Trans isomer (hereinafter referred to as the present organic sulfur compound (115t)) 4.13 g and cis isomer (hereinafter referred to as the present organic sulfur compound (115c), provided that the trans isomer / cis isomer = 1/9) 3.38 g was obtained.
This organic sulfur compound (115)

This organic sulfur compound (115t)
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.04-1.19 (4H, m), 1.30 (1H, t), 1.45 to 1.49 (1H, m), 1.84-1.89 (2H, m), 2.04-2.10 (3H, m), 2.62-2.74 (2H, m), 2.93 (2H, d), 3. 15-3.19 (2H, m), 3.45 (2H, dd)
This organic sulfur compound (115c)
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.04-1.19 (4H, m), 1.30 (1H, t), 1.45 to 1.49 (1H, m), 1.84-1.89 (2H, m), 2.04-2.10 (3H, m), 2.62-2.74 (2H, m), 2.93 (2H, d), 3. 15-3.19 (2H, m), 3.45 (2H, dd)

本有機硫黄化合物（１１６ｔ）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．１８−１．２７（２Ｈ，ｍ），１．３３−１．４３（２Ｈ，ｍ），２．０６−２．２４（６Ｈ，ｍ），２．６３−２．７４（２Ｈ，ｍ），２．９５（２Ｈ，ｄ），３．１６−３．２１（２Ｈ，ｍ），９．６２（１Ｈ，ｓ） Reference production example 92
7.46 g of oxalyl chloride was dissolved in 50 ml of dichloromethane and cooled to −78 ° C. under a nitrogen atmosphere. To this solution, 9.53 g of dimethyl sulfoxide dissolved in 50 ml of dichloromethane was added dropwise over 20 minutes and stirred at −50 ° C. for 30 minutes. To the reaction mixture, 13.51 g of the present organic sulfur compound (115t) dissolved in 150 ml of dichloromethane was added dropwise over 30 minutes, stirred at −50 ° C. for 40 minutes, and 15.70 g of triethylamine was added dropwise over 40 minutes. The reaction mixture was stirred at room temperature for 18 hours. 100 ml of water was added to the reaction mixture, and the organic layer was separated and extracted twice with 100 ml of chloroform. The organic layers were combined, washed successively with 150 ml of 1N aqueous hydrochloric acid solution, 150 ml of saturated aqueous sodium hydrogen carbonate solution and 150 ml of water, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and the trans isomer of 4- (3,3,3-trifluoropropanesulfonylmethyl) cyclohexanecarbaldehyde (hereinafter referred to as the present organic sulfur compound (116)) represented by the following formula: (Hereinafter referred to as the present organic sulfur compound (116t).) 10.04 g was obtained.
This organic sulfur compound (116)

This organic sulfur compound (116t)
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.18-1.27 (2H, m), 1.33-1.43 (2H, m), 2.06-2.24 (6H) M), 2.63-2.74 (2H, m), 2.95 (2H, d), 3.16-3.21 (2H, m), 9.62 (1H, s)

本有機硫黄化合物（１１７ｔ）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．１６−１．２９（４Ｈ，ｍ），１．８４−１．８６（２Ｈ，ｍ），２．０４−２．０８（２Ｈ，ｍ），２．２１−２．２６（１Ｈ，ｍ），２．６２−２．７４（２Ｈ，ｓ），２．９２（２Ｈ，ｄ），３．１５−３．２２（２Ｈ，ｍ），６．１９（２Ｈ，ｄ） Reference Production Example 93
23.21 g of carbon tetrabromide was dissolved in 100 ml of dichloromethane and cooled to 0 ° C. under a nitrogen atmosphere. To this, 36.72 g of triphenylphosphine was added over 30 minutes, and the mixture was further stirred for 30 minutes. To this solution, 10.4 g of the present organic sulfur compound (116t) dissolved in 50 ml of dichloromethane was added dropwise over 30 minutes, followed by stirring at room temperature for 6 hours. 150 ml of t-butyl methyl ether was added to the reaction mixture, the solid was filtered, and the filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 1- (2,2-dibromovinyl) -4- (3,3,3-trifluoropropylsulfonylmethyl) cyclohexane represented by the following formula (hereinafter referred to as the present organic sulfur compound ( 17). 12.9 g of a trans isomer (hereinafter referred to as the present organic sulfur compound (117t)) was obtained.
This organic sulfur compound (117)

This organic sulfur compound (117t)
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.16-1.29 (4H, m), 1.84-1.86 (2H, m), 2.04-2.08 (2H) M), 2.21-2.26 (1H, m), 2.62-2.74 (2H, s), 2.92 (2H, d), 3.15-3.22 (2H, m ), 6.19 (2H, d)

本有機硫黄化合物（１１８ｔ）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．１１−１．２０（２Ｈ，ｍ），１．４３−１．５３（２Ｈ，ｍ），２．０２−２．１３（６Ｈ，ｍ），２．１９−２．２３（１Ｈ，ｍ），２．６２−２．７３（２Ｈ，ｍ），２．９１（２Ｈ，ｄ），３．１５−３．１９（２Ｈ，ｍ） Reference production example 94
This organic sulfur compound (117t) 12.90g was melt | dissolved in tetrahydrofuran 60ml, and it cooled to -78 degreeC under nitrogen atmosphere. A 1.6M n-butyllithium / n-hexane solution was added dropwise to the solution over 30 minutes, and the mixture was stirred at -50 ° C for 1 hour and at 0 ° C for 2 hours. The reaction mixture was poured into 100 ml of 1N aqueous hydrochloric acid cooled in an ice bath and extracted twice with 200 ml of t-butyl methyl ether. The organic layers were combined, washed with 100 ml of saturated aqueous sodium hydrogen carbonate solution and 100 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 1-ethynyl-4- (3,3,3-trifluoropropylsulfonylmethyl) cyclohexane (hereinafter referred to as the present organic sulfur compound (118)) represented by the following formula: 5.59 g of trans form (hereinafter referred to as the present organic sulfur compound (118t)) was obtained.
This organic sulfur compound (118)

This organic sulfur compound (118t)
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.11-1.20 (2H, m), 1.43-1.53 (2H, m), 2.02-2.13 (6H) M), 2.19-2.23 (1H, m), 2.62-2.73 (2H, m), 2.91 (2H, d), 3.15-3.19 (2H, m). )

Reference production example 95
[Step 1]
7.87 g of oxalyl chloride was dissolved in 50 ml of dichloromethane and cooled to −78 ° C. in a nitrogen atmosphere. To the solution, 4.85 g of dimethyl sulfoxide dissolved in 50 ml of dichloromethane was added dropwise over 20 minutes and stirred at −50 ° C. for 30 minutes. To the reaction mixture, 9.28 g of the present organic sulfur compound (15) (trans form / cis form = 6/4) dissolved in 150 ml of dichloromethane was added dropwise over 30 minutes, and the mixture was stirred at −50 ° C. for 40 minutes. 18.22 g was dripped over 40 minutes. The reaction mixture was stirred at room temperature for 18 hours. 100 ml of water was added to the reaction mixture, and the organic layer was separated and extracted twice with 100 ml of chloroform. The combined organic layers were sequentially washed with 150 ml of 1N hydrochloric acid aqueous solution, 150 ml of saturated aqueous sodium hydrogen carbonate solution and 150 ml of water, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 8.41 g of the present organic sulfur compound (116). The obtained organic sulfur compound (116) was a mixture of trans isomer / cis isomer = 6/4.

[Step 2]
19.90 g of carbon tetrabromide was dissolved in 100 ml of dichloromethane and cooled to 0 ° C. under a nitrogen atmosphere. To this was added 31.48 g of triphenylphosphine over 30 minutes, and the mixture was further stirred for 30 minutes. To this solution, 8.41 g of the present organic sulfur compound (116) (where trans isomer / cis isomer = 6/4) dissolved in 50 ml of dichloromethane was added dropwise over 30 minutes, followed by stirring at room temperature for 6 hours. 150 ml of t-butyl methyl ether was added to the reaction mixture, the solid was filtered, and the filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 12.7 g of the present organic sulfur compound (17). The obtained organic sulfur compound (117) was trans isomer / cis isomer = 6/4.

[Step 3]
12.7 g of this organic sulfur compound (117) (however, trans / cis = 6/4) was dissolved in 60 ml of tetrahydrofuran and cooled to −78 ° C. in a nitrogen atmosphere. To this solution, 40 ml of 1.6Mn-butyllithium / n-hexane solution was added dropwise over 30 minutes, followed by stirring at -50 ° C for 1 hour and at 0 ° C for 2 hours. The reaction mixture was poured into 100 ml of 1N aqueous hydrochloric acid cooled in an ice bath and extracted twice with 200 ml of t-butyl methyl ether. The combined organic layers were washed with 100 ml of saturated aqueous sodium hydrogen carbonate solution and 100 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 1.68 g of a cis form of the present organic sulfur compound (118) (hereinafter referred to as the present organic sulfur compound (118c)).
This organic sulfur compound (118c)
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.58-1.67 (2H, m), 1.82-1.84 (3H, m), 2.01-2.17 (5H) M), 2.62-2.74 (2H, m), 2.78 (1H, br. S), 2.97 (2H, d), 3.15-3.19 (2H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．１４−１．２０（２Ｈ，ｍ），１．４３−１．５６（２Ｈ，ｍ），２．０２−２．２２（８Ｈ，ｍ），２．３１−２．４０（２Ｈ，ｍ），２．５４−２．６０（１Ｈ，ｍ），２．６０−２．７１（１Ｈ，ｍ），２．８９−２．９６（３Ｈ，ｍ），３．２４−３．２６（１Ｈ，ｍ），３．７０（３Ｈ，ｓ） Reference production example 96
1.88 g of this organic sulfur compound (117) was dissolved in 10 ml of tetrahydrofuran, and cooled to −78 ° C. in a nitrogen atmosphere. To the solution, 2.8 ml of 1.6M n-butyllithium / n-hexane solution was added dropwise over 10 minutes, stirred at −50 ° C. for 1 hour, 0.37 g of methyl acrylate was added, and at 0 ° C. for 2 hours. Stir. The reaction mixture was poured into 30 ml of 1N aqueous hydrochloric acid cooled in an ice bath and extracted twice with 30 ml of t-butyl methyl ether. The organic layers were combined, washed with 30 ml of saturated aqueous sodium hydrogen carbonate solution and 30 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 5- [4- (3,3,3-trifluoropropylsulfonylmethyl) cyclohexyl] -4-pentynoic acid methyl ester represented by the following formula (hereinafter referred to as the present organic sulfur compound ( 119).) 0.70 g was obtained.
This organic sulfur compound (119)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.14-1.20 (2H, m), 1.43-1.56 (2H, m), 2.02-2.22 (8H) M), 2.31-2.40 (2H, m), 2.54-2.60 (1H, m), 2.60-2.71 (1H, m), 2.89-2.96. (3H, m), 3.24-3.26 (1H, m), 3.70 (3H, s)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．１４−１．２６（２Ｈ，ｍ），１．６３−１．７３（１Ｈ，ｍ），２．０３−２．４３（７Ｈ，ｍ），２．６４−２．７４（２Ｈ，ｍ），２．９２（２Ｈ，ｄ），３．１６−３．２０（２Ｈ，ｍ） Reference production example 97
To 0.57 g of the organic sulfur compound (116), 0.32 g of pyridine and 0.14 g of hydroxylamine hydrochloride were added and stirred for 1 hour. 1 ml of acetic anhydride was added to the mixture and stirred at 100 ° C. for 2 hours. To the reaction mixture was added 30 ml of saturated aqueous sodium hydrogen carbonate solution, and the mixture was extracted twice with 30 ml of ethyl acetate. The organic layers were combined, washed with 30 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 1-cyano-4- (3,3,3-trifluoropropylsulfonylmethyl) cyclohexane (hereinafter referred to as the present organic sulfur compound (120)) represented by the following formula: 0 .32 g was obtained.
This organic sulfur compound (120)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.14 to 1.26 (2H, m), 1.63-1.73 (1H, m), 2.03 to 2.43 (7H) , M), 2.64-2.74 (2H, m), 2.92 (2H, d), 3.16-3.20 (2H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．３０−１．３９（２Ｈ，ｍ），１．８４−１．９２（１Ｈ，ｍ），２．１２−２．２３（３Ｈ，ｍ），２．３７−２．４６（２Ｈ，ｍ），２．６５−２．７２（２Ｈ，ｍ），２．９６（２Ｈ，ｄ），３．１７−３．２４（２Ｈ，ｍ） Reference production example 98
0.19 g of this organic sulfur compound (103) was dissolved in 1 ml of pyridine, 0.08 g of O-methylhydroxylamine hydrochloride was added thereto, and the mixture was stirred at room temperature for 5 hours. 30 ml of water was added to the reaction solution and extracted twice with 30 ml of ethyl acetate. The organic layers were combined and washed with 50 ml of saturated brine. The obtained organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue is subjected to silica gel column chromatography, and is represented by 4- (3,3,3-trifluoropropylsulfonylmethyl) -cyclohexanone = O-methyloxime (hereinafter referred to as the present organic sulfur compound (121)) represented by the following formula. ) 0.19 g was obtained.
This organic sulfur compound (121)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.30-1.39 (2H, m), 1.84-1.92 (1H, m), 2.12-2.23 (3H) M), 2.37-2.46 (2H, m), 2.65-2.72 (2H, m), 2.96 (2H, d), 3.17-3.24 (2H, m). )

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．４７−１．６１（１Ｈ，ｍ），１．９７−２．０６（２Ｈ，ｍ），２．２４−２．３０（２Ｈ，ｍ），２．４２−２．４７（２Ｈ，ｍ），２．６５−２．７５（２Ｈ，ｍ）２．８４（１Ｈ，ｓ），３．００−３．０３（２Ｈ，ｍ），３．１７−３．２１（２Ｈ，ｍ），６．１４（１Ｈ，ｂｒ．ｓ） Reference Production Example 99
0.58 g of the organic sulfur compound (107) was dissolved in 4 ml of tetrahydrofuran, and 2.2 ml of a 0.9 M methylmagnesium bromide / tetrahydrofuran solution was added thereto at 0 ° C. in a nitrogen atmosphere, followed by stirring at room temperature for 5 hours. 20 ml of water was added to the reaction solution and extracted twice with 20 ml of ethyl acetate. The organic layers were combined and washed with 50 ml of saturated brine. The obtained organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and described as 1-ethynyl-4- (3,3,3-trifluoropropyl-1-sulfonylmethyl) cyclohexene (hereinafter referred to as the present organic sulfur compound (122)) represented by the following formula. .) 0.21 g was obtained.
This organic sulfur compound (122)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.47-1.61 (1H, m), 1.97-2.06 (2H, m), 2.24-2.30 (2H M), 2.42-2.47 (2H, m), 2.65-2.75 (2H, m) 2.84 (1H, s), 3.00-3.03 (2H, m) 3.17-3.21 (2H, m), 6.14 (1H, br.s)

本有機硫黄化合物（１２３ｃ）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．０５−１．１６（２Ｈ，ｍ），１．４９−１．６６（３Ｈ，ｍ），１．７２−１．８０（２Ｈ，ｍ），２．０７−２．１６（２Ｈ，ｍ），２．３０−２．４７（５Ｈ，ｍ），２．６３−２．６７（２Ｈ，ｍ），９．６２（１Ｈ，ｄ）
本有機硫黄化合物（１２３ｔ）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）０．９９−１．１０（２Ｈ，ｍ），１．２４−１．３４（２Ｈ，ｍ），１．４０−１．５３（１Ｈ，ｍ），１．９７−２．０８（４Ｈ，ｍ），２．１３−２．２５（１Ｈ，ｍ），２．３１−２．４３（２Ｈ，ｍ），２．４６（２Ｈ，ｍ），２．６５−２．６９（２Ｈ，ｍ），９．６９（１Ｈ，ｄ） Reference production example 100
62.83 g of oxalyl chloride was dissolved in 250 ml of dichloromethane and cooled to −78 ° C. under a nitrogen atmosphere. To this solution, 77.35 g of dimethyl sulfoxide dissolved in 250 ml of dichloromethane was added dropwise over 60 minutes, followed by stirring at −50 ° C. for 60 minutes. To this reaction mixture, 84.54 g of the present organic sulfur compound (114) (mixture of trans isomer / cis isomer = 6/4) dissolved in 250 ml of dichloromethane was added dropwise over 60 minutes, followed by stirring at −50 ° C. for 90 minutes. 100.18 g was added dropwise over 90 minutes. The reaction mixture was stirred at room temperature for 18 hours. 300 ml of water was added to the reaction mixture, the organic layer was separated, and the aqueous layer was extracted twice with 200 ml of chloroform. The organic layers were combined, washed sequentially with 300 ml of 1N hydrochloric acid aqueous solution, 300 ml of saturated aqueous sodium hydrogen carbonate solution and 300 ml of water, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and the cis form of 4- (3,3,3-trifluoropropylthiomethyl) cyclohexanecarbaldehyde represented by the following formula (hereinafter referred to as the present organic sulfur compound (123)). (Hereinafter referred to as the present organic sulfur compound (123c)) 23.03 g and trans form (hereinafter referred to as the present organic sulfur compound (123t)) 38.51 g were obtained.
This organic sulfur compound (123)

This organic sulfur compound (123c)
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.05-1.16 (2H, m), 1.49-1.66 (3H, m), 1.72-1.80 (2H M), 2.07-2.16 (2H, m), 2.30-2.47 (5H, m), 2.63-2.67 (2H, m), 9.62 (1H, d). )
This organic sulfur compound (123t)
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 0.99-1.10 (2H, m), 1.24-1.34 (2H, m), 1.40-1.53 (1H , M), 1.97-2.08 (4H, m), 2.13-2.25 (1H, m), 2.31-2.43 (2H, m), 2.46 (2H, m ), 2.65-2.69 (2H, m), 9.69 (1H, d)

本有機硫黄化合物（１２４ｔ）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）０．９８−１．０８（２Ｈ，ｍ），１．１０−１．２０（２Ｈ，ｍ），１．３７−１．４９（１Ｈ，ｍ），１．７８−１．８５（２Ｈ，ｍ），１．８８−１．９５（２Ｈ，ｍ），２．１７−２．２９（１Ｈ，ｍ），２．３１−２．４１（２Ｈ，ｍ），２．４３（２Ｈ，ｍ），２．６４−２．６８（２Ｈ，ｍ），６．１９（１Ｈ，ｄ） Reference production example 101
100.48 g of carbon tetrabromide was dissolved in 300 ml of dichloromethane, cooled to 0 ° C. under a nitrogen atmosphere, 158.86 g of triphenylphosphine was added over 90 minutes, and the mixture was further stirred for 30 minutes. The organic sulfur compound (123t) (38.51 g) dissolved in 100 ml of dichloromethane was added dropwise to the solution over 30 minutes, and the mixture was stirred at room temperature for 6 hours. 500 ml of t-butyl methyl ether was added to the reaction mixture, the solid was filtered, and the filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 1- (2,2-dibromovinyl) -4- (3,3,3-trifluoropropylthiomethyl) cyclohexane (hereinafter referred to as the present organic sulfur compound ( 124). 66.56 g of a trans isomer (hereinafter referred to as the present organic sulfur compound (124t)) was obtained.
This organic sulfur compound (124)

This organic sulfur compound (124t)
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 0.98-1.08 (2H, m), 1.10-1.20 (2H, m), 1.37-1.49 (1H M), 1.78-1.85 (2H, m), 1.88-1.95 (2H, m), 2.17-2.29 (1H, m), 2.31-2.41. (2H, m), 2.43 (2H, m), 2.64-2.68 (2H, m), 6.19 (1H, d)

本有機硫黄化合物（１２５ｔ）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）０．９２−１．０３（２Ｈ，ｍ），１．３４−１．５３（３Ｈ，ｍ），１．８６−１．９４（２Ｈ，ｍ），１．９８−２．０６（３Ｈ，ｍ），２．１５−２．２４（１Ｈ，ｍ），２．３０−２．４１（２Ｈ，ｍ），２．４２（２Ｈ，ｄ），２．６４−２．６８（２Ｈ，ｍ） Reference production example 102
The organic sulfur compound (124t) (53.78 g) was dissolved in tetrahydrofuran (300 ml) and cooled to -78 ° C under a nitrogen atmosphere. To this solution, 180 ml of 1.6Mn-butyllithium hexane solution was added dropwise over 60 minutes, followed by stirring at −50 ° C. for 1 hour and at 0 ° C. for 2 hours. The reaction mixture was poured into 300 ml of 1N aqueous hydrochloric acid cooled in an ice bath and extracted twice with 300 ml of t-butyl methyl ether. The organic layers were combined, washed with 300 ml of saturated aqueous sodium hydrogen carbonate solution and 300 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and represented by 1-ethynyl-4- (3,3,3-trifluoropropyl-1-sulfonylmethyl) cyclohexane (hereinafter referred to as the present organic sulfur compound (125)) represented by the following formula. ) Was obtained in an amount of 31.54 g (hereinafter referred to as the present organic sulfur compound (125t)).
This organic sulfur compound (125)

This organic sulfur compound (125t)
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 0.92-1.03 (2H, m), 1.34-1.53 (3H, m), 1.86-1.94 (2H) M), 1.98-2.06 (3H, m), 2.15-2.24 (1H, m), 2.30-2.41 (2H, m), 2.42 (2H, d). ), 2.64-2.68 (2H, m)

Reference production example 103
It replaces with this organic sulfur compound (123t), uses this organic sulfur compound (123c) according to the method of the reference manufacture example 94 and the reference manufacture example 95, and is the cis body (following and below) of this organic sulfur compound 25 This organic sulfur compound (referred to as 125c) was produced.
This organic sulfur compound (125c)
¹ H-NMR (CDCl ₃ , TMS, δ (ppm)): 1.38-1.53 (5H, m), 1.67-1.75 (2H, m), 1.78-1.86 ( 2H, m), 2.05 (1H, d), 2.31-2.44 (2H, m), 2.47 (2H, d), 2.65-2.69 (2H, m), 2 .74-2.79 (1H, m)

本有機硫黄化合物（１２６ｔ）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．０２−１．２１（２Ｈ，ｍ），１．４１−１．５３（２Ｈ，ｍ），１．８２−２．００（２Ｈ，ｍ），２．００−２．０９（４Ｈ，ｍ），２．２０−２．２７（１Ｈ，ｍ），２．４０−２．４６（１Ｈ，ｍ），２．５７−２．６８（２Ｈ，ｍ），２．７１−２．９２（３Ｈ，ｍ） Reference production example 104
20.30 g of a double salt of 2KHSO ₅ · KHSO ₄ · K2SO ₄ (Oxone (registered trademark)) is suspended in 60 ml of water, and a solution of 7.51 g of the present organic sulfur compound (124t) in 60 ml of methanol is added at −20 ° C. in a nitrogen atmosphere. The solution was added dropwise over 60 minutes and stirred for 2 hours. 50 ml of 10% aqueous sodium sulfite solution was added to the reaction mixture, and the mixture was extracted twice with 100 ml of ethyl acetate. The organic layers were combined, washed with 50 ml of 10% aqueous sodium sulfite solution and 50 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 1-ethynyl-4- (3,3,3-trifluoropropylsulfinylmethyl) cyclohexane (hereinafter referred to as the present organic sulfur compound (126)) represented by the following formula: 4.88 g of trans form (hereinafter referred to as the present organic sulfur compound (126t)) was obtained.
This organic sulfur compound (126)

This organic sulfur compound (126t)
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.02-1.21 (2H, m), 1.41-1.53 (2H, m), 1.82-2.00 (2H M), 2.00-2.09 (4H, m), 2.20-2.27 (1H, m), 2.40-2.46 (1H, m), 2.57-2.68. (2H, m), 2.71-2.92 (3H, m)

Reference production example 105
[Step 1]
7.35 g of potassium thioacetate was suspended in 30 ml of N-methyl-2-pyrrolidone, and 11.39 g of 3-bromo-1,1,1-trifluoropropane was added dropwise over 15 minutes at 0 ° C. under a nitrogen atmosphere. Stir at room temperature for 1 hour. The reaction mixture was heated to 80 ° C. and distilled under reduced pressure to obtain 9.99 g of 3,3,3-trifluoropropylthioacetic acid ester.

[Step 2]
After 9.99 g of 3,3,3-trifluoropropylthioacetic acid ester was dissolved in 60 ml of tetrahydrofuran and cooled to 0 ° C., 11.2 g of 28% sodium methoxide / methanol solution was added dropwise over 15 minutes. Stir for 1 hour. To the mixture, 4.38 g of chloroacetonitrile was added at 0 ° C., and the mixture was stirred at room temperature for 3 hours. The reaction vessel was cooled in an ice bath, saturated brine was added, and the mixture was extracted twice with 100 ml of t-butyl methyl ether. The combined organic layers were washed with saturated brine, dried over sodium sulfate, filtered, and reduced pressure. Concentrated. The residue was subjected to silica gel column chromatography to obtain 7.56 g of (3,3,3-trifluoropropylthio) acetonitrile.

[Step 3]
While stirring a suspension of 4.97 g of (3,3,3-trifluoropropylthio) acetonitrile and 0.07 g of sodium tungstate dihydrate in 7 mL of water, 2.3 ml of 31% hydrogen peroxide solution was stirred. Was added. During the reaction, a portion of the solid precipitated in the reaction solution was collected and purified by thin layer chromatography. As a result, (3,3,3-trifluoropropylsulfinyl) acetonitrile ( ¹ H-NMR is described below) It was confirmed that this occurred. The mixture was heated to 65 ° C., and further 2.3 ml of 31% hydrogen peroxide solution was added, followed by stirring at 70 ° C. for 1 hour. The reaction mixture was cooled to room temperature, 5 ml of 10% aqueous sodium sulfite solution was added, and the mixture was extracted 3 times with 30 ml of ethyl acetate. The organic layers were combined, washed with saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was crystallized with chloroform: hexane = 1: 2 to obtain 5.44 g of (3,3,3-trifluoropropylsulfonyl) acetonitrile.

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．６１−１．９０（７Ｈ，ｍ），２．１３−２．２３（１Ｈ，ｍ），２．３９−２．５１（１Ｈ，ｍ），２．６７−２．８６（２Ｈ，ｍ），３．３９−３．４７（１Ｈ，ｍ），３．５１−３．６０（１Ｈ，ｍ），３．８５（１Ｈ，ｄ），３．９２−３．９９（４Ｈ，ｍ） [Step 4]
(3,3,3-trifluoropropylsulfonyl) acetonitrile 4.02 g, toluene 100 ml, DL-proline 0.23 g and 1,4-cyclohexanedione monoethylene ketal 3.32 g were heated and stirred under reflux conditions for 3 hours. . After distilling off 20 ml of toluene from the reaction mixture, it was cooled to room temperature. 100 ml of tetrahydrofuran was added to the reaction mixture, and after cooling to 0 ° C., 1.01 g of sodium borohydride was added. After stirring at room temperature for 6 hours, the mixture was cooled to 0 ° C., and 100 ml of water and 100 ml of ethyl acetate were added. While stirring the solution, 100 ml of 1N hydrochloric acid was added dropwise, and extracted twice with 100 ml of ethyl acetate. The organic layer was washed with 100 ml of saturated aqueous sodium hydrogencarbonate, 100 ml of saturated brine, and 100 ml of water, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (1,4-dioxaspiro [4,5] dec-8-yl) -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile represented by the following formula: (Hereinafter referred to as the present organic sulfur compound (127).) 5.45 g was obtained.
This organic sulfur compound (127)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.61-1.90 (7H, m), 2.13-2.23 (1H, m), 2.39-2.51 (1H M), 2.67-2.86 (2H, m), 3.39-3.47 (1H, m), 3.51-3.60 (1H, m), 3.85 (1H, d) ), 3.92-3.99 (4H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．８７−１．９７（２Ｈ，ｍ），２．１８−２．２５（１Ｈ，ｍ），２．４２−２．６０（５Ｈ，ｍ），２．７３−２．９５（３Ｈ，ｍ），３．４１−３．５１（１Ｈ，ｍ），３．５５−３．６６（１Ｈ，ｍ），３．９７（１Ｈ，ｄ） Reference production example 106
7 ml of acetic acid and 3 ml of water were added to 3.20 g of this organic sulfur compound (127), heated to 70 ° C. and stirred for 10 hours. After the reaction mixture was cooled to room temperature, 100 ml of ethyl acetate was added and slowly added to 100 ml of saturated aqueous sodium bicarbonate. The solution was stirred for 1 hour and extracted twice with 100 ml of ethyl acetate. The organic layers were combined, washed with 100 ml of saturated aqueous sodium bicarbonate and 100 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (4-oxocyclohexyl) -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound (128) and 2.59 g was obtained.
This organic sulfur compound (128)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.87-1.97 (2H, m), 2.18-2.25 (1H, m), 2.42-2.60 (5H M), 2.73-2.95 (3H, m), 3.41-3.51 (1H, m), 3.55-3.66 (1H, m), 3.97 (1H, d) )

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．４１−１．９９（５Ｈ，ｍ），２．１６−２．３２（３Ｈ，ｍ），２．４２−２．５８（１Ｈ，ｍ），２．７０−２．８６（２Ｈ，ｍ），３．３８−３．４９（１Ｈ，ｍ），３．５４−３．６８（１Ｈ，ｍ），３．８７（１Ｈ，ｄ） Reference production example 107
0.15 g of this organic sulfur compound (128) was dissolved in 5 ml of dichloromethane, 0.21 g of diethylaminosulfur trifluoride was added thereto at −20 ° C. under a nitrogen atmosphere, and the mixture was stirred at room temperature for 5 hours. The reaction solution was diluted with 30 ml of chloroform, 30 ml of water was added, and the organic layer was separated. The aqueous layer was extracted twice with 30 ml of chloroform, and the organic layers were combined and washed with 50 ml of saturated brine. The obtained organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (4,4-difluorocyclohexyl) -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound (129) represented by the following formula: ) Was obtained.) 0.16 was obtained.
This organic sulfur compound (129)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.41-1.99 (5H, m), 2.16-2.32 (3H, m), 2.42 to 2.58 (1H , M), 2.70-2.86 (2H, m), 3.38-3.49 (1H, m), 3.54-3.68 (1H, m), 3.87 (1H, d) )

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．５９−２．２８（９Ｈ，ｍ），２．２８−２．４７（１Ｈ，ｍ），２．６１（１Ｈ，ｓ），２．７１−２．８４（２Ｈ，ｍ），３．４０−３．４８（１Ｈ，ｍ），３．５２−３．６０（１Ｈ，ｍ），３．８７（１Ｈ，ｄ） Reference production example 108
1.49 g of the organic sulfur compound (128) was dissolved in 20 ml of tetrahydrofuran, and 30 ml of a 0.5 M ethynylmagnesium bromide tetrahydrofuran solution was added thereto at 0 ° C. under a nitrogen atmosphere, followed by stirring at 0 ° C. for 5 hours. To the reaction solution was added 50 ml of 1N aqueous hydrochloric acid solution, and the mixture was extracted twice with 50 ml of ethyl acetate. The organic layers were combined and washed with 50 ml of saturated aqueous sodium hydrogen carbonate solution and 50 ml of saturated brine. The obtained organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (4-ethynyl-4-hydroxycyclohexyl) -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound) represented by the following formula: (Described as (130).) 1.69 g was obtained.
This organic sulfur compound (130)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.59-2.28 (9H, m), 2.28-2.47 (1H, m), 2.61 (1H, s), 2.71-2.84 (2H, m), 3.40-3.48 (1H, m), 3.52-3.60 (1H, m), 3.87 (1H, d)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．７３−２．１５（６Ｈ，ｍ），２．２５−２．２．３９（２Ｈ，ｍ），２．４４−２．５４（１Ｈ，ｍ），２．６６（１Ｈ，ｄ），２．７１−２．８４（２Ｈ，ｍ），３．４０−３．４８（１Ｈ，ｍ），３．５３−３．６１（１Ｈ，ｍ），３．８７（１Ｈ，ｄ）
本有機硫黄化合物（１３２）：１：１の異性体混合物

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．６８−２．８４（９Ｈ，ｍ），２．８４（１Ｈ，ｄ），３．３９−３．４９（１Ｈ，ｍ），３．５１−３．６６（１Ｈ，ｍ），３．８９（１Ｈ，ｄ），６．１０−６．１８（２Ｈ，ｍ） Reference Production Example 109
0.65 g of this organic sulfur compound (130) was dissolved in 6 ml of dichloromethane, and 0.48 g of diethylaminosulfur trifluoride was added thereto at 0 ° C. under a nitrogen atmosphere, followed by stirring at room temperature for 5 hours. The reaction solution was diluted with 20 ml of chloroform, 20 ml of water was added, and then the organic layer was separated. The aqueous layer was extracted twice with 20 ml of chloroform. The organic layers were combined and washed with 50 ml of saturated brine. The obtained organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (4-ethynyl-4-fluorocyclohexyl) -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound) represented by the following formula: (Referred to as (131).) 0.31 g and 2- (4-ethynyl-cyclohexen-3-yl) -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present organic compound) represented by the following formula: 0.23 g of the sulfur compound (132) was obtained.
This organic sulfur compound (131)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.73-2.15 (6H, m), 2.25-2.2.39 (2H, m), 2.44-2.54 (1H, m), 2.66 (1H, d), 2.71-2.84 (2H, m), 3.40-3.48 (1H, m), 3.53-3.61 (1H , M), 3.87 (1H, d)
The present organic sulfur compound (132): 1: 1 isomer mixture

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.68-2.84 (9H, m), 2.84 (1H, d), 3.39-3.49 (1H, m), 3.51-3.66 (1H, m), 3.89 (1H, d), 6.10-6.18 (2H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．５０−１．７１（２Ｈ，ｍ），１．８０−１．９１（１Ｈ，ｍ），１．９５−２．０８（１Ｈ，ｍ），２．１６−２．２７（１Ｈ，ｍ），２．３０−２．４４（１Ｈ，ｍ），２．４９−２．５７（１Ｈ，ｍ），２．６２−２．７１（１Ｈ，ｍ），２．７２−２．８６（２Ｈ，ｍ），３．３２−３．４８（２Ｈ，ｍ），３．５２−３．６１（１Ｈ，ｍ），３．８３（３Ｈ，ｓ），３．８７（１Ｈ，ｄ） Reference production example 110
The organic sulfur compound (128) (2.81 g) was dissolved in tetrahydrofuran (10 ml), pyridine (0.75 g) and methoxyamine hydrochloride (0.79) were added, and the mixture was stirred at room temperature for 3 hours. 30 ml of 1N aqueous hydrochloric acid solution was added to the reaction solution, and the mixture was extracted twice with 50 ml of ethyl acetate. The organic layers were combined and washed with 50 ml of saturated aqueous sodium hydrogen carbonate solution and 50 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- [4- (methoxyimino) cyclohexyl] -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound ( 133).) 2.86 g was obtained.
This organic sulfur compound (133)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.50-1.71 (2H, m), 1.80-1.91 (1H, m), 1.95-2.08 (1H M), 2.16-2.27 (1H, m), 2.30-2.44 (1H, m), 2.49-2.57 (1H, m), 2.62-2.71 (1H, m), 2.72-2.86 (2H, m), 3.32-3.48 (2H, m), 3.52-3.61 (1H, m), 3.83 (3H , S), 3.87 (1H, d)

^１Ｈ−ＮＭＲ（ＣＤ_３ＯＤ，ＴＭＳ）：δ（ｐｐｍ）１．２９−１．４８（２Ｈ，ｍ），１．６９−１．８５（１Ｈ，ｍ），１．８７−２．０１（１Ｈ，ｍ），２．０７−２．２７（２Ｈ，ｍ），２．２９−２．３８（１Ｈ，ｍ），２．５１−２．５９（１Ｈ，ｍ），２．６７−２．８１（２Ｈ，ｍ），３．１８−３．２２（１Ｈ，ｍ），３．２６−３．３４（２Ｈ，ｍ），４．４７（１Ｈ，ｂｒ．ｓ） Reference Production Example 111
The organic sulfur compound (128) (0.20 g) was dissolved in pyridine (2 ml), hydroxylamine hydrochloride (0.06 g) was added, and the mixture was stirred at room temperature for 3 hours. To the reaction solution, 50 ml of hexane was added and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- [4- (hydroxyimino) cyclohexyl] -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound ( 134).) 0.093 g was obtained.
This organic sulfur compound (134)

¹ H-NMR (CD ₃ OD, TMS): δ (ppm) 1.29-1.48 (2H, m), 1.69-1.85 (1H, m), 1.87-2.01 ( 1H, m), 2.07-2.27 (2H, m), 2.29-2.38 (1H, m), 2.51-2.59 (1H, m), 2.67-2. 81 (2H, m), 3.18-3.22 (1H, m), 3.26-3.34 (2H, m), 4.47 (1H, br.s)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．２５（３Ｈ，ｔ），１．５１−１．７２（２Ｈ，ｍ），１．７９−１．９２（１Ｈ，ｍ），１．９５−２．０７（１Ｈ，ｍ），２．１７−２．２７（１Ｈ，ｍ），２．３１−２．４３（１Ｈ，ｍ），２．４９−２．５９（１Ｈ，ｍ），２．６１−２．７１（１Ｈ，ｍ），２．７２−２．８６（２Ｈ，ｍ），３．３５−３．４９（２Ｈ，ｍ），３．５１−３．６１（１Ｈ，ｍ），３．８５（１Ｈ，ｄ），４．０５（２Ｈ，ｑ） Reference production example 112
In place of hydroxylamine hydrochloride, 0.008 g of ethoxyamine hydrochloride is used, and 2- [4- (ethoxyimino) cyclohexyl] -2- (2) represented by the following formula is used according to the method described in Reference Production Example 102. 0.095 g of (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound (135)) was obtained.
This organic sulfur compound (135)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.25 (3H, t), 1.51-1.72 (2H, m), 1.79-1.92 (1H, m), 1.95-2.07 (1H, m), 2.17-2.27 (1H, m), 2.31-2.43 (1H, m), 2.49-2.59 (1H, m ), 2.61-2.71 (1H, m), 2.62-2.86 (2H, m), 3.35-3.49 (2H, m), 3.51-3.61 (1H) M), 3.85 (1H, d), 4.05 (2H, q)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．２６（９Ｈ，ｓ），１．４９−１．７０（２Ｈ，ｍ），１．７５−１．８８（１Ｈ，ｍ），１．９１−２．０６（１Ｈ，ｍ），２．１４−２．２５（１Ｈ，ｍ），２．２７−２．４２（１Ｈ，ｍ），２．５１−２．５９（１Ｈ，ｍ），２．５９−２．７０（１Ｈ，ｍ），２．７１−２．８８（２Ｈ，ｍ），３．３５−３．４８（２Ｈ，ｍ），３．５２−３．６８（１Ｈ，ｍ），３．８６−３．８８（１Ｈ，ｍ） Reference production example 113
In place of hydroxylamine hydrochloride, 0.01 g of t-butoxyamine hydrochloride was used and 2- [4- (t-butoxyimino) cyclohexyl represented by the following formula was prepared according to the method described in Reference Production Example 102. ] 0.19 g of 2- (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound (136)) was obtained.
This organic sulfur compound (136)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.26 (9H, s), 1.49-1.70 (2H, m), 1.75-1.88 (1H, m), 1.91-2.06 (1H, m), 2.14-2.25 (1H, m), 2.27-2.42 (1H, m), 2.51-2.59 (1H, m ), 2.59-2.70 (1H, m), 2.71-2.88 (2H, m), 3.35-3.48 (2H, m), 3.52-3.68 (1H) , M), 3.86-3.88 (1H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．５２−１．７２（２Ｈ，ｍ），１．７９−１．９４（１Ｈ，ｍ），１．９６−２．０９（１Ｈ，ｍ），２．１６−２．２８（１Ｈ，ｍ），２．３１−２．４２（１Ｈ，ｍ），２．５０−２．５９（１Ｈ，ｍ），２．６１−２．７２（１Ｈ，ｍ），２．７２−２．８６（２Ｈ，ｍ），３．３８−３．４８（２Ｈ，ｍ），３．５２−３．６１（１Ｈ，ｍ），３．８５−３．８８（１Ｈ，ｍ），４．５２−４．５５（２Ｈ，ｍ），５．１９−５．３３（２Ｈ，ｍ），５．９２−６．０４（２Ｈ，ｍ） Reference production example 114
In place of hydroxylamine hydrochloride, 0.009 g of O-allylhydroxylamine hydrochloride was used and 2- [4- (O-allyloxyimino) represented by the following formula was prepared according to the method described in Reference Production Example 102. ) Cyclohexyl] -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound (137)) was obtained in an amount of 0.061 g.
This organic sulfur compound (137)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.52-1.72 (2H, m), 1.79-1.94 (1H, m), 1.96-2.09 (1H M), 2.16-2.28 (1H, m), 2.31-2.42 (1H, m), 2.50-2.59 (1H, m), 2.61-2.72. (1H, m), 2.72-2.86 (2H, m), 3.38-3.48 (2H, m), 3.52-3.61 (1H, m), 3.85-3 .88 (1H, m), 4.52-4.55 (2H, m), 5.19-5.33 (2H, m), 5.92-6.04 (2H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．４９−１．７２（２Ｈ，ｍ），１．８１−２．０８（２Ｈ，ｍ），２．１６−２．２７（１Ｈ，ｍ），２．３０−２．４３（１Ｈ，ｍ），２．５０−２．５８（１Ｈ，ｍ），２．６１−２．７０（１Ｈ，ｍ），２．７２−２．８３（２Ｈ，ｍ），３．３８−３．４８（２Ｈ，ｍ），３．５１−３．６１（１Ｈ，ｍ），３．８４−３．８７（１Ｈ，ｍ），５．０７（２Ｈ，ｓ），７．２８−７．３４（１Ｈ，ｍ），７．３５−７．３６（４Ｈ，ｍ） Reference production example 115
In place of hydroxylamine hydrochloride, 0.009 g of O-benzylhydroxylamine hydrochloride was used and 2- [4- (O-benzyloxyimino) represented by the following formula was prepared according to the method described in Reference Production Example 102. ) Cyclohexyl] -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound (138)) was obtained in an amount of 0.10 g.
This organic sulfur compound (138)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.49-1.72 (2H, m), 1.81-2.08 (2H, m), 2.16-2.27 (1H) M), 2.30-2.43 (1H, m), 2.50-2.58 (1H, m), 2.61-2.70 (1H, m), 2.72-2.83. (2H, m), 3.38-3.48 (2H, m), 3.51-3.61 (1H, m), 3.84-3.87 (1H, m), 5.07 (2H , S), 7.28-7.34 (1H, m), 7.35-7.36 (4H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．５６−１．７２（２Ｈ，ｍ），１．８８−２．１１（２Ｈ，ｍ），２．１７−２．２９（１Ｈ，ｍ），２．３１−２．４３（１Ｈ，ｍ），２．４７−２．５６（１Ｈ，ｍ），２．６０−２．７０（１Ｈ，ｍ），２．７３−２．８４（２Ｈ，ｍ），３．３８−３．４３（４Ｈ，ｍ），４．５７（２Ｈ，ｓ） Reference production example 116
The organic sulfur compound (128) (0.20 g) was dissolved in pyridine (2 ml), O-carboxymethylhydroxylamine hydrochloride (0.06 g) was added, and the mixture was stirred at room temperature for 3 hours. 30 ml of 1N aqueous hydrochloric acid was added to the reaction solution, and the mixture was extracted twice with 30 ml of ethyl acetate. The obtained organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- [4- (O-carboxymethyloxyimino) cyclohexyl] -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present compound) represented by the following formula: 0.094 g of organic sulfur compound (described as 139) was obtained.
This organic sulfur compound (139)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.56-1.72 (2H, m), 1.88-2.11 (2H, m), 2.17-2.29 (1H M), 2.31-2.43 (1H, m), 2.47-2.56 (1H, m), 2.60-2.70 (1H, m), 2.73-2.84. (2H, m), 3.38-3.43 (4H, m), 4.57 (2H, s)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．３１−１．６４（２Ｈ，ｍ），１．７５（３Ｈ，ｓ），１．７６−１．９１（１Ｈ，ｍ），２．１３−２．３２（３Ｈ，ｍ），２．４８−２．６２（２Ｈ，ｍ），２．６９−２．８７（２Ｈ，ｍ），３．３２−３．４７（２Ｈ，ｍ），３．５５−３．６４（１Ｈ，ｍ），３．８３（３Ｈ，ｓ） Reference Production Example 117
0.16 g of the organic sulfur compound (133) was dissolved in 3 ml of dimethyl sulfoxide and cooled to 0 ° C. in a nitrogen atmosphere. To the mixture, 0.05 g of 60% sodium hydride was added and stirred for 30 minutes, then 0.11 g of methyl iodide was added and stirred overnight at room temperature. To the reaction solution was added 10 ml of 1N aqueous hydrochloric acid solution, and the mixture was extracted twice with 30 ml of ethyl acetate. The organic layers were combined, washed with 10 ml of saturated aqueous sodium hydrogen carbonate solution and 10 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- [4- (methoxyimino) cyclohexyl] -2- (3,3,3-trifluoropropylsulfonyl) propionitrile (hereinafter referred to as the present organic sulfur) represented by the following formula: 0.13 g of compound (140) was obtained.
This organic sulfur compound (140)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.31-1.64 (2H, m), 1.75 (3H, s), 1.76-1.91 (1H, m), 2.13-2.32 (3H, m), 2.48-2.62 (2H, m), 2.69-2.87 (2H, m), 3.32-3.47 (2H, m ), 3.55-3.64 (1H, m), 3.83 (3H, s)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）：１．２７（３Ｈ，ｔ），１．４３−１．６９（２Ｈ，ｍ），１．７３−１．８７（１Ｈ，ｍ），２．１０−２．３１（５Ｈ，ｍ），２．４９−２．６１（２Ｈ，ｍ），２．７１−２．８７（２Ｈ，ｍ），３．３３−３．４７（２Ｈ，ｍ），３．５５−３．６６（１Ｈ，ｍ），３．８３（３Ｈ，ｓ） Reference production example 118
Instead of methyl iodide, 0.13 g of ethyl iodide was used and 2- [4- (methoxyimino) cyclohexyl] -2- (3 represented by the following formula according to the method described in Reference Production Example 108 , 3,3-trifluoropropylsulfonyl) butyronitrile (hereinafter referred to as the present organic sulfur compound (141)) (0.13 g) was obtained.
This organic sulfur compound (141)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm): 1.27 (3H, t), 1.43-1.69 (2H, m), 1.73-1.87 (1H, m) , 2.10-2.31 (5H, m), 2.49-2.61 (2H, m), 2.71-2.87 (2H, m), 3.33-3.47 (2H, m), 3.55-3.66 (1H, m), 3.83 (3H, s)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．０６（３Ｈ，ｔ），１．４４−１．７１（４Ｈ，ｍ），１．７３−１．８６（１Ｈ，ｍ），１．９４−２．１３（２Ｈ，ｍ），２．１５−２．３１（３Ｈ，ｍ），２．４８−２．６１（２Ｈ，ｍ），２．７３−２．８３（２Ｈ，ｍ），３．３２−３．４６（２Ｈ，ｍ），３．５５−３．６５（１Ｈ，ｍ），３．８３（３Ｈ，ｓ） Reference Production Example 119
In place of methyl iodide, 0.14 g of 1-iodopropane was used, and according to the method described in Reference Production Example 108, 2- [4- (methoxyimino) cyclohexyl] -2- (3 , 3,3-trifluoropropylsulfonyl) pentanenitrile (hereinafter referred to as the present organic sulfur compound (142)) was obtained in an amount of 0.055 g.
This organic sulfur compound (142)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.06 (3H, t), 1.44-1.71 (4H, m), 1.73-1.86 (1H, m), 1.94-2.13 (2H, m), 2.15-2.31 (3H, m), 2.48-2.61 (2H, m), 2.73-2.83 (2H, m ), 3.32-3.46 (2H, m), 3.55-3.65 (1H, m), 3.83 (3H, s)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．４１−１．６８（２Ｈ，ｍ），１．７３−１．８７（１Ｈ，ｍ），２．１２−２．３３（３Ｈ，ｍ），２．４７−２．８２（５Ｈ，ｍ），２．８６−２．９１（１Ｈ，ｍ），３．３１−３．４８（２Ｈ，ｍ），３．６１−３．６８（１Ｈ，ｍ），３．８３（３Ｈ，ｓ），５．４０−５．４９（２Ｈ，ｍ），５．８７−６．０２（１Ｈ，ｍ） Reference production example 120
2- [4- (methoxyimino) cyclohexyl] -3-methyl represented by the following formula, using 0.10 g of 3-bromopropene instead of methyl iodide, according to the method described in Reference Production Example 108 0.14 g of -2- (3,3,3-trifluoropropylsulfonyl) -4-pentenenitrile (hereinafter referred to as the present organic sulfur compound (143)) was obtained.
This organic sulfur compound (143)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.41-1.68 (2H, m), 1.73-1.87 (1H, m), 2.12-2.33 (3H M), 2.47-2.82 (5H, m), 2.86-2.91 (1H, m), 3.31-3.48 (2H, m), 3.61-3.68. (1H, m), 3.83 (3H, s), 5.40-5.49 (2H, m), 5.87-6.02 (1H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．２９−１．４７（１Ｈ，ｍ），１．５０−１．６８（１Ｈ，ｍ），１．７４−１．９１（１Ｈ，ｍ），２．１３−２．３５（３Ｈ，ｍ），２．４３−２．４５（１Ｈ，ｍ），２．４９−２．６１（１Ｈ，ｍ），２．７３−２．８６（３Ｈ，ｍ），２．９１−３．１１（２Ｈ，ｍ），３．３２−３．４７（１Ｈ，ｍ），３．７３−３．８９（２Ｈ，ｍ），３．８３（３Ｈ，ｓ） Reference production example 121
2- [4- (methoxyimino) cyclohexyl] -3-methyl- represented by the following formula, using 0.10 g of 3-bromopropyne instead of methyl iodide, according to the method described in Reference Production Example 108 0.14 g of 2- (3,3,3-trifluoropropylsulfonyl) -4-pentynenitrile (hereinafter referred to as the present organic sulfur compound (144)) was obtained.
This organic sulfur compound (144)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.29-1.47 (1H, m), 1.50-1.68 (1H, m), 1.74-1.91 (1H M), 2.13-2.35 (3H, m), 2.43-2.45 (1H, m), 2.49-2.61 (1H, m), 2.73-2.86. (3H, m), 2.91-3.11 (2H, m), 3.32-3.47 (1H, m), 3.73-3.89 (2H, m), 3.83 (3H , S)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．５２−１．９１（３Ｈ，ｍ），２．１６−２．２９（１Ｈ，ｍ），２．３４−２．４８（２Ｈ，ｍ），２．５２−２．６３（１Ｈ，ｍ），２．７４−２．８９（３Ｈ，ｍ），３．３６−３．４６（１Ｈ，ｍ），３．６４−３．８２（２Ｈ，ｍ），３．８４（３Ｈ，ｓ） Reference Production Example 122
0.45 g of the organic sulfur compound (133) was dissolved in 5 ml of tetrahydrofuran and cooled to 0 ° C. under a nitrogen atmosphere. After adding 0.10 g of 60% sodium hydride and stirring for 30 minutes, 0.20 g of N-chlorosuccinimide was added and stirred overnight at room temperature. To the reaction solution was added 10 ml of 1N aqueous hydrochloric acid solution, and the mixture was extracted twice with 30 ml of ethyl acetate. The organic layers were combined, washed with 10 ml of saturated aqueous sodium hydrogen carbonate solution and 10 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2-chloro-2- [4- (methoxyimino) cyclohexyl] -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present) represented by the following formula: 0.39 g of organic sulfur compound (145) is obtained.
This organic sulfur compound (145)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.52-1.91 (3H, m), 2.16-2.29 (1H, m), 2.34-2.48 (2H M), 2.52-2.63 (1H, m), 2.74-2.89 (3H, m), 3.36-3.46 (1H, m), 3.64-3.82. (2H, m), 3.84 (3H, s)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．４６−１．５６（１Ｈ，ｍ），１．５９−１．７１（３Ｈ，ｍ），１．７３−１．８５（２Ｈ，ｍ），２．０２−２．１７（２Ｈ，ｍ），２．６６−２．８６（３Ｈ，ｍ），３．３８−３．５６（２Ｈ，ｍ），４．０３（１Ｈ，ｄ） Reference Production Example 123
1.00 g of (3,3,3-trifluoropropylsulfonyl) acetonitrile, 30 ml of tetrahydrofuran, 0.12 g of DL-proline and 1.01 g of cyclopentanone were heated and stirred for 6 hours under reflux conditions. The reaction mixture was cooled to 0 ° C., 0.42 g of sodium borohydride was added, and the mixture was stirred at room temperature for 6 hours. After the reaction mixture was cooled to 0 ° C., 10 ml of water and 30 ml of ethyl acetate were added. While stirring the mixture, 50 ml of 1N hydrochloric acid was added dropwise, and then extracted twice with 30 ml of ethyl acetate. The organic layers were combined, washed successively with 30 ml of saturated aqueous sodium bicarbonate and 30 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2-cyclopentyl-2- (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound (146)) represented by the following formula: 1. 01 g was obtained.
This organic sulfur compound (146)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.46-1.56 (1H, m), 1.59-1.71 (3H, m), 1.73-1.85 (2H M), 2.02-2.17 (2H, m), 2.66-2.86 (3H, m), 3.38-3.56 (2H, m), 4.03 (1H, d) )

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．１６−１．２８（１Ｈ，ｍ），１．３０−１．４７（４Ｈ，ｍ），１．６９−１．７７（１Ｈ，ｍ），１．７９−１．８８（３Ｈ，ｍ），２．１５−２．２２（１Ｈ，ｍ），２．３９−２．４９（１Ｈ，ｍ），２．７０−２．８４（２Ｈ，ｍ），３．３７−３．４６（１Ｈ，ｍ），３．４８−３．５６（１Ｈ，ｍ），３．８０（１Ｈ，ｄ） Reference production example 124
In place of cyclopentanone, 1.14 g of cyclohexanone was used and 2-cyclohexyl-2- (3,3,3-trifluoropropylsulfonyl) represented by the following formula was prepared according to the method described in Reference Production Example 114. 1.01 g of acetonitrile (hereinafter referred to as the present organic sulfur compound (147)) was obtained.
This organic sulfur compound (147)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.16-1.28 (1H, m), 1.30-1.47 (4H, m), 1.69-1.77 (1H) M), 1.79-1.88 (3H, m), 2.15-2.22 (1H, m), 2.39-2.49 (1H, m), 2.70-2.84. (2H, m), 3.37-3.46 (1H, m), 3.48-3.56 (1H, m), 3.80 (1H, d)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．５０−１．８６（１１Ｈ，ｍ），２．１４−２．２２（１Ｈ，ｍ），２．５６−２．６２（１Ｈ，ｍ），２．７０−２．８３（２Ｈ，ｍ），３．３６−３．４４（１Ｈ，ｍ），３．４８−３．５６（１Ｈ，ｍ），３．８４（１Ｈ，ｄ） Reference production example 125
In place of cyclopentanone, 1.23 g of cycloheptanone was used and 2-cyclohexyl-2- (3,3,3-trifluoropropyl) represented by the following formula was prepared according to the method described in Reference Production Example 114. 1.24 g of sulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound (148)) was obtained.
This organic sulfur compound (148)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.50-1.86 (11H, m), 2.14-2.22 (1H, m), 2.56-2.62 (1H) M), 2.70-2.83 (2H, m), 3.36-3.44 (1H, m), 3.48-3.56 (1H, m), 3.84 (1H, d) )

本有機硫黄化合物（１４９）の主異性体
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）０．９８（３Ｈ，ｄ），１．００−１．１２（１Ｈ，ｍ），１．３２−１．９７（８Ｈ，ｍ），２．４５−２．５４（１Ｈ，ｍ），２．７１−２．８７（２Ｈ，ｍ），３．３７−３．５９（２Ｈ，ｍ），３．９２（１Ｈ，ｄ）
本有機硫黄化合物（１４９）の副異性体
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）０．９１（３Ｈ，ｄ），１．３２−１．９７（８Ｈ，ｍ），２．１４−２．２３（１Ｈ，ｍ），２．３３−２．４３（１Ｈ，ｍ），２．７１−２．８７（２Ｈ，ｍ），３．３７−３．５９（２Ｈ，ｍ），３．８２（１Ｈ，ｄ） Reference Production Example 126
In place of cyclopentanone, 1.34 g of 4-methylcyclohexanone was used and 2- (4-methylcyclohexyl) -2- (3,3) represented by the following formula was prepared according to the method described in Reference Production Example 114. , 3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound (149)) 1.12 g was obtained.
This organic sulfur compound (149): 6/4 isomer mixture

Main isomer of the present organic sulfur compound (149)
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 0.98 (3H, d), 1.00-1.12 (1H, m), 1.32-1.97 (8H, m), 2.45-2.54 (1H, m), 2.71-2.87 (2H, m), 3.37-3.59 (2H, m), 3.92 (1H, d)
Sub-isomer of the present organic sulfur compound (149)
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 0.91 (3H, d), 1.32-1.97 (8H, m), 2.14-2.23 (1H, m), 2.33-2.43 (1H, m), 2.71-2.87 (2H, m), 3.37-3.59 (2H, m), 3.82 (1H, d)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）０．９３（３Ｈ，ｓ），０．９４（３Ｈ，ｓ），１．２５−１．３６（２Ｈ，ｍ），１．４５−１．６９（５Ｈ，ｍ），１．９４−２．０３（１Ｈ，ｍ），２．３０−２．３９（１Ｈ，ｍ），２．６９−２．８３（２Ｈ，ｍ），３．３７−３．４６（１Ｈ，ｍ），３．４８−３．５６（１Ｈ，ｍ），３．８４（１Ｈ，ｄ） Reference Production Example 127
In place of cyclopentanone, 1.24 g of 4,4-dimethylcyclohexanone was used and 2- (4,4-dimethylcyclohexyl) -2-2 represented by the following formula was prepared according to the method described in Reference Production Example 114. 0.98 g of (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound (150)) was obtained.
This organic sulfur compound (150)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 0.93 (3H, s), 0.94 (3H, s), 1.25-1.36 (2H, m), 1.45 1.69 (5H, m), 1.94-2.03 (1H, m), 2.30-2.39 (1H, m), 2.69-2.83 (2H, m), 3. 37-3.46 (1H, m), 3.48-3.56 (1H, m), 3.84 (1H, d)

本有機硫黄化合物（１５０ｃ）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．４０−１．５４（２Ｈ，ｍ），１．６４−１．７９（２Ｈ，ｍ），１．８９−１．９９（１Ｈ，ｍ），２．２１−２．３０（２Ｈ，ｍ），２．３０−２．３８（１Ｈ，ｍ），２．４１−２．５４（２Ｈ，ｍ），２．６９−２．８４（２Ｈ，ｍ），３．３７−３．４７（１Ｈ，ｍ），３．５１−３．５９（１Ｈ，ｍ），３．８３（１Ｈ，ｄ）
本有機硫黄化合物（１５０ｔ）
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．６４−１．８８（４Ｈ，ｍ），１．９５−２．０２（１Ｈ，ｍ），２．０９−２．１９（２Ｈ，ｍ），２．１９−２．２９（１Ｈ，ｍ），２．４１−２．５１（１Ｈ，ｍ），２．５１−２．６９（２Ｈ，ｍ），３．００−３．０５（１Ｈ，ｍ），３．４１−３．５０（１Ｈ，ｍ），３．５４−３．６３（１Ｈ，ｍ），３．８３（１Ｈ，ｄ） Reference production example 128
3.33 g of (3,3,3-trifluoropropylsulfonyl) acetonitrile, 60 ml of tetrahydrofuran, 0.19 g of DL-proline and 2.03 g of 4-cyanocyclohexanone were heated and stirred for 6 hours under reflux conditions. The reaction mixture was cooled to 0 ° C., 0.62 g of sodium borohydride was added, and the mixture was stirred at room temperature for 6 hours. After the reaction mixture was cooled to 0 ° C., 30 ml of water and 50 ml of ethyl acetate were added. While stirring the mixture, 90 ml of 1N hydrochloric acid was added dropwise, followed by extraction three times with 50 ml of ethyl acetate. The organic layer was washed with 50 ml of saturated aqueous sodium hydrogen carbonate and 50 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (4-cyanocyclohexyl) -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound (151)) represented by the following formula: 0.51 g of trans form (hereinafter referred to as the present organic sulfur compound (151t)) and 0.59 g of cis form (hereinafter referred to as the present organic sulfur compound (151c)) were obtained.
This organic sulfur compound (151)

This organic sulfur compound (150c)
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.40-1.54 (2H, m), 1.64-1.79 (2H, m), 1.89-1.99 (1H M), 2.21-2.30 (2H, m), 2.30-2.38 (1H, m), 2.41-2.54 (2H, m), 2.69-2.84. (2H, m), 3.37-3.47 (1H, m), 3.51-3.59 (1H, m), 3.83 (1H, d)
This organic sulfur compound (150t)
¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.64-1.88 (4H, m), 1.95-2.02 (1H, m), 2.09-2.19 (2H M), 2.19-2.29 (1H, m), 2.41-2.51 (1H, m), 2.51-2.69 (2H, m), 3.00-3.05 (1H, m), 3.41-3.50 (1H, m), 3.54-3.63 (1H, m), 3.83 (1H, d)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．６７−１．８３（２Ｈ，ｍ），１．８８−１．９７（１Ｈ，ｍ），１．９８−２．０９（２Ｈ，ｍ），２．１７−２．３０（３Ｈ，ｍ），２．３６−２．４８（１Ｈ，ｍ），２．６７−２．８５（２Ｈ，ｍ），３．２４−３．３６（４Ｈ，ｍ），３．４８−３．５０（１Ｈ，ｍ），３．６０−３．８３（１Ｈ，ｍ），３．８６（１Ｈ，ｄ） Reference Production Example 129
The organic sulfur compound (127) (0.34 g) was dissolved in acetonitrile (10 ml), 1,2-ethanedithiol (0.21 g) and tetrabutylammonium tribromide (0.05 g) were added, and the mixture was stirred at room temperature for 1 hour. 100 ml of ethyl acetate was added to the reaction mixture, and 50 ml of saturated aqueous sodium hydrogen carbonate solution was added. The solution was stirred for 1 hour and extracted twice with 50 ml of ethyl acetate. The organic layers were combined, washed with 50 ml of saturated aqueous sodium bicarbonate and 50 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (1,4-dithiaspiro [4,5] dec-8-yl) -2- (3,3,3-trifluoropropylsulfonyl) acetonitrile represented by the following formula: (Hereinafter referred to as the present organic sulfur compound (152).) 0.36 g was obtained.
This organic sulfur compound (152)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.67-1.83 (2H, m), 1.88-1.97 (1H, m), 1.98-2.09 (2H M), 2.17-2.30 (3H, m), 2.36-2.48 (1H, m), 2.67-2.85 (2H, m), 3.24-3.36. (4H, m), 3.48-3.50 (1H, m), 3.60-3.83 (1H, m), 3.86 (1H, d)

Reference Production Example 130
[Step 1]
22.85 g of potassium thioacetate was suspended in 200 ml of methanol, and 54.79 g of 1-iodo-3,3,4,4,4-pentafluorobutane was added dropwise over 30 minutes at 0 ° C. under a nitrogen atmosphere. Stir for 1 hour. At this time, the reaction solution was analyzed by TLC (thin layer chromatography) to confirm the formation of 3,3,4,4,4-pentafluorobutylthioacetate. After the mixture was cooled to 0 ° C., 40.52 g of 28% sodium methoxide / methanol solution was added dropwise over 15 minutes and stirred at room temperature for 1 hour. To the mixture, 16.61 g of chloroacetonitrile was added at 0 ° C., and the mixture was stirred at room temperature for 3 hours. The reaction vessel was cooled in an ice bath, 1N aqueous hydrochloric acid solution was added, and methanol was distilled off under reduced pressure. Extraction was performed twice with 200 ml of t-butyl methyl ether, and the combined organic layer was washed with saturated brine, dried over sodium sulfate, filtered, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 17.81 g of (3,3,4,4,4-pentafluorobutylthio) acetonitrile.

[Step 2]
While stirring a suspension of 17.81 g of (3,3,4,4,4-pentafluorobutylthio) acetonitrile and 0.28 g of sodium tungstate dihydrate in 30 mL of water, 31% hydrogen peroxide After adding 8.94 ml of water, the temperature was raised to 65 ° C., 8.94 ml of 31% hydrogen peroxide was added, and the mixture was stirred at 70 ° C. for 1 hour. During the reaction, the formation of a compound presumed to be a sulfoxide form was confirmed by TLC (thin layer chromatography) analysis. The reaction mixture was cooled to room temperature, 30 ml of aqueous sodium sulfite solution was added, and the mixture was extracted 3 times with 150 ml of ethyl acetate. The organic layers were combined, washed with saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was crystallized with chloroform: hexane = 1: 2 to obtain 17.84 g of (3,3,4,4,4-pentafluorobutylsulfonyl) acetonitrile.

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．５８−１．９１（７Ｈ，ｍ），２．１３−２．２２（１Ｈ，ｍ），２．３９−２．５１（１Ｈ，ｍ），２．５８−２．８２（２Ｈ，ｍ），３．４０−３．５０（１Ｈ，ｍ），３．５３−３．６３（１Ｈ，ｍ），３．８７（１Ｈ，ｄ），３．９３−３．９８（４Ｈ，ｍ） [Step 3]
(3,3,4,4,4-pentafluorobutylsulfonyl) 7.74 g of acetonitrile, 100 ml of toluene, 0.23 g of DL-proline and 4.81 g of 1,4-cyclohexanedione monoethylene ketal for 3 hours under reflux conditions And stirred with heating. After distilling off 20 ml of toluene from the reaction mixture, it was cooled to room temperature. 100 ml of tetrahydrofuran was added to the reaction mixture, and after cooling to 0 ° C., 1.17 g of sodium borohydride was added. After stirring at room temperature for 6 hours, the mixture was cooled to 0 ° C., and 100 ml of water and 100 ml of ethyl acetate were added. While stirring the solution, 100 ml of 1N hydrochloric acid was added dropwise, and extracted twice with 100 ml of ethyl acetate. The organic layer was washed with 100 ml of saturated aqueous sodium hydrogencarbonate, 100 ml of saturated brine, and 100 ml of water, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (1,4-dioxaspiro [4,5] dec-8-yl) -2- (3,3,4,4,4-pentafluoro represented by the following formula: Butylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound (153)) (5.00 g) was obtained.
This organic sulfur compound (153)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.58-1.91 (7H, m), 2.13-2.22 (1H, m), 2.39-2.51 (1H M), 2.58-2.82 (2H, m), 3.40-3.50 (1H, m), 3.53-3.63 (1H, m), 3.87 (1H, d) ), 3.93-3.98 (4H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．８４−１．９７（２Ｈ，ｍ），２．１７−２．２６（１Ｈ，ｍ），２．４０−２．６１（５Ｈ，ｍ），２．８１−２．８５（２Ｈ，ｍ），３．４４−３．５４（１Ｈ，ｍ），３．５９−３．７０（１Ｈ，ｍ），３．９９（１Ｈ，ｄ） Reference Production Example 131
To 5.00 g of this organic sulfur compound (153), 14 ml of acetic acid and 6 ml of water were added, heated to 70 ° C. and stirred for 10 hours. After the reaction mixture was cooled to room temperature, 100 ml of ethyl acetate was added and slowly added to 100 ml of saturated aqueous sodium bicarbonate. The solution was stirred for 1 hour and extracted twice with 100 ml of ethyl acetate. The organic layers were combined, washed with 100 ml of saturated aqueous sodium bicarbonate and 100 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (4-oxocyclohexyl) -2- (3,3,4,4,4-pentafluorobutylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound) represented by the following formula: (Described as (154).) 3.56 g was obtained.
This organic sulfur compound (154)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.84-1.97 (2H, m), 2.17-2.26 (1H, m), 2.40-2.61 (5H) , M), 2.81-2.85 (2H, m), 3.44-3.54 (1H, m), 3.59-3.70 (1H, m), 3.99 (1H, d) )

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．５５−１．７２（２Ｈ，ｍ），１．８０−１．９２（１Ｈ，ｍ），１．９５−２．１１（１Ｈ，ｍ），２．１７−２．２８（１Ｈ，ｍ），２．３１−２．４５（１Ｈ，ｍ），２．４８−２．５８（１Ｈ，ｍ），２．６１−２．８０（３Ｈ，ｍ），３．３３−３．４０（１Ｈ，ｍ），３．４２−３．５０（１Ｈ，ｍ），３．５５−３．６５（１Ｈ，ｍ），３．８３（３Ｈ，ｓ），３．８９（１Ｈ，ｄ） Reference production example 132
0.35 g of this organic sulfur compound (154) was dissolved in 10 ml of tetrahydrofuran, 0.75 g of pyridine and 0.79 g of methoxyamine hydrochloride were added, and the mixture was stirred at room temperature for 3 hours. 30 ml of 1N aqueous hydrochloric acid solution was added to the reaction solution, and the mixture was extracted twice with 50 ml of ethyl acetate. The organic layers were combined and washed with 50 ml of saturated aqueous sodium hydrogen carbonate solution and 50 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography. 0.34 g of organic sulfur compound (described as 155) was obtained.
This organic sulfur compound (155)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.55-1.72 (2H, m), 1.80-1.92 (1H, m), 1.95-2.11 (1H M), 2.17-2.28 (1H, m), 2.31-2.45 (1H, m), 2.48-2.58 (1H, m), 2.61-2.80. (3H, m), 3.33-3.40 (1H, m), 3.42-3.50 (1H, m), 3.55-3.65 (1H, m), 3.83 (3H , S), 3.89 (1H, d)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．２０−１．３１（２Ｈ，ｍ），２．０３−２．１７（４Ｈ，ｍ），２．２２−２．３６（３Ｈ，ｍ），２．６２−２．７４（２Ｈ，ｍ），２．９５（２Ｈ，ｄ），３．１６−３．２１（２Ｈ，ｍ），４．６６（２Ｈ，ｓ） Reference Production Example 133
2.88 g of this organic sulfur compound (115) was dissolved in 10 ml of pyridine, p-toluenesulfonyl chloride 1.91 was added, and the mixture was stirred at room temperature for 3 hours. 30 ml of 1N aqueous hydrochloric acid solution was added to the reaction solution, and the mixture was extracted twice with 50 ml of ethyl acetate. The organic layers were combined and washed with 50 ml of saturated aqueous sodium hydrogen carbonate solution and 50 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was dissolved in 20 ml of toluene, 1.50 g of sodium iodide and 1.52 g of 1,8-diazabicyclo [5.4.0] undec-7-ene were added, heated to 110 ° C., and stirred for 10 hours. 30 ml of 1N aqueous hydrochloric acid solution was added to the reaction solution, and the mixture was extracted twice with 50 ml of ethyl acetate. The organic layers were combined, washed successively with 50 ml of saturated aqueous sodium hydrogen carbonate solution and 50 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 1-methylene-4- (3,3,3-trifluoropropylsulfonylmethyl) -cyclohexane (hereinafter referred to as the present organic sulfur compound (156)) represented by the following formula. 1.01 g was obtained.
This organic sulfur compound (156)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.20-1.31 (2H, m), 2.03-2.17 (4H, m), 2.22-2.36 (3H) M), 2.62-2.74 (2H, m), 2.95 (2H, d), 3.16-3.21 (2H, m), 4.66 (2H, s)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．２３−１．３４（２Ｈ，ｍ），１．３９（２Ｈ，ｓ），１．５９−１．６７（２Ｈ，ｍ），１．８５−１．９５（２Ｈ，ｍ），２．０７−２．１５（２Ｈ，ｍ），２．１６−２．２５（１Ｈ，ｍ），２．６３−２．７５（２Ｈ，ｍ），２．９９（２Ｈ，ｄ），３．１７−３．２１（２Ｈ，ｍ） Reference Production Example 134
0.60 g of this organic sulfur compound (156) is dissolved in 4 ml of dichloromethane, 0.86 g of bromoform, 0.44 g of sodium hydroxide and 0.02 g of benzyltriethylammonium chloride are added, and the mixture is subjected to ultrasonic irradiation conditions at 30 ° C. for 4 hours. Stir. 20 ml of 2N aqueous hydrochloric acid was added to the reaction mixture, and the mixture was extracted twice with 30 ml of ethyl acetate. The organic layers were combined, washed successively with 30 ml of saturated aqueous sodium hydrogen carbonate solution and 30 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 1,1-dibromo-6- (3,3,3-trifluoropropylsulfonylmethyl) -spiro [2.5] octane (hereinafter referred to as the present organic sulfur) represented by the following formula: Compound (157).) 0.31 g was obtained.
This organic sulfur compound (157)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.23-1.34 (2H, m), 1.39 (2H, s), 1.59-1.67 (2H, m), 1.85-1.95 (2H, m), 2.07-2.15 (2H, m), 2.16-2.25 (1H, m), 2.63-2.75 (2H, m ), 2.99 (2H, d), 3.17-3.21 (2H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．２４−１．３５（２Ｈ，ｍ），１．５３−１．６２（４Ｈ，ｍ），１．８４−１．９３（２Ｈ，ｍ），２．０８−２．１５（２Ｈ，ｍ），２．１６−２．２６（１Ｈ，ｍ），２．６３−２．７５（２Ｈ，ｍ），２．９９（２Ｈ，ｄ），３．１８−３．２２（２Ｈ，ｍ） Reference Production Example 135
1,1-dichloro-6- (3,3,3-trifluoropropylsulfonylmethyl represented by the following formula was used in accordance with the method described in Reference Production Example 125, using 0.71 g of chloroform instead of bromoform. ) -Spiro [2.5] octane (hereinafter referred to as the present organic sulfur compound (158)) 0.41 g was obtained.
This organic sulfur compound (158)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.24-1.35 (2H, m), 1.53-1.62 (4H, m), 1.84-1.93 (2H) M), 2.08-2.15 (2H, m), 2.16-2.26 (1H, m), 2.62-2.75 (2H, m), 2.99 (2H, d) ), 3.18-3.22 (2H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．２５（３Ｈ，ｔ），１．５５−１．７３（２Ｈ，ｍ），１．７６−１．９２（１Ｈ，ｍ），１．９４−２．０９（１Ｈ，ｍ），２．１６−２．２９（１Ｈ，ｍ），２．３１−２．４４（１Ｈ，ｍ），２．４８−２．５７（１Ｈ，ｍ），２．６２−２．７９（３Ｈ，ｍ），３．３６−３．５１（２Ｈ，ｍ），３．５４−３．６５（１Ｈ，ｍ），３．８８（１Ｈ，ｄ），４．０８（２Ｈ，ｑ） Reference Production Example 136
0.46 g of this organic sulfur compound (154) was dissolved in 10 ml of tetrahydrofuran, 0.86 g of pyridine and 0.86 g of 30% ethoxyamine hydrochloride aqueous solution were added, and the mixture was stirred at room temperature for 3 hours. 30 ml of 1N aqueous hydrochloric acid solution was added to the reaction solution, and the mixture was extracted twice with 50 ml of ethyl acetate. The organic layers were combined and washed with 50 ml of saturated aqueous sodium hydrogen carbonate solution and 50 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- [4- (methoxyimino) cyclohexyl] -2- (3,3,4,4,4-pentafluorobutylsulfonyl) acetonitrile (hereinafter referred to as the present compound) represented by the following formula: 0.34 g of organic sulfur compound (159) is obtained.
This organic sulfur compound (159)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.25 (3H, t), 1.55-1.73 (2H, m), 1.76-1.92 (1H, m), 1.94-2.09 (1H, m), 2.16-2.29 (1H, m), 2.31-2.44 (1H, m), 2.48-2.57 (1H, m ), 2.62-2.79 (3H, m), 3.36-3.51 (2H, m), 3.54-3.65 (1H, m), 3.88 (1H, d), 4.08 (2H, q)

Reference Production Example 137
[Step 1]
Instead of 1-iodo-3,3,4,4,4-pentafluorobutane, 4.19 g of 1-iodo-3- (trifluoromethyl) -3,4,4,4-tetrafluorobutane was used. According to the method described in [Step 1] of Reference Production Example 121, 4.77 g of (3- (trifluoromethyl) -3,4,4,4-pentafluorobutylthio) acetonitrile was obtained.

[Step 2]
16.14 g of a double salt of 2KHSO ₅ · KHSO ₄ · K2SO ₄ (Oxone (registered trademark)) was suspended in 50 ml of water, and (3- (trifluoromethyl) -3,4,4,4-pentafluoro was suspended in a nitrogen atmosphere. A solution of 4.77 g of butylthio) acetonitrile in 50 ml of methanol was added dropwise over 60 minutes and stirred for 2 hours. 50 ml of 10% aqueous sodium sulfite solution was added to the reaction mixture, and the mixture was extracted twice with 100 ml of ethyl acetate. The organic layers were combined, washed with 50 ml of 10% aqueous sodium sulfite solution and 50 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 4.00 g of (3- (trifluoromethyl) -3,4,4,4-pentafluorobutylsulfonyl) acetonitrile.

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．５１−２．２２（８Ｈ，ｍ），２．４０−２．５１（１Ｈ，ｍ），２．６４−２．８３（２Ｈ，ｍ），３．３７−３．４８（１Ｈ，ｍ），３．４９−３．６１（１Ｈ，ｍ），３．８６−３．８９（１Ｈ，ｍ），３．９０−３．９９（４Ｈ，ｍ） [Step 3]
4.00 g of (3- (trifluoromethyl) -3,4,4,4-pentafluorobutylsulfonyl) acetonitrile, 50 ml of toluene, 0.15 g of DL-proline and 2.28 g of 1,4-cyclohexanedione monoethylene ketal The mixture was heated and stirred under reflux conditions for 3 hours. 30 ml of toluene was distilled off from the reaction mixture, and then cooled to 0 ° C. 0.25 g of sodium borohydride and 2 ml of N, N-dimethylformamide were added. After stirring at room temperature for 6 hours, the mixture was cooled to 0 ° C., and 50 ml of water and 50 ml of ethyl acetate were added. While stirring the solution, 20 ml of 1N hydrochloric acid was added dropwise and extracted twice with 100 ml of ethyl acetate. The organic layer was washed with 100 ml of saturated aqueous sodium hydrogencarbonate and 100 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (1,4-dioxaspiro [4,5] dec-8-yl) -2- (3- (trifluoromethyl) -3,4, represented by the following formula: 4.41 g of 4,4-pentafluorobutylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound (160)) was obtained.
This organic sulfur compound (160)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.51-2.22 (8H, m), 2.40-2.51 (1H, m), 2.64-2.83 (2H M), 3.37-3.48 (1H, m), 3.49-3.61 (1H, m), 3.86-3.89 (1H, m), 3.90-3.99. (4H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．５２−１．７２（２Ｈ，ｍ），１．８１−１．９１（１Ｈ，ｍ），１．９６−２．０８（１Ｈ，ｍ），２．１６−２．２８（１Ｈ，ｍ），２．３１−２．４４（１Ｈ，ｍ），２．５０−２．５７（１Ｈ，ｍ），２．６２−２．８２（３Ｈ，ｍ），３．３３−３．４８（２Ｈ，ｍ），３．５３−３．６３（１Ｈ，ｍ），３．８３（３Ｈ，ｓ），３．８９（１Ｈ，ｄ） Reference Production Example 138
To 4.41 g of the organic sulfur compound (160), 14 ml of acetic acid and 6 ml of water, 1.50 g of methoxyamine hydrochloride and 1.47 g of sodium acetate were added, heated to 100 ° C. and stirred for 10 hours. After the reaction mixture was cooled to room temperature, 100 ml of ethyl acetate was added and slowly added to 100 ml of saturated aqueous sodium bicarbonate. The solution was stirred for 1 hour and extracted twice with 100 ml of ethyl acetate. The organic layers were combined, washed with 100 ml of saturated aqueous sodium bicarbonate and 100 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (4-methoxyiminocyclohexyl) -2- (3- (trifluoromethyl) -3,4,4,4-pentafluorobutylsulfonyl) acetonitrile represented by the following formula (Hereinafter referred to as the present organic sulfur compound (161).) 3.61 g was obtained.
This organic sulfur compound (161)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.52-1.72 (2H, m), 1.81-1.91 (1H, m), 1.96-2.08 (1H M), 2.16-2.28 (1H, m), 2.31-2.44 (1H, m), 2.50-2.57 (1H, m), 2.62-2.82. (3H, m), 3.33-3.48 (2H, m), 3.53-3.63 (1H, m), 3.83 (3H, s), 3.89 (1H, d)

Reference Production Example 139
[Step 1]
A mixture of 42,65 g of 3,3,4,4,5,5,6,6,6-nonafluorohexyl-1-toluenesulfonate, 11.65 g of potassium thioacetate and 100 ml of N, N-dimethylformamide in a nitrogen atmosphere Under stirring at 80 ° C. for 4 hours. The reaction vessel is cooled in an ice bath, 1N aqueous hydrochloric acid solution is added, and the mixture is extracted twice with 200 ml of ethyl acetate. The combined organic layers are washed with saturated brine, dried over sodium sulfate, filtered, and the solvent is distilled off under reduced pressure. did. The residue was subjected to silica gel column chromatography to obtain 18.91 g of 3,3,4,4,5,5,6,6,6-nonafluorohexylthioacetate.

[Step 2]
After 3,91,4,4,5,5,6,6,6-nonafluorohexylthioacetate (18.91 g) was dissolved in 60 ml of tetrahydrofuran and cooled to 0 ° C., 28% sodium methoxide / methanol solution 11 .32 g was added dropwise over 15 minutes and stirred at room temperature for 1 hour. To the mixture, 4.40 g of chloroacetonitrile was added at 0 ° C., and the mixture was stirred at room temperature for 3 hours. The reaction vessel was cooled in an ice bath, saturated brine was added, and the mixture was extracted twice with 100 ml of t-butyl methyl ether. The combined organic layers were washed with saturated brine, dried over sodium sulfate, filtered, and reduced pressure. Concentrated. The residue was subjected to silica gel column chromatography to obtain 15.70 g of (3,3,4,4,5,5,6,6,6-nonafluorohexylthio) acetonitrile.

[Step 3]
15.10 g of a double salt of 2KHSO ₅ · KHSO ₄ · K2SO ₄ (Oxone (registered trademark)) was suspended in 100 ml of water, and suspended at −20 ° C. under a nitrogen atmosphere ( ₃ , ₃ , ₄ , ₄ , ₅ , ₅ , 6, (6,6-nonafluorohexylthio) A solution of 15.70 g of acetonitrile in 100 ml of methanol was added dropwise over 60 minutes and stirred for 2 hours. 50 ml of 10% aqueous sodium sulfite solution was added to the reaction mixture, and the mixture was extracted twice with 100 ml of ethyl acetate. The organic layers were combined, washed with 50 ml of 10% aqueous sodium sulfite solution and 50 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 12.56 g of (3,3,4,4,5,5,6,6,6-nonafluorohexylsulfinyl) acetonitrile.

[Step 4]
9.21 g of a double salt of 2KHSO ₅ · KHSO ₄ · K2SO ₄ (Oxone (registered trademark)) was suspended in 50 ml of water, and ((3,3,4,4,5,5,6,6,6) was suspended in a nitrogen atmosphere. -Nonafluorohexylsulfinyl) A solution of 6.80 g of acetonitrile in 50 ml of methanol was added dropwise over 60 minutes and stirred overnight, 25 ml of 10% aqueous sodium sulfite was added to the reaction mixture, and the mixture was extracted twice with 100 ml of ethyl acetate. The layers were combined, washed with 25 ml of 10% aqueous sodium sulfite solution and 50 ml of saturated brine, dried over sodium sulfate, filtered and concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (3, 3, There was obtained 5.40 g of 4,4,5,5,6,6,6-nonafluorohexylsulfonyl) acetonitrile.

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．８３−１．９８（２Ｈ，ｍ），２．１７−２．２６（１Ｈ，ｍ），２．３８−２．５９（５Ｈ，ｍ），２．６７−２．９７（３Ｈ，ｍ），３．４４−３．５４（１Ｈ，ｍ），３．６０−３．７０（１Ｈ，ｍ），４．００（１Ｈ，ｄ） [Step 5]
(3,3,4,4,5,5,6,6,6-nonafluorohexylsulfonyl) acetonitrile 5.40 g, toluene 60 ml, DL-proline 0.18 g and 1,4-cyclohexanedione monoethylene ketal 77 g was heated and stirred under reflux conditions for 3 hours. After 40 ml of toluene was distilled off from the reaction mixture, it was cooled to 0 ° C. 0.61 g of sodium borohydride and 3 ml of N, N-dimethylformamide were added. After stirring at room temperature for 6 hours, the mixture was cooled to 0 ° C., and 50 ml of water and 50 ml of ethyl acetate were added. While stirring the solution, 20 ml of 1N hydrochloric acid was added dropwise and extracted twice with 100 ml of ethyl acetate. The organic layer was washed with 100 ml of saturated aqueous sodium hydrogen carbonate and 100 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. 14 ml of acetic acid and 6 ml of water were added to the residue, heated to 100 ° C. and stirred for 8 hours. After the reaction mixture was cooled to room temperature, 100 ml of ethyl acetate was added and slowly added to 100 ml of saturated aqueous sodium bicarbonate. The solution was stirred for 1 hour and extracted twice with 100 ml of ethyl acetate. The organic layers were combined, washed with 100 ml of saturated aqueous sodium bicarbonate and 100 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (4-oxocyclohexyl) -2- (3,3,4,4,5,5,6,6,6-nonafluorohexylsulfonyl) represented by the following formula: 2.94 g of acetonitrile (hereinafter referred to as the present organic sulfur compound (162)) was obtained.
This organic sulfur compound (162)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.83-1.98 (2H, m), 2.17-2.26 (1H, m), 2.38-2.59 (5H) M), 2.67-2.97 (3H, m), 3.44-3.54 (1H, m), 3.60-3.70 (1H, m), 4.00 (1H, d) )

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．４９−１．７３（２Ｈ，ｍ），１．７７−１．９１（１Ｈ，ｍ），１．９５−２．０９（１Ｈ，ｍ），２．１７−２．２７（１Ｈ，ｍ），２．３１−２．４３（１Ｈ，ｍ），２．４９−２．５７（１Ｈ，ｍ），２．６２−２．８６（３Ｈ，ｍ），３．３２−３．３９（１Ｈ，ｍ），３．４２−３．５３（１Ｈ，ｍ），３．５５−３．６６（１Ｈ，ｍ），３．８４（３Ｈ，ｓ），３．９０（１Ｈ，ｄ） Reference production example 140
2.69 g of this organic sulfur compound (162) was dissolved in 12 ml of tetrahydrofuran, 0.52 g of pyridine and 0.55 of methoxyamine hydrochloride were added, and the mixture was stirred at room temperature for 3 hours. 30 ml of 1N aqueous hydrochloric acid solution was added to the reaction solution, and the mixture was extracted twice with 50 ml of ethyl acetate. The organic layers were combined and washed with 50 ml of saturated aqueous sodium hydrogen carbonate solution and 50 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- [4- (methoxyimino) cyclohexyl] -2- (3,3,4,4,5,5,6,6,6-nonafluoro represented by the following formula: 2.86 g of hexylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound (163)) was obtained.
This organic sulfur compound (163)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.49-1.73 (2H, m), 1.77-1.91 (1H, m), 1.95-2.09 (1H M), 2.17-2.27 (1H, m), 2.31-2.43 (1H, m), 2.49-2.57 (1H, m), 2.62-2.86. (3H, m), 3.32-3.39 (1H, m), 3.42-3.53 (1H, m), 3.55-3.66 (1H, m), 3.84 (3H , S), 3.90 (1H, d)

Reference Production Example 141
[Step 1]
A mixture of 23.8 g of 1-iodo-4,4,4-trifluorobutane, 100 ml of N, N-dimethylformamide and 11.42 g of potassium thioacetate was stirred at 80 ° C. for 4 hours under a nitrogen atmosphere. The reaction vessel was cooled in an ice bath, 1N hydrochloric acid was added dropwise, and the mixture was extracted twice with 100 ml of t-butyl methyl ether. The organic layers were combined, washed with 100 ml of saturated aqueous sodium bicarbonate and 100 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 18.20 g of 4,4,4-trifluorobutylthioacetate represented by the following formula.

[Step 2]
After dissolving 18.20 g of 4,4,4-trifluorobutylthioacetic acid ester in 60 ml of tetrahydrofuran and cooling to 0 ° C., 19.29 g of a 28% sodium methoxide / methanol solution was added dropwise over 15 minutes. Stir for 1 hour. To the mixture, 7.50 g of chloroacetonitrile was added at 0 ° C., and the mixture was stirred at room temperature for 3 hours. The reaction vessel was cooled in an ice bath, saturated brine was added, and the mixture was extracted twice with 200 ml of t-butyl methyl ether. The combined organic layer was washed with saturated brine, dried over sodium sulfate, filtered, and reduced pressure. Concentrated. The residue was subjected to silica gel column chromatography to obtain 17.82 g of (4,4,4-trifluorobutylthio) acetonitrile.

[Step 3]
67.50 g of double salt of 2KHSO ₅ · KHSO ₄ · K2SO ₄ (Oxone (registered trademark)) is suspended in 100 ml of water, and under nitrogen atmosphere, (4,4,4-trifluorobutylthio) acetonitrile 17.82 g of methanol 100 ml The solution was added dropwise over 60 minutes and stirred overnight. 50 ml of 10% aqueous sodium sulfite solution was added to the reaction mixture, and the mixture was extracted twice with 200 ml of ethyl acetate. The organic layers were combined, washed with 50 ml of 10% aqueous sodium sulfite solution and 50 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 22.34 g of (4,4,4-trifluorobutylsulfonyl) acetonitrile.

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．５６−２．４９（１３Ｈ，ｍ），３．２７−３．４３（２Ｈ，ｍ），３．８１（１Ｈ，ｄ），３．９０−４．００（４Ｈ，ｍ） [Step 4]
(4,4,4-trifluorobutylsulfonyl) acetonitrile 24.10 g, toluene 200 ml, DL-proline 1.11 g and 1,4-cyclohexanedione monoethylene ketal 16.58 g were heated and stirred under reflux conditions for 5 hours. . After 100 ml of toluene was distilled off from the reaction mixture, it was cooled to 0 ° C. 1.89 g of sodium borohydride and 5 ml of N, N-dimethylformamide were added. After stirring at room temperature for 12 hours, the mixture was cooled to 0 ° C., and 200 ml of water and 200 ml of ethyl acetate were added. While stirring the solution, 100 ml of 1N hydrochloric acid was added dropwise and extracted twice with 200 ml of ethyl acetate. The organic layer was washed with 100 ml of saturated aqueous sodium hydrogencarbonate and 100 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (1,4-dioxaspiro [4,5] dec-8-yl) -2- (4,4,4-triobutylsulfonyl) acetonitrile represented by the following formula: (Hereinafter referred to as the present organic sulfur compound (164).) 22.03 g was obtained.
This organic sulfur compound (164)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.56-2.49 (13H, m), 3.27-3.43 (2H, m), 3.81 (1H, d), 3.90-4.00 (4H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．８１−１．９９（２Ｈ，ｍ），２．１７−２．６４（１０Ｈ，ｍ），２．８２−２．９５（１Ｈ，ｍ），３．３０−３．８９（２Ｈ，ｍ），３．９３（１Ｈ，ｄ） Reference Production Example 142
70 ml of acetic acid and 30 ml of water were added to 20.03 g of this organic sulfur compound (164), heated to 100 ° C. and stirred for 8 hours. After cooling the reaction mixture to room temperature, 300 ml of ethyl acetate was added and slowly added to 300 ml of saturated aqueous sodium bicarbonate. The solution was stirred for 1 hour and extracted twice with 200 ml of ethyl acetate. The organic layers were combined, washed with 300 ml of saturated aqueous sodium hydrogen carbonate and 300 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (4-oxocyclohexyl) -2- (4,4,4-triobutylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound (165)) represented by the following formula: 15.82 g was obtained.
This organic sulfur compound (165)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.81-1.99 (2H, m), 2.17-2.64 (10H, m), 2.82-2.95 (1H M), 3.30-3.89 (2H, m), 3.93 (1H, d)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．４９−２．０８（４Ｈ，ｍ），２．１４−２．４４（６Ｈ，ｍ），２．４７−２．５７（１Ｈ，ｍ），２．５９−２．７０（１Ｈ，ｍ），３．２８−３．４５（３Ｈ，ｍ），３．８０−３．８５（４Ｈ，ｍ） Reference Production Example 143
The organic sulfur compound (165) (3.11 g) was dissolved in tetrahydrofuran (10 ml), pyridine (0.87 g) and methoxyamine hydrochloride (0.92 g) were added, and the mixture was stirred at room temperature for 3 hours. 30 ml of 1N aqueous hydrochloric acid solution was added to the reaction solution, and the mixture was extracted twice with 50 ml of ethyl acetate. The organic layers were combined and washed with 50 ml of saturated aqueous sodium hydrogen carbonate solution and 50 ml of saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- [4- (methoxyimino) cyclohexyl] -2- (4,4,4-triobutylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound ( 166).) 3.26 g was obtained.
This organic sulfur compound (166)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.49-2.08 (4H, m), 2.14-2.44 (6H, m), 2.47-2.57 (1H M), 2.59-2.70 (1H, m), 3.28-3.45 (3H, m), 3.80-3.85 (4H, m)

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，ＴＭＳ）：δ（ｐｐｍ）１．２５（３Ｈ，ｔ），１．４６−２．０７（４Ｈ，ｍ），２．１４−２．４３（６Ｈ，ｍ），２．４８−２．５６（１Ｈ，ｍ），２．５９−２．７０（１Ｈ，ｍ），３．２８−３．４４（３Ｈ，ｍ），３．８３（１Ｈ，ｄ），４．０５（２Ｈ，ｑ） Reference Production Example 144
In place of hydroxylamine hydrochloride, 1.72 g of ethoxyamine hydrochloride was used and 2- [4- (ethoxyimino) cyclohexyl] -2- (4,4,4) was prepared according to the method described in Reference Production Example 104. 4-87 g of 4-tributylbutylsulfonyl) acetonitrile (hereinafter referred to as the present organic sulfur compound (167)) was obtained.
This organic sulfur compound (167)

¹ H-NMR (CDCl ₃ , TMS): δ (ppm) 1.25 (3H, t), 1.46-2.07 (4H, m), 2.14-2.43 (6H, m), 2.48-2.56 (1H, m), 2.59-2.70 (1H, m), 3.28-3.44 (3H, m), 3.83 (1H, d), 4. 05 (2H, q)

  Next, formulation examples of the pest control composition of the present invention are shown. In addition, a part shows a weight part.

Formulation Example 1
2 parts of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), and 7 parts of thiamethoxam are mixed with 37.5 parts of xylene and N, N- Dissolve in 37.5 parts of dimethylformamide, add 10 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate and mix well with stirring to obtain an emulsion.

Formulation Example 2
57.5 parts of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167) and 4 parts of thiamethoxam are mixed with 37.5 parts of xylene and N, N- Dissolve in 37.5 parts of dimethylformamide, add 10 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate and mix well with stirring to obtain an emulsion.

Formulation Example 3
Solpol 5060 (registered trademark of Toho Chemical Co., Ltd.) was added to a mixture of 20 parts of one organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167) and 20 parts of thiamethoxam. ) Add 5 parts, mix well, add 32 parts of Carplex # 80 (registered trademark of Shionogi Pharmaceutical Co., Ltd., synthetic silicon hydroxide fine powder), 23 parts of 300 mesh diatomaceous earth, mix with juice mixer and hydrate Get the agent.

Formulation Example 4
1 part of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 2 parts of thiamethoxam, 5 parts of synthetic silicon hydroxide fine powder, dodecylbenzenesulfone Add 5 parts of sodium acid, 30 parts of bentonite and 57 parts of clay, mix well with stirring, then add an appropriate amount of water to these mixtures, stir further, granulate with a granulator, dry by ventilation and granulate Get.

Formulation Example 5
1.5 parts of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 3 parts of thiamethoxam, 1 part of synthetic hydrous silicon oxide fine powder, agglomeration 1 part of Doreles B (manufactured by Sankyo Co., Ltd.) and 7 parts of clay are mixed well in a mortar and mixed with a juice mixer. 86.5 parts of cut clay is added to the resulting mixture and mixed thoroughly with stirring to obtain a powder.

Formulation Example 6
5 parts of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167); 5 parts of thiamethoxam; and 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt White carbon (35 parts) and water (55 parts) are mixed and finely pulverized by a wet pulverization method to obtain a preparation.

Formulation Example 7
A mixture of 0.2 part of one organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167) and 0.3 part of thiamethoxam is dissolved in 10 parts of dichloromethane. This is mixed with 89.5 parts of Isopar M (Isoparaffin: Exxon Chemical Registration) to obtain an oil.

Formulation Example 8
One organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 0.05 part of thiamethoxam, and neothiozole (Chuo Kasei Co., Ltd.) After putting 49.9 parts in an aerosol can and mounting an aerosol valve, 25 parts of dimethyl ether and 25 parts of LPG are filled, and an actuator is attached to obtain an oily aerosol.

Formulation Example 9
One part of organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 0.4 part of thiamethoxam, 0.01 part of BHT, 5 parts of xylene , 3.39 parts of deodorized kerosene and 1 part of an emulsifier {Atmos 300 (registered trademark name of Atmos Chemical Co., Ltd.)} and 50 parts of distilled water are filled in an aerosol container, and a valve part is attached. Through pressure, 40 parts of propellant (LPG) is pressure-filled to obtain an aqueous aerosol.

Formulation Example 10
1 part of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167) and 3 parts of thiamethoxam are dissolved in 80 parts of diethylene glycol monoethyl ether. Is mixed with 15 parts of propylene carbonate to obtain a spot-on solution.

Formulation Example 11
5 parts of one organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167) and 5 parts of thiamethoxam are dissolved in 70 parts of diethylene glycol monoethyl ether, And 20 parts of 2-octyldodecanol are mixed to obtain a pour-on solution.

Formulation Example 12
A mixture of 0.25 part of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167) and 0.25 part of thiamethoxam is added to Nikkor TEALS-42. (42% aqueous solution of Nikko Chemicals lauryl sulfate triethanolamine) 60 parts, 20 parts of propylene glycol were added and stirred and mixed until a homogeneous solution was obtained, and then 19.5 parts of water was added and further stirred and mixed. A uniform solution shampoo is obtained.

Formulation Example 13
A mixture of 0.05 g of one organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167) and 0.05 g of thiamethoxam is dissolved in 2 ml of propylene glycol. Impregnation into a porous ceramic plate of 4.0 × 4.0 cm and a thickness of 1.2 cm to obtain a heating smoke.

Formulation Example 14
2.5 parts of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 2.5 parts of thiamethoxam, and ethylene-methyl methacrylate 95 parts of a polymer (ratio of methyl methacrylate in the copolymer: 10% by weight, ACRlift WD301, manufactured by Sumitomo Chemical Co., Ltd.) was melt-kneaded with a closed pressure kneader (manufactured by Moriyama Seisakusho), and the resulting kneaded product was Extrusion is performed from an extrusion molding machine through a molding die to obtain a rod-shaped molded body having a length of 15 cm and a diameter of 3 mm.

Formulation Example 15
2.5 parts of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 2.5 parts of thiamethoxam, and 95 parts of a soft vinyl chloride resin. The mixture is melt-kneaded with a closed pressure kneader (manufactured by Moriyama Seisakusho), and the resulting kneaded product is extruded from an extrusion molding machine through a molding die to obtain a rod-shaped molded body having a length of 15 cm and a diameter of 3 mm.

Formulation Example 16
2 parts of one organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), and 7 parts of clothianidin, 37.5 parts of xylene and N, N- Dissolve in 37.5 parts of dimethylformamide, add 10 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate and mix well with stirring to obtain an emulsion.

Formulation Example 17
5 parts of one organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), and 4 parts of clothianidin, 37.5 parts of xylene and N, N- Dissolve in 37.5 parts of dimethylformamide, add 10 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate and mix well with stirring to obtain an emulsion.

Formulation Example 18
Solpol 5060 (registered trademark of Toho Chemical Co., Ltd) ) Add 5 parts, mix well, add 32 parts of Carplex # 80 (registered trademark of Shionogi Pharmaceutical Co., Ltd., synthetic silicon hydroxide fine powder), 23 parts of 300 mesh diatomaceous earth, mix with juice mixer and hydrate Get the agent.

Formulation Example 19
1 part of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 2 parts of clothianidin, 5 parts of synthetic silicon hydroxide-containing fine powder, dodecylbenzenesulfone Add 5 parts of sodium acid, 30 parts of bentonite and 57 parts of clay, mix well with stirring, then add an appropriate amount of water to these mixtures, further stir, granulate with a granulator, dry by ventilation and granulate Get.

Formulation Example 20
1.5 parts of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 3 parts of clothianidin, 1 part of synthetic hydrous silicon oxide fine powder, agglomeration As a preparation, 1 part of Doriles B (manufactured by Sankyo Co., Ltd.) and 7 parts of clay are mixed well in a mortar and then stirred and mixed with a juice mixer. 86.5 parts of cut clay is added to the resulting mixture and mixed thoroughly with stirring to obtain a powder.

Formulation Example 21
5 parts of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167); 5 parts of clothianidin; 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt White carbon (35 parts) and water (55 parts) are mixed and finely pulverized by a wet pulverization method to obtain a preparation.

Formulation Example 22
A mixture of 0.2 part of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167) and 0.3 part of clothianidin is dissolved in 10 parts of dichloromethane. This is mixed with 89.5 parts of Isopar M (Isoparaffin: Exxon Chemical Registration) to obtain an oil.

Formulation Example 23
One organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 0.05 part of clothianidin, and neothiozole (Chuo Kasei Co., Ltd.) After putting 49.9 parts in an aerosol can and mounting an aerosol valve, 25 parts of dimethyl ether and 25 parts of LPG are filled, and an actuator is attached to obtain an oily aerosol.

Formulation Example 24
0.2 part of organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 0.4 part of clothianidin, 0.01 part of BHT, 5 parts of xylene , 3.39 parts of deodorized kerosene and 1 part of an emulsifier {Atmos 300 (registered trademark name of Atmos Chemical Co., Ltd.)} and 50 parts of distilled water are filled in an aerosol container, and a valve part is attached. Through pressure, 40 parts of propellant (LPG) is pressure-filled to obtain an aqueous aerosol.

Formulation Example 25
1 part of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167) and 3 parts of clothianidin are dissolved in 80 parts of diethylene glycol monoethyl ether. Is mixed with 15 parts of propylene carbonate to obtain a spot-on solution.

Formulation Example 26
5 parts of one organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167) and 5 parts of clothianidin are dissolved in 70 parts of diethylene glycol monoethyl ether. And 20 parts of 2-octyldodecanol are mixed to obtain a pour-on solution.

Formulation Example 27
Nikkor TEALS-42 is added to a mixture of 0.25 part of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167) and 0.25 part of clothianidin. (42% aqueous solution of Nikko Chemicals lauryl sulfate triethanolamine) 60 parts, 20 parts of propylene glycol were added and stirred and mixed until a homogeneous solution was obtained, and then 19.5 parts of water was added and further stirred and mixed. A uniform solution shampoo is obtained.

Formulation Example 28
A mixture of 0.05 g of one organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167) and 0.05 g of clothianidin is dissolved in 2 ml of propylene glycol. Impregnation into a porous ceramic plate of 4.0 × 4.0 cm and a thickness of 1.2 cm to obtain a heating smoke.

Formulation Example 29
2.5 parts of one organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 2.5 parts of clothianidin, and ethylene-methyl methacrylate copolymer 95 parts of a polymer (ratio of methyl methacrylate in the copolymer: 10% by weight, ACRlift WD301, manufactured by Sumitomo Chemical Co., Ltd.) was melt-kneaded with a closed pressure kneader (manufactured by Moriyama Seisakusho), and the resulting kneaded product was Extrusion is performed from an extrusion molding machine through a molding die to obtain a rod-shaped molded body having a length of 15 cm and a diameter of 3 mm.

Formulation Example 30
2.5 parts of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 2.5 parts of clothianidin, and 95 parts of a soft vinyl chloride resin. The mixture is melt-kneaded with a closed pressure kneader (manufactured by Moriyama Seisakusho), and the resulting kneaded product is extruded from an extrusion molding machine through a molding die to obtain a rod-shaped molded body having a length of 15 cm and a diameter of 3 mm.

Formulation Example 31
2 parts of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 2- (2,6-difluorophenyl) -4- [4- tert-butyl-2-ethoxyphenyl] -4,5-dihydrooxazole and 5 parts clothianidin are dissolved in 37.5 parts of xylene and 37.5 parts of N, N-dimethylformamide. Add 10 parts of styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate and mix well with stirring to obtain an emulsion.

Formulation Example 32
5 parts of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 2- (2,6-difluorophenyl) -4- [4- tert-butyl-2-ethoxyphenyl] -4,5-dihydrooxazole and 2 parts clothianidin are dissolved in 37.5 parts of xylene and 37.5 parts of N, N-dimethylformamide. Add 10 parts of styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate and mix well with stirring to obtain an emulsion.

Formulation Example 33
20 parts of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 2- (2,6-difluorophenyl) -4- [4- tert-butyl-2-ethoxyphenyl] -4,5-dihydrooxazole and 10 parts of clothianidin, 5 parts of Solpol 5060 (trade name of Toho Chemical) are added and mixed well to obtain Carplex # 80. (Shionogi Pharmaceutical registered trade name, synthetic hydrous silicon oxide fine powder) 32 parts and 300 mesh diatomaceous earth 23 parts are added and mixed with a juice mixer to obtain a wettable powder.

Formulation Example 34
1 part of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 2- (2,6-difluorophenyl) -4- [4- tert-Butyl-2-ethoxyphenyl] -4,5-dihydrooxazole, 1 part of clothianidin, 5 parts of synthetic silicon hydroxide fine powder, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 57 parts of clay were added. Mix well, then add an appropriate amount of water to these mixtures, further stir, granulate with a granulator, and dry by ventilation to obtain granules.

Formulation Example 35
1.5 parts of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 2- (2,6-difluorophenyl) -4- [ 4-tert-butyl-2-ethoxyphenyl] -4,5-dihydrooxazole 1 part, clothianidin 2 parts, synthetic silicon hydroxide fine powder 1 part, Doreles B (manufactured by Sankyo) as a flocculant, 7 parts clay After mixing well in a mortar, stir and mix with a juice mixer. 86.5 parts of cut clay is added to the resulting mixture and mixed thoroughly with stirring to obtain a powder.

Formulation Example 36
5 parts of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167); 2- (2,6-difluorophenyl) -4- [4- tert-butyl-2-ethoxyphenyl] -4,5-dihydrooxazole; 3 parts clothianidin; 35 parts white carbon containing 50 parts polyoxyethylene alkyl ether sulfate ammonium salt; The formulation is obtained by pulverization by the method.

Formulation Example 37
0.2 part of one kind of organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 2- (2,6-difluorophenyl) -4- [ 4-tert-Butyl-2-ethoxyphenyl] -4,5-dihydrooxazole and a mixture of 0.1 part of clothianidin were dissolved in 10 parts of dichloromethane and dissolved in Isopar M (isoparaffin: Exxon Chemical Registration). Name) Mix to 89.5 parts to obtain oil.

Formulation Example 38
0.05 part of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 2- (2,6-difluorophenyl) -4- [ 4-tert-butyl-2-ethoxyphenyl] -4,5-dihydrooxazole 0.02 part, clothianidin 0.03 part, and neothiozole (Chuo Kasei Co., Ltd.) 49.9 parts are put into an aerosol can, and an aerosol valve is set. After mounting, 25 parts of dimethyl ether and 25 parts of LPG are filled, and an oily aerosol is obtained by mounting the actuator.

Formulation Example 39
0.2 part of one kind of organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 2- (2,6-difluorophenyl) -4- [ 4-tert-butyl-2-ethoxyphenyl] -4,5-dihydrooxazole, 0.2 part of clothianidin, 0.01 part of BHT, 5 parts of xylene, 3.39 parts of deodorized kerosene, and an emulsifier {Atmos 300 (registered trade name of Atmos Chemical Co., Ltd.)} 1 part mixed and dissolved and 50 parts distilled water are filled into an aerosol container, a valve part is attached, and 40 parts propellant (LPG) is pressurized and filled through the valve. Thus, an aqueous aerosol is obtained.

Formulation Example 40
2 parts of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 2- (2,6-difluorophenyl) -4- [4- tert-butyl-2-ethoxyphenyl] -4,5-dihydrooxazole and 1 part of clothianidin are dissolved in 80 parts of diethylene glycol monoethyl ether, and 15 parts of propylene carbonate are mixed with this to obtain a spot-on solution. .

Formulation Example 41
5 parts of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 2- (2,6-difluorophenyl) -4- [4- 2 parts of tert-butyl-2-ethoxyphenyl] -4,5-dihydrooxazole and 3 parts of clothianidin are dissolved in 70 parts of diethylene glycol monoethyl ether, and 20 parts of 2-octyldodecanol is mixed therewith to prepare a pour-on solution. Get.

Formulation Example 42
0.25 part of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 2- (2,6-difluorophenyl) -4- [ 4-tert-butyl-2-ethoxyphenyl] -4,5-dihydrooxazole and a mixture of 0.15 part of clothianidin were added to a 42% aqueous solution of Nikkor TEALS-42 (Nikko Chemicals, lauryl sulfate triethanolamine). ) 60 parts and 20 parts of propylene glycol are added and stirred and mixed until a uniform solution is obtained. Then 19.5 parts of water is added and further stirred and mixed to obtain a shampoo agent of a uniform solution.

Formulation Example 43
0.05 g of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), 2- (2,6-difluorophenyl) -4- [4 -Tert-Butyl-2-ethoxyphenyl] -4,5-dihydrooxazole 0.02 g and clothianidin 0.03 g were dissolved in 2 ml of propylene glycol, 4.0 × 4.0 cm, thickness 1.2 cm. The porous ceramic plate is impregnated to obtain a heating smoke.

Formulation Example 44
2.5 parts of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167), and 2- (2,6-difluorophenyl) -4- 1 part of [4-tert-butyl-2-ethoxyphenyl] -4,5-dihydrooxazole and 1.5 parts of clothianidin and ethylene-methyl methacrylate copolymer (ratio of methyl methacrylate in the copolymer: 10 parts by weight, 95 parts by weight of ACLIFT WD301 (manufactured by Sumitomo Chemical Co., Ltd.) are melt-kneaded with a closed pressure kneader (manufactured by Moriyama Seisakusho), and the resulting kneaded product is extruded from an extrusion molding machine through a molding die, and has a length of 15 cm. A rod-shaped molded body having a diameter of 3 mm is obtained.

Formulation Example 45
2.5 parts of an organic sulfur compound selected from the group consisting of the present organic sulfur compounds (1) to (78) and (101) to (167) and 2- (2,6-difluorophenyl) -4- [ 4-tert-butyl-2-ethoxyphenyl] -4,5-dihydrooxazole 1 part, clothianidin 1.5 parts and soft vinyl chloride resin 95 parts are melt-kneaded in a closed pressure kneader (Moriyama Seisakusho), The obtained kneaded product is extruded from an extrusion molding machine through a molding die to obtain a rod-shaped molded body having a length of 15 cm and a diameter of 3 mm.

  Next, it is shown as a test example that the pest control composition of the present invention has an excellent control effect against pests.

Test example 1
Acetone solutions having a predetermined concentration of the organic sulfur compound and the neonicotinoid compound were prepared. After 1 μl of the acetone solution was dropped on the ventral side of the chest of a female German cockroach (Blattella germanica), the test insect was transferred to a plastic cup with a diameter of about 9 cm and a height of about 4.5 cm, and left at 25 ° C. with food and water. did. Seven days later, the life and death of the test insects were observed to determine the death rate. The German cockroaches tested were 10 in one test, and one cup was transferred.
The results are shown in Table 1 below.

  As a result, the pest control composition of the present invention showed high control efficacy.

  The pest control composition of the present invention has an excellent control effect against pests and is useful.

Claims (10)

Formula (I) below

[Where,
Cy is a phenyl group which may be substituted with a group selected from groups E1 to E2, a 5- to 6-membered heteroaryl group which may be substituted with a group selected from groups E1 to E2, and a group E1 to E3. A 3- to 7-membered cycloalkyl group optionally substituted with a group or a 5- to 7-membered cycloalkenyl group optionally substituted with a group selected from the groups E1 to E3,
R ¹ represents a C1-C4 chain hydrocarbon group optionally substituted with a halogen atom, a halogen atom or a hydrogen atom,
R ² represents a C1-C4 chain hydrocarbon group optionally substituted with a halogen atom, —C (═G) R ⁴ , a cyano group, a halogen atom or a hydrogen atom;
R ³ represents a C1-C5 haloalkyl group containing at least one fluorine atom or a fluorine atom,
G represents an oxygen atom or a sulfur atom,
R ⁴ is a C1-C4 alkyl group which may be substituted with a halogen atom, a C1-C4 alkoxy group which may be substituted with a halogen atom, a C3-C6 alkenyloxy group which may be substituted with a halogen atom, halogen A C3-C6 alkynyloxy group optionally substituted with an atom, a C1-C4 alkylamino group optionally substituted with a halogen atom, a di (C1-C4 alkyl) amino group optionally substituted with a halogen atom, Represents a hydroxyl group, an amino group, a C2-C5 cyclic amino group or a hydrogen atom;
m represents 0 or 1, n represents 0, 1 or 2,
Group E1 is group substituted by C1~C6 may chain hydrocarbon group selected from the group L, optionally substituted C3~C6 cycloalkyl group with a halogen atom, -OR ^5, -SR ^5, -S (= O) R ⁵ , -S (= O) ₂ R ⁵ , -C (= O) R ⁶ , -OC (= O) R ⁷ , cyano group, nitro group, hydroxyl group and halogen atom Represents a group of monovalent groups,
Group E2 is a C2-C6 alkanediyl group optionally substituted with a group selected from Group L, a 1,3-butadiene-1,4-diyl group optionally substituted with a group selected from Group L; Represents a group of divalent groups consisting of -G-T-G- and -T-G-T-;
Group E3 represents a group of divalent groups consisting of ═O, ═NO—R ⁵ , ═C═CH ₂ and ═C (R ⁸ ) R ⁹ ;
T represents a methylene group or an ethylene group,
R ⁵ represents a C1-C4 chain hydrocarbon group which may be substituted with a group selected from Group L or a C3-C6 cycloalkyl group which may be substituted with a group selected from Group L;
R ⁶ is a C1-C4 alkoxy group which may be substituted with a halogen atom, a C3-C6 alkenyloxy group which may be substituted with a halogen atom, a C3-C6 alkynyloxy group which may be substituted with a halogen atom, A C1-C4 alkylamino group optionally substituted with a halogen atom, a di (C1-C4 alkyl) amino group optionally substituted with a halogen atom, a C1-C4 alkyl group optionally substituted with a halogen atom, Represents a hydroxyl group, an amino group, a C2-C5 cyclic amino group or a hydrogen atom;
R ⁷ is a C1-C4 alkoxy group which may be substituted with a halogen atom, a C3-C6 alkenyloxy group which may be substituted with a halogen atom, a C3-C6 alkynyloxy group which may be substituted with a halogen atom, A C1-C4 alkylamino group optionally substituted with a halogen atom, a di (C1-C4 alkyl) amino group optionally substituted with a halogen atom, a C1-C4 alkyl group optionally substituted with a halogen atom, Represents an amino group, a C2-C5 cyclic amino group or a hydrogen atom,
R ⁸ and R ⁹ are the same or different and represent a C1-C4 alkoxy group which may be substituted with a halogen atom, a C1-C4 chain hydrocarbon group which may be substituted with a halogen atom, a halogen atom or a hydrogen atom. Represent,
Group L is a hydroxyl group, a C1-C4 alkoxy group optionally substituted with a halogen atom, a C3-C6 alkenyloxy group optionally substituted with a halogen atom, or a C3-C6 optionally substituted with a halogen atom. An alkynyloxy group, an amino group, a C1-C4 alkylamino group optionally substituted with a halogen atom, a di (C1-C4 alkyl) amino group optionally substituted with a halogen atom, a C2-C5 cyclic amino group,- It represents a group consisting of C (═O) R ⁶ , —OC (═O) R ⁷ and a halogen atom. ]
An organic sulfur compound represented by
A pest control composition comprising a neonicotinoid compound selected from the group consisting of imidacloprid, thiacloprid, acetamiprid, nitenpyram, clothianidin and thiamethoxam. The composition according to claim 1, wherein in formula (I), Cy is a phenyl group optionally substituted with a group selected from groups E1 to E2. The composition according to claim 1, wherein in formula (I), Cy is a 5- to 6-membered heteroaryl group optionally substituted with a group selected from groups E1 to E2. The composition according to claim 1, wherein in formula (I), Cy is a pyridyl group optionally substituted with a group selected from groups E1 to E2. In formula (I), Cy may be substituted with a group selected from 3 to 7-membered cycloalkyl groups or groups selected from groups E1 to E3 which may be substituted with groups selected from groups E1 to E3. The composition of claim 1 which is a membered cycloalkenyl group. 2. The formula (I), wherein Cy is a cyclohexyl group optionally substituted with a group selected from groups E1 to E3 or a cyclohexenyl group optionally substituted with a group selected from groups E1 to E3. Composition. The composition according to any one of claims 1 to 6, wherein the neonicotinoid compound is a compound selected from the group consisting of clothianidin and thiamethoxam. The composition according to any one of claims 1 to 6, wherein the neonicotinoid compound is clothianidin. A method for controlling pests, which comprises applying the composition according to any one of claims 1 to 8 to pests or habitats of pests. Use of the composition according to any one of claims 1 to 8 for controlling pests.