JP2021070630A - Fluoroalkylating agent and fluoroalkylation reaction - Google Patents

Abstract

To provide an industrially preferable fluoroalkylating agent, and use of the same.SOLUTION: A compound represented by formula (1) and a fluoroalkylating agent are provided. In the formula, R1 represents a C1-C8 fluoroalkyl group; R2 represents an optionally substituted C4-C10 alkyl group or the like; R3 represents a C1-C3 alkyl group; Y1, Y2, Y3 and Y4 each independently represent a hydrogen atom, a halogen atom, or the like; and X- represents a halogen ion, an alkyl sulfate ion, or the like.SELECTED DRAWING: None

Description

The present invention relates to an asymmetrically substituted novel fluoroalkylating agent having different substituents at the 1- and 3-positions of the benzimidazole ring.

The present invention also relates to a method for producing a compound having a fluoroalkyl group by carrying out a fluoroalkylation reaction using a novel fluoroalkylating agent.

Compounds having a fluoroalkyl group are useful as various chemical products (for example, pharmaceuticals, agricultural chemicals, electronic materials, etc.) and their production intermediates. In particular, compounds having a trifluoromethylthio group (CF 3 _S-) are themselves useful as insecticides and / or acaricides, and other insecticides and / or manufacturing intermediates other miticides (See Patent Documents 1 and 2).

In order to produce compounds having a fluoroalkyl group, various fluoroalkylating agents such as (trifluoromethyl) trimethylsilane (Ruppert-Prakash reagent) and fluoroalkylation reactions have been developed so far (non-fluoroalkylating agents). See Patent Documents 1 and 2). However, the methods of Non-Patent Documents 1 and 2 use trifluoromethane (CHF ₃ , HFC-23), _{which is a greenhouse gas, or trifluoroiodomethane (CF 3} I) or bromotrifluoromethane (CBrF ₃ ), which is a chlorofluorocarbon gas. I need. Therefore, these fluoroalkylating agents and fluoroalkylation reactions impose a heavy load on the environment.
Further, the present inventor has developed a non-conventional fluoroalkylating agent and fluoroalkylating reaction in order to solve the above-mentioned problems in the fluoroalkylating agent and the fluoroalkylating reaction (see Patent Document 3). The method described in Patent Document 3 is an extremely excellent method from the viewpoint of industrial manufacturing, which does not impose a burden on the environment and is economically efficient as compared with the prior art known before Patent Document 3.

WO96 / 33168 WO2013 / 157229A1 WO2015 / 199109A1

Tetrahedon Lett., 25 (21), 2195-2198 (1984) Tetrahedon, 54, 13771-13782 (1998)

An object of the present invention is to provide a further improved and excellent method for the fluoroalkylating agent and the fluoroalkylation reaction provided in Patent Document 3.

The fluoroalkylating agent disclosed in Patent Document 3 is an excellent reagent from the viewpoint of industrial production, but has hygroscopicity peculiar to salts, and improvement in storage stability has been desired. Further, the fluoroalkylation reaction disclosed in Patent Document 3 is an excellent method from the viewpoint of industrial production, but improvement in versatility has been desired. An object of the present invention is to provide a method in which these points are improved.

In view of the above situation, as a result of intensive research by the present inventor on fluoroalkylating agents and fluoroalkylation reactions, surprisingly, different substituents at the 1st and 3rd positions of the benzimidazole ring (particularly, in particular). It has been found that an asymmetrically substituted fluoroalkylating agent having different alkyl groups) can solve the above-mentioned problems. The present inventor has completed the present invention based on this finding.

That is, the present invention solves the above-mentioned problems by providing the inventions described in the following items [1] to [34].

（式中、Ｒ^１はＣ_１〜Ｃ_８フルオロアルキル基を示し、
Ｒ^２は１又は２個以上の同一又は異なる置換基Ａにより置換されていてもよいＣ_４〜Ｃ_１０アルキル基、１又は２個以上の同一又は異なる置換基Ａにより置換されていてもよいＣ_４〜Ｃ_１０アルケニル基、１又は２個以上の同一又は異なる置換基Ａにより置換されていてもよいＣ_４〜Ｃ_１０アルキニル基又は、１又は２個以上の同一又は異なる置換基Ａにより置換されていてもよいＣ_３〜Ｃ_８シクロアルキル基を示し、
Ｒ^３はＣ_１〜Ｃ_３アルキル基を示し、
Ｙ^１、Ｙ^２、Ｙ^３及びＹ^４は、それぞれ独立して、
水素原子、ハロゲン原子、Ｃ_１〜Ｃ_６アルキル基、Ｃ_３〜Ｃ_８シクロアルキル基、ヒドロキシ基、Ｃ_１〜Ｃ_６アルコキシ基、Ｃ_１〜Ｃ_６アルキルチオ基、Ｃ_１〜Ｃ_６アルキルスルフィニル基、Ｃ_１〜Ｃ_６アルキルスルホニル基、アミノ基、モノ（Ｃ_１〜Ｃ_６アルキル）アミノ基、ジ（Ｃ_１〜Ｃ_６アルキル）アミノ基、Ｃ_１〜Ｃ_６アシルアミノ基、ホルミル基、カルボキシ基、Ｃ_１〜Ｃ_６アルコキシカルボニル基、Ｃ_１〜Ｃ_６アルキルカルボニルオキシ基、ニトロ基、シアノ基又は、１又は２個以上の同一又は異なる置換基Ｂにより置換されていてもよいＣ_６〜Ｃ_１０アリール基を示し、
又は、Ｙ^１とＹ^２、Ｙ^２とＹ^３、Ｙ^３とＹ^４の２つの隣接する置換基は、それらが結合している炭素原子と一緒になって、４〜８員の炭素環を形成してもよく、
Ｘ⁻はハロゲンイオン、テトラフルオロホウ酸イオン、メタンスルホナートイオン、トリフルオロメタンスルホナートイオン、ｐ−トルエンスルホナートイオン、過塩素酸イオン、リン酸二水素イオン、硫酸水素イオン又は硫酸アルキルイオンを示し、
置換基ＡはＣ_１〜Ｃ_６アルコキシ基、Ｃ_１〜Ｃ_６アルコキシカルボニル基又はＣ_１〜Ｃ_６アルキルカルボニルオキシ基を示し、
置換基Ｂはハロゲン原子、Ｃ_１〜Ｃ_６アルキル基、Ｃ_３〜Ｃ_８シクロアルキル基、ヒドロキシ基、Ｃ_１〜Ｃ_６アルコキシ基、Ｃ_１〜Ｃ_６アルキルチオ基、Ｃ_１〜Ｃ_６アルキルスルフィニル基、Ｃ_１〜Ｃ_６アルキルスルホニル基、Ｃ_１〜Ｃ_６ハロアルキルチオ基、Ｃ_１〜Ｃ_６ハロアルキルスルフィニル基、Ｃ_１〜Ｃ_６ハロアルキルスルホニル基、アミノ基、モノ（Ｃ_１〜Ｃ_６アルキル）アミノ基、ジ（Ｃ_１〜Ｃ_６アルキル）アミノ基、Ｃ_１〜Ｃ_６アシルアミノ基、ホルミル基、カルボキシ基、Ｃ_１〜Ｃ_６アルコキシカルボニル基、Ｃ_１〜Ｃ_６アルキルカルボニルオキシ基、ニトロ基又はシアノ基を示す。）
で表される化合物。 [1] Equation (1):

(In the formula, R ¹ represents a C _{1 to} C ₈ fluoroalkyl group,
R ² may be substituted with one or more identical or different substituents A C _{4 to} C ₁₀ alkyl groups may be substituted with one or more identical or different substituents A C _{4 to} C ₁₀ Alkyne groups may be substituted with 1 or more identical or different substituents A C _{4 to} C ₁₀ Alkynyl groups or 1 or more identical or different substituents A Shows _{C 3 to C 8} cycloalkyl groups that may be present.
R ³ represents a C _{1 to} C ₃ alkyl group,
Y ¹ , Y ² , Y ³ and Y ⁴ are independent of each other.
Hydrogen atom, halogen atom, C _{1 to} C ₆ alkyl group, C _{3 to} C ₈ cycloalkyl group, hydroxy group, C _{1 to} C ₆ alkoxy group, C _{1 to} C ₆ alkylthio group, C _{1 to} C ₆ alkyl sulfinyl group , C _{1 to} C ₆ alkylsulfonyl groups, amino groups, mono (C _{1 to} C ₆ alkyl) amino groups, di (C _{1 to} C ₆ alkyl) amino groups, C _{1 to} C ₆ acylamino groups, formyl groups, carboxy groups , C _{1 to} C ₆ alkoxycarbonyl groups, C _{1 to} C _{6 alkylcarbonyloxy groups, nitro groups, cyano groups or C 6 to} C which may be substituted with one or more identical or different substituents B. _{Shows a 10} aryl group,
Alternatively, ^{two adjacent substituents, Y 1} and Y ² , Y ² and Y ³ , Y ³ and Y ⁴ , together with the carbon atom to which they are attached form a 4- to 8-membered carbon ring. May be formed,
X ^- indicates halogen ion, tetrafluoroborate ion, methanesulfonate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, perchlorate ion, dihydrogen phosphate ion, hydrogen sulfate ion or alkyl sulfate ion. ,
Substituent A represents a C _{1 to} C ₆ alkoxy group, a C _{1 to} C ₆ alkoxycarbonyl group or a C _{1 to} C ₆ alkylcarbonyloxy group.
Substituent B is a halogen atom, C _{1 to} C ₆ alkyl group, C _{3 to} C ₈ cycloalkyl group, hydroxy group, C _{1 to} C ₆ alkoxy group, C _{1 to} C ₆ alkyl thio group, C _{1 to} C ₆ alkyl sulfinyl. _group, C 1 -C ₆ alkylsulfonyl _group, C 1 -C ₆ haloalkylthio _group, C 1 -C ₆ haloalkylsulfinyl _group, C 1 -C ₆ haloalkylsulfonyl group, an amino group, a mono _(C 1 -C ₆ alkyl) Amino group, di (C _{1 to} C ₆ alkyl) amino group, C _{1 to} C ₆ acylamino group, formyl group, carboxy group, C _{1 to} C ₆ alkoxycarbonyl group, C _{1 to} C ₆ alkylcarbonyloxy group, nitro group Alternatively, it indicates a cyano group. )
The compound represented by.

[2] R ¹ represents a C _{1 to} C ₄ fluoroalkyl group.
R ² _{represents a C 4 to} C ₁₀ alkyl group that may be substituted with one or more identical or different substituents A.
R ³ represents a C _{1 to} C ₃ alkyl group,
Y ¹ , Y ² , Y ³ and Y ⁴ are independent of each other.
Hydrogen atom, halogen atom, C _{1 to} C ₆ alkyl group, C _{3 to} C ₈ cycloalkyl group, hydroxy group, C _{1 to} C ₆ alkoxy group, C _{1 to} C ₆ alkylthio group, C _{1 to} C ₆ alkyl sulfinyl group , C _{1 to} C ₆ alkylsulfonyl groups, amino groups, mono (C _{1 to} C ₆ alkyl) amino groups, di (C _{1 to} C ₆ alkyl) amino groups, C _{1 to} C ₆ acylamino groups, formyl groups, carboxy groups , C _{1 to} C ₆ alkoxycarbonyl groups, C _{1 to} C ₆ alkylcarbonyloxy groups, nitro groups, cyano groups or phenyl groups optionally substituted with one or more identical or different substituents B. ,
Alternatively, ^{two adjacent substituents, Y 1} and Y ² , Y ² and Y ³ , Y ³ and Y ⁴ , together with the carbon atom to which they are attached form a 4- to 8-membered carbon ring. May be formed,
X ^- indicates halogen ion, tetrafluoroborate ion, methanesulfonate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, perchlorate ion, dihydrogen phosphate ion, hydrogen sulfate ion or alkyl sulfate ion. ,
Substituent A represents a C _{1 to} C ₆ alkoxy group, a C _{1 to} C ₆ alkoxycarbonyl group or a C _{1 to} C ₆ alkylcarbonyloxy group.
Substituent B is a halogen atom, C _{1 to} C ₆ alkyl group, C _{3 to} C ₈ cycloalkyl group, hydroxy group, C _{1 to} C ₆ alkoxy group, C _{1 to} C ₆ alkyl thio group, C _{1 to} C ₆ alkyl sulfinyl. _group, C 1 -C ₆ alkylsulfonyl _group, C 1 -C ₆ haloalkylthio _group, C 1 -C ₆ haloalkylsulfinyl _group, C 1 -C ₆ haloalkylsulfonyl group, an amino group, a mono _(C 1 -C ₆ alkyl) Amino group, di (C _{1 to} C ₆ alkyl) amino group, C _{1 to} C ₆ acylamino group, formyl group, carboxy group, C _{1 to} C ₆ alkoxycarbonyl group, C _{1 to} C ₆ alkylcarbonyloxy group, nitro group Alternatively, the compound according to [1], which exhibits a cyano group.

[3] R ¹ represents a C _{1 to} C ₄ fluoroalkyl group.
R ² _{represents a C 4 to} C ₁₀ alkyl group that may be substituted with one or more identical or different substituents A.
R ³ represents a C _{1 to} C ₃ alkyl group,
Y ¹ , Y ² , Y ³ and Y ⁴ are independent of each other.
A hydrogen atom, a halogen _atom, C 1 -C ₆ alkyl _group, C 1 -C ₆ alkoxy _group, C 1 -C ₆ alkylthio _group, C 1 -C ₆ alkylsulfinyl _group, C 1 -C ₆ alkylsulfonyl group, a nitro group Or show a cyano group,
X ^- indicates halogen ion, tetrafluoroborate ion, methanesulfonate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, perchlorate ion, dihydrogen phosphate ion, hydrogen sulfate ion or alkyl sulfate ion. ,
The compound according to [1], wherein the substituent A represents a C _{1 to} C ₆ alkoxy group, a C _{1 to} C ₆ alkoxycarbonyl group, or a C _{1 to} C _{6 alkylcarbonyloxy group.}

[4] R ¹ represents a C _{1 to} C ₄ perfluoroalkyl group.
R ² may be substituted with one or more identical or different C _{1 to} C ₆ alkoxy groups, C _{1 to} C ₆ alkoxycarbonyl groups or C _{1 to} C _{6 alkylcarbonyloxy groups C 4 to} C ₁₀ Shows an alkyl group,
R ³ represents a C _{1 to} C ₃ alkyl group,
Y ¹ , Y ² , Y ³ and Y ⁴ represent hydrogen atoms,
The compound according to [1], wherein X ⁻ represents a halogen ion or an alkyl sulfate ion.

[5] R ¹ represents a C _{1 to} C ₄ perfluoroalkyl group.
R ² represents a C _{4 to} C ₁₀ alkyl group and represents
R ³ represents a C _{1 to} C ₃ alkyl group,
Y ¹ , Y ² , Y ³ and Y ⁴ represent hydrogen atoms,
The compound according to [1], wherein X ^{− represents an alkyl sulfate ion.}

[6] R ¹ represents a trifluoromethyl group or a pentafluoroethyl group.
R ² represents an n-butyl group, a sec-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group or an n-heptyl group.
R ³ represents a methyl group, an ethyl group, an n-propyl group or an isopropyl group.
Y ¹ , Y ² , Y ³ and Y ⁴ represent hydrogen atoms,
The compound according to [1], wherein X ⁻ represents a chloride ion, a bromine ion, an iodine ion, a methyl sulfate ion or an ethyl sulfate ion.

[7] R ¹ represents a trifluoromethyl group and represents
R ² represents an n-butyl group
R ³ represents a methyl group
Y ¹ , Y ² , Y ³ and Y ⁴ represent hydrogen atoms,
The compound according to [1], wherein X ^{− represents a methyl sulfate ion.}

[8] A fluoroalkylating agent containing the compound according to any one of the above [1] to [7] as an active ingredient.

[9] A fluoroalkylating agent represented by the formula (1) according to any one of the above [1] to [7].

[10] Use of the compound according to any one of the above [1] to [7] as a fluoroalkylating agent.

（式中、Ｒ^１はＣ_１〜Ｃ_８フルオロアルキル基を示し、
Ｒ^４は１又は２個以上の同一又は異なる置換基Ｃにより置換されてもよいＣ_１〜Ｃ_１０アルキル基、１又は２個以上の同一又は異なる置換基Ｃにより置換されてもよいＣ_２〜Ｃ_１０アルケニル基、１又は２個以上の同一又は異なる置換基Ｃにより置換されてもよいＣ_２〜Ｃ_１０アルキニル基又は、１又は２個以上の同一又は異なる置換基Ｂにより置換されてもよいＣ_６〜Ｃ_１０アリール基を示し、
置換基Ｂはハロゲン原子、Ｃ_１〜Ｃ_６アルキル基、Ｃ_３〜Ｃ_８シクロアルキル基、ヒドロキシ基、Ｃ_１〜Ｃ_６アルコキシ基、Ｃ_１〜Ｃ_６アルキルチオ基、Ｃ_１〜Ｃ_６アルキルスルフィニル基、Ｃ_１〜Ｃ_６アルキルスルホニル基、Ｃ_１〜Ｃ_６ハロアルキルチオ基、Ｃ_１〜Ｃ_６ハロアルキルスルフィニル基、Ｃ_１〜Ｃ_６ハロアルキルスルホニル基、アミノ基、モノ（Ｃ_１〜Ｃ_６アルキル）アミノ基、ジ（Ｃ_１〜Ｃ_６アルキル）アミノ基、Ｃ_１〜Ｃ_６アシルアミノ基、ホルミル基、カルボキシ基、Ｃ_１〜Ｃ_６アルコキシカルボニル基、Ｃ_１〜Ｃ_６アルキルカルボニルオキシ基、ニトロ基又はシアノ基を示し、
置換基Ｃはハロゲン原子、ヒドロキシ基、Ｃ_１〜Ｃ_６アルコキシ基、カルボキシ基、Ｃ_１〜Ｃ_６アルコキシカルボニル基、Ｃ_１〜Ｃ_６アルキルカルボニルオキシ基、１又は２個以上の同一又は異なるハロゲン原子、Ｃ_１〜Ｃ_６アルキル基、Ｃ_１〜Ｃ_６ハロアルキルチオ基又はＣ_１〜Ｃ_６ハロアルキルスルフィニル基により置換されてもよいＣ_６〜Ｃ_１０アリール基、１又は２個以上の同一又は異なるハロゲン原子、Ｃ_１〜Ｃ_６アルキル基、Ｃ_１〜Ｃ_６ハロアルキルチオ基又はＣ_１〜Ｃ_６ハロアルキルスルフィニル基により置換されてもよいＣ_６〜Ｃ_１０アリールオキシ基又は、１又は２個以上の同一又は異なるハロゲン原子、Ｃ_１〜Ｃ_６アルキル基、Ｃ_１〜Ｃ_６ハロアルキルチオ基又はＣ_１〜Ｃ_６ハロアルキルスルフィニル基により置換されてもよいＣ_６〜Ｃ_１０アリール（Ｃ_１〜Ｃ_４）アルコキシ基を示す。）
の化合物の製造方法であって、式（３）：

（式中、Ｒ^４は前記で定義したとおりであり、
Ｚはシアノ基、Ｃ_１〜Ｃ_６アルキルスルホニル基、１又は２個以上の同一又は異なるハロゲン原子又はＣ_１〜Ｃ_６アルキル基により置換されてもよいＣ_６〜Ｃ_１０アリールスルホニル基を示す。）
の化合物を塩基の存在下、式（１）：

（式中、Ｒ^１は前記で定義したとおりであり、
Ｒ^２は１又は２個以上の同一又は異なる置換基Ａにより置換されていてもよいＣ_４〜Ｃ_１０アルキル基、１又は２個以上の同一又は異なる置換基Ａにより置換されていてもよいＣ_４〜Ｃ_１０アルケニル基、１又は２個以上の同一又は異なる置換基Ａにより置換されていてもよいＣ_４〜Ｃ_１０アルキニル基又は、１又は２個以上の同一又は異なる置換基Ａにより置換されていてもよいＣ_３〜Ｃ_８シクロアルキル基を示し、
Ｒ^３はＣ_１〜Ｃ_３アルキル基を示し、
Ｙ^１、Ｙ^２、Ｙ^３及びＹ^４は、それぞれ独立して、
水素原子、ハロゲン原子、Ｃ_１〜Ｃ_６アルキル基、Ｃ_３〜Ｃ_８シクロアルキル基、ヒドロキシ基、Ｃ_１〜Ｃ_６アルコキシ基、Ｃ_１〜Ｃ_６アルキルチオ基、Ｃ_１〜Ｃ_６アルキルスルフィニル基、Ｃ_１〜Ｃ_６アルキルスルホニル基、アミノ基、モノ（Ｃ_１〜Ｃ_６アルキル）アミノ基、ジ（Ｃ_１〜Ｃ_６アルキル）アミノ基、Ｃ_１〜Ｃ_６アシルアミノ基、ホルミル基、カルボキシ基、Ｃ_１〜Ｃ_６アルコキシカルボニル基、Ｃ_１〜Ｃ_６アルキルカルボニルオキシ基、ニトロ基、シアノ基又は、１又は２個以上の同一又は異なる置換基Ｂにより置換されていてもよいＣ_６〜Ｃ_１０アリール基を示し、
又は、Ｙ^１とＹ^２、Ｙ^２とＹ^３、Ｙ^３とＹ^４の２つの隣接する置換基は、それらが結合している炭素原子と一緒になって、４〜８員の炭素環を形成してもよく、
Ｘ⁻はハロゲンイオン、テトラフルオロホウ酸イオン、メタンスルホナートイオン、トリフルオロメタンスルホナートイオン、ｐ−トルエンスルホナートイオン、過塩素酸イオン、リン酸二水素イオン、硫酸水素イオン又は硫酸アルキルイオンを示し、
置換基ＡはＣ_１〜Ｃ_６アルコキシ基、Ｃ_１〜Ｃ_６アルコキシカルボニル基又はＣ_１〜Ｃ_６アルキルカルボニルオキシ基を示し、
置換基Ｂは前記で定義したとおりである。）
で表されるフルオロアルキル化剤と反応させることを特徴とする方法。 [11] Equation (2):

(In the formula, R ¹ represents a C _{1 to} C ₈ fluoroalkyl group,
R ⁴ may be substituted with one or more identical or different substituents C _{1 to} C ₁₀ alkyl groups may be substituted with one or more identical or different substituents C ₂ to C ₁₀ alkenyl group, one or more identical or different optionally substituted with a substituent C C ₂ -C ₁₀ alkynyl group, or may be substituted by one or more identical or different substituents B Shows C _{6 to C 10} aryl groups,
Substituent B is a halogen atom, C _{1 to} C ₆ alkyl group, C _{3 to} C ₈ cycloalkyl group, hydroxy group, C _{1 to} C ₆ alkoxy group, C _{1 to} C ₆ alkyl thio group, C _{1 to} C ₆ alkyl sulfinyl. _group, C 1 -C ₆ alkylsulfonyl _group, C 1 -C ₆ haloalkylthio _group, C 1 -C ₆ haloalkylsulfinyl _group, C 1 -C ₆ haloalkylsulfonyl group, an amino group, a mono _(C 1 -C ₆ alkyl) Amino group, di (C _{1 to} C ₆ alkyl) amino group, C _{1 to} C ₆ acylamino group, formyl group, carboxy group, C _{1 to} C ₆ alkoxycarbonyl group, C _{1 to} C ₆ alkylcarbonyloxy group, nitro group Or show a cyano group,
Substituent C is a halogen atom, a hydroxy group, a C _{1 to} C ₆ alkoxy group, a carboxy group, a C _{1 to} C ₆ alkoxycarbonyl group, a C _{1 to} C ₆ alkylcarbonyloxy group, or one or more identical or different halogens. Atomic, C _{6 to} C ₁₀ aryl groups optionally substituted with _{C 1 to} C ₆ alkyl groups, C _{1 to} C ₆ haloalkylthio groups or C _{1 to} C ₆ haloalkylsulfinyl groups, one or more identical or different _{C 6 to} C ₁₀ aryloxy groups or one or more, which may be substituted with halogen atoms, C _{1 to} C ₆ alkyl groups, C _{1 to} C ₆ haloalkylthio groups or C _{1 to} C _{6 haloalkylsulfinyl groups. C 6 to} C ₁₀ aryl (C _{1 to} C ₄ ) may be substituted with the same or different halogen atoms, C _{1 to} C ₆ alkyl groups, C _{1 to} C ₆ haloalkylthio groups or C _{1 to} C _{6 haloalkylsulfinyl groups.} Indicates an alkoxy group. )
A method for producing the compound according to the formula (3):

(In the equation, R ⁴ is as defined above,
Z represents a cyano group, a C _{1 to} C _{6 alkyl sulfonyl group, or a C 6 to} C ₁₀ aryl sulfonyl group that may be substituted with one or more identical or different halogen atoms or C _{1 to} C _{6 alkyl groups.} )
In the presence of a base, the compound of the formula (1):

(In the equation, R ¹ is as defined above,
R ² may be substituted with one or more identical or different substituents A C _{4 to} C ₁₀ alkyl groups may be substituted with one or more identical or different substituents A C _{4 to} C ₁₀ Alkyne groups may be substituted with 1 or more identical or different substituents A C _{4 to} C ₁₀ Alkynyl groups or 1 or more identical or different substituents A Shows _{C 3 to C 8} cycloalkyl groups that may be present.
R ³ represents a C _{1 to} C ₃ alkyl group,
Y ¹ , Y ² , Y ³ and Y ⁴ are independent of each other.
Hydrogen atom, halogen atom, C _{1 to} C ₆ alkyl group, C _{3 to} C ₈ cycloalkyl group, hydroxy group, C _{1 to} C ₆ alkoxy group, C _{1 to} C ₆ alkylthio group, C _{1 to} C ₆ alkyl sulfinyl group , C _{1 to} C ₆ alkylsulfonyl groups, amino groups, mono (C _{1 to} C ₆ alkyl) amino groups, di (C _{1 to} C ₆ alkyl) amino groups, C _{1 to} C ₆ acylamino groups, formyl groups, carboxy groups , C _{1 to} C ₆ alkoxycarbonyl groups, C _{1 to} C _{6 alkylcarbonyloxy groups, nitro groups, cyano groups or C 6 to} C which may be substituted with one or more identical or different substituents B. _{Shows a 10} aryl group,
Alternatively, ^{two adjacent substituents, Y 1} and Y ² , Y ² and Y ³ , Y ³ and Y ⁴ , together with the carbon atom to which they are attached form a 4- to 8-membered carbon ring. May be formed,
X ^- indicates halogen ion, tetrafluoroborate ion, methanesulfonate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, perchlorate ion, dihydrogen phosphate ion, hydrogen sulfate ion or alkyl sulfate ion. ,
Substituent A represents a C _{1 to} C ₆ alkoxy group, a C _{1 to} C ₆ alkoxycarbonyl group or a C _{1 to} C ₆ alkylcarbonyloxy group.
Substituent B is as defined above. )
A method characterized by reacting with a fluoroalkylating agent represented by.

[12] R ¹ represents a C _{1 to} C ₄ fluoroalkyl group.
R ² _{represents a C 4 to} C ₁₀ alkyl group that may be substituted with one or more identical or different substituents A.
R ³ represents a C _{1 to} C ₃ alkyl group,
R ⁴ may be substituted with one or more identical or different substituents C C _{1 to} C ₁₀ alkyl groups or one or more phenyl groups optionally substituted with the same or different substituents B. Indicates,
Y ¹ , Y ² , Y ³ and Y ⁴ are independent of each other.
Hydrogen atom, halogen atom, C _{1 to} C ₆ alkyl group, C _{3 to} C ₈ cycloalkyl group, hydroxy group, C _{1 to} C ₆ alkoxy group, C _{1 to} C ₆ alkylthio group, C _{1 to} C ₆ alkyl sulfinyl group , C _{1 to} C ₆ alkylsulfonyl groups, amino groups, mono (C _{1 to} C ₆ alkyl) amino groups, di (C _{1 to} C ₆ alkyl) amino groups, C _{1 to} C ₆ acylamino groups, formyl groups, carboxy groups , C _{1 to} C ₆ alkoxycarbonyl groups, C _{1 to} C ₆ alkylcarbonyloxy groups, nitro groups, cyano groups or phenyl groups optionally substituted with one or more identical or different substituents B. ,
Alternatively, ^{two adjacent substituents, Y 1} and Y ² , Y ² and Y ³ , Y ³ and Y ⁴ , together with the carbon atom to which they are attached form a 4- to 8-membered carbon ring. May be formed,
X ^- indicates halogen ion, tetrafluoroborate ion, methanesulfonate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, perchlorate ion, dihydrogen phosphate ion, hydrogen sulfate ion or alkyl sulfate ion. ,
Z represents a cyano group, C ₁ -C ₆ alkylsulfonyl group, one or more identical or different halogen atoms or C ₁ -C ₆ alkyl optionally phenylsulfonyl group optionally substituted by a group,
Substituent A represents a C _{1 to} C ₆ alkoxy group, a C _{1 to} C ₆ alkoxycarbonyl group or a C _{1 to} C ₆ alkylcarbonyloxy group.
Substituent B is a halogen atom, C _{1 to} C ₆ alkyl group, C _{3 to} C ₈ cycloalkyl group, hydroxy group, C _{1 to} C ₆ alkoxy group, C _{1 to} C ₆ alkyl thio group, C _{1 to} C ₆ alkyl sulfinyl. _group, C 1 -C ₆ alkylsulfonyl _group, C 1 -C ₆ haloalkylthio _group, C 1 -C ₆ haloalkylsulfinyl _group, C 1 -C ₆ haloalkylsulfonyl group, an amino group, a mono _(C 1 -C ₆ alkyl) Amino group, di (C _{1 to} C ₆ alkyl) amino group, C _{1 to} C ₆ acylamino group, formyl group, carboxy group, C _{1 to} C ₆ alkoxycarbonyl group, C _{1 to} C ₆ alkylcarbonyloxy group, nitro group Or show a cyano group,
Substituent C is a halogen atom, a hydroxy group, a C _{1 to} C ₆ alkoxy group, a carboxy group, a C _{1 to} C ₆ alkoxycarbonyl group, a C _{1 to} C ₆ alkylcarbonyloxy group, or one or more identical or different halogens. Atomic, _{phenyl group optionally substituted with C 1 to} C ₆ alkyl group, C _{1 to} C ₆ haloalkylthio group or C _{1 to} C ₆ haloalkylsulfinyl group, 1 or more identical or different halogen atoms, C ₁ -C ₆ alkyl _group, C 1 -C ₆ haloalkylthio group or a _C 1 -C ₆ haloalkylsulfinyl phenyl group or be substituted by a group, one or more identical or different halogen _atoms, C 1 -C The method according to [11], which shows a _{phenyl (C 1 to} C ₄ ) alkoxy group which may be substituted with a ₆ alkyl group, a C _{1 to} C ₆ haloalkylthio group or a C _{1 to} C _{6 haloalkylsulfinyl group.}

[13] R ¹ represents a C _{1 to} C ₄ fluoroalkyl group.
R ² _{represents a C 4 to} C ₁₀ alkyl group that may be substituted with one or more identical or different substituents A.
R ³ represents a C _{1 to} C ₃ alkyl group,
R ⁴ _{represents a C 1 to} C ₁₀ alkyl group that may be substituted with one or more identical or different substituents C.
Y ¹ , Y ² , Y ³ and Y ⁴ are independent of each other.
A hydrogen atom, a halogen _atom, C 1 -C ₆ alkyl _group, C 1 -C ₆ alkoxy _group, C 1 -C ₆ alkylthio _group, C 1 -C ₆ alkylsulfinyl _group, C 1 -C ₆ alkylsulfonyl group, a nitro group Or show a cyano group,
X ^- indicates halogen ion, tetrafluoroborate ion, methanesulfonate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, perchlorate ion, dihydrogen phosphate ion, hydrogen sulfate ion or alkyl sulfate ion. ,
Z represents a cyano group, C ₁ -C ₆ alkylsulfonyl group, one or more identical or different halogen atoms or C ₁ -C ₆ alkyl optionally phenylsulfonyl group optionally substituted by a group,
Substituent A represents a C _{1 to} C ₆ alkoxy group, a C _{1 to} C ₆ alkoxycarbonyl group or a C _{1 to} C ₆ alkylcarbonyloxy group.
Substituent C is a halogen atom, a hydroxy group, a C _{1 to} C ₆ alkoxy group, a carboxy group, a C _{1 to} C ₆ alkoxycarbonyl group, a C _{1 to} C ₆ alkylcarbonyloxy group, or one or more identical or different halogens. _atom, C 1 -C ₆ alkyl _group, C 1 -C ₆ haloalkylthio group or a _C 1 -C ₆ haloalkylsulfinyl phenyl group or be substituted by a group, one or more identical or different halogen atoms, The phenyl (C _{1 to} C _{4 ) alkoxy group optionally substituted with a C 1 to} C ₆ alkyl group, a C _{1 to} C ₆ haloalkylthio group or a C _{1 to} C ₆ haloalkylsulfinyl group, according to [11]. Method.

[14] R ¹ represents a C _{1 to} C ₄ perfluoroalkyl group.
R ² may be substituted with one or more identical or different C _{1 to} C ₆ alkoxy groups, C _{1 to} C ₆ alkoxycarbonyl groups or C _{1 to} C _{6 alkylcarbonyloxy groups C 4 to} C ₁₀ Shows an alkyl group,
R ³ represents a C _{1 to} C ₃ alkyl group,
R ⁴ is one or more identical or different halogen atoms, C ₁ -C ₄ alkylcarbonyloxy group or a benzyl group optionally substituted C ₁ may be -C ₆ alkyl group or one or more identical Alternatively, it may be substituted with a different halogen atom, a C _{1 to} C ₆ alkyl group, a C _{1 to} C ₆ haloalkylthio group or a C _{1 to} C _{6 haloalkylsulfinyl group, or a phenyloxy group. C 1 to} C ₆ Shows an alkyl group,
Y ¹ , Y ² , Y ³ and Y ⁴ represent hydrogen atoms,
X ⁻ indicates a halogen ion or an alkyl sulfate ion, and represents
Z represents a cyano group, C ₁ -C ₄ alkylsulfonyl group or one or more identical or different C ₁ -C ₆ alkyl optionally phenylsulfonyl group optionally substituted by a group, the method of [11] ..

[15] R ¹ represents a C _{1 to} C ₄ perfluoroalkyl group.
R ² represents a C _{4 to} C ₁₀ alkyl group and represents
R ³ represents a C _{1 to} C ₃ alkyl group,
R ⁴ _{represents a C 1-} C ₆ alkyl group that may be substituted with one or more identical or different halogen atoms.
Y ¹ , Y ² , Y ³ and Y ⁴ represent hydrogen atoms,
X ^- is shown an alkyl sulfate ion,
11. The method of [11], wherein Z represents a phenylsulfonyl group that may be substituted with one or more identical or different C _1- C _{6 alkyl groups.}

[16] R ¹ represents a trifluoromethyl group or a pentafluoroethyl group.
R ² represents an n-butyl group, a sec-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group or an n-heptyl group.
R ³ represents a methyl group, an ethyl group, an n-propyl group or an isopropyl group.
R ⁴ is 5-acetoxymethyl-pentyl group, 6- acetoxy-hexyl group, 5-bromopentyl group, 6-bromo-hexyl group, 5-chloropentyl group, 6-chloro-hexyl group, 5-benzyloxy-pentyl group, 6-benzyloxy Hexyl group, 5- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenoxy] pentyl group, 5- [4-chloro-2-fluoro-5- (2,2) , 2-Trifluoroethylsulfinyl) phenoxy] pentyl group, 6- [2,4-dimethyl-5- (2,2,2-trifluoroethylthio) phenoxy] hexyl group, 6- [2,4-dimethyl- Shows a 5- (2,2,2-trifluoroethylsulfinyl) phenoxy] hexyl group,
Y ¹ , Y ² , Y ³ and Y ⁴ represent hydrogen atoms,
X ⁻ indicates chloride ion, bromine ion, iodine ion, methyl sulfate ion or ethyl sulfate ion.
The method according to [11], wherein Z represents a cyano group, a methanesulfonyl group, and a p-toluenesulfonyl group.

[17] R ¹ represents a trifluoromethyl group and represents
R ² represents an n-butyl group
R ³ represents a methyl group
R ⁴ represents a 5-chloropentyl group,
Y ¹ , Y ² , Y ³ and Y ⁴ represent hydrogen atoms,
X ^- is shown methyl sulfate ion,
The method according to [11], wherein Z represents a p-toluenesulfonyl group.

[18] The item according to any one of [11] to [17], wherein the base used in the reaction is an alkali metal hydride, an alkali metal hydroxide, an alkali metal carbonate, or a mixture thereof. Method.

[19] The method according to any one of [11] to [17], wherein the base used in the reaction is an alkali metal hydroxide.

[20] Any of [11] to [17], wherein the base used in the reaction is sodium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or a mixture thereof. Or the method described in item 1.

[21] The method according to any one of [11] to [17], wherein the base used in the reaction is lithium hydroxide, sodium hydroxide, potassium hydroxide, or a mixture thereof.

[22] The method according to any one of [11] to [17], wherein the base used in the reaction is potassium hydroxide.

[23] The item according to any one of [11] to [22], wherein a base in the range of 1.5 equivalents or more and 10.0 equivalents or less is used with respect to 1.0 mol of the compound of the formula (3). Method.

[24] The item according to any one of [11] to [22], wherein a base in the range of 2.0 equivalents or more and 5.0 equivalents or less is used with respect to 1.0 mol of the compound of the formula (3). Method.

[25] Any of [11] to [24], wherein the compound of the formula (1) in the range of 1.0 mol or more and 2.0 mol or less is used with respect to 1.0 mol of the compound of the formula (3). The method according to item 1.

[26] Any of [11] to [24], wherein the compound of the formula (1) in the range of 1.0 mol or more and 1.5 mol or less is used with respect to 1.0 mol of the compound of the formula (3). The method according to item 1.

[27] The method according to any one of [11] to [26], wherein the reaction is carried out in the presence of zeolite.

[28] The method according to any one of [11] to [26], wherein the zeolite used in the reaction is molecular sieve 3A, molecular sieve 4A or molecular sieve 5A.

[29] The method according to any one of [11] to [26], wherein the reaction is carried out in the absence of zeolite.

[30] The method according to any one of [11] to [29], wherein the reaction is carried out at a temperature in the range of −50 ° C. or higher and 35 ° C. or lower.

[31] The method according to any one of [11] to [29], wherein the reaction is carried out at a temperature in the range of −30 ° C. or higher and 0 ° C. or lower.

[32] The method according to any one of [11] to [31], wherein the solvent used in the reaction is nitriles, ethers, amides, aromatic hydrocarbons, or a mixture thereof. ..

[33] The method according to any one of [11] to [31], wherein the solvent used in the reaction is an amide.

[34] The method according to any one of [11] to [31], wherein the solvent used in the reaction is N, N-dimethylformamide.

According to the present invention, a novel fluoroalkylating agent of the formula (1) and an industrially excellent fluoroalkylation reaction using the same are provided.

The fluoroalkylating agent of the present invention is characterized by having an asymmetrically substituted structure having different substituents (particularly different alkyl groups) at the 1- and 3-positions of the benzimidazole ring. The fluoroalkylating agent of the present invention has improved physical properties of the fluoroalkylating agent described in Patent Document 3.

The fluoroalkylating agent of the present invention has improved the problem of hygroscopicity of the fluoroalkylating agent described in Patent Document 3. The fluoroalkylating agent of the present invention has high storage stability due to its low hygroscopicity.

The fluoroalkylating agent of the present invention has improved solubility of the fluoroalkylating agent described in Patent Document 3. Since the fluoroalkylating agent of the present invention has high solubility in a solvent, the fluoroalkylation reaction of the present invention can be used under a wider range of conditions than the method described in Patent Document 3.

The fluoroalkylating agent of the present invention has improved blocking properties of the fluoroalkylating agent described in Patent Document 3. Blocking means that compounds form agglomerates when external pressure is applied, which not only deteriorates handling, but also causes a decrease in yield due to adhesion to the stirrer during the reaction, damage to the stirrer, and the like. is there.

Further, the 2,3-dihydrobenzimidazol-2-one compound derived from the fluoroalkylating agent of the present invention, that is, the impurities after the reaction are liquid at room temperature and have a high boiling point, so that they can be easily separated from the target compound. .. Generally, if the impurities are liquid at room temperature, the extraction operation after the reaction is easy. Further, generally, if the impurities have a high boiling point, separation and purification by a distillation operation is easy.

Further, the fluoroalkylation reaction of the present invention can be applied to a wider range of conditions than the method described in Patent Document 3 by using a fluoroalkylating agent having favorable physical properties for industrial production. That is, the versatility was improved.

1. 1. The symbols and terms described herein will be described.

The term "fluoroalkylation reaction" means a reaction for introducing a fluoroalkyl group into a starting compound (raw material compound) which is an organic compound. In other words, the term "fluoroalkylation reaction" means a reaction for producing a target compound having a fluoroalkyl group by reacting a starting compound (raw material compound) which is an organic compound with a fluoroalkylating agent.

The term "fluoroalkylating agent" means one used as a source of fluoroalkyl groups in the fluoroalkylation reactions defined above.

The "fluoroalkylation reaction" includes a "perfluoroalkylation reaction".

"Fluoroalkylating agent" includes "perfluoroalkylating agent".

The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Element symbols such as C _{1 to} C ₃ and subscripted numbers indicate that the number of elements in the group that follows is in the range indicated by the subscripted numbers. For _example, the notation C 1 -C ₃ shows that it is 1 to 3 carbon _atoms, in the notation of C 1 -C _6, shows that a carbon number of 1 to _{6, C} 1 ~ the notation C _12, indicates that the carbon number of 1-12.

The C _{1 to} C ₃ alkyl groups indicate linear or branched alkyl groups having 1 to 3 carbon atoms. Examples of the C _{1 to} C ₃ alkyl group include a methyl group, an ethyl group, an n-propyl group and an isopropyl group.
Preferred C _{1 to} C ₃ alkyl groups include, for example, a methyl group, an ethyl group, an n-propyl group and the like.

The C _{4 to} C ₁₀ alkyl groups indicate linear or branched alkyl groups having 4 to 10 carbon atoms. Examples of the C _{4 to} C ₁₀ alkyl groups include n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, 1-. Ethylpropyl group, 1,1-dimethylpropyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, isohexyl group, 1 -Ethylbutyl group, 2-ethylbutyl group, 3,3-dimethylbutyl group, 1,3-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1 -Methylpropyl group, 1-ethyl-2-methylpropyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, isoheptyl group, 1- Ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1,1-dimethylpentyl group, 1,4-dimethylpentyl group, 1-propylbutyl group, 1,1,3-trimethylbutyl group, 1, 3,3-trimethylbutyl group, 2,2,3-trimethylbutyl group, 2,3,3-trimethylbutyl group, 1,1,2,2-tetramethylpropyl group, n-octyl group, 1-methylheptyl Group, 2-methylheptyl group, 3-methylheptyl group, isooctyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 1,1-dimethylhexyl group, 5,5-dimethylhexyl group, 1, 5-Dimethylhexyl group, n-nonyl group, 1-methyloctyl group, 2-methyloctyl group, 3-methyloctyl group, isononyl group, 1-ethylheptyl group, 2-ethylheptyl group, 3-ethylheptyl group, 1,1-dimethylheptyl group, 6,6-dimethylheptyl group, 1,6-dimethylheptyl group, n-decyl group, 1-methylnonyl group, 2-methylnonyl group, 3-methylnonyl group, isodecyl group, 1-ethyl Examples thereof include, but are limited to, an octyl group, a 2-ethyloctyl group, a 3-ethyloctyl group, a 3,3-dimethyloctyl group, a 7,7-dimethyloctyl group, and a 3,7-dimethyloctyl group. It's not something.
Preferred C _{4 to} C ₁₀ alkyl groups include, for example, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, 1 -Ethylpropyl group, 1,1-dimethylpropyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, isohexyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3,3-dimethylbutyl group, 1,3-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl- 1-Methylpropyl group, 1-ethyl-2-methylpropyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, isoheptyl group, 1 -Ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1,1-dimethylpentyl group, 1,4-dimethylpentyl group, 1-propylbutyl group, 1,1,3-trimethylbutyl group, 1 , 3,3-trimethylbutyl group, 2,2,3-trimethylbutyl group, 2,3,3-trimethylbutyl group, 1,1,2,2-tetramethylpropyl group and the like, more preferably n -Butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, neopentyl Group, 1,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, isohexyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3,3- Dimethylbutyl group, 1,3-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl Butyl etc. can be mentioned.

The C _{1 to} C ₆ alkyl groups indicate linear or branched alkyl groups having 1 to 6 carbon atoms. Examples of the C _{1 to} C ₆ alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1 -Methylbutyl group, 2-methylbutyl group, isopentyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2- Methylpentyl group, 3-methylpentyl group, isohexyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3,3-dimethylbutyl group, 1,3-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1 , 2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group and the like, but are not limited thereto.
Preferred C _{1 to} C ₆ alkyl groups include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group and the like.

The C _{1 to} C ₁₀ alkyl groups indicate linear or branched alkyl groups having 1 to 10 carbon atoms. As _{examples of C 1 to} C ₁₀ alkyl groups, the above-mentioned examples of C _{1 to} C ₃ alkyl groups, C _{4 to} C ₁₀ alkyl groups and C _{1 to} C ₆ alkyl groups can be referred to.
The preferred C _{1 to} C ₁₀ alkyl groups can be appropriately selected from the preferred examples of the above C _{1 to} C ₃ alkyl groups, C _{4 to} C ₁₀ alkyl groups and C _{1 to} C _{6 alkyl groups.}

The C ₂ -C ₁₀ alkenyl group, a straight-chain or branched alkenyl group having a carbon number of 2-10. The C ₂ -C ₁₀ alkenyl group include a vinyl group, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl group , 1-Methyl-1-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1,3-pentadienyl group, 2,4-pentadienyl group, 1-methyl-1- Butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1,3-hexadienyl group, 2,4-hexadienyl group, 3,5-hexadienyl group, 1 , 3,5-Hexatrienyl group, 1-methyl-1-pentenyl group, 1-heptenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 5-heptenyl group, 6-heptenyl group, 1 , 3-Heptadienyl group, 2,4-Heptadienyl group, 3,5-Heptadienyl group, 1,3,5-Heptatrienyl group, 2,4,6-Heptatrienyl group, 1-octenyl group, 2-octenyl group, 3- Octenyl group, 4-octenyl group, 5-octenyl group, 6-octenyl group, 7-octenyl group, 1,3-octadienyl group, 2,4-octadienyl group, 3,5-octadienyl group, 1,3,5- Octatrienyl group, 2,4,6-octatrienyl group, 1,3,5,7-octatetraenyl group, 1-nonenyl group, 2-nonenyl group, 3-nonenyl group, 4-nonenyl group, 5 -Nonenyl group, 6-nonenyl group, 7-nonenyl group, 8-nonenyl group, 1,3-nonazienyl group, 2,4-nonazienyl group, 3,5-nonazienyl group, 1,3,5-nonatienyl group, 2 , 4,6-Nonatrienyl group, 1,3,5,7-Nonatetraenyl group, 2,4,6,8-Nonatetraenyl group, 1-decenyl group, 2-decenyl group, 3-decenyl group, 4-decenyl group, 5-decenyl group, 6-decenyl group, 7-decenyl group, 8-decenyl group, 9-decenyl group, 1,3-decadienyl group, 2,4-decazienyl group, 3,5-decadienyl group, 1,3 5-decatrienyl group, 2,4,6-decatrienyl group, 1,3,5,7-decatetetraenyl group, 2,4,6,8-decatetetraenyl group, 1,3,5,7-9- Examples thereof include a decapentaenyl group, but the present invention is not limited thereto.
Preferred _C 2 _{-C 10} alkenyl group include a vinyl group, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl Group, 1-methyl-1-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1,3-pentadienyl group, 2,4-pentadienyl group, 1-methyl-1 -Butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1,3-hexadienyl group, 2,4-hexadienyl group, 3,5-hexadienyl group, 1,3,5-hexatrienyl group, 1-methyl-1-pentenyl group, 1-heptenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 5-heptenyl group, 6-heptenyl group, Examples thereof include 1,3-heptadienyl group, 2,4-heptadienyl group, 3,5-heptadienyl group, 1,3,5-heptatrienyl group, 2,4,6-heptatrienyl group, and more preferably vinyl group, 1 -Propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, 1-methyl-1-propenyl group, 1-pentenyl group, 2 -Pentenyl group, 3-pentenyl group, 4-pentenyl group, 1,3-pentadienyl group, 2,4-pentadienyl group, 1-methyl-1-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl Group, 4-hexenyl group, 5-hexenyl group, 1,3-hexadienyl group, 2,4-hexadienyl group, 3,5-hexadienyl group, 1,3,5-hexatrienyl group, 1-methyl-1- Examples include a pentanyl group.

The C _{4 to} C ₁₀ alkenyl groups are linear or branched alkenyl groups having 4 to 10 carbon atoms. As _{an example of the C 4 to} C ₁₀ alkenyl group, the above example of the C _{2 to} C ₁₀ alkenyl group can be referred to.
Preferred C _{4 to} C ₁₀ alkenyl groups can be appropriately selected from the preferred examples _{of C 2 to} C _{10 alkenyl groups described above.}

The C ₂ -C ₁₀ alkynyl group, a straight or branched chain alkynyl group having a carbon number of 2-10. The C ₂ -C ₁₀ alkynyl group include an ethynyl group, 1-propynyl, 2-propynyl, 1-butynyl group, 2-butynyl, 3-butynyl, 1,3-butadiynyl group, 1-methyl -2-Propinyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1,3-pentadiynyl group, 3-methyl-1-butynyl group, 1-methyl-2-butynyl group , 1-Methyl-3-butynyl group, 2-methyl-3-butynyl group, 1-ethyl-2-propynyl group, 1,1-dimethyl-2-propynyl group, 1-hexynyl group, 2-hexynyl group, 3 -Hexinyl group, 4-hexynyl group, 5-hexynyl group, 1,3-hexadiynyl group, 2,4-hexadiynyl group, 3,5-hexadiynyl group, 1,3,5-hexatriinyl group, 1-heptynyl group , 2-Heptynyl group, 3-Heptynyl group, 4-Heptynyl group, 5-Heptynyl group, 6-Heptynyl group, 1,3-Heptadynyl group, 1,3,5-Heptatryinyl group, 2,4,6-Heptatryinyl group , 1-octynyl group, 2-octynyl group, 3-octynyl group, 4-octynyl group, 5-octynyl group, 6-octynyl group, 7-octynyl group, 1,3-octadynyl group, 1,3,5-octa Triinyl group, 1,3,5,7-octatetrinyl group, 1-noninyl group, 2-noninyl group, 3-noninyl group, 4-noninyl group, 5-noninyl group, 6-noninyl group, 7- Noninyl group, 8-noninyl group, 2,4-nonadynyl group, 1-decynyl group, 2-decynyl group, 3-decynyl group, 4-decynyl group, 5-decynyl group, 6-decynyl group, 7-decynyl group, Examples thereof include, but are not limited to, 8-decynyl group, 9-decynyl group, 1,3-decadynyl group and the like.
Preferred C _{2 to} C ₁₀ alkynyl groups include, for example, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1,3-butadiyl group, 1-. Methyl-2-propynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1,3-pentadiynyl group, 3-methyl-1-butynyl group, 1-methyl-2-butynyl group Group, 1-methyl-3-butynyl group, 2-methyl-3-butynyl group, 1-ethyl-2-propynyl group, 1,1-dimethyl-2-propynyl group, 1-hexynyl group, 2-hexynyl group, 3-Hexinyl group, 4-Hexinyl group, 5-Hexinyl group, 1,3-Hexadiynyl group, 2,4-Hexadiynyl group, 3,5-Hexadiynyl group, 1,3,5-Hexatriinyl group, 1-heptynyl Group, 2-heptinyl group, 3-heptinyl group, 4-heptinyl group, 5-heptinyl group, 6-heptinyl group, 1,3-heptadiynyl group, 1,3,5-heptatriinyl group, 2,4,6-heptatriinyl Groups and the like, more preferably ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1,3-butadiynyl group, 1-methyl-2- Propinyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1,3-pentadiynyl group, 3-methyl-1-butynyl group, 1-methyl-2-butynyl group, 1- Methyl-3-butynyl group, 2-methyl-3-butynyl group, 1-ethyl-2-propynyl group, 1,1-dimethyl-2-propynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group , 4-Hexinyl group, 5-Hexinyl group, 1,3-Hexadynyl group, 2,4-Hexadynyl group, 3,5-Hexadynyl group, 1,3,5-Hexatriinyl group and the like.

The C _{4 to} C ₁₀ alkynyl groups are linear or branched alkynyl groups having 4 to 10 carbon atoms. As _{an example of the C 4 to} C ₁₀ alkynyl group, the above example of the C _{2 to} C ₁₀ alkynyl group can be referred to.
The preferred C _{4 to} C ₁₀ alkynyl group can be appropriately selected from the above-mentioned _{preferred examples of the C 2 to} C _{10 alkynyl group.}

The C _{3 to} C ₈ cycloalkyl group refers to a cyclic alkyl group having 3 to 8 carbon atoms. Examples of the C _{3 to} C ₈ cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like.
Preferred C _{3 to} C ₈ cycloalkyl groups include, for example, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like, and more preferably cyclopentyl group, cyclohexyl group and the like.

The C _{1 to} C ₆ alkoxy groups are linear or branched alkoxy groups having 1 to 6 carbon atoms. Examples of the C _{1 to} C ₆ alkoxy groups include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a t-butoxy group and an n-pentyloxy group. , Isopentyloxy group, neopentyloxy group, n-hexyloxy group, isohexyloxy group and the like, but are not limited thereto.
Preferred C _{1 to} C ₆ alkoxy groups include, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a t-butoxy group and an n-pentyloxy group. Examples thereof include a group, an n-hexyloxy group, and more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group and the like. More preferably, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group and the like can be mentioned.

The C _{1 to} C ₆ alkoxycarbonyl groups indicate (alkoxy) -C (= O) -groups having 1 to 6 carbon atoms in which the alkoxy moiety has the above meaning. Examples of the C _{1 to} C ₆ alkoxycarbonyl groups include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, a sec-butoxycarbonyl group, an isobutoxycarbonyl group, and t. -Butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group and the like can be mentioned, but the present invention is not limited thereto.
Preferred C _{1 to} C ₆ alkoxycarbonyl groups include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, a t-butoxycarbonyl group and the like.

The C _{1 to} C ₆ alkylcarbonyloxy group refers to a (alkyl) -C (= O) -O- group having 1 to 6 carbon atoms in which the alkyl moiety has the above meaning. Examples of the C _{1 to} C ₆ alkylcarbonyloxy groups include a methylcarbonyloxy group (acetoxy group), an ethylcarbonyloxy group (propionyloxy group), an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, and an n-butylcarbonyloxy group. Groups, sec-butylcarbonyloxy group, isobutylcarbonyloxy group, t-butylcarbonyloxy group (pivaloyloxy group), n-pentylcarbonyloxy group, n-hexylcarbonyloxy group and the like can be mentioned, but are limited thereto. It's not something.
Preferred C _{1 to} C ₆ alkylcarbonyloxy groups include, for example, methylcarbonyloxy group (acetoxy group), ethylcarbonyloxy group (propionyloxy group), n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyl. Examples thereof include an oxy group and a t-butylcarbonyloxy group (pivaloyloxy group).

Examples of the C _{6 to} C ₁₀ aryl group include, but are not limited to, a phenyl group, a 1- or 2-naphthyl group, and the like.

The C _{6 to} C ₁₀ aryloxy group refers to an aryl-O-group having 6 to 10 carbon atoms in which the aryl moiety has the above meaning. Examples of the C _{6 to} C ₁₀ aryloxy groups include, but are not limited to, a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group and the like.

C _{6 to} C ₁₀ aryl (C _{1 to} C ₄ ) alkoxy groups have 1 to 4 carbon atoms substituted with aryl groups having 6 to 10 carbon atoms, wherein the aryl moiety and the alkoxy moiety have the above meanings. Indicates an alkoxy group. Examples of the C _{6 to} C ₁₀ aryl (C _{1 to} C ₄ ) alkoxy group include a benzyloxy group, a 1-phenylethoxy group, a 2-phenylethoxy group, a 3-phenylpropoxy group, a 4-phenylbutoxy group and the like. It can, but is not limited to these.
Preferred C _{6 to} C ₁₀ aryl (C _{1 to} C ₄ ) alkoxy groups include, for example, a benzyloxy group, a 2-phenylethoxy group and the like.

The C _{1 to} C ₆ haloalkyl groups are linear or branched alkyl groups having 1 to 6 carbon atoms substituted with the same or different 1 to 13 halogen atoms. Examples of the C _{1 to} C ₄ haloalkyl groups include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a difluoromethyl group, a dichloromethyl group, a trifluoromethyl group, a trichloromethyl group, a chlorodifluoromethyl group, and a bromodifluoromethyl group. 2-Fluoroethyl group, 1-chloroethyl group, 2-chloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group, 2-chloro-1- Methyl ethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, heptafluoropropyl group, 1,2,2,2-tetra Fluoro-1-trifluoromethylethyl group, 4-fluorobutyl group, 4-chlorobutyl group, 2,2,3,3,4,5,4-heptafluorobutyl group, nonafluorobutyl group, 1,1, 2,3,3,3-hexafluoro-2-trifluoromethylpropyl group, 2,2,2-trifluoro-1,1-di (trifluoromethyl) ethyl group, undecafluoropentyl group, tridecafluoro Hexyl groups and the like can be mentioned, but are not limited thereto.
Preferred C _{1 to} C ₆ haloalkyl groups include, for example, fluoromethyl group, difluoromethyl group, trifluoromethyl group, trichloromethyl group, chlorodifluoromethyl group, bromodifluoromethyl group, 2-fluoroethyl group, 2,2. 2-Trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, Propylfluoropropyl group, 1,2,2,2-tetrafluoro-1-trifluoromethylethyl group, 4-fluorobutyl group, 2,2,3,3,4,5,4-heptafluorobutyl group, Nonafluorobutyl group, 1,1,2,3,3,3-hexafluoro-2-trifluoromethylpropyl group, 2,2,2-trifluoro-1,1-di (trifluoromethyl) ethyl group, etc. More preferably, fluoromethyl group, difluoromethyl group, trifluoromethyl group, trichloromethyl group, chlorodifluoromethyl group, bromodifluoromethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group. , Pentafluoroethyl group, 3-fluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, heptafluoropropyl group, 1 , 2,2,2-Tetrafluoro-1-trifluoromethylethyl group and the like.

The C _{1 to} C ₈ fluoroalkyl groups refer to linear or branched alkyl groups having 1 to 8 carbon atoms substituted with 1 to 17 fluorine atoms. Examples of the C _{1 to} C ₈ fluoroalkyl groups include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group, a 1-fluoroethyl group, a 2,2,2-trifluoroethyl group and a penta. Fluoroethyl group, 3-fluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, heptafluoropropyl group, 1,2 , 2,2-Tetrafluoro-1-trifluoromethylethyl group, 2,2,3,3,4,5,4-heptafluorobutyl group, nonafluorobutyl group, 1,2,2,3,3 , 3-Hexafluoro-1-trifluoromethylpropyl group, 1,1,2,3,3,3-hexafluoro-2-trifluoromethylpropyl group, 2,2,2-trifluoro-1,1- Di (trifluoromethyl) ethyl group, undecafluoropentyl group and its isomer, tridecafluorohexyl group and its isomer, pentadecafluoropentyl group and its isomer, heptadecafluorohexyl group and its isomer, etc. It can be mentioned, but it is not limited to these.
Preferred C _{1 to} C ₈ fluoroalkyl groups include, for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group, a 1-fluoroethyl group, a 2,2,2-trifluoroethyl group, and the like. Pentafluoroethyl group, 3-fluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, heptafluoropropyl group, 1, 2,2,2-Tetrafluoro-1-trifluoromethylethyl group, 2,2,3,3,4,5,4-heptafluorobutyl group, nonafluorobutyl group, 1,2,2,3 3,3-Hexafluoro-1-trifluoromethylpropyl group, 1,1,2,3,3,3-hexafluoro-2-trifluoromethylpropyl group, 2,2,2-trifluoro-1,1 -Di (trifluoromethyl) ethyl group and the like are mentioned, and more preferably, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group, a 1-fluoroethyl group and a 2,2,2-trifluoro group. Ethyl group, pentafluoroethyl group, 3-fluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, heptafluoropropyl group , 1,2,2,2-tetrafluoro-1-trifluoromethylethyl group and the like.

The C _{1 to} C ₄ fluoroalkyl groups refer to linear or branched alkyl groups having 1 to 4 carbon atoms substituted with 1 to 9 fluorine atoms. As _{an example of the C 1 to} C ₄ fluoroalkyl group, the above example of the C _{1 to} C ₈ fluoroalkyl group can be referred to.
Preferred C _{1 to} C ₄ fluoroalkyl groups can be appropriately selected from the preferred examples _{of C 1 to} C _{8 fluoroalkyl groups described above.}

The C _{1 to} C ₄ perfluoroalkyl groups are linear or branched alkyl groups having 1 to 4 carbon atoms in which all hydrogen atoms are substituted with fluorine atoms. Examples of the C _{1 to} C ₄ perfluoroalkyl groups include trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, 1,2,2,2-tetrafluoro-1-trifluoromethylethyl group and nonafluoro. Butyl group, 1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl group, 1,1,2,3,3,3-hexafluoro-2-trifluoromethylpropyl group, 2 , 2,2-Trifluoro-1,1-di (trifluoromethyl) ethyl group and the like, but are not limited thereto.
Preferred C _{1 to} C ₄ perfluoroalkyl groups include, for example, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a 1,2,2,2-tetrafluoro-1-trifluoromethylethyl group and the like. These include, more preferably, a trifluoromethyl group.

The C _{1 to} C ₆ alkylthio groups refer to linear or branched (alkyl) -S- groups having 1 to 6 carbon atoms in which the alkyl moiety has the above meaning. Examples of the C _{1 to} C ₆ alkylthio groups include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, n-pentylthio group, n-hexylthio group and the like. It is not limited to.
Preferred C _{1 to} C ₆ alkylthio groups include, for example, methylthio group, ethylthio group, n-propylthio group, isopropylthio group and the like, and more preferably methylthio group.

The C _{1 to} C ₆ alkylsulfinyl group refers to a linear or branched (alkyl) -SO- group having 1 to 6 carbon atoms in which the alkyl moiety has the above meaning. Examples of the C _{1 to} C ₆ alkylsulfinyl groups include methylsulfinyl group, ethylsulfinyl group, n-propylsulfinyl group, isopropylsulfinyl group, n-butylsulfinyl group, n-pentylsulfinyl group, n-hexylsulfinyl group and the like. It can be mentioned, but it is not limited to these.
Preferred C _{1 to} C ₆ alkylsulfinyl groups include, for example, methylsulfinyl group, ethylsulfinyl group, n-propylsulfinyl group, isopropylsulfinyl group and the like, and more preferably methylsulfinyl group.

The C _{1 to} C ₆ alkyl sulfonyl group refers to a linear or branched (alkyl) -SO2- group having 1 to 6 carbon atoms in which the alkyl moiety has the above meaning. Examples of the C _{1 to} C ₆ alkyl sulfonyl groups include methyl sulfonyl groups, ethyl sulfonyl groups, n-propyl sulfonyl groups, isopropyl sulfonyl groups, n-butyl sulfonyl groups, n-pentyl sulfonyl groups, n-hexyl sulfonyl groups and the like. It can be mentioned, but it is not limited to these.
Preferred C _{1 to} C ₆ alkyl sulfonyl groups include, for example, a methyl sulfonyl group, an ethyl sulfonyl group, an n-propyl sulfonyl group, an isopropyl sulfonyl group and the like, and more preferably a methyl sulfonyl group.

C _{1 to} C ₆ haloalkylthio groups are linear or branched chain (haloalkyl) having 1 to 6 carbon atoms in which the haloalkyl moiety has the above meaning and is substituted with the same or different 1 to 9 halogen atoms. ) -S- group is shown. Examples of the C _{1 to} C ₆ haloalkylthio groups include a fluoromethylthio group, a difluoromethylthio group, a trifluoromethylthio group, a 2-fluoroethylthio group, a 2,2-difluoroethylthio group and a 2,2,2-trifluoro group. Ethylthio group, 3-fluoropropylthio group, 3,3-difluoropropylthio group, 3,3,3-trifluoropropylthio group, 4-fluorobutylthio group, 4,4-difluorobutylthio group, 4, Examples thereof include, but are not limited to, 4,4-trifluorobutylthio group, 5,5,5-trifluoropentylthio group, 6,6,6-trifluorohexylthio group and the like.
Preferred C _{1 to} C ₆ haloalkylthio groups include, for example, fluoromethylthio group, difluoromethylthio group, trifluoromethylthio group, 2-fluoroethylthio group, 2,2-difluoroethylthio group, 2,2,2-tri. Fluoroethylthio group, 3-fluoropropylthio group, 3,3-difluoropropylthio group, 3,3,3-trifluoropropylthio group, 4-fluorobutylthio group, 4,4-difluorobutylthio group, etc. More preferably, a trifluoromethylthio group, a 2,2,2-trifluoroethylthio group, a 3,3,3-trifluoropropylthio group and the like can be mentioned.

A C _{1 to} C ₆ haloalkylsulfinyl group is a linear or branched chain (haloalkyl) having 1 to 6 carbon atoms in which the haloalkyl moiety has the above meaning and is substituted with the same or different 1 to 9 halogen atoms. ) -SO- group is shown. Examples of the C _{1 to} C ₆ haloalkylsulfinyl groups include fluoromethylsulfinyl group, difluoromethylsulfinyl group, trifluoromethylsulfinyl group, 2-fluoroethylsulfinyl group, 2,2-difluoroethylsulfinyl group, 2,2,2. -Trifluoroethylsulfinyl group, 3-fluoropropylsulfinyl group, 3,3-difluoropropylsulfinyl group, 3,3,3-trifluoropropylsulfinyl group, 4-fluorobutylsulfinyl group, 4,4-difluorobutylsulfinyl group , 4,4,4-trifluorobutylsulfinyl group, 5,5,5-trifluoropentylsulfinyl group, 6,6,6-trifluorohexylsulfinyl group and the like, but are limited thereto. is not it.
Preferred C _{1 to} C ₆ haloalkylsulfinyl groups include, for example, fluoromethylsulfinyl group, difluoromethylsulfinyl group, trifluoromethylsulfinyl group, 2-fluoroethylsulfinyl group, 2,2-difluoroethylsulfinyl group, 2,2. 2-Trifluoroethylsulfinyl group, 3-fluoropropylsulfinyl group, 3,3-difluoropropylsulfinyl group, 3,3,3-trifluoropropylsulfinyl group, 4-fluorobutylsulfinyl group, 4,4-difluorobutylsulfinyl group Examples thereof include a trifluoromethylsulfinyl group, a 2,2,2-trifluoroethylsulfinyl group, a 3,3,3-trifluoropropylsulfinyl group and the like.

The C _{1 to} C ₆ haloalkyl sulfonyl groups are linear or branched chain (haloalkyl) having 1 to 6 carbon atoms in which the haloalkyl moiety has the above meaning and is substituted with the same or different 1 to 9 halogen atoms. ) -SO2- shows a group. Examples of the C _{1 to} C ₆ haloalkyl sulfonyl groups include a fluoromethyl sulfonyl group, a difluoromethyl sulfonyl group, a trifluoromethyl sulfonyl group, a 2-fluoroethyl sulfonyl group, a 2,2-difluoroethyl sulfonyl group, and 2,2,2. -Trifluoroethyl sulfonyl group, 3-fluoropropyl sulfonyl group, 3,3-difluoropropyl sulfonyl group, 3,3,3-trifluoropropyl sulfonyl group, 4-fluorobutyl sulfonyl group, 4,4-difluorobutyl sulfonyl group , 4,4,4-trifluorobutylsulfonyl group, 5,5,5-trifluoropentylsulfonyl group, 6,6,6-trifluorohexylsulfonyl group and the like, but are limited thereto. is not it.
Preferred C _{1 to} C ₆ haloalkyl sulfonyl groups include, for example, a fluoromethyl sulfonyl group, a difluoromethyl sulfonyl group, a trifluoromethyl sulfonyl group, a 2-fluoroethyl sulfonyl group, a 2,2-difluoroethyl sulfonyl group, 2,2. 2-Trifluoroethyl sulfonyl group, 3-fluoropropyl sulfonyl group, 3,3-difluoropropyl sulfonyl group, 3,3,3-trifluoropropyl sulfonyl group, 4-fluorobutyl sulfonyl group, 4,4-difluorobutyl sulfonyl group Examples thereof include a trifluoromethylsulfonyl group, a 2,2,2-trifluoroethylsulfonyl group, a 3,3,3-trifluoropropylsulfonyl group and the like.

The mono (C _{1 to} C ₆ alkyl) amino group refers to a (C _{1 to} C ₆ alkyl) NH- group whose alkyl moiety has the above meaning. Examples of the mono (C _{1 to} C ₆ alkyl) amino group include methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, pentylamino group, hexylamino group and the like. , Not limited to these.
Preferred mono (C _{1 to} C ₆ alkyl) amino groups include, for example, methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group and the like, and more preferably methylamino group and ethylamino group. Groups, propylamino groups, isopropylamino groups and the like can be mentioned.

The di (C _{1 to} C ₆ alkyl) amino group refers to a (C _{1 to} C ₆ alkyl) ₂ N- group in which the alkyl moiety has the above meaning. Examples of the di (C _{1 to} C ₆ alkyl) amino group include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a dipentylamino group, a dihexylamino group, a methylethylamino group, a methylhexylamino group and the like. However, the present invention is not limited to these.
Preferred di (C _{1 to} C ₆ alkyl) amino groups include, for example, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group and the like, and more preferably dimethylamino group, diethylamino group and dipropylamino. The group etc. can be mentioned.

The C _{1 to} C ₆ acyl amino group means an amino group substituted with a C _{1 to} C _{6 acyl group.} The C _{1 to} C ₆ acyl groups represent a (alkyl) -C (= O) -group having 0 to 5 carbon atoms, and a formyl group having 0 carbon atoms. Examples of the C _{1 to} C ₆ acylamino groups include formylamino groups, acetylamino groups, propionylamino groups, isopropionylamino groups, butyrylamino groups, isobutyrylamino groups, valerylamino groups, isovalerylamino groups, and pivaloylamino groups. Hexanoylamino group, acryloylamino group, crotonoylamino group, methacryloylamino group and the like can be mentioned, but the present invention is not limited thereto.
Preferred C _{1 to} C ₆ acylamino groups include, for example, formylamino groups, acetylamino groups, propionylamino groups and the like.

2. The fluoroalkylating agent of the present invention will be described.

（式中、Ｒ^１はＣ_１〜Ｃ_８フルオロアルキル基を示し、
Ｒ^２は１又は２個以上の同一又は異なる置換基Ａにより置換されていてもよいＣ_４〜Ｃ_１０アルキル基、１又は２個以上の同一又は異なる置換基Ａにより置換されていてもよいＣ_４〜Ｃ_１０アルケニル基、１又は２個以上の同一又は異なる置換基Ａにより置換されていてもよいＣ_４〜Ｃ_１０アルキニル基又は、１又は２個以上の同一又は異なる置換基Ａにより置換されていてもよいＣ_３〜Ｃ_８シクロアルキル基を示し、
Ｒ^３はＣ_１〜Ｃ_３アルキル基を示し、
Ｙ^１、Ｙ^２、Ｙ^３及びＹ^４は、それぞれ独立して、
水素原子、ハロゲン原子、Ｃ_１〜Ｃ_６アルキル基、Ｃ_３〜Ｃ_８シクロアルキル基、ヒドロキシ基、Ｃ_１〜Ｃ_６アルコキシ基、Ｃ_１〜Ｃ_６アルキルチオ基、Ｃ_１〜Ｃ_６アルキルスルフィニル基、Ｃ_１〜Ｃ_６アルキルスルホニル基、アミノ基、モノ（Ｃ_１〜Ｃ_６アルキル）アミノ基、ジ（Ｃ_１〜Ｃ_６アルキル）アミノ基、Ｃ_１〜Ｃ_６アシルアミノ基、ホルミル基、カルボキシ基、Ｃ_１〜Ｃ_６アルコキシカルボニル基、Ｃ_１〜Ｃ_６アルキルカルボニルオキシ基、ニトロ基、シアノ基又は、１又は２個以上の同一又は異なる置換基Ｂにより置換されていてもよいＣ_６〜Ｃ_１０アリール基を示し、
又は、Ｙ^１とＹ^２、Ｙ^２とＹ^３、Ｙ^３とＹ^４の２つの隣接する置換基は、それらが結合している炭素原子と一緒になって、４〜８員の炭素環を形成してもよく、
Ｘ⁻はハロゲンイオン、テトラフルオロホウ酸イオン、メタンスルホナートイオン、トリフルオロメタンスルホナートイオン、ｐ−トルエンスルホナートイオン、過塩素酸イオン、リン酸二水素イオン、硫酸水素イオン又は硫酸アルキルイオンを示し、
置換基ＡはＣ_１〜Ｃ_６アルコキシ基、Ｃ_１〜Ｃ_６アルコキシカルボニル基又はＣ_１〜Ｃ_６アルキルカルボニルオキシ基を示し、
置換基Ｂはハロゲン原子、Ｃ_１〜Ｃ_６アルキル基、Ｃ_３〜Ｃ_８シクロアルキル基、ヒドロキシ基、Ｃ_１〜Ｃ_６アルコキシ基、Ｃ_１〜Ｃ_６アルキルチオ基、Ｃ_１〜Ｃ_６アルキルスルフィニル基、Ｃ_１〜Ｃ_６アルキルスルホニル基、Ｃ_１〜Ｃ_６ハロアルキルチオ基、Ｃ_１〜Ｃ_６ハロアルキルスルフィニル基、Ｃ_１〜Ｃ_６ハロアルキルスルホニル基、アミノ基、モノ（Ｃ_１〜Ｃ_６アルキル）アミノ基、ジ（Ｃ_１〜Ｃ_６アルキル）アミノ基、Ｃ_１〜Ｃ_６アシルアミノ基、ホルミル基、カルボキシ基、Ｃ_１〜Ｃ_６アルコキシカルボニル基、Ｃ_１〜Ｃ_６アルキルカルボニルオキシ基、ニトロ基又はシアノ基を示す。）
で表される化合物である。 The fluoroalkylating agent of the present invention has the formula (1):

(In the formula, R ¹ represents a C _{1 to} C ₈ fluoroalkyl group,
R ² may be substituted with one or more identical or different substituents A C _{4 to} C ₁₀ alkyl groups may be substituted with one or more identical or different substituents A C _{4 to} C ₁₀ Alkyne groups may be substituted with 1 or more identical or different substituents A C _{4 to} C ₁₀ Alkynyl groups or 1 or more identical or different substituents A Shows _{C 3 to C 8} cycloalkyl groups that may be present.
R ³ represents a C _{1 to} C ₃ alkyl group,
Y ¹ , Y ² , Y ³ and Y ⁴ are independent of each other.
Hydrogen atom, halogen atom, C _{1 to} C ₆ alkyl group, C _{3 to} C ₈ cycloalkyl group, hydroxy group, C _{1 to} C ₆ alkoxy group, C _{1 to} C ₆ alkylthio group, C _{1 to} C ₆ alkyl sulfinyl group , C _{1 to} C ₆ alkylsulfonyl groups, amino groups, mono (C _{1 to} C ₆ alkyl) amino groups, di (C _{1 to} C ₆ alkyl) amino groups, C _{1 to} C ₆ acylamino groups, formyl groups, carboxy groups , C _{1 to} C ₆ alkoxycarbonyl groups, C _{1 to} C _{6 alkylcarbonyloxy groups, nitro groups, cyano groups or C 6 to} C which may be substituted with one or more identical or different substituents B. _{Shows a 10} aryl group,
Alternatively, ^{two adjacent substituents, Y 1} and Y ² , Y ² and Y ³ , Y ³ and Y ⁴ , together with the carbon atom to which they are attached form a 4- to 8-membered carbon ring. May be formed,
X ^- indicates halogen ion, tetrafluoroborate ion, methanesulfonate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, perchlorate ion, dihydrogen phosphate ion, hydrogen sulfate ion or alkyl sulfate ion. ,
Substituent A represents a C _{1 to} C ₆ alkoxy group, a C _{1 to} C ₆ alkoxycarbonyl group or a C _{1 to} C ₆ alkylcarbonyloxy group.
Substituent B is a halogen atom, C _{1 to} C ₆ alkyl group, C _{3 to} C ₈ cycloalkyl group, hydroxy group, C _{1 to} C ₆ alkoxy group, C _{1 to} C ₆ alkyl thio group, C _{1 to} C ₆ alkyl sulfinyl. _group, C 1 -C ₆ alkylsulfonyl _group, C 1 -C ₆ haloalkylthio _group, C 1 -C ₆ haloalkylsulfinyl _group, C 1 -C ₆ haloalkylsulfonyl group, an amino group, a mono _(C 1 -C ₆ alkyl) Amino group, di (C _{1 to} C ₆ alkyl) amino group, C _{1 to} C ₆ acylamino group, formyl group, carboxy group, C _{1 to} C ₆ alkoxycarbonyl group, C _{1 to} C ₆ alkylcarbonyloxy group, nitro group Alternatively, it indicates a cyano group. )
It is a compound represented by.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｙ^１、Ｙ^２、Ｙ^３、Ｙ^４、及びＸ⁻は上記の通りである。） The compound represented by the formula (1) can have the tautomers shown below. Both of these and mixtures thereof are included within the scope of the invention. That is, the compound represented by the following formula (1) and the compound represented by the following formula (1') are equivalent.

(In the equation, R ¹ , R ² , R ³ , Y ¹ , Y ² , Y ³ , Y ⁴ , and X ⁻ are as described above.)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｙ^１、Ｙ^２、Ｙ^３、Ｙ^４、及びＸ⁻は上記の通りである。） In the present specification, the numbers indicating the positions of the substituents are as follows.

(In the equation, R ¹ , R ² , R ³ , Y ¹ , Y ² , Y ³ , Y ⁴ , and X ⁻ are as described above.)

Specific examples of the fluoroalkylating agent of the formula (1) are preferably 1-butyl-3-methyl-2-trifluoromethylbenzoimidazolium fluoride, 1-butyl-3-methyl-2-trifluoromethylbenzo. Imidazolium chloride, 1-butyl-3-methyl-2-trifluoromethylbenzoimidazolium bromide, 1-butyl-3-methyl-2-trifluoromethylbenzoimidazolium iodide, 1-butyl-3-methyl-2 -Trifluoromethylbenzoimidazolium tetrafluoroborate, 1-butyl-3-methyl-2-trifluoromethylbenzoimidazolium hexafluorophosphate, 1-butyl-3-methyl-2-trifluoromethylbenzoimidazolium methanesulfonate, 1-Butyl-3-methyl-2-trifluoromethylbenzoimidazolium trifurate, 1-butyl-3-methyl-2-trifluoromethylbenzoimidazolium methyl sulfate, 1-butyl-3-ethyl-2-trifluoro Methylbenzoimidazolium fluoride, 1-butyl-3-ethyl-2-trifluoromethylbenzoimidazolium chloride, 1-butyl-3-ethyl-2-trifluoromethylbenzoimidazolium bromide, 1-butyl-3-ethyl -2-Trifluoromethylbenzoimidazolium iodide, 1-butyl-3-ethyl-2-trifluoromethylbenzoimidazolium tetrafluoroborate, 1-butyl-3-ethyl-2-trifluoromethylbenzoimidazolium hexafluoro Phosphate, 1-butyl-3-ethyl-2-trifluoromethylbenzoimidazolium methanesulfonate, 1-butyl-3-ethyl-2-trifluoromethylbenzoimidazolium trifurate, 1-butyl-3-ethyl-2- Trifluoromethylbenzoimidazolium ethyl sulfate, 3-methyl-1-pentyl-2-trifluoromethylbenzoimidazolium methyl sulfate, 1-hexyl-3-methyl-2-trifluoromethylbenzoimidazolium methyl sulfate, 1-heptyl -3-Methyl-2-trifluoromethylbenzoimidazolium methyl sulfate, 3-methyl-1-octyl-2-trifluoromethylbenzoimidazolium methyl sulfate, 3-methyl-1-nonyl-2-trifluoromethylbenzoimidazole Rium methyl sulfate, 1-decyl-3-methi Lu-2-trifluoromethylbenzoimidazolium methyl sulfate, 1-butyl-5-chloro-3-methyl-2-trifluoromethylbenzoimidazolium methyl sulfate, 1-butyl-5,6-dichloro-3-methyl- 2-Trifluoromethylbenzoimidazolium methyl sulfate, 1-butyl-3-methyl-4,5,6,7-tetrachloro-2-trifluoromethylbenzoimidazolium methyl sulfate, 1-butyl-3,5-dimethyl -2-Trifluoromethylbenzoimidazolium methyl sulfate, 1-butyl-2-trifluoromethyl-3,5,6-trimethylbenzoimidazolium methyl sulfate, 1-butyl-3-methyl-5-nitro-2-tri Fluoromethylbenzoimidazolium methyl sulfate and the like can be mentioned, and more preferably 1-butyl-3-methyl-2-trifluoromethylbenzoimidazolium fluoride and 1-butyl-3-methyl-2-trifluoromethylbenzoimidazolium. Chloride, 1-butyl-3-methyl-2-trifluoromethylbenzoimidazolium bromide, 1-butyl-3-methyl-2-trifluoromethylbenzoimidazolium iodide, 1-butyl-3-methyl-2-tri Fluoromethylbenzoimidazolium tetrafluoroborate, 1-butyl-3-methyl-2-trifluoromethylbenzoimidazolium hexafluorophosphate, 1-butyl-3-methyl-2-trifluoromethylbenzoimidazolium methanesulfonate, 1- Butyl-3-methyl-2-trifluoromethylbenzoimidazolium trifurate, 1-butyl-3-methyl-2-trifluoromethylbenzoimidazolium methyl sulfate, 1-butyl-3-ethyl-2-trifluoromethylbenzo Imidazolium ethyl sulfate, 3-methyl-1-pentyl-2-trifluoromethylbenzoimidazolium methyl sulfate, 1-hexyl-3-methyl-2-trifluoromethylbenzoimidazolium methyl sulfate, 1-heptyl-3-methyl Examples thereof include -2-trifluoromethylbenzoimidazolium methyl sulfate, 3-methyl-1-octyl-2-trifluoromethylbenzoimidazolium methyl sulfate, and more preferably 1-butyl-3-methyl-2-trifluoro. Methylbenzoimidazolium methyl sulfate, 3-methyl -1-Pentyl-2-trifluoromethylbenzoimidazolium methyl sulfate, 1-hexyl-3-methyl-2-trifluoromethylbenzoimidazolium methyl sulfate and the like can be mentioned, and 1-butyl-3-methyl- is particularly preferable. 2-Trifluoromethylbenzoimidazolium methyl sulfate can be mentioned.

(Method for producing a compound represented by the formula (1))
The method for producing the compound represented by the formula (1) will be described below. However, the method for producing the compound represented by the formula (1) is not limited to these methods.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｙ^１、Ｙ^２、Ｙ^３、Ｙ^４、及びＸ⁻は上記の通りであり、
Ｑはヒドロキシ基又はハロゲン原子（好ましくは塩素原子）であり、
Ｗは脱離基である。） The compound represented by the formula (1) of the present invention can be produced, for example, according to the following method.

(In the equation, R ¹ , R ² , R ³ , Y ¹ , Y ² , Y ³ , Y ⁴ , and X ⁻ are as described above.
Q is a hydroxy group or a halogen atom (preferably a chlorine atom).
W is a leaving group. )

(Manufacturing process 1)
The production step 1 is a step of reacting the compound of the formula (4) with the compound of the formula (5) to produce the compound of the formula (6).

The compound of the formula (4) is a known compound, or can be produced from a known compound by a known method. Examples of the compound of the formula (4) include 1,2-phenylenediamine, 4-chloro-1,2-phenylenediamine, 4,5-dichloro-1,2-phenylenediamine, 3,4,5,6-tetra. Examples thereof include chloro-1,2-phenylenediamine, 4-methyl-1,2-phenylenediamine, 4,5-dimethyl-1,2-phenylenediamine, 4-nitro-1,2-phenylenediamine, and the like. It is not limited to.

Q in the formula (5) is a hydroxy group or a halogen atom (preferably a chlorine atom).
The compound of the formula (5) is a known compound, or can be produced from a known compound by a known method. Examples of the compound of the formula (5) include trifluoroacetic acid, trifluoroacetic acid chloride, pentafluoropropionic acid, pentafluoropropionic acid chloride, heptafluorobutanoic acid, heptafluorobutanoic acid chloride, nonafluoropentanoic acid, and nonafluoropentanoic acid. Examples thereof include, but are not limited to, chloride, undecafluorohexanoic acid, undecafluorohexanoic acid chloride, difluoroacetic acid, and difluoroacetic acid chloride.

The amount of the compound represented by the formula (5) may be any amount as long as the reaction proceeds. From the viewpoint of yield, suppression of by-products, economic efficiency, etc., the amount is usually 1.0 mol or more, preferably 1.0 to 10.0 mol, more preferably 1.0 mol, based on 1.0 mol of the compound of the formula (4). The range of 1.0 to 5.0 mol can be exemplified.

In the production step 1, a base may be used as long as the reaction proceeds. For example, when the compound of the formula (5) is an acid chloride, a base may be used. When a base is used in the production step 1, the base may be any base as long as the reaction proceeds. Examples of the base used in the production step 1 include alkali metal hydroxides (eg, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.) and alkaline earth metal hydroxides (eg, magnesium hydroxide, water). Calcium oxide, barium hydroxide, etc.), alkali metal carbonates (eg, lithium carbonate, sodium carbonate, potassium carbonate, etc.), alkaline earth metal carbonates (eg, magnesium carbonate, calcium carbonate, barium carbonate, etc.), alkali metal carbonates Hydrogen salts (eg, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc.), alkaline earth metal bicarbonates (eg, magnesium hydrogen carbonate, calcium hydrogen carbonate, barium hydrogen carbonate, etc.), amines (eg, triethylamine, etc.) Tributylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] -7-undec-7-ene (DBU), 1,4-diazabicyclo [2.2.2] octane (DABCO), N, N -Dimethylaniline, N, N-diethylaniline, pyridine, 4- (dimethylamino) -pyridine, 2,6-rutidine, etc.), etc.), but are not limited thereto.

When a base is used in the production step 1, the amount of the base used may be any amount as long as the reaction proceeds. From the viewpoints of yield, by-product suppression, economic efficiency, etc., it is usually 1.0 to 10.0 equivalents, preferably 1.0 to 5.0 equivalents, and more preferably 1 with respect to the compound of the formula (4). The range of 0 to 2.0 equivalents can be exemplified.

The reaction of production step 1 is carried out in the presence or absence of a solvent. When a solvent is used in the production step 1, the solvent may be any solvent as long as the reaction proceeds. Examples of the solvent used in the production step 1 include nitriles (for example, acetonitrile, propionitrile, etc.), ethers (for example, diethyl ether, diisopropyl ether, cyclopentylmethyl ether (CPME), tetrahydrofuran (THF), 1, 4-Dioxane, monoglime, diglime, etc.), halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, etc.), aromatic hydrocarbons (eg, benzene, chlorobenzene, dichlorobenzene, nitrobenzene, etc.) Toluene, xylene, etc.), amides (eg, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), etc.), imidazolinones (eg, 1,3) -Dimethyl-2-imidazolinone (DMI), etc.), sulfoxides (eg, dimethyl sulfoxide (DMSO), etc.), sulfones (eg, sulfolane, etc.), etc., but are not limited thereto. These solvents can be used alone or as a mixed solvent of any mixing ratio.

When the solvent is used in the production step 1, the amount of the solvent used may be any amount as long as the reaction proceeds. From the viewpoints of yield, suppression of by-products, economic efficiency and the like, the range of usually 0 (zero) to 10 L (liter), preferably 0 to 5 L can be exemplified with respect to the compound of the formula (4).

The reaction temperature in the production step 1 may be any temperature as long as the reaction proceeds. From the viewpoint of yield, suppression of by-products, economic efficiency, etc., the reaction temperature is usually in the range of −20 (minus 20) to 200 ° C., preferably -20 to 150 ° C., and more preferably 0 to 130 ° C. it can.

The reaction time of the manufacturing step 1 is not particularly limited. Those skilled in the art can appropriately adjust the reaction time of the manufacturing process 1. From the viewpoint of yield, suppression of by-products, economic efficiency, etc., the range of usually 0.1 hour to 48 hours, preferably 0.1 hour to 36 hours can be exemplified.

(Manufacturing process 2)
The production step 2 is a step of reacting the compound of the formula (6) with the compound of the formula (7) to produce the compound of the formula (8).

The compound of the formula (6) is a known compound, or can be produced from a known compound by a known method. As the compound of the formula (6), the product produced in the production step 1 can be used.

W in formula (7) is a leaving group. W in the formula (7) may be any atom or atomic group as long as it functions as a leaving group in the reaction of the production step 2.
W in the formula (7) includes, for example, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), a C1 to C4 alkylsulfonyloxy group (for example, a methanesulfonyloxy group, an ethanesulfonyloxy group, etc.), C1 to C1. C4 haloalkylsulfonyloxy group (eg, difluoromethanesulfonyloxy group, trifluoromethanesulfonyloxy group, etc.), C1-C4 alkyl group or benzenesulfonyloxy group which may have a halogen atom (eg, benzenesulfonyloxy group, 4) -Methylbenzenesulfonyloxy group, 4-chlorobenzenesulfonyloxy group, etc.), etc.), but are not limited to these.
The compound of the formula (7) is a known compound, or can be produced from a known compound by a known method. As the compound of the formula (7), a known alkylating agent can be used without particular limitation. Examples of the compound of the formula (7) include butyl bromide, butyl iodide, butyl methanesulfonate, butyl triflate, dibutyl sulfate, pentyl bromide, pentyl iodide, pentyl methanesulfonate, pentilt refrate, dipentyl sulfate, and the like. Examples thereof include, but are not limited to, hexyl bromide, hexyl iodide, hexyl methanesulfonic acid, hexyl trifrate, and dihexyl sulfate.

The amount of the compound represented by the formula (7) may be any amount as long as the reaction proceeds. From the viewpoints of yield, suppression of by-products, economic efficiency, etc., it is usually 1.0 equivalent or more, preferably 1.0 to 10.0 equivalent, more preferably 1.0 molar with respect to 1.0 mol of the compound of the formula (6). The range of 1.0 to 5.0 equivalents can be exemplified.

The reaction of production step 2 is preferably carried out in the presence of a base. The base used in the production step 2 may be any base as long as the reaction proceeds. Examples of the base used in the production step 2 include alkali metal hydroxides (eg, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.) and alkaline earth metal hydroxides (eg, magnesium hydroxide, water). Calcium oxide, barium hydroxide, etc.), alkali metal carbonates (eg, lithium carbonate, sodium carbonate, potassium carbonate, etc.), alkaline earth metal carbonates (eg, magnesium carbonate, calcium carbonate, barium carbonate, etc.), alkali metal carbonates Hydrogen salts (eg, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc.), alkaline earth metal bicarbonates (eg, magnesium hydrogen carbonate, calcium hydrogen carbonate, barium hydrogen carbonate, etc.), amines (eg, triethylamine, etc.) Tributylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] -7-undec-7-ene (DBU), 1,4-diazabicyclo [2.2.2] octane (DABCO), N, N -Dimethylaniline, N, N-diethylaniline, pyridine, 4- (dimethylamino) -pyridine, 2,6-rutidine, etc.), etc.), but are not limited thereto.

The amount of the base used in the production step 2 may be any amount as long as the reaction proceeds. From the viewpoints of yield, by-product suppression, economic efficiency, etc., it is usually 1.0 to 10.0 equivalents, preferably 1.0 to 5.0 equivalents, and more preferably 1 with respect to the compound of the formula (6). The range of 0 to 2.0 equivalents can be exemplified.

The reaction of production step 2 is carried out in the presence or absence of a solvent. When a solvent is used in the production step 2, the solvent may be any solvent as long as the reaction proceeds. Examples of the solvent used in the production step 2 include nitriles (for example, acetonitrile, propionitrile, etc.), ethers (for example, diethyl ether, diisopropyl ether, cyclopentylmethyl ether (CPME), tetrahydrofuran (THF), 1, 4-Dioxane, monoglime, diglime, etc.), halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, etc.), aromatic hydrocarbons (eg, benzene, chlorobenzene, dichlorobenzene, nitrobenzene, etc.) Toluene, xylene, etc.), amides (eg, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), etc.), imidazolinones (eg, 1,3) -Dimethyl-2-imidazolinone (DMI), etc.), sulfoxides (eg, dimethyl sulfoxide (DMSO), etc.), sulfones (eg, sulfolane, etc.), etc., but are not limited thereto. These solvents can be used alone or as a mixed solvent of any mixing ratio.

When the solvent is used in the production step 2, the amount of the solvent used may be any amount as long as the reaction proceeds. From the viewpoints of yield, suppression of by-products, economic efficiency and the like, the range of usually 0 (zero) to 10 L (liter), preferably 0 to 5 L can be exemplified with respect to the compound of the formula (6).

The reaction temperature in the production step 2 may be any temperature as long as the reaction proceeds. From the viewpoint of yield, suppression of by-products, economic efficiency, etc., the reaction temperature is usually in the range of −20 (minus 20) to 200 ° C., preferably -20 to 150 ° C., and more preferably 0 to 130 ° C. it can.

The reaction time of the manufacturing step 2 is not particularly limited. Those skilled in the art can appropriately adjust the reaction time of the manufacturing process 2. From the viewpoint of yield, suppression of by-products, economic efficiency, etc., the range of usually 0.1 hour to 48 hours, preferably 0.1 hour to 36 hours can be exemplified.

(Manufacturing process 3)
The production step 3 is a step of reacting the compound of the formula (8) with the compound of the formula (9) to produce the compound of the formula (1).

The compound of the formula (8) is a known compound, or can be produced from a known compound by a known method. As the compound of the formula (8), the product produced in the production step 2 can be used.

X in the formula (9) is a leaving group corresponding to ^{X − in the formula (1).}
The compound of the formula (9) is a known compound, or can be produced from a known compound by a known method. As the compound of the formula (9), a known alkylating agent can be used without particular limitation. Examples of the compound of the formula (9) include methyl chloride, methyl bromide, methyl iodide, methyl methanesulfonate, methyl triflate, methyl p-toluenesulfonate, dimethyl sulfuric acid, ethyl chloride, ethyl bromide, ethyl iodide. , Ethyl methanesulfonate, ethyl triflate, ethyl p-toluenesulfonate, diethyl sulfuric acid, propyl bromide, propyl iodide, propyl methanesulfonate, propyl truffleate, dipropyl sulfuric acid and the like, but are limited thereto. It's not a thing.

The amount of the compound represented by the formula (9) may be any amount as long as the reaction proceeds. From the viewpoints of yield, suppression of by-products, economic efficiency, etc., it is usually 1.0 equivalent or more, preferably 1.0 to 10.0 equivalent, more preferably 1.0 molar with respect to 1.0 mol of the compound of the formula (8). The range of 1.0 to 5.0 equivalents can be exemplified.

The reaction of production step 3 is carried out in the presence or absence of a solvent. When a solvent is used in the production step 3, the solvent may be any solvent as long as the reaction proceeds. Examples of the solvent used in the production step 3 include nitriles (for example, acetonitrile, propionitrile, etc.), ethers (for example, diethyl ether, diisopropyl ether, cyclopentylmethyl ether (CPME), tetrahydrofuran (THF), 1, 4-Dioxane, monoglime, diglime, etc.), carboxylic acid esters (eg, ethyl acetate, butyl acetate, etc.), halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, etc.), aromatics Hydrocarbons (eg, benzene, chlorobenzene, dichlorobenzene, nitrobenzene, toluene, xylene, etc.), amides (eg, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone) (NMP), etc.), imidazolinones (eg, 1,3-dimethyl-2-imidazolinone (DMI), etc.), sulfoxides (eg, dimethyl sulfoxide (DMSO), etc.), sulfones (eg, sulfolane, etc.), etc. However, the present invention is not limited to these. These solvents can be used alone or as a mixed solvent of any mixing ratio.

When the solvent is used in the production step 3, the amount of the solvent used may be any amount as long as the reaction proceeds. From the viewpoints of yield, suppression of by-products, economic efficiency and the like, the range of usually 0 (zero) to 10 L (liter), preferably 0 to 5 L can be exemplified with respect to the compound of the formula (8).

The reaction temperature in the production step 3 may be any temperature as long as the reaction proceeds. From the viewpoint of yield, suppression of by-products, economic efficiency, etc., the reaction temperature is usually in the range of −20 (minus 20) to 200 ° C., preferably -20 to 150 ° C., and more preferably 0 to 130 ° C. it can.

The reaction time of the manufacturing step 3 is not particularly limited. Those skilled in the art can appropriately adjust the reaction time of the manufacturing process 3. From the viewpoint of yield, suppression of by-products, economic efficiency, etc., the range of usually 0.1 hour to 48 hours, preferably 0.1 hour to 36 hours can be exemplified.

3. 3. The fluoroalkylation reaction of the present invention will be described.

（式中、Ｒ^１はＣ_１〜Ｃ_８フルオロアルキル基を示し、
Ｒ^４は１又は２個以上の同一又は異なる置換基Ｃにより置換されてもよいＣ_１〜Ｃ_１０アルキル基、１又は２個以上の同一又は異なる置換基Ｃにより置換されてもよいＣ_２〜Ｃ_１０アルケニル基、１又は２個以上の同一又は異なる置換基Ｃにより置換されてもよいＣ_２〜Ｃ_１０アルキニル基又は、１又は２個以上の同一又は異なる置換基Ｂにより置換されてもよいＣ_６〜Ｃ_１０アリール基を示し、
置換基Ｂはハロゲン原子、Ｃ_１〜Ｃ_６アルキル基、Ｃ_３〜Ｃ_８シクロアルキル基、ヒドロキシ基、Ｃ_１〜Ｃ_６アルコキシ基、Ｃ_１〜Ｃ_６アルキルチオ基、Ｃ_１〜Ｃ_６アルキルスルフィニル基、Ｃ_１〜Ｃ_６アルキルスルホニル基、Ｃ_１〜Ｃ_６ハロアルキルチオ基、Ｃ_１〜Ｃ_６ハロアルキルスルフィニル基、Ｃ_１〜Ｃ_６ハロアルキルスルホニル基、アミノ基、モノ（Ｃ_１〜Ｃ_６アルキル）アミノ基、ジ（Ｃ_１〜Ｃ_６アルキル）アミノ基、Ｃ_１〜Ｃ_６アシルアミノ基、ホルミル基、カルボキシ基、Ｃ_１〜Ｃ_６アルコキシカルボニル基、Ｃ_１〜Ｃ_６アルキルカルボニルオキシ基、ニトロ基又はシアノ基を示し、
置換基Ｃはハロゲン原子、ヒドロキシ基、Ｃ_１〜Ｃ_６アルコキシ基、カルボキシ基、Ｃ_１〜Ｃ_６アルコキシカルボニル基、Ｃ_１〜Ｃ_６アルキルカルボニルオキシ基、１又は２個以上の同一又は異なるハロゲン原子、Ｃ_１〜Ｃ_６アルキル基、Ｃ_１〜Ｃ_６ハロアルキルチオ基又はＣ_１〜Ｃ_６ハロアルキルスルフィニル基により置換されてもよいＣ_６〜Ｃ_１０アリール基、１又は２個以上の同一又は異なるハロゲン原子、Ｃ_１〜Ｃ_６アルキル基、Ｃ_１〜Ｃ_６ハロアルキルチオ基又はＣ_１〜Ｃ_６ハロアルキルスルフィニル基により置換されてもよいＣ_６〜Ｃ_１０アリールオキシ基又は、１又は２個以上の同一又は異なるハロゲン原子、Ｃ_１〜Ｃ_６アルキル基、Ｃ_１〜Ｃ_６ハロアルキルチオ基又はＣ_１〜Ｃ_６ハロアルキルスルフィニル基により置換されてもよいＣ_６〜Ｃ_１０アリール（Ｃ_１〜Ｃ_４）アルコキシ基を示す。）
の化合物の製造方法であって、式（３）：

（式中、Ｒ^４は前記で定義したとおりであり、
Ｚはシアノ基、Ｃ_１〜Ｃ_６アルキルスルホニル基、１又は２個以上の同一又は異なるハロゲン原子又はＣ_１〜Ｃ_６アルキル基により置換されてもよいＣ_６〜Ｃ_１０アリールスルホニル基を示す。）
の化合物を塩基の存在下、式（１）：

（式中、Ｒ^１は前記で定義したとおりであり、
Ｒ^２は１又は２個以上の同一又は異なる置換基Ａにより置換されていてもよいＣ_４〜Ｃ_１０アルキル基、１又は２個以上の同一又は異なる置換基Ａにより置換されていてもよいＣ_４〜Ｃ_１０アルケニル基、１又は２個以上の同一又は異なる置換基Ａにより置換されていてもよいＣ_４〜Ｃ_１０アルキニル基又は、１又は２個以上の同一又は異なる置換基Ａにより置換されていてもよいＣ_３〜Ｃ_８シクロアルキル基を示し、
Ｒ^３はＣ_１〜Ｃ_３アルキル基を示し、
Ｙ^１、Ｙ^２、Ｙ^３及びＹ^４は、それぞれ独立して、
水素原子、ハロゲン原子、Ｃ_１〜Ｃ_６アルキル基、Ｃ_３〜Ｃ_８シクロアルキル基、ヒドロキシ基、Ｃ_１〜Ｃ_６アルコキシ基、Ｃ_１〜Ｃ_６アルキルチオ基、Ｃ_１〜Ｃ_６アルキルスルフィニル基、Ｃ_１〜Ｃ_６アルキルスルホニル基、アミノ基、モノ（Ｃ_１〜Ｃ_６アルキル）アミノ基、ジ（Ｃ_１〜Ｃ_６アルキル）アミノ基、Ｃ_１〜Ｃ_６アシルアミノ基、ホルミル基、カルボキシ基、Ｃ_１〜Ｃ_６アルコキシカルボニル基、Ｃ_１〜Ｃ_６アルキルカルボニルオキシ基、ニトロ基、シアノ基又は、１又は２個以上の同一又は異なる置換基Ｂにより置換されていてもよいＣ_６〜Ｃ_１０アリール基を示し、
又は、Ｙ^１とＹ^２、Ｙ^２とＹ^３、Ｙ^３とＹ^４の２つの隣接する置換基は、それらが結合している炭素原子と一緒になって、４〜８員の炭素環を形成してもよく、
Ｘ⁻はハロゲンイオン、テトラフルオロホウ酸イオン、メタンスルホナートイオン、トリフルオロメタンスルホナートイオン、ｐ−トルエンスルホナートイオン、過塩素酸イオン、リン酸二水素イオン、硫酸水素イオン又は硫酸アルキルイオンを示し、
置換基ＡはＣ_１〜Ｃ_６アルコキシ基、Ｃ_１〜Ｃ_６アルコキシカルボニル基又はＣ_１〜Ｃ_６アルキルカルボニルオキシ基を示し、
置換基Ｂは前記で定義したとおりである。）
で表されるフルオロアルキル化剤と反応させる方法である。以下、本発明のフルオロアルキル化反応で使用する化合物や反応条件等について詳細に説明する。 The fluoroalkylation reaction of the present invention has the formula (2):

(In the formula, R ¹ represents a C _{1 to} C ₈ fluoroalkyl group,
R ⁴ may be substituted with one or more identical or different substituents C _{1 to} C ₁₀ alkyl groups may be substituted with one or more identical or different substituents C ₂ to C ₁₀ alkenyl group, one or more identical or different optionally substituted with a substituent C C ₂ -C ₁₀ alkynyl group, or may be substituted by one or more identical or different substituents B Shows C _{6 to C 10} aryl groups,
Substituent B is a halogen atom, C _{1 to} C ₆ alkyl group, C _{3 to} C ₈ cycloalkyl group, hydroxy group, C _{1 to} C ₆ alkoxy group, C _{1 to} C ₆ alkyl thio group, C _{1 to} C ₆ alkyl sulfinyl. _group, C 1 -C ₆ alkylsulfonyl _group, C 1 -C ₆ haloalkylthio _group, C 1 -C ₆ haloalkylsulfinyl _group, C 1 -C ₆ haloalkylsulfonyl group, an amino group, a mono _(C 1 -C ₆ alkyl) Amino group, di (C _{1 to} C ₆ alkyl) amino group, C _{1 to} C ₆ acylamino group, formyl group, carboxy group, C _{1 to} C ₆ alkoxycarbonyl group, C _{1 to} C ₆ alkylcarbonyloxy group, nitro group Or show a cyano group,
Substituent C is a halogen atom, a hydroxy group, a C _{1 to} C ₆ alkoxy group, a carboxy group, a C _{1 to} C ₆ alkoxycarbonyl group, a C _{1 to} C ₆ alkylcarbonyloxy group, or one or more identical or different halogens. Atomic, C _{6 to} C ₁₀ aryl groups optionally substituted with _{C 1 to} C ₆ alkyl groups, C _{1 to} C ₆ haloalkylthio groups or C _{1 to} C ₆ haloalkylsulfinyl groups, one or more identical or different _{C 6 to} C ₁₀ aryloxy groups or one or more, which may be substituted with halogen atoms, C _{1 to} C ₆ alkyl groups, C _{1 to} C ₆ haloalkylthio groups or C _{1 to} C _{6 haloalkylsulfinyl groups. C 6 to} C ₁₀ aryl (C _{1 to} C ₄ ) may be substituted with the same or different halogen atoms, C _{1 to} C ₆ alkyl groups, C _{1 to} C ₆ haloalkylthio groups or C _{1 to} C _{6 haloalkylsulfinyl groups.} Indicates an alkoxy group. )
A method for producing the compound according to the formula (3):

(In the equation, R ⁴ is as defined above,
Z represents a cyano group, a C _{1 to} C _{6 alkyl sulfonyl group, or a C 6 to} C ₁₀ aryl sulfonyl group that may be substituted with one or more identical or different halogen atoms or C _{1 to} C _{6 alkyl groups.} )
In the presence of a base, the compound of the formula (1):

(In the equation, R ¹ is as defined above,
R ² may be substituted with one or more identical or different substituents A C _{4 to} C ₁₀ alkyl groups may be substituted with one or more identical or different substituents A C _{4 to} C ₁₀ Alkyne groups may be substituted with 1 or more identical or different substituents A C _{4 to} C ₁₀ Alkynyl groups or 1 or more identical or different substituents A Shows _{C 3 to C 8} cycloalkyl groups that may be present.
R ³ represents a C _{1 to} C ₃ alkyl group,
Y ¹ , Y ² , Y ³ and Y ⁴ are independent of each other.
Hydrogen atom, halogen atom, C _{1 to} C ₆ alkyl group, C _{3 to} C ₈ cycloalkyl group, hydroxy group, C _{1 to} C ₆ alkoxy group, C _{1 to} C ₆ alkylthio group, C _{1 to} C ₆ alkyl sulfinyl group , C _{1 to} C ₆ alkylsulfonyl groups, amino groups, mono (C _{1 to} C ₆ alkyl) amino groups, di (C _{1 to} C ₆ alkyl) amino groups, C _{1 to} C ₆ acylamino groups, formyl groups, carboxy groups , C _{1 to} C ₆ alkoxycarbonyl groups, C _{1 to} C _{6 alkylcarbonyloxy groups, nitro groups, cyano groups or C 6 to} C which may be substituted with one or more identical or different substituents B. _{Shows a 10} aryl group,
Alternatively, ^{two adjacent substituents, Y 1} and Y ² , Y ² and Y ³ , Y ³ and Y ⁴ , together with the carbon atom to which they are attached form a 4- to 8-membered carbon ring. May be formed,
X ^- indicates halogen ion, tetrafluoroborate ion, methanesulfonate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, perchlorate ion, dihydrogen phosphate ion, hydrogen sulfate ion or alkyl sulfate ion. ,
Substituent A represents a C _{1 to} C ₆ alkoxy group, a C _{1 to} C ₆ alkoxycarbonyl group or a C _{1 to} C ₆ alkylcarbonyloxy group.
Substituent B is as defined above. )
It is a method of reacting with a fluoroalkylating agent represented by. Hereinafter, the compounds used in the fluoroalkylation reaction of the present invention, reaction conditions and the like will be described in detail.

(Raw material compound)
The raw material used in the fluoroalkylation reaction of the present invention is a compound represented by the formula (3), and can be a known compound or can be produced from a known compound by a known method. Examples of the compound of the formula (3) include p-toluenethiosulfonic acid S- (5-acetoxypentyl), p-toluenethiosulfonic acid S- (6-acetoxyhexyl), and p-toluenethiosulfonic acid S- (5). -Bromopentyl), p-toluenethiosulfonic acid S- (6-bromohexyl), p-toluenethiosulfonic acid S- (5-chloropentyl), p-toluenethiosulfonic acid S- (6-chlorohexyl), p-toluenethiosulfonic acid S- (5-benzyloxypentyl), p-toluenethiosulfonic acid S- (6-benzyloxyhexyl), p-toluenethiosulfonic acid S- [5- [4-chloro-2-] Fluoro-5- (2,2,2-trifluoroethylthio) phenoxy] pentyl], p-toluenethiosulfonic acid S- [5- [4-chloro-2-fluoro-5- (2,2,2-) Trifluoroethylsulfinyl) phenoxy] pentyl], p-toluenethiosulfonic acid S- [6- [2,4-dimethyl-5- (2,2,2-trifluoroethylthio) phenoxy] hexyl], p-toluene Thiosulfonic acid S- [6- [2,4-dimethyl-5- (2,2,2-trifluoroethylsulfinyl) phenoxy] hexyl], 1-acetoxy-5-thiocyanatopentane, 1-acetoxy-6 -Thiocyanatohexane, 1-bromo-5-thiocyanatopentane, 1-bromo-6-thiocyanatohexane, 1-chloro-5-thiocyanatopentane, 1-chloro-6-thiocyanatohexane, 1-benzyloxy-5-thiocyanatopentane, 1-benzyloxy-6-thiocyanatohexane, 5-thiosianatopentyl [4-chloro-2-fluoro-5- (2,2,2-trifluoro) Ethylthio) phenyl] ether, 5-thiosianatopentyl [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether, 6-thiosianatohexyl [2,4 -Dimethyl-5- (2,2,2-trifluoroethylthio) phenyl] ether, 6-thiocyanatohexyl [2,4-dimethyl-5- (2,2,2-trifluoroethylsulfinyl) phenyl] Examples thereof include, but are not limited to, ethers and the like.

The compounds of formula (3) are preferably p-toluenethiosulfonic acid S- (5-acetoxypentyl), p-toluenethiosulfonic acid S- (6-acetoxyhexyl), p-toluenethiosulfonic acid S- (5). -Bromopentyl), p-toluenethiosulfonic acid S- (6-bromohexyl), p-toluenethiosulfonic acid S- (5-chloropentyl), p-toluenethiosulfonic acid S- (6-chlorohexyl), p-toluenethiosulfonic acid S- (5-benzyloxypentyl), p-toluenethiosulfonic acid S- (6-benzyloxyhexyl), p-toluenethiosulfonic acid S- [5- [4-chloro-2-] Fluoro-5- (2,2,2-trifluoroethylthio) phenoxy] pentyl], p-toluenethiosulfonic acid S- [5- [4-chloro-2-fluoro-5- (2,2,2-) Trifluoroethylsulfinyl) phenoxy] pentyl], p-toluenethiosulfonic acid S- [6- [2,4-dimethyl-5- (2,2,2-trifluoroethylthio) phenoxy] hexyl], p-toluene Examples thereof include thiosulfonic acid S- [6- [2,4-dimethyl-5- (2,2,2-trifluoroethylsulfinyl) phenoxy] hexyl], and more preferably p-toluenethiosulfonic acid S- ( 5-acetoxypentyl), p-toluenethiosulfonic acid S- (5-bromopentyl), p-toluenethiosulfonic acid S- (5-chloropentyl), p-toluenethiosulfonic acid S- (5-benzyloxypentyl) ), P-Toluenethiosulfonic acid S- [5- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenoxy] pentyl], p-toluenethiosulfonic acid S- [ 5- [4-Chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenoxy] pentyl] and the like are mentioned, and more preferably, p-toluenethiosulfonic acid S- (5-bromopentyl) is used. ), P-Toluenethiosulfonic acid S- (5-chloropentyl) and the like.

(Amount of fluoroalkylating agent used)
The amount of the compound of the formula (1) used in the fluoroalkylation reaction may be any amount as long as the reaction proceeds. From the viewpoint of yield, suppression of by-products, economic efficiency, etc., the amount is usually 0.5 to 10.0 mol, preferably 1.0 to 5.0 mol, based on 1.0 mol of the compound of the formula (3). A range of 1.0 to 2.0 mol, more preferably 1.0 to 1.5 mol can be exemplified.

(base)
The base used in the fluoroalkylation reaction may be any base as long as the reaction proceeds. Examples of the base used in the fluoroalkylation reaction include alkali metal hydrides (eg, sodium hydroxide, etc.), metal alkoxides (eg, sodium methoxydo, sodium ethoxydo, potassium tert-butoxide, etc.), and alkali metal water. Oxides (eg, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkaline earth metal hydroxides (eg, magnesium hydroxide, calcium hydroxide, barium hydroxide, etc.), alkali metal bicarbonates (eg, eg, magnesium hydroxide, barium hydroxide, etc.) Lithium carbonate, sodium carbonate, potassium carbonate, etc.), alkaline earth metal bicarbonate (eg, magnesium carbonate, calcium carbonate, barium carbonate, etc.), alkali metal bicarbonate (eg, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc.) Etc.), alkaline earth metal bicarbonates (eg magnesium bicarbonate, calcium bicarbonate, etc.), phosphates (eg, sodium phosphate, potassium phosphate, calcium phosphate, etc.), hydrogen phosphates (eg, phosphates) Sodium hydrogen hydrogen, potassium hydrogen phosphate, calcium hydrogen phosphate, etc.), and amines (eg, triethylamine, tributylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] -7-undec-7-ene (eg, triethylamine, tributylamine, diisopropylethylamine, etc.) DBU), 1,4-diazabicyclo [2.2.2] octane (DABCO), N, N-dimethylaniline, N, N-diethylaniline, pyridine, 4- (dimethylamino) -pyridine, 2,6-rutidine Etc.), but is not limited to these.

From the viewpoint of reactivity, yield, economic efficiency, etc., the base used in the fluoroalkylation reaction is preferably alkali metal hydride, alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate, alkali. Examples thereof include earth metal carbonates, alkali metal hydrogen carbonates and alkaline earth metal hydrogen carbonates, and more preferably alkali metal hydrides, alkali metal hydroxides, alkali metal carbonates and the like.

Specific examples of the bases used in the fluoroalkylation reaction are preferably sodium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, sodium carbonate. Examples thereof include potassium, magnesium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, magnesium hydrogen carbonate, calcium hydrogen carbonate and the like, and more preferably sodium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc. Examples thereof include sodium carbonate and potassium carbonate, and more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like.

The bases used in the fluoroalkylation reaction may be used alone or in any combination of two or more at any ratio. The form of the base used in the fluoroalkylation reaction may be any form as long as the reaction proceeds. The form of the base used in the fluoroalkylation reaction can be appropriately selected by those skilled in the art.

(Amount of base used)
The amount of the base used in the fluoroalkylation reaction may be any amount as long as the reaction proceeds. From the viewpoints of yield, suppression of by-products, economic efficiency, etc., the amount of the base used in the fluoroalkylation reaction is usually 1.0 to 20 with respect to 1.0 mol of the compound of the formula (3). The range of 0 equivalents, preferably 1.5 to 10.0 equivalents, more preferably 2.0 to 5.0 equivalents can be exemplified.

(Use of zeolite in fluoroalkylation reaction)
In the fluoroalkylation reaction, zeolite may or may not be used as long as the reaction proceeds. The zeolite used in the fluoroalkylation reaction may be any zeolite as long as the reaction proceeds. The zeolite used in the fluoroalkylation reaction may be a natural zeolite or a synthetic zeolite.

Zeolites used in the fluoroalkylation reaction include, for example, zeolite A, ZK-5, chabazite, ZSM-5, zeolite L, zeolite Y, zeolite X, and mixtures thereof. It is not limited to.

The pore size of the zeolite used in the fluoroalkylation reaction may be any pore size as long as the reaction proceeds. From the viewpoint of yield, economic efficiency, etc., the range of usually 10 Å or less, preferably 1 to 10 Å, more preferably 2 to 7 Å, and further preferably 3 to 5 Å can be exemplified.

Specific examples of the zeolite used in the fluoroalkylation reaction are preferably molecular sieve 3A, molecular sieve 4A, molecular sieve 5A, molecular sieve 13X, more preferably molecular sieve 3A, molecular sieve 4A, molecular sieve 5A and the like. Can be mentioned.

Zeolites used in the fluoroalkylation reaction may be used alone or in any combination of two or more at any ratio. The form of zeolite used in the fluoroalkylation reaction may be any form as long as the reaction proceeds. The form of zeolite used in the fluoroalkylation reaction can be appropriately selected by those skilled in the art.

(Amount of zeolite used)
The amount of zeolite used in the fluoroalkylation reaction may be any amount as long as the reaction proceeds. From the viewpoint of yield, economic efficiency and the like, a range of usually 0 to 10 kg, preferably 0 to 2 kg, more preferably 0 to 1 kg can be exemplified with respect to 1.0 mol of the compound of the formula (3).

(Phase transfer catalyst)
The fluoroalkylation reaction may be carried out in the presence or absence of a phase transfer catalyst. Whether or not to use a phase transfer catalyst can be appropriately selected by those skilled in the art. Examples of the phase transfer catalyst include quaternary ammonium salts (eg, tetrabutylammonium bromide, tetrabutylammonium hydrogensulfate, trimethylbenzylammonium chloride, etc.) and quaternary phosphonium salts (eg, tetrabutylphosphonium bromide, tetraoctylphosphonium bromide). , Tetraphenylphosphonium bromide, etc.), crown ethers (eg, 12-crown-4, 15-crown-5, 18-crown-6, etc.), but are not limited thereto.

From the viewpoint of reactivity, yield, economic efficiency and the like, the phase transfer catalyst is preferably a quaternary ammonium salt or a quaternary phosphonium salt, and more preferably a quaternary ammonium salt.

Specific examples of interphase transfer catalysts for fluoroalkylation reactions are preferably tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydroxide, tetra. Butylammonium hydrogensulfate, tributylmethylammonium chloride, tributylmethylammonium bromide, trimethylbenzylammonium chloride, trimethylbenzylammonium bromide, trimethylbenzylammonium hydroxide, triethylbenzylammonium chloride, triethylbenzylammonium bromide, lauryltrimethylammonium chloride, lauryltrimethylammonium Bromid, benzyl lauryl dimethyl ammonium chloride, benzyl lauryl dimethyl ammonium bromide, trioctyl methyl ammonium chloride, trioctyl methyl ammonium bromide, trioctyl ethyl ammonium chloride, trioctyl ethyl ammonium bromide, benzyl dimethyl octadecyl ammonium chloride, benzyl dimethyl octadecyl ammonium bromide, Myristyltrimethylammonium bromide, N, N-dimethylpyrrolidinium chloride, N, N-dimethylpiperidinium iodide, N-ethyl-N-methylpyrrolidinium bromide, N-ethyl-N-methylpyrrolidinium iodide , N-Butyl-N-methylpyrrolidinium bromide, N-benzyl-N-methylpyrrolidinium chloride, N-butyl-N-methylmorpholinium bromide, N-butyl-N-methylmorpholinium iodide, N-allyl-N-methylmorpholinium bromide, N-methyl-N-ethylpiperidinium acetate, N-methyl-N-ethylpiperidinium iodide, N-methyl-N-benzylpiperidinium chloride, N -Methyl-N-benzylpiperidinium bromide, tetrabutylphosphonium bromide, tetraoctylphosphonium bromide, tetraphenylphosphonium bromide and the like can be mentioned, and more preferably tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, trimethylbenzylammonium chloride, etc. Trimethylbenzylammonium bromide, trioctylmethylammonium chloride, trioctylmethylammonium bu Examples thereof include lomid, benzyl lauryl dimethyl ammonium chloride, benzyl dimethyl octadecyl ammonium chloride, benzyl dimethyl octadecyl ammonium bromide, and myristyl trimethyl ammonium bromide.

(Amount of phase transfer catalyst used)
The amount of the phase transfer catalyst used in the fluoroalkylation reaction may be any amount as long as the reaction proceeds. Those skilled in the art can appropriately adjust the amount of the phase transfer catalyst used in the fluoroalkylation reaction. From the viewpoints of yield, suppression of by-products, economic efficiency, etc., it is usually 0 to 1.0 equivalent, preferably 0 to 0.8 equivalent, more preferably 0, based on 1.0 mol of the compound of the formula (3). The range of ~ 0.5 equivalents can be exemplified.

The phase transfer catalyst may be used alone or in a combination of two or more at any ratio. The form of the phase transfer catalyst may be any form as long as the reaction proceeds. The form of the phase transfer catalyst can be appropriately selected by those skilled in the art.

(solvent)
The fluoroalkylation reaction is preferably carried out using a solvent. The solvent used in the fluoroalkylation reaction may be any solvent as long as the reaction proceeds. Solvents used in the fluoroalkylation reaction include, for example, nitriles (eg, acetonitrile, propionitrile, etc.), ethers (eg, diethyl ether, diisopropyl ether, cyclopentylmethyl ether (CPME), tetrahydrofuran (THF), 1, , 4-Dioxane, monoglime, diglime, etc.), carboxylic acid esters (eg, ethyl acetate, butyl acetate, etc.), halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, etc.), fragrance Group hydrocarbons (eg, benzene, chlorobenzene, dichlorobenzene, nitrobenzene, toluene, xylene, etc.), amides (eg, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methyl) Pyrrolidone (NMP), etc.), imidazolinones (eg, 1,3-dimethyl-2-imidazolinone (DMI), etc.), sulfoxides (eg, dimethyl sulfoxide (DMSO), etc.), etc., but are limited thereto. It is not something that is done. These solvents can be used alone or as a mixed solvent of any mixing ratio.

From the viewpoint of reactivity, yield, economic efficiency and the like, nitriles, ethers, aromatic hydrocarbons and amides are preferable as the solvent for the fluoroalkylation reaction, and nitriles and amides are more preferable. However, amides are more preferable.

Specific examples of solvents for the fluoroalkylation reaction are preferably acetonitrile, propionitrile, diethyl ether, diisopropyl ether, cyclopentylmethyl ether (CPME), tetrahydrofuran (THF), 1,4-dioxane, monoglime, diglime, benzene. , Chlorobenzene, dichlorobenzene, nitrobenzene, toluene, xylene, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP) and the like, more preferably acetonitrile and pro. Pionitrile, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP) and the like can be mentioned, and more preferably N, N-dimethylformamide (DMF), N, Examples thereof include N-dimethylacetamide (DMAC) and N-methylpyrrolidone (NMP), and particularly preferably N, N-dimethylformamide (DMF).

(Amount of solvent used)
The amount of the solvent used in the fluoroalkylation reaction may be any amount as long as the reaction proceeds. From the viewpoint of yield, suppression of by-products, economic efficiency, etc., it is usually 0.01 to 50 L (liter), preferably 0.1 to 15 L, more preferably 0.1 to 15 L, based on 1.0 mol of the compound of the formula (3). The range of 0.1 to 10 L, more preferably 0.1 to 5 L can be exemplified.

(Reaction temperature)
The reaction temperature of the fluoroalkylation reaction may be any temperature as long as the reaction proceeds. From the viewpoint of yield, suppression of by-products, economic efficiency, etc., the reaction temperature is usually in the range of -80 ° C (-80 ° C) or higher and the boiling point or lower of the solvent used, preferably -80 ° C or higher and 50 ° C or lower. The range of -50 ° C or higher and 35 ° C or lower, more preferably -30 ° C or higher and 0 ° C or lower can be exemplified.

(Reaction time)
The reaction time of the fluoroalkylation reaction is not particularly limited. Those skilled in the art can appropriately adjust the reaction time of the fluoroalkylation reaction. From the viewpoint of yield, suppression of by-products, economic efficiency, etc., it is usually 0.1 hour to 48 hours, preferably 0.1 hour to 36 hours, more preferably 0.1 hour to 24 hours, still more preferably 0. The range of 1 hour to 12 hours can be exemplified.

(Product)
The product produced by the fluoroalkylation reaction is a compound represented by the formula (2). Examples of the compound of the formula (2) include (5-acetoxypentyl) trifluoromethylsulfide, (6-acetoxyhexyl) trifluoromethylsulfide, (5-bromopentyl) trifluoromethylsulfide, and (6-bromohexyl) tri. Fluoromethylsulfide, (5-chloropentyl) trifluoromethylsulfide, (6-chlorohexyl) trifluoromethylsulfide, (5-benzyloxypentyl) trifluoromethylsulfide, (6-benzyloxyhexyl) trifluoromethylsulfide, 5-Trifluoromethylthiopentyl [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether, 5-trifluoromethylthiopentyl [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether, 6-trifluoromethylthiohexyl [2,4-dimethyl-5- (2,2,2-trifluoroethylthio) phenyl] ether, 6-tri Fluoromethylthiohexyl [2,4-dimethyl-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether and the like can be mentioned, but the present invention is not limited thereto.

The compound of formula (2) is preferably (5-acetoxypentyl) trifluoromethyl sulfide, (5-bromopentyl) trifluoromethyl sulfide, (5-chloropentyl) trifluoromethyl sulfide, (5-benzyloxypentyl). Trifluoromethylsulfide, 5-trifluoromethylthiopentyl [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether, 5-trifluoromethylthiopentyl [4-chloro-2 −Fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether and the like, more preferably (5-bromopentyl) trifluoromethylsulfide, (5-chloropentyl) trifluoromethylsulfide and the like. Can be mentioned.

（式中、Ｒ^２、Ｒ^３、Ｙ^１、Ｙ^２、Ｙ^３及びＹ^４は上記の通りである。）
で表される２，３−ジヒドロベンゾイミダゾール−２−オン化合物が生成する。この化合物は、当業者に知られた常法（例えば、蒸留、抽出、再結晶、カラムクロマトグラフィー及び／又はその他の操作、好ましくは蒸留等）により反応混合物から除去することができる。 In the fluoroalkylation reaction of the present invention, as a product derived from the compound of the formula (1), the formula (10):

(In the formula, R ² , R ³ , Y ¹ , Y ² , Y ³ and Y ⁴ are as described above.)
The 2,3-dihydrobenzimidazol-2-one compound represented by is produced. The compound can be removed from the reaction mixture by conventional methods known to those of skill in the art (eg, distillation, extraction, recrystallization, column chromatography and / or other operations, preferably distillation, etc.).

Next, the production method of the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

In the following examples, room temperature is usually in the range of 10 ° C to 35 ° C.

In the present specification, the following devices were used to measure the physical properties of Examples, Comparative Examples, and Reference Examples.
( ¹ H nuclear magnetic resonance spectrum ( ¹ H-NMR))
Varian Mercury-300, internal reference material: tetramethylsilane (TMS)
(HPLC: High Performance Liquid Chromatography)
Pump: LC-2010A (manufactured by Shimadzu Corporation), Column: CERI L-colum ODS (4.6 x 250 mm), L-C18, 5 μm, 12 nm
Regarding the HPLC analysis method, the following documents can be referred to as needed.
(A): "New Experimental Chemistry Course 9 Analytical Chemistry II" edited by The Chemical Society of Japan, pp. 86-112 (1977), Publisher Shingo Iizumi, Maruzen Co., Ltd. (For example, fillings that can be used for columns) See pages 93-96 for agent-mobile phase combinations.)
(B): "Experimental Chemistry Lecture 20-1 Analytical Chemistry", 5th edition, pp. 130-151 (2007), Publisher Seishiro Murata, Maruzen Co., Ltd. (For example, reverse phase) See pages 135-137 for specific uses and conditions of chromatographic analysis.)
(LC / MS: Liquid Chromatograph Mass Spectrometry)
Pump: Waters Accuracy H Class, Detector: Waters Q-Tof Premier, Column: CERI L-colum ODS (4.6 x 250 mm), L-C18, 5 μm, 12 nm
(Method of measuring pH)
The pH was measured with a glass electrode type hydrogen ion concentration indicator. As the glass electrode type hydrogen ion concentration indicator, for example, a model manufactured by DKK-TOA CORPORATION, type: HM-20P can be used.
(Measuring method of melting point)
It was measured by a DSC differential scanning calorimeter. The differential scanning calorimetry was performed using a model: DSC-60 (manufactured by Shimadzu Corporation) at a heating rate of 10 ° C./min in a temperature range of 40 ° C. to 400 ° C. Regarding the differential scanning calorimetry method, the following documents can be referred to as necessary.
(A): The Chemical Society of Japan, "4th Edition Experimental Chemistry Course 4 Heat, Pressure", pp. 57-93 (1992), Publisher Kumao Ebihara, Maruzen Co., Ltd. (b): (Company) The Chemical Society of Japan, "5th Edition Experimental Chemistry Course 6 Temperature / Heat, Pressure", pp. 203-205 (2005), Publisher Seishiro Murata, Maruzen Co., Ltd.

(Example 1)
Production of 1-Butyl-2-trifluoromethylbenzimidazole

750 mL of toluene and 324.4 g (3.00 mol) of 1,2-phenylenediamine were added to a 3 L four-necked flask equipped with a stirrer, Dean-Stark apparatus, thermometer and dropping funnel. While stirring the mixture at a bath temperature of 110 ° C., 342.1 g (3.00 mol) of trifluoroacetic acid was added dropwise over 1 hour, and the mixture was further stirred for 3 hours. Then, an azeotropic dehydration operation was performed by a Dean-Stark apparatus for 1 hour until the temperature of the reaction mixture reached 105 ° C. After the temperature of the reaction mixture reached 105 ° C., 102.6 g (900 mmol) of trifluoroacetic acid was further added dropwise over 0.5 hours, and the mixture was stirred for 2 hours. After confirming the disappearance of the raw materials, 150 mL of water and 767.8 g of a 25% sodium hydroxide aqueous solution were added dropwise to the obtained reaction mixture under ice-cooling, and the mixture was stirred for 1 hour and then separated into an organic layer and an aqueous layer. , 2-Trifluoromethylbenzimidazole sodium salt was obtained as an aqueous solution.
To a 3 L four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, 94.3 g (300 mmol) of the above aqueous solution and a 75% tributylmethylammonium chloride aqueous solution was added. While stirring the mixture at 80 ° C., 452.2 g (3.30 mol) of n-butyl bromide was added dropwise, and the mixture was stirred at 80 ° C. for 1 hour. After confirming the completion of the reaction, 1.20 L of toluene was added to the obtained reaction mixture, and the mixture was stirred for 0.5 hours and separated into an organic layer and an aqueous layer. 62.5 g of 35% hydrochloric acid and 600 mL of water were added to the obtained organic layer to wash the organic layer, and the organic layer was further washed with 600 mL of water. Toluene was distilled off from the obtained organic layer under reduced pressure to obtain 704.5 g of 1-butyl-2-trifluoromethylbenzimidazole (crude yield 96.9%, purity 98.0%) as a pale yellow oil. It was. The purity was calculated by the LC absolute calibration curve method, and the yield was calculated from the obtained purity. As a result, the yield was 95.0%.

^{1 1} H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.90-7.87 (m, 1H), 7.46-7.35 (m, 2H), 4.31 (t, J = 7) .5Hz, 2H), 1.87 (q, J = 7.5Hz, 2H), 1.47 (sep, J = 7.5Hz, 2H), 0.99 (t, J = 7.5Hz, 3H)

(Example 2)
Production of 1-Butyl-3-methyl-2-trifluoromethylbenzoimidazolium methylsulfate

178.2 g (1.41 mol) of dimethyl sulfate and 190 mL of toluene were added to a 1 L four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel. While stirring the mixture at 80 ° C., a solution of 232.8 g (942 mmol) of 1-butyl-2-trifluoromethylbenzimidazole having a purity of 98.0% dissolved in 200 mL of toluene was added dropwise over 3 hours at 80 ° C. Was stirred for 5 hours. The reaction mixture was cooled and the precipitated solid was collected by filtration and washed with 380 mL of toluene. The obtained solid was dried under reduced pressure to obtain 335.2 g (yield 96.6%) of 1-butyl-3-methyl-2-trifluoromethylbenzoimidazolium methylsulfate as pale pink crystals.

^{1 1} H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 8.05-8.01 (m, 1H), 7.89-7.85 (m, 1H), 7.81-7.76 (m) , 2H), 4.69 (t, J = 7.8Hz, 2H), 4.33 (s, 3H), 3.38 (s, 3H), 1.96 (quin, J = 7.8Hz, 2H) ), 1.50 (sep, J = 7.8Hz, 2H), 1.01 (t, J = 7.8Hz, 3H)

Melting point: 150.0 ° C

(Reference example 1)
Production of 1-Methyl-2-trifluoromethylbenzimidazole

To a 100 mL eggplant-shaped flask equipped with a magnetic stirrer, 10.8 g (100 mmol) of 1,2-phenylenediamine and 17.1 g (150 mmol) of trifluoroacetic acid were added, and the mixture was stirred under heating under reflux for 4 hours. After confirming the completion of the reaction, the reaction mixture was cooled, poured into an aqueous sodium hydrogen carbonate solution, and extracted with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give 18.7 g of 2-trifluoromethylbenzimidazole as gray crystals.
To a 200 mL eggplant-shaped flask equipped with a magnetic stirrer, add 18.7 g (100 mmol) of 2-trifluoromethylbenzimidazole, 16.6 g (120 mmol) of potassium carbonate, 17.0 g (120 mmol) of methyl iodide and 100 mL of acetone. , The mixture was stirred under heating under reflux for 3 hours. After confirming the completion of the reaction, the reaction mixture was cooled, water was added thereto, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to 19.7 g (yield 98%) of 1-methyl-2-trifluoromethylbenzimidazole. Was obtained as gray crystals.

^{1 1} H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 3.96 (s, 3H), 7.37-7.46 (m, 3H), 7.88 (d, J = 6.0 Hz, 1H) )

(Reference example 2)
Production of 1,3-dimethyl-2-trifluoromethylbenzoimidazolium methylsulfate

To a 200 mL eggplant-shaped flask equipped with a magnetic stirrer, 15.3 g (76 mmol) of 1-methyl-2-trifluoromethylbenzimidazole, 14.7 g (117 mmol) of dimethyl sulfate and 100 mL of toluene were added, and the mixture was heated under reflux. The mixture was stirred for 4 hours. The reaction mixture was cooled and the solvent was evaporated under reduced pressure. The obtained residue was dissolved in dichloromethane, and diethyl ether was added dropwise thereto. The precipitated crystals were collected by filtration and dried to obtain 21.8 g (yield 88%) of 1,3-dimethyl-2-trifluoromethylbenzoimidazolium methyl sulfate as gray crystals.

^{1 1} H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 3.38 (s, 3H), 4.321 (s, 3H), 4.326 (s, 3H), 7.78-7.82, m, 2H), 7.91-7.94 (m, 2H)

(Example 3)
Production of p-toluenethiosulfonic acid S- (5-chloropentyl)

40.8 g (540 mmol) of 73.6% pure sodium hydrosulfide, 54.2 g (540 mmol) of triethylamine and N, N-dimethyl in a 1 L four-necked flask equipped with a stirrer, reflux condenser, thermometer and dropping funnel. 260 mL of formamide was added and the mixture was stirred at room temperature for 1 hour. Then, while stirring the mixture at 10 ° C., a solution of 102.1 g (540 mmol) of p-toluenesulfonyl chloride in 260 mL of toluene was added dropwise, and the mixture was stirred at 10 ° C. for 1 hour. 94.6 g (510 mmol) of 1-bromo-5-chloropentane was added to the resulting reaction mixture, and the mixture was stirred at 50 ° C. for 5 hours. After confirming the completion of the reaction, 310 mL of water was added to the obtained reaction mixture, and the mixture was stirred for 0.5 hours and then separated into an organic layer and an aqueous layer. 5.3 g of 35% hydrochloric acid and 100 mL of water were added to the obtained organic layer, and the organic layer was washed. The organic layer was further washed with a mixed aqueous solution of 42.8 g (50 mmol) of 5% aqueous sodium hydrogen carbonate and 100 mL of water and 150 mL of 15% saline. Toluene was distilled off from the obtained organic layer under reduced pressure, and 146.3 g (crude yield 97.9%, purity 82.1%) of p-toluenethiosulfonic acid S- (5-chloropentyl) was light brown. Obtained as oil. The purity was calculated by the LC absolute calibration curve method, and the yield was calculated from the obtained purity. As a result, the yield was 80.4%.

^{1 1} H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.84-7.80 (m, 2H), 7.37-7.34 (m, 2H), 3.47 (t, J = 6) .3Hz, 2H), 2.99 (t, J = 7.5Hz, 2H), 2.46 (s, 3H), 2.46-1.60 (m, 4H), 1.51-1.42 (M, 2H)

(Example 4)
Production of (5-chloropentyl) trifluoromethyl sulfide

1.72 g (5.0 mmol) of p-toluenethiosulfonic acid S- (5-chloropentyl) with a purity of 85.3%, 1-butyl-3-methyl-2- in a 100 mL reaction flask equipped with a magnetic stirrer. 2.03 g (5.5 mmol) of trifluoromethylbenzoimidazolium methyl sulfate, 1.5 g of molecular sieve 4A (manufactured by Toso Co., Ltd .; Zeolam (trade name); A-4; powder) and 15 mL of N, N-dimethylformamide. added. While stirring the mixture at −10 ° C., 0.65 g (11.5 mmol) of potassium hydroxide was added, and the mixture was stirred at −10 ° C. for 1 hour. When the obtained reaction solution was analyzed by the GC internal standard method using biphenyl as an internal standard substance, the yield was 60.1%.

^{1 1} H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 3.55 (t, J = 6.6 Hz, 2H), 2.90 (t, J = 7.2 Hz, 2H), 1.86-1 .69 (m, 4H), 1.62-1.54 (m, 2H)

(Reference example 3)
Production of (5-chloropentyl) trifluoromethyl sulfide

1.72 g (5.0 mmol) of p-toluenethiosulfonic acid S- (5-chloropentyl) with a purity of 85.3%, 1,3-dimethyl-2-trifluoro in a 100 mL reaction flask equipped with a magnetic stirrer. Methylbenzoimidazolium methylsulfate 1.80 g (5.5 mmol), molecular sieve 4A (manufactured by Tosoh Corporation; Zeolam (trade name); A-4; powder) 1.5 g and N, N-dimethylformamide 15 mL were added. .. While stirring the mixture at −10 ° C., 0.65 g (15 mmol) of potassium hydroxide was added, and the mixture was stirred at −10 ° C. for 1 hour. When the obtained reaction solution was analyzed by the GC internal standard method using biphenyl as an internal standard substance, the yield was 56.0%.

(Example 5)
Production of (5-chloropentyl) trifluoromethyl sulfide

1.72 g (5.0 mmol) of p-toluenethiosulfonic acid S- (5-chloropentyl) with a purity of 85.3%, 1-butyl-3-methyl-2- in a 100 mL reaction flask equipped with a magnetic stirrer. 2.03 g (5.5 mmol) of trifluoromethylbenzoimidazolium methylsulfate, 1.61 g (5.0 mmol) of tetrabutylammonium bromide and 15 mL of toluene were added. To add 2.07 g (15 mmol) of potassium carbonate while stirring the mixture at room temperature, the mixture was stirred at room temperature for 48 hours. When the obtained reaction solution was analyzed by the GC internal standard method using biphenyl as an internal standard substance, the yield was 16.4%.

(Comparative Example 1)
Production of (5-chloropentyl) trifluoromethyl sulfide

1.72 g (5.0 mmol) of p-toluenethiosulfonic acid S- (5-chloropentyl) with a purity of 85.3%, 1,3-dimethyl-2-trifluoro in a 100 mL reaction flask equipped with a magnetic stirrer. 1.80 g (5.5 mmol) of methylbenzoimidazolium methylsulfate, 1.61 g (5.0 mmol) of tetrabutylammonium bromide and 15 mL of toluene were added. To add 2.07 g (15 mmol) of potassium carbonate while stirring the mixture at room temperature, the mixture was stirred at room temperature for 48 hours. When the obtained reaction solution was analyzed by the GC internal standard method using biphenyl as an internal standard substance, the yield was 3.3%.

In Example 5 and Comparative Example 1, the base of Example 4 and Reference Example 3 was changed from potassium hydroxide to potassium carbonate, the solvent was changed from N, N-dimethylformamide to toluene without using molecular sieves. The reaction was carried out at room temperature. As a result, the yields of Example 6 and Comparative Example 2 were 16.4% and 3.3%. This result shows that the fluoroalkylating agent of the formula (1) of the present invention, for example, the fluoroalkylating agent (1a), is more versatile than the fluoroalkylating agent (1b) of the prior art. It shows that.

(Example 6)
(Hygroscopic comparison experiment of fluoroalkylating agent)
A petri dish and a digital hygrometer filled with 100 mL of water were placed in an 8 L desiccator and left at 20 ° C. for 2 hours until the humidity in the desiccator became stable. After the humidity in the desiccator stabilizes at 99%, about 10 g each of the fluoroalkylating agent (1a) and the fluoroalkylating agent (1b) are weighed in a petri dish and placed in the above desiccator at 20 ° C. and 99% humidity. I left it. The weight of the petri dish was measured periodically, and the increased weight was used as the water content to calculate the water absorption rate. The experiment was carried out for 72 hours.

The results of Example 6 show that the fluoroalkylating agent of the formula (1) of the present invention, for example, the fluoroalkylating agent (1a), has properties peculiar to the salt compound as compared with the conventional fluoroalkylating agent (1b). It shows that some hygroscopic problems have been improved.

(Reference manufacturing example 1)
Production of 5-Trifluoromethylthiopentyl [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether

In a 100 mL reaction flask equipped with a magnetic stirrer, 10.1 g (30 mmol) of 4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenol having a purity of 77.1% and a purity of 88. Add 7.7 g (33 mmol) of 2% (5-chloropentyl) trifluoromethyl sulfide, 3.5 g (33 mmol) of sodium carbonate, 0.45 g (3 mmol) of sodium iodide and 15 mL of N, N-dimethylformamide and mix. Was stirred at 90 ° C. for 8 hours. After confirming the completion of the reaction, the reaction mixture was cooled, 4.8 g of a 25% aqueous sodium hydroxide solution and 30 mL of water were added, and the mixture was extracted with 15 mL of dichloromethane. It was partitioned between the organic layer and water to give 5-trifluoromethylthiopentyl [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether as 31.9 g of a dichloromethane solution. When the obtained dichloromethane solution was analyzed by the LC absolute calibration curve method, the purity was 36.6% and the yield was 90.3%. A part of the obtained dichloromethane solution was isolated and purified by a method well known to those skilled in the art, and subjected to NMR measurement to confirm the following spectra.

^{1 1} H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.23 (d, J = 3.9 Hz, 1H), 7.20 (d, J = 6.0 Hz, 1H), 4.03 (t) , J = 6.3Hz, 2H), 3.41 (q, J = 9.9Hz, 2H), 2.92 (t, J = 7.2Hz, 2H), 1.90-1.74 (m, 4H), 1.66-1.58 (m, 2H)

According to the present invention, a novel fluoroalkylating agent and an industrially excellent fluoroalkylation reaction using the same are provided.
Further, according to the present invention, a trifluoromethylthio compound useful as a medical pesticide and an intermediate thereof can be produced on an industrial scale.
For example, the (5-chloropentyl) trifluoromethyl sulfide prepared in Example 4 is 5-trifluoromethylthiopentyl [4-chloro-2-fluoro-5- (2,2) according to the method described in Reference Production Example 1. , 2-Trifluoroethylthio) phenyl] ether, and then the oxidation reaction disclosed in International Publication No. 2013/157229, etc., can lead to a compound having excellent pest control activity.
Therefore, the present invention has high industrial utility value.

Claims (11)

Equation (1):

(In the formula, R ¹ represents a C _{1 to} C ₈ fluoroalkyl group,
R ² may be substituted with one or more identical or different substituents A C _{4 to} C ₁₀ alkyl groups may be substituted with one or more identical or different substituents A C _{4 to} C ₁₀ Alkyne groups may be substituted with 1 or more identical or different substituents A C _{4 to} C ₁₀ Alkynyl groups or 1 or more identical or different substituents A Shows _{C 3 to C 8} cycloalkyl groups that may be present.
R ³ represents a C _{1 to} C ₃ alkyl group,
Y ¹ , Y ² , Y ³ and Y ⁴ are independent of each other.
Hydrogen atom, halogen atom, C _{1 to} C ₆ alkyl group, C _{3 to} C ₈ cycloalkyl group, hydroxy group, C _{1 to} C ₆ alkoxy group, C _{1 to} C ₆ alkylthio group, C _{1 to} C ₆ alkyl sulfinyl group , C _{1 to} C ₆ alkylsulfonyl groups, amino groups, mono (C _{1 to} C ₆ alkyl) amino groups, di (C _{1 to} C ₆ alkyl) amino groups, C _{1 to} C ₆ acylamino groups, formyl groups, carboxy groups , C _{1 to} C ₆ alkoxycarbonyl groups, C _{1 to} C _{6 alkylcarbonyloxy groups, nitro groups, cyano groups or C 6 to} C which may be substituted with one or more identical or different substituents B. _{Shows a 10} aryl group,
Alternatively, ^{two adjacent substituents, Y 1} and Y ² , Y ² and Y ³ , Y ³ and Y ⁴ , together with the carbon atom to which they are attached form a 4- to 8-membered carbon ring. May be formed,
X ^- indicates halogen ion, tetrafluoroborate ion, methanesulfonate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, perchlorate ion, dihydrogen phosphate ion, hydrogen sulfate ion or alkyl sulfate ion. ,
Substituent A represents a C _{1 to} C ₆ alkoxy group, a C _{1 to} C ₆ alkoxycarbonyl group or a C _{1 to} C ₆ alkylcarbonyloxy group.
Substituent B is a halogen atom, C _{1 to} C ₆ alkyl group, C _{3 to} C ₈ cycloalkyl group, hydroxy group, C _{1 to} C ₆ alkoxy group, C _{1 to} C ₆ alkyl thio group, C _{1 to} C ₆ alkyl sulfinyl. _group, C 1 -C ₆ alkylsulfonyl _group, C 1 -C ₆ haloalkylthio _group, C 1 -C ₆ haloalkylsulfinyl _group, C 1 -C ₆ haloalkylsulfonyl group, an amino group, a mono _(C 1 -C ₆ alkyl) Amino group, di (C _{1 to} C ₆ alkyl) amino group, C _{1 to} C ₆ acylamino group, formyl group, carboxy group, C _{1 to} C ₆ alkoxycarbonyl group, C _{1 to} C ₆ alkylcarbonyloxy group, nitro group Alternatively, it indicates a cyano group. )
The compound represented by. R ¹ represents a C _{1 to} C ₄ perfluoroalkyl group,
R ² may be substituted with one or more identical or different C _{1 to} C ₆ alkoxy groups, C _{1 to} C ₆ alkoxycarbonyl groups or C _{1 to} C _{6 alkylcarbonyloxy groups C 4 to} C ₁₀ Shows an alkyl group,
R ³ represents a C _{1 to} C ₃ alkyl group,
Y ¹ , Y ² , Y ³ and Y ⁴ represent hydrogen atoms,
The compound according to claim 1, wherein X ⁻ represents a halogen ion or an alkyl sulfate ion. R ¹ represents a C _{1 to} C ₄ perfluoroalkyl group,
R ² represents a C _{4 to} C ₁₀ alkyl group and represents
R ³ represents a C _{1 to} C ₃ alkyl group,
Y ¹ , Y ² , Y ³ and Y ⁴ represent hydrogen atoms,
The compound according to claim 1, wherein X ^{− represents an alkyl sulfate ion.} A fluoroalkylating agent comprising the compound according to any one of claims 1 to 3 as an active ingredient. A fluoroalkylating agent represented by the formula (1) according to any one of claims 1 to 3. Equation (2):

(In the formula, R ¹ represents a C _{1 to} C ₈ fluoroalkyl group,
R ⁴ may be substituted with one or more identical or different substituents C _{1 to} C ₁₀ alkyl groups may be substituted with one or more identical or different substituents C ₂ to C ₁₀ alkenyl group, one or more identical or different optionally substituted with a substituent C C ₂ -C ₁₀ alkynyl group, or may be substituted by one or more identical or different substituents B Shows C _{6 to C 10} aryl groups,
Substituent B is a halogen atom, C _{1 to} C ₆ alkyl group, C _{3 to} C ₈ cycloalkyl group, hydroxy group, C _{1 to} C ₆ alkoxy group, C _{1 to} C ₆ alkyl thio group, C _{1 to} C ₆ alkyl sulfinyl. _group, C 1 -C ₆ alkylsulfonyl _group, C 1 -C ₆ haloalkylthio _group, C 1 -C ₆ haloalkylsulfinyl _group, C 1 -C ₆ haloalkylsulfonyl group, an amino group, a mono _(C 1 -C ₆ alkyl) Amino group, di (C _{1 to} C ₆ alkyl) amino group, C _{1 to} C ₆ acylamino group, formyl group, carboxy group, C _{1 to} C ₆ alkoxycarbonyl group, C _{1 to} C ₆ alkylcarbonyloxy group, nitro group Or show a cyano group,
Substituent C is a halogen atom, a hydroxy group, a C _{1 to} C ₆ alkoxy group, a carboxy group, a C _{1 to} C ₆ alkoxycarbonyl group, a C _{1 to} C ₆ alkylcarbonyloxy group, or one or more identical or different halogens. Atomic, C _{6 to} C ₁₀ aryl groups optionally substituted with _{C 1 to} C ₆ alkyl groups, C _{1 to} C ₆ haloalkylthio groups or C _{1 to} C ₆ haloalkylsulfinyl groups, one or more identical or different _{C 6 to} C ₁₀ aryloxy groups or one or more, which may be substituted with halogen atoms, C _{1 to} C ₆ alkyl groups, C _{1 to} C ₆ haloalkylthio groups or C _{1 to} C _{6 haloalkylsulfinyl groups. C 6 to} C ₁₀ aryl (C _{1 to} C ₄ ) may be substituted with the same or different halogen atoms, C _{1 to} C ₆ alkyl groups, C _{1 to} C ₆ haloalkylthio groups or C _{1 to} C _{6 haloalkylsulfinyl groups.} Indicates an alkoxy group. )
A method for producing the compound according to the formula (3):

(In the equation, R ⁴ is as defined above,
Z represents a cyano group, a C _{1 to} C _{6 alkyl sulfonyl group, or a C 6 to} C ₁₀ aryl sulfonyl group that may be substituted with one or more identical or different halogen atoms or C _{1 to} C _{6 alkyl groups.} )
In the presence of a base, the compound of the formula (1):

(In the equation, R ¹ is as defined above,
R ² may be substituted with one or more identical or different substituents A C _{4 to} C ₁₀ alkyl groups may be substituted with one or more identical or different substituents A C _{4 to} C ₁₀ Alkyne groups may be substituted with 1 or more identical or different substituents A C _{4 to} C ₁₀ Alkynyl groups or 1 or more identical or different substituents A Shows _{C 3 to C 8} cycloalkyl groups that may be present.
R ³ represents a C _{1 to} C ₃ alkyl group,
Y ¹ , Y ² , Y ³ and Y ⁴ are independent of each other.
Hydrogen atom, halogen atom, C _{1 to} C ₆ alkyl group, C _{3 to} C ₈ cycloalkyl group, hydroxy group, C _{1 to} C ₆ alkoxy group, C _{1 to} C ₆ alkylthio group, C _{1 to} C ₆ alkyl sulfinyl group , C _{1 to} C ₆ alkylsulfonyl groups, amino groups, mono (C _{1 to} C ₆ alkyl) amino groups, di (C _{1 to} C ₆ alkyl) amino groups, C _{1 to} C ₆ acylamino groups, formyl groups, carboxy groups , C _{1 to} C ₆ alkoxycarbonyl groups, C _{1 to} C _{6 alkylcarbonyloxy groups, nitro groups, cyano groups or C 6 to} C which may be substituted with one or more identical or different substituents B. _{Shows a 10} aryl group,
Alternatively, ^{two adjacent substituents, Y 1} and Y ² , Y ² and Y ³ , Y ³ and Y ⁴ , together with the carbon atom to which they are attached form a 4- to 8-membered carbon ring. May be formed,
X ^- indicates halogen ion, tetrafluoroborate ion, methanesulfonate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, perchlorate ion, dihydrogen phosphate ion, hydrogen sulfate ion or alkyl sulfate ion. ,
Substituent A represents a C _{1 to} C ₆ alkoxy group, a C _{1 to} C ₆ alkoxycarbonyl group or a C _{1 to} C ₆ alkylcarbonyloxy group.
Substituent B is as defined above. )
A method characterized by reacting with a fluoroalkylating agent represented by. R ¹ represents a C _{1 to} C ₄ perfluoroalkyl group,
R ² may be substituted with one or more identical or different C _{1 to} C ₆ alkoxy groups, C _{1 to} C ₆ alkoxycarbonyl groups or C _{1 to} C _{6 alkylcarbonyloxy groups C 4 to} C ₁₀ Shows an alkyl group,
R ³ represents a C _{1 to} C ₃ alkyl group,
R ⁴ is one or more identical or different halogen atoms, C ₁ -C ₄ alkylcarbonyloxy group or a benzyl group optionally substituted C ₁ may be -C ₆ alkyl group or one or more identical Alternatively, it may be substituted with a different halogen atom, a C _{1 to} C ₆ alkyl group, a C _{1 to} C ₆ haloalkylthio group or a C _{1 to} C _{6 haloalkylsulfinyl group, or a phenyloxy group. C 1 to} C ₆ Shows an alkyl group,
Y ¹ , Y ² , Y ³ and Y ⁴ represent hydrogen atoms,
X ⁻ indicates a halogen ion or an alkyl sulfate ion, and represents
Z represents a cyano group, C ₁ -C ₄ alkylsulfonyl group or one or more identical or different C ₁ -C ₆ alkyl optionally phenylsulfonyl group optionally substituted by a group A method according to claim 6 .. R ¹ represents a C _{1 to} C ₄ perfluoroalkyl group,
R ² represents a C _{4 to} C ₁₀ alkyl group and represents
R ³ represents a C _{1 to} C ₃ alkyl group,
R ⁴ _{represents a C 1-} C ₆ alkyl group that may be substituted with one or more identical or different halogen atoms.
Y ¹ , Y ² , Y ³ and Y ⁴ represent hydrogen atoms,
X ^- is shown an alkyl sulfate ion,
The method of claim 6, wherein Z represents a phenylsulfonyl group that may be substituted with one or more identical or different C _1- C _{6 alkyl groups.} The method according to claim 6, wherein the base used in the reaction is an alkali metal hydride, an alkali metal hydroxide, an alkali metal carbonate, or a mixture thereof. The method of claim 6, wherein the reaction is carried out in the presence of zeolite. The method according to claim 6, wherein the reaction is carried out at a temperature in the range of −50 ° C. or higher and 35 ° C. or lower.