JP2010280600A - Method for producing sulfonium salt - Google Patents

Abstract

で表されるスルホニウム塩を製造する方法。
【選択図】なしA method for producing a sulfonium salt free of halide ions is provided.
By contacting and mixing a sulfonium compound having a sulfonate anion as a counter anion and a sulfonimide salt, the following general formula (5):

The manufacturing method of the sulfonium salt represented by these.
[Selection figure] None

Description

  The present invention relates to a method for producing a sulfonium salt useful as a photoacid generator used in the field of paints, coating agents, photocurable adhesives, and semiconductor photolithography.

  Photo acid generators are used in the fields of paints, coating agents, photo-curing adhesives and the like because they generate an acid upon irradiation with light and can cationically polymerize epoxy monomers, oxetane monomers and the like. Also, in the field of semiconductor photolithography, acid is generated by exposure, and its catalytic action removes the protective group that has insolubilized the resist resin, and it is also used for chemically amplified resists that are soluble in alkaline developers. Has been.

The molecular structure of the photoacid generator is composed of a cation moiety that absorbs irradiated light and an anion moiety that is a source of acid generation. Typical examples of photoacid generators are onium salts such as sulfonium salts and iodonium salts. Is mentioned. Since the sulfonium salt has better storage stability and the absorption wavelength is longer than that of the iodonium salt, sulfonium salts having various structures have been developed. As the anion sites of these sulfonium salts, SbF ₆ ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ^{− and the} like are used, but Sb is a deleterious substance, As is Since they are poisonous, onium salts containing these metal elements have safety problems and their use is limited. In the field of semiconductor photolithography, a photoacid having an element such as metal (SbF ₆ ⁻ , AsF ₆ ⁻ ), phosphorus (PF ₆ ⁻ ), boron (BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ ) or the like. The generator cannot be used for chemically amplified resist applications. This is because these elements become impurities and greatly affect transistor performance (see, for example, Non-Patent Document 1).

｛式中、Ｘは、ハロゲン原子であり、Ｍ’は、アルカリ金属であり、そしてＲｆ”は、フッ素残基を示す。｝。 As a photoacid generator for solving the above-mentioned problems, for example, a sulfonium salt having a cation moiety made of triarylsulfonium and an anion moiety made of fluorine-containing sulfonimidate can be mentioned. Conventionally, the sulfonium salt is synthesized from the following two steps.
1st process: A triarylsulfonium halide is synthesize | combined from a Grignard reagent and diaryl sulfoxide (for example, refer nonpatent literature 2-3).
Second step: A triarylsulfonium halide and a sulfonimide salt are reacted to synthesize a triarylsulfonium sulfonamidate (see, for example, Patent Document 1).

{Wherein X is a halogen atom, M ′ is an alkali metal, and Rf ″ represents a fluorine residue.}.

  However, in the case of the above-mentioned production method, halide ions are liberated as a by-product in the second step. Therefore, the inclusion of halide ions in the sulfonium salt of the final product is unavoidable. Ions may remain. If a sulfonium salt containing a halide ion is used as a photoacid generator, it may cause coloration of the product or deterioration of performance. For this reason, it is required to produce a (free) sulfonium salt that does not contain halide ions, but the operation of removing the halide ions is necessary, and the operation becomes complicated. As described above, in the conventional method for producing a sulfonium salt via a triarylsulfonium halide, it is difficult to avoid the liberation / mixing of halide ions, and therefore development of a new production method is strongly desired.

JP 2008-89777 A JP 2001-288193 A JP 2008-222657 A

2. Supervised by Mitsuru Ueda, edited by Radtech Study Group, “Latest Trends in UV / EB Curing Technology”, Chapter 2 Material Development Trends. Photopolymerization initiator CMC Publishing (2006) Journal of the American Chemical Society 112 6004 (1990) Synthesis 1648 (2004) Journal of Organic Chemistry 63, 7522 (1998). Chemical and Pharmaceutical Bulletin 29, 3753 (1981). Macromolecular Chemistry and Physics 200, 1257 (1999). Inorganic Chemisty 23 3720 (1984) Inorganic Chemisty 32, 5007 (1993)

  In view of the above problems, the problem to be solved by the present invention is to provide a novel method for producing a sulfonium salt capable of producing a sulfonium salt in a high yield while avoiding the liberation / mixing of halide ions. is there.

  The present inventors diligently studied a method capable of producing a sulfonium salt in a high yield without liberation and mixing of halide ions. As a result, it was found that a sulfonium salt can be produced in a high yield without contacting and mixing halide ions, by contacting and mixing a sulfonium salt having a sulfonate at the anion site and a sulfonimide salt. It came to be completed.

｛式中、Ｒ^１、Ｒ^２、及びＲ^３は、各々独立に、炭素数１〜８個のアルキル基、ナフチル基又は下記一般式（２）：

（式中、Ａは、水素原子、ハロゲン原子、炭素数１〜８個のアルキル基、炭素数１〜８個のアルコキシ基、フェノキシ基、炭素数１〜８個のアルキルチオ基又はフェニルチオ基のいずれかである。）で表されるアリール基であり、ｘは、１〜８の整数であり、そしてｙは、０又は１である。｝で表されるスルホニウム化合物と、下記一般式（３）：

｛式中、Ｍは、Ma又はMb_1/2であり、Maは、アルカリ金属であり、Mb_1/2は、アルカリ土類金属であり、Ｒｆ、及びＲｆ’は、各々独立に、Ｆ、Ｃ_６Ｆ_５若しくはＣ_ａＦ_{２ａ＋１−ｂ}Ｈ_ｂ（ａは１〜８の整数であり、そしてｂは０又は１である）のいずれかであるか又は下記一般式（４）：

（式中、ｎは、１〜５の整数であり、そしてＭは、前記したものと同じである。）で表される構造を含む。｝で表されるスルホンイミド塩とを接触・混合させることにより、下記一般式（５）：

｛式中、Ｒ^１、Ｒ^２、及びＲ^３は、上記一般式（１）において定義したものと同じであり、そしてＲｆ、及びＲｆ’は、上記一般式（３）において定義したものと同じである。｝で表されるスルホニウム塩を製造する方法。 That is, the present invention is as follows.
[1] The following general formula (1):

{Wherein R ¹ , R ² , and R ³ are each independently an alkyl group having 1 to 8 carbon atoms, a naphthyl group, or the following general formula (2):

(In the formula, A is any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenoxy group, an alkylthio group having 1 to 8 carbon atoms, or a phenylthio group. Wherein x is an integer of 1 to 8 and y is 0 or 1. } And the following general formula (3):

{Wherein M is Ma or Mb _1/2 , Ma is an alkali metal, Mb _1/2 is an alkaline earth metal, and Rf and Rf ′ are each independently F, C ₆ F ₅ or C _a F _{2a + 1-b} H _b (a is an integer of 1 to 8, and b is 0 or 1), or the following general formula (4):

(Wherein n is an integer of 1 to 5 and M is the same as described above). } Is contacted and mixed with a sulfonimide salt represented by the following general formula (5):

{Wherein R ¹ , R ² and R ³ are the same as those defined in the general formula (1), and Rf and Rf ′ are the same as those defined in the general formula (3). It is. } The manufacturing method of the sulfonium salt represented by this.

[2] In the general formula (1), R ¹ , R ² , and R ³ are each independently an alkyl group having 1 to 4 carbon atoms, a naphthyl group, or A in the formula is a hydrogen atom, a halogen atom, It is represented by the above general formula (2), which is any one of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, an alkylthio group having 1 to 4 carbon atoms, or a phenylthio group. The method for producing a sulfonium salt represented by the general formula (5) according to the above [1], which is an aryl group, x is an integer of 1 to 4, and y is 0 or 1.

[3] In the general formula (3), Rf and Rf ′ are each independently F, C ₆ F ₅ or C _a F _{2a + 1-b} H _b (a is an integer of 1 to 6 and b Is a general formula according to [1], including a structure represented by the general formula (4), wherein n is an integer of 1 to 4 The manufacturing method of the sulfonium salt represented by (5).

  [4] The method for producing a sulfonium salt represented by the general formula (5) according to any one of the above [1] to [3], wherein M is an alkali metal in the general formula (3).

  According to the present invention, a sulfonium salt can be produced in a high yield without liberation and mixing of halide ions.

に示すように、一般式（１）で表されるスルホニウム化合物と、一般式（３）で表されるスルホンイミド塩とを接触・混合させることにより、ハロゲン化物イオンが遊離・混入することなく、一般式（５）で表されるスルホニウム塩が高収率で得られる製造法に関するものである。 The present invention will be described in detail below.
The present invention provides the following reaction scheme:

As shown in the above, by contacting and mixing the sulfonium compound represented by the general formula (1) and the sulfonimide salt represented by the general formula (3), halide ions are not liberated and mixed, The present invention relates to a production method in which the sulfonium salt represented by the general formula (5) is obtained in high yield.

｛式中、Ａは、水素原子、ハロゲン原子、炭素数１〜８個のアルキル基、炭素数１〜８個のアルコキシ基、フェノキシ基、炭素数１〜８個のアルキルチオ基又はフェニルチオ基のいずれかである。｝で表されるアリール基であり、ｘは、１〜８の整数であり、そしてｙは、０又は１である。 R ¹ , R ² , and R ³ of the sulfonium compound represented by the general formula (1) used in the present invention are each independently an alkyl group having 1 to 8 carbon atoms, a naphthyl group, or the following general formula ( 2):

{In the formula, A is any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenoxy group, an alkylthio group having 1 to 8 carbon atoms, or a phenylthio group. It is. }, X is an integer of 1 to 8, and y is 0 or 1.

・Ａが水素原子

・Ａがハロゲン原子

・Ａが炭素数１〜８個のアルキル基

・Ａが炭素数１〜８個のアルコキシ基

・Ａがフェノキシ基

・Ａが炭素数１〜８個のアルキルチオ基

・Ａがフェニルチオ基

。 Specific examples of R ¹ , R ² , and R ³ include the following:
An alkyl group having 1 to 8 carbon atoms,
_{-CH 3, -CH 2 CH 3,} -CH 2 CH 2 CH 3, -CH (CH 3) 2, -CH 2 CH 2 CH 2 CH 3, -CH 2 CH (CH 3) 2, -C (CH ₃ ) ₃ ,-(CH ₂ ) ₄ CH ₃ ,-(CH ₂ ) ₅ CH ₃ ,-(CH ₂ ) ₆ CH ₃ ,-(CH ₂ ) ₇ CH ₃ ,
・ Naphthyl group

・ A is a hydrogen atom

A is a halogen atom

A is an alkyl group having 1 to 8 carbon atoms

A is an alkoxy group having 1 to 8 carbon atoms

A is a phenoxy group

A is an alkylthio group having 1 to 8 carbon atoms

A is a phenylthio group

.

Specific examples of the sulfonate that is the anion moiety of the general formula (1) include the following: CF ₃ SO ₃ ⁻ , HCF ₂ SO ₃ ⁻ , CF ₃ CF ₂ SO ₃ ⁻ , HCF ₂ CF ₂ SO ₃ ⁻ , CF ₃ CFHSO ₃ ⁻ , CF ₃ (CF ₂ ) ₂ SO ₃ ⁻ , HCF ₂ (CF ₂ ) ₂ SO ₃ ⁻ , CF ₃ (CF ₂ ) ₃ SO ₃ ⁻ , HCF ₂ (CF ₂ ) ₃ SO ₃ ⁻ , CF ₃ (CF ₂ ) ₄ SO ₃ ⁻ , HCF ₂ (CF ₂ ) ₄ SO ₃ ⁻ , CF ₃ (CF ₂ ) ₅ SO ₃ ⁻ , HCF ₂ (CF ₂ ) ₅ SO ₃ ⁻ , CF ₃ (CF ₂ ) ₆ SO ₃ ⁻ , HCF ₂ (CF ₂ ) ₆ SO ₃ ⁻ , CF ₃ (CF ₂ ) ₇ SO ₃ ⁻ , HCF ₂ (CF ₂ ) ₇ SO ₃ ^{— and the} like.

Sulfonium compound represented by the general formula (1) is to be produced using the fluorine-containing sulfonic acid _{(C x F 2x + 1-} y H y SO 3 H) as described below, to obtain a fluorine-containing sulfonic acid In the general formula (1), preferably, R ¹ , R ² , and R ^{3 each} have 1 to 1 carbon atoms, for reasons such as properties and handling during the synthesis of the sulfonium compound represented by the general formula (1). 4 alkyl groups, naphthyl groups, or in the formula, A is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or 1 to 4 carbon atoms Or an aryl group represented by the general formula (2) which is either an alkylthio group or a phenylthio group, x is an integer of 1 to 4, and y is 0 or 1. More preferably, R ¹ , R ² , and R ³ are a methyl group, a naphthyl group, or a group in which A is a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a methoxy group, a phenoxy group, a methylthio group, or a phenylthio group. Any one of the aryl groups represented by the general formula (2), x is an integer of 1 to 4, and y is 0 or 1. Particularly preferably, R ¹ , R ² , and R ³ are a naphthyl group or an aryl group represented by the general formula (2) in which A is either a hydrogen atom or a phenylthio group, and an anionic site Is either CF ₃ SO ₃ ⁻ , CF ₃ CF ₂ SO ₃ ⁻ , HCF ₂ CF ₂ SO ₃ ^— or CF ₃ (CF ₂ ) ₃ SO ₃ ^— .

（２）スルホキシド化合物と芳香族化合物とを、含フッ素スルホン酸、トリフルオロ酢酸無水物の存在下、反応させる方法（例えば、非特許文献５参照）

（３）スルホキシド化合物と芳香族化合物とを、含フッ素スルホン酸、Ｐ_２Ｏ_５の存在下、反応させる方法（例えば、非特許文献６参照）

等が開示されており、その製造方法は特に限定されない。 The production method of the sulfonium compound represented by the general formula (1) is as follows:
(1) A method in which a sulfide compound and an ester compound are reacted in the presence of a fluorine-containing sulfonic acid (see, for example, Non-Patent Document 4)

(2) A method of reacting a sulfoxide compound and an aromatic compound in the presence of fluorine-containing sulfonic acid or trifluoroacetic anhydride (see, for example, Non-Patent Document 5)

(3) A method of reacting a sulfoxide compound and an aromatic compound in the presence of fluorine-containing sulfonic acid and P ₂ O ₅ (see, for example, Non-Patent Document 6)

Etc. are disclosed, and the manufacturing method thereof is not particularly limited.

で表されるスルホンイミド塩について説明する。
上記一般式（３）において、Ｒｆ、及びＲｆ’は、各々独立に、Ｆ、Ｃ_６Ｆ_５若しくはもしくはＣ_ａＦ_{２ａ＋１−ｂ}Ｈ _ｂ（ａは１〜８の整数であり、そしてｂは０又は１である）のいずれかであるか又は下記一般式（４）：

｛式中、ｎは、１〜５の整数であり、そしてＭは、上記一般式（３）で定義したものと同じである。｝で表される構造を含む。上記一般式（３）中のＭは、Ma又はMb_1/2であり、Maは、アルカリ金属であり、そしてMb_1/2は、アルカリ土類金属である。 Next, the following general formula (3) used in the present invention:

The sulfonimide salt represented by these is demonstrated.
In the general formula (3), Rf and Rf ′ are each independently F, C ₆ F ₅ or C _a F _{2a + 1-b} H _b (a is an integer of 1 to 8, and b is 0 Or 1) or the following general formula (4):

{In the formula, n is an integer of 1 to 5, and M is the same as defined in the general formula (3). } Is included. In the general formula (3), M is Ma or Mb _1/2 , Ma is an alkali metal, and Mb _1/2 is an alkaline earth metal.

Specific examples of the anion moiety of the general formula (3) are as follows:
^- N _{(SO 2 F)} 2
_{^{- N (SO 2 CF 3)}} SO 2 F
_{^{- N (SO 2 CF 3)}} 2
_{^{- N (SO 2 CF 2 CF}} 3) SO 2 F
_{^{- N (SO 2 CF 2 CF}} 3) SO 2 CF 3
_{^{- N (SO 2 CF 2 CF}} 3) 2
_{^{- N [SO 2 (CF 2}} ) 2 CF 3] SO 2 F
_{^{- N [SO 2 (CF 2}} ) 2 CF 3] SO 2 CF 3
_{^{- N [SO 2 (CF 2}} ) 2 CF 3] SO 2 CF 2 CF 3
_{^{- N [SO 2 (CF 2}} ) 2 CF 3] 2
_{^{- N [SO 2 (CF 2}} ) 3 CF 3] SO 2 F
_{^{- N [SO 2 (CF 2}} ) 3 CF 3] SO 2 CF 3
_{^{- N [SO 2 (CF 2}} ) 3 CF 3] SO 2 CF 2 CF 3
_{^{- N [SO 2 (CF 2}} ) 3 CF 3] SO 2 (CF 2) 2 CF 3
_{^{- N [SO 2 (CF 2}} ) 3 CF 3] 2
_{^{- N [SO 2 (CF 2}} ) 4 CF 3] SO 2 F
_{^{- N [SO 2 (CF 2}} ) 4 CF 3] SO 2 CF 3
_{^{- N [SO 2 (CF 2}} ) 4 CF 3] SO 2 CF 2 CF 3
_{^{- N [SO 2 (CF 2}} ) 4 CF 3] SO 2 (CF 2) 2 CF 3
_{^{- N [SO 2 (CF 2}} ) 4 CF 3] SO 2 (CF 2) 3 CF 3
_{^{- N [SO 2 (CF 2}} ) 4 CF 3] 2
_{^{- N [SO 2 (CF 2}} ) 5 CF 3] SO 2 F
_{^{- N [SO 2 (CF 2}} ) 5 CF 3] SO 2 CF 3
_{^{- N [SO 2 (CF 2}} ) 5 CF 3] SO 2 CF 2 CF 3
_{^{- N [SO 2 (CF 2}} ) 5 CF 3] SO 2 (CF 2) 2 CF 3
_{^{- N [SO 2 (CF 2}} ) 5 CF 3] SO 2 (CF 2) 3 CF 3
_{^{- N [SO 2 (CF 2}} ) 5 CF 3] SO 2 (CF 2) 4 CF 3
_{^{- N [SO 2 (CF 2}} ) 5 CF 3] 2
_{^{- N [SO 2 (CF 2}} ) 6 CF 3] SO 2 F
_{^{- N [SO 2 (CF 2}} ) 6 CF 3] SO 2 CF 3
_{^{- N [SO 2 (CF 2}} ) 6 CF 3] SO 2 CF 2 CF 3
_{^{- N [SO 2 (CF 2}} ) 6 CF 3] SO 2 (CF 2) 2 CF 3
_{^{- N [SO 2 (CF 2}} ) 6 CF 3] SO 2 (CF 2) 3 CF 3
_{^{- N [SO 2 (CF 2}} ) 6 CF 3] SO 2 (CF 2) 4 CF 3
_{^{- N [SO 2 (CF 2}} ) 6 CF 3] SO 2 (CF 2) 5 CF 3
_{^{- N [SO 2 (CF 2}} ) 6 CF 3] 2
_{^{- N [SO 2 (CF 2}} ) 7 CF 3] SO 2 F
_{^{- N [SO 2 (CF 2}} ) 7 CF 3] SO 2 CF 3
_{^{- N [SO 2 (CF 2}} ) 7 CF 3] SO 2 CF 2 CF 3
_{^{- N [SO 2 (CF 2}} ) 7 CF 3] SO 2 (CF 2) 2 CF 3
_{^{- N [SO 2 (CF 2}} ) 7 CF 3] SO 2 (CF 2) 3 CF 3
_{^{- N [SO 2 (CF 2}} ) 7 CF 3] SO 2 (CF 2) 4 CF 3
_{^{- N [SO 2 (CF 2}} ) 7 CF 3] SO 2 (CF 2) 5 CF 3
_{^{- N [SO 2 (CF 2}} ) 7 CF 3] SO 2 (CF 2) 6 CF 3
_{^{- N [SO 2 (CF 2}} ) 7 CF 3] 2
_{^{- N (SO 2 CF 2 CF}} 2 H) SO 2 F
_{^{- N (SO 2 CF 2 CF}} 2 H) SO 2 CF 3
_{^{- N (SO 2 CF 2 CF}} 2 H) SO 2 CF 2 H
_{^{- N (SO 2 CF 2 CF}} 2 H) SO 2 CF 2 CF 3
_{^{- N (SO 2 CF 2 CF}} 2 H) 2
_{^{- N (SO 2 CF 2 CF}} 2 H) SO 2 (CF 2) 2 CF 3
_{^{- N (SO 2 CF 2 CF}} 2 H) SO 2 (CF 2) 3 CF 3
_{^{- N (SO 2 CF 2 CF}} 2 H) SO 2 (CF 2) 4 CF 3
_{^{- N (SO 2 CF 2 CF}} 2 H) SO 2 (CF 2) 5 CF 3
_{^{- N (SO 2 CF 2 CF}} 2 H) SO 2 (CF 2) 6 CF 3
_{^{- N (SO 2 CF 2 CF}} 2 H) SO 2 (CF 2) 7 CF 3
_{^{- N (SO 2 CFHCF 3)}} SO 2 F
_{^{- N (SO 2 CFHCF 3)}} SO 2 CF 3
_{^{- N (SO 2 CFHCF 3)}} SO 2 CF 2 H
_{^{- N (SO 2 CFHCF 3)}} SO 2 CF 2 CF 3
_{^{- N (SO 2 CFHCF 3)}} SO 2 CF 2 CF 2 H
_{^{- N (SO 2 CFHCF 3)}} 2
_{^{- N (SO 2 CFHCF 3)}} SO 2 (CF 2) 2 CF 3
_{^{- N (SO 2 CFHCF 3)}} SO 2 (CF 2) 3 CF 3
_{^{- N (SO 2 CFHCF 3)}} SO 2 (CF 2) 4 CF 3
_{^{- N (SO 2 CFHCF 3)}} SO 2 (CF 2) 5 CF 3
_{^{- N (SO 2 CFHCF 3)}} SO 2 (CF 2) 6 CF 3
_{^{- N (SO 2 CFHCF 3)}} SO 2 (CF 2) 7 CF 3

が挙げられる。

Is mentioned.

As will be described later, the sulfonimide salt represented by the general formula (3) is synthesized using a sulfonyl halide as a starting material, but for reasons such as availability of the sulfonyl halide, handling during the synthesis of the sulfonimide salt, and the like, Rf and Rf ′ in the general formula (3) are preferably F, C ₆ F ₅ or C _a F _{2a + 1-b} H _b (a is an integer of 1 to 6 and b is 0 or 1 Or a structure of the general formula (4) in which n is an integer of 1 to 4. More preferably, Rf and Rf ′ are F, C ₆ F ₅ or C _a F _{2a + 1-b} H _b (a is an integer from 1 to 4 and b is 0 or 1) or Wherein n is an integer of 2 to 4, and more preferably Rf and Rf ′ are F, C ₆ F ₅ or C _a F _{2a + 1-b} H _b (a is Or an integer of 1 to 4 and b is 0 or 1, or a structure of general formula (4) wherein n is an integer of 2 to 3.

  In addition, M of the sulfonimide salt represented by the general formula (3) may be an alkali metal for reasons such as availability of the sulfonimide salt and handling during the production of the sulfonimide salt described below. More preferably, it is any one of lithium, sodium or potassium.

The method for producing the sulfonimide salt represented by the general formula (3) is as follows:
(4) A method of reacting perfluoroalkylsulfonyl fluoride with an alkali metal salt of a trimethylsilyl group-containing perfluoroalkylsulfonamide (for example, Non-Patent Documents 7 to 8)
RfSO ₂ F + Rf'SO ₂ N (SiMe ₃ ) Na → RfSO ₂ N (Na) SO ₂ Rf '+ Me ₃ SiF
(5) A method of reacting perfluoroalkylsulfonyl halide and perfluoroalkylsulfonamide in the presence of an alkali metal fluoride (see, for example, Patent Document 2)
RfSO ₂ X + Rf'SO ₂ NH ₂ + 4MF → RfSO ₂ N (M) SO ₂ Rf '+ 2MFHF + MX
(6) A method of reacting a fluorinated alkylsulfonyl halide and a fluorinated alkylsulfonamide in the presence of a carbonate (see, for example, Patent Document 3)
RfSO ₂ X + Rf'SO ₂ NH ₂ + M ₂ CO ₃ → RfSO ₂ N (M) SO ₂ Rf '+ MX + CO ₂ + H ₂ O
Etc. are disclosed, and the manufacturing method thereof is not particularly limited.

By contacting and mixing the sulfonium compound represented by the above general formula (1) and the sulfonimide salt represented by the above general formula (3), the above general formula ( A high-purity sulfonium salt represented by 5) can be obtained.
Any solvent may be used as long as it is inert to the reactants. Examples of the solvent used in the present invention include water, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol. Examples include ether solvents such as dimethyl ether and tetraethylene glycol dimethyl ether, nitrile solvents such as acetonitrile, propionitrile, and butyronitrile, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, dimethyl sulfoxide, and sulfolane. It is done. These solvents can be used alone or in combination.

0.95 mol-10 mol is preferable with respect to 1 mol of sulfonium compounds represented by the said General formula (1), and the usage-amount of the sulfonimide salt represented by the said General formula (3) is 0.98 mol-5 mol. More preferably, 1 mol to 4 mol is more preferable.
The reaction temperature is usually −20 ° C. to 100 ° C., preferably −10 ° C. to 80 ° C., more preferably 0 ° C. to 50 ° C., further preferably 10 ° C. to 30 ° C.
The reaction time is usually 0.01 hours to 48 hours, preferably 0.1 hours to 36 hours, more preferably 0.2 hours to 24 hours, and even more preferably 0.5 hours to 12 hours.

  After completion of the reaction, for example, the solvent in the reaction mixture is distilled off under reduced pressure, and then an organic solvent such as dichloromethane, chloroform, ethyl acetate and water are added to separate the organic layer, and the aqueous layer is extracted with the organic solvent. Further, by repeating these two to three times and combining these organic layers together, the organic solvent is distilled off under reduced pressure to obtain the sulfonium salt represented by the general formula (5). The obtained sulfonium salt may be purified by a conventionally known purification method such as crystallization or column chromatography.

。 As shown in the following reaction scheme, the present inventors synthesized triarylsulfonium sulfonidate (C-1, C-2) from a conventional triarylsulfonium halide and a sulfonimide salt, and the present invention. In the case of synthesizing triarylsulfonium sulphonimidate (P-5, P-6) obtained from triarylsulfonium sulfonate and sulfonimide salt, the halogen contained in the obtained sulfonium salt by ion chromatography. Ions were measured (see Examples 5 and 6, Comparative Examples 1 and 2).

.

As a result, bromide ions were detected at 0.4 ppm and 0.6 ppm from C-1 and C-2, respectively, but bromide ions were below the detection limit (less than 0.1 ppm) from P-5 and P-6. Met.
In this way, when producing a sulfonium salt having a fluorine-containing sulfonimidate at the anion site, it is inevitable that halide ions are liberated and mixed in the conventional method. Therefore, the water is washed several times to obtain a high-purity sulfonium salt. However, in the production method of the present invention, since there is no liberation and contamination of halide ions, it is possible to obtain a high-purity sulfonium salt in a high yield, which is extremely industrially difficult. It turns out that it is useful.

EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, this invention is not limited to these.
・ Molecular structure analysis by ¹ H NMR and ¹⁹ F NMR
Using a JNM-GSX400G type nuclear magnetic resonance apparatus (manufactured by JEOL Ltd.), deuterated chloroform as solvent, tetramethylsilane ( ¹ H NMR), Freon-11 (CFCl ₃ ) ( ¹⁹ F NMR) as reference materials It was.
Ion Analysis by ion chromatography ion chromatograph IC-2001 (manufactured by Tosoh Corporation), column TSKgel SuperIC-AP, eluent 1.7 mmol / l NaHCO _3, was used 1.8mmol / L Na ₂ CO _3.

アセトニトリル(10mL)、水(2mL)が入った50mLの３口フラスコに、室温でビス（ペルフルオロエタンスルホニル）イミドリチウム (1.785g, 4.61mmol)を加えて均一に溶解させた。（４―フェニルチオフェニル）ジフェニルスルホニウム トリフルオロメタンスルホネート (0.600g、1.15mmol)をアセトニトリル(10mL)に溶解させた溶液を室温で３口フラスコの中に滴下し、滴下後、室温で３時間攪拌した。反応混合物中の溶媒を減圧留去後、残渣に水とクロロホルムを加えてクロロホルム層を分液した。残った水層は、クロロホルムでさらに２回抽出操作を行った。これらのクロロホルム溶液を一緒にした後、硫酸ナトリウムで乾燥後、クロロホルムを減圧留去して、（４―フェニルチオフェニル）ジフェニルスルホニウム ビス（ペルフルオロエタンスルホニル）イミデート（Ｐ−１）(0.860g)を得た（収率99.5%）。
¹H NMR 7.87-8.35 ppm (m, 19H)
¹⁹F NMR −78.53 ppm (s, 6F)、−117.36 ppm (s, 4F) [Example 1] Synthesis of (4-phenylthiophenyl) diphenylsulfonium bis (perfluoroethanesulfonyl) imidate (P-1)

Bis (perfluoroethanesulfonyl) imidolithium (1.785 g, 4.61 mmol) was added to a 50 mL three-necked flask containing acetonitrile (10 mL) and water (2 mL) at room temperature and dissolved uniformly. A solution prepared by dissolving (4-phenylthiophenyl) diphenylsulfonium trifluoromethanesulfonate (0.600 g, 1.15 mmol) in acetonitrile (10 mL) was dropped into a three-necked flask at room temperature, and then stirred at room temperature for 3 hours. . After the solvent in the reaction mixture was distilled off under reduced pressure, water and chloroform were added to the residue, and the chloroform layer was separated. The remaining aqueous layer was further extracted twice with chloroform. These chloroform solutions were combined, dried over sodium sulfate, and then chloroform was distilled off under reduced pressure to give (4-phenylthiophenyl) diphenylsulfonium bis (perfluoroethanesulfonyl) imidate (P-1) (0.860 g). Obtained (yield 99.5%).
¹ H NMR 7.87-8.35 ppm (m, 19H)
¹⁹ F NMR −78.53 ppm (s, 6F), −117.36 ppm (s, 4F)

実施例１において、ビス（ペルフルオロエタンスルホニル）イミドリチウムの代わりに、（１，１，２，２−テトラフルオロエタンスルホニル）（トリフルオロメタンスルホニル）イミドナトリウム (1.544g, 4.61mmol)を用いた以外は、実施例１と同様の操作を行い、（４―フェニルチオフェニル）ジフェニルスルホニウム （１，１，２，２−テトラフルオロエタンスルホニル）（トリフルオロメタンスルホニル）イミデート（Ｐ−２）(0.786g)を得た（収率100%）。
¹H NMR 7.86-8.34 ppm (m, 19H)、7.21 ppm (m, 1H)
¹⁹F NMR −78.52 ppm (s, 3F)、−121.38 ppm (m, 2F)、−135.02 ppm (m, 2F) [Example 2] Synthesis of (4-phenylthiophenyl) diphenylsulfonium (1,1,2,2-tetrafluoroethanesulfonyl) (trifluoromethanesulfonyl) imidate (P-2)

In Example 1, (1,1,2,2-tetrafluoroethanesulfonyl) (trifluoromethanesulfonyl) imide sodium (1.544 g, 4.61 mmol) was used instead of bis (perfluoroethanesulfonyl) imide lithium. In the same manner as in Example 1, (4-phenylthiophenyl) diphenylsulfonium (1,1,2,2-tetrafluoroethanesulfonyl) (trifluoromethanesulfonyl) imidate (P-2) (0.786 g) was obtained. Obtained (yield 100%).
¹ H NMR 7.86-8.34 ppm (m, 19H), 7.21 ppm (m, 1H)
¹⁹ F NMR −78.52 ppm (s, 3F), −121.38 ppm (m, 2F), −135.02 ppm (m, 2F)

実施例１において、ビス（ペルフルオロエタンスルホニル）イミドリチウムの代わりに、（ペルフルオロ−１−ブタンスルホニル）（トリフルオロメタンスルホニル）イミドリチウム(2.015g, 4.61mmol)を用いた以外は、実施例１と同様の操作を行い、（４―フェニルチオフェニル）ジフェニルスルホニウム （ペルフルオロ−１−ブタンスルホニル）（トリフルオロメタンスルホニル）イミデート（Ｐ−３）(0.923g)を得た（収率100%）。
¹H NMR 7.85-8.33 ppm (m, 19H)、
¹⁹F NMR −78.78 ppm (s, 3F)、−80.36 ppm (m, 3F)、−113.32 ppm (m, 2F)、−121.04 ppm (m, 2F)、−125.71 ppm (m, 2F) [Example 3] Synthesis of (4-phenylthiophenyl) diphenylsulfonium (perfluoro-1-butanesulfonyl) (trifluoromethanesulfonyl) imidate (P-3)

In Example 1, (perfluoro-1-butanesulfonyl) (trifluoromethanesulfonyl) imide lithium (2.015 g, 4.61 mmol) was used in place of bis (perfluoroethanesulfonyl) imide lithium, as in Example 1. Thus, (4-phenylthiophenyl) diphenylsulfonium (perfluoro-1-butanesulfonyl) (trifluoromethanesulfonyl) imidate (P-3) (0.923 g) was obtained (yield 100%).
¹ H NMR 7.85-8.33 ppm (m, 19H),
¹⁹ F NMR −78.78 ppm (s, 3F), −80.36 ppm (m, 3F), −113.32 ppm (m, 2F), −121.04 ppm (m, 2F), −125.71 ppm (m, 2F)

実施例１において、ビス（ペルフルオロエタンスルホニル）イミドリチウムの代わりに、ビス（ペルフルオロ−１−ブタンスルホニル）イミドリチウム(2.641g, 4.61mmol)を用いた以外は、実施例１と同様に行い、（４―フェニルチオフェニル）ジフェニルスルホニウム ビス（ペルフルオロ−１−ブタンスルホニル）イミデート（Ｐ−４）(1.067g)を得た（収率99.0%）。
¹H NMR 7.87-8.78 ppm (m, 19H)、
¹⁹F NMR −80.42 ppm (m, 6F)、−113.39 ppm (m, 4F)、−121.14 ppm (m, 4F)、−125.73 ppm (m, 4F) [Example 4] Synthesis of (4-phenylthiophenyl) diphenylsulfonium bis (perfluoro-1-butanesulfonyl) imidate (P-4)

Example 1 was carried out in the same manner as in Example 1 except that bis (perfluoro-1-butanesulfonyl) imide lithium (2.641 g, 4.61 mmol) was used instead of bis (perfluoroethanesulfonyl) imide lithium. 4-Phenylthiophenyl) diphenylsulfonium bis (perfluoro-1-butanesulfonyl) imidate (P-4) (1.067 g) was obtained (yield 99.0%).
¹ H NMR 7.87-8.78 ppm (m, 19H),
¹⁹ F NMR −80.42 ppm (m, 6F), −113.39 ppm (m, 4F), −121.14 ppm (m, 4F), −125.73 ppm (m, 4F)

実施例１において、ビス（ペルフルオロエタンスルホニル）イミドリチウムの代わりに、ビス（トリフルオロメタンスルホニル）イミドカリウム(1.472g, 4.61mmol)を用いた以外は、実施例１と同様の操作を行い、（４―フェニルチオフェニル）ジフェニルスルホニウム ビス（トリフルオロメタンスルホニル）イミデート（Ｐ−５）(1.150g)を得た（収率100%）。
¹H NMR 8.06-8.59 ppm (m, 19H)、
¹⁹F NMR −80.41 ppm (s, 6F)
上記の方法で得られたＰ−５をイオンクロマトグラフで測定したところ、臭化物イオンの残存量は検出限界以下（0.1ppm未満）であった。 [Example 5] Synthesis of (4-phenylthiophenyl) diphenylsulfonium bis (trifluoromethanesulfonyl) imidate (P-5)

In Example 1, the same operation as in Example 1 was carried out except that bis (trifluoromethanesulfonyl) imide potassium (1.472 g, 4.61 mmol) was used instead of bis (perfluoroethanesulfonyl) imide lithium, and (4 -Phenylthiophenyl) diphenylsulfonium bis (trifluoromethanesulfonyl) imidate (P-5) (1.150 g) was obtained (yield 100%).
¹ H NMR 8.06-8.59 ppm (m, 19H),
¹⁹ F NMR −80.41 ppm (s, 6F)
When P-5 obtained by the above method was measured by an ion chromatograph, the residual amount of bromide ions was below the detection limit (less than 0.1 ppm).

アセトニトリル(10mL)、水(5mL)が入った50mLの３口フラスコに、室温でトリフェニルスルホニウムブロミド(1.050g、3.06mmol)を加えて均一に溶解させた。次に、ビス（トリフルオロメタンスルホニル）イミドカリウム(0.991g, 3.11mmol)をアセトニトリル(10mL)に溶解させた溶液を、室温で３口フラスコの中に滴下し、滴下後、室温で３時間攪拌した。反応混合物中の溶媒を減圧留去後、残渣に水とクロロホルムを加えてクロロホルム層を分液した。残った水層は、クロロホルムでさらに２回抽出操作を行った。これらのクロロホルム溶液を一緒にした後、硫酸ナトリウムで乾燥後、クロロホルムを減圧留去して、トリフェニルスルホニウム ビス（トリフルオロメタンスルホニル）イミデート（Ｃ−１）(1.640g)を得た（収率98.7%）。
¹H NMR 7.60-7.80 ppm (m, 15H)
¹⁹F NMR −79.24 ppm (s, 6F)
上記の方法で得られたＣ−１をイオンクロマトグラフで測定したところ、臭化物イオンが0.4ppm残存していた。 [Comparative Example 1] Synthesis of triphenylsulfonium bis (trifluoromethanesulfonyl) imidate (C-1)

Triphenylsulfonium bromide (1.050 g, 3.06 mmol) was added to a 50 mL three-necked flask containing acetonitrile (10 mL) and water (5 mL) at room temperature and dissolved uniformly. Next, a solution in which potassium bis (trifluoromethanesulfonyl) imide (0.991 g, 3.11 mmol) was dissolved in acetonitrile (10 mL) was dropped into a three-necked flask at room temperature, followed by stirring at room temperature for 3 hours. . After the solvent in the reaction mixture was distilled off under reduced pressure, water and chloroform were added to the residue, and the chloroform layer was separated. The remaining aqueous layer was further extracted twice with chloroform. These chloroform solutions were combined, dried over sodium sulfate, and then chloroform was distilled off under reduced pressure to obtain triphenylsulfonium bis (trifluoromethanesulfonyl) imidate (C-1) (1.640 g) (yield 98.7). %).
¹ H NMR 7.60-7.80 ppm (m, 15H)
¹⁹ F NMR −79.24 ppm (s, 6F)
When C-1 obtained by the above method was measured by ion chromatography, 0.4 ppm of bromide ions remained.

実施例１において、ビス（ペルフルオロエタンスルホニル）イミドリチウムの代わりに、１，１，２，２，３，３−ヘキサフルオロプロパン−１，３−ジスルホニルイミドリチウム (1.379g, 4.61mmol)を用いた以外は、実施例１と同様の操作を行い、（４―フェニルチオフェニル）ジフェニルスルホニウム １，１，２，２，３，３−ヘキサフルオロプロパン−１，３−ジスルホニルイミデート（Ｐ−６）(1.058g)を得た（収率91.8%）。
¹H NMR 7.87-8.31 ppm (m, 19H)
¹⁹F NMR −119.54 ppm (s, 4F)、−125.79ppm (s, 2F)
上記の方法で得られたＰ−６をイオンクロマトグラフで測定したところ、臭化物イオンの残存量は検出限界以下（0.1ppm未満）であった。 Example 6 Synthesis of (4-phenylthiophenyl) diphenylsulfonium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonylimidate (P-6)

In Example 1, 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonylimide lithium (1.379 g, 4.61 mmol) was used instead of bis (perfluoroethanesulfonyl) imide lithium. The procedure was the same as in Example 1, except that (4-phenylthiophenyl) diphenylsulfonium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonylimidate (P- 6) (1.058 g) was obtained (yield 91.8%).
¹ H NMR 7.87-8.31 ppm (m, 19H)
¹⁹ F NMR −119.54 ppm (s, 4F), −125.79 ppm (s, 2F)
When P-6 obtained by the above method was measured by ion chromatography, the residual amount of bromide ions was below the detection limit (less than 0.1 ppm).

アセトニトリル(10mL)、水(5mL)が入った50mLの３口フラスコに、室温でトリフェニルスルホニウムブロミド(1.080g、3.15mmol)を加えて均一に溶解させた。次に、１，１，２，２，３，３−ヘキサフルオロプロパン−１，３−ジスルホニルイミドカリウム(1.060g, 3.20mmol)をアセトニトリル(10mL)に溶解させた溶液を、室温で３口フラスコの中に滴下し、滴下後、室温で３時間攪拌した。反応混合物中の溶媒を減圧留去後、残渣に水とクロロホルムを加えてクロロホルム層を分液した。残った水層は、クロロホルムでさらに２回抽出操作を行った。これらのクロロホルム溶液を一緒にした後、硫酸ナトリウムで乾燥後、クロロホルムを減圧留去すると、トリフェニルスルホニウム １，１，２，２，３，３−ヘキサフルオロプロパン−１，３−ジスルホニルイミデート（Ｃ−２）(1.580g)を得た（収率90.4%）。
¹H NMR 7.62-7.78 ppm (m, 15H)
¹⁹F NMR −119.86 ppm (s, 4F)、−126.50 ppm (s, 2F)
上記の方法で得られたＣ−２をイオンクロマトグラフで測定したところ、臭化物イオンが0.6ppm残存していた。 [Comparative Example 2] Synthesis of triphenylsulfonium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonylimidate (C-2)

Triphenylsulfonium bromide (1.080 g, 3.15 mmol) was added to a 50 mL three-necked flask containing acetonitrile (10 mL) and water (5 mL) at room temperature and dissolved uniformly. Next, a solution of potassium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonylimide (1.060 g, 3.20 mmol) dissolved in acetonitrile (10 mL) The solution was dropped into the flask and stirred at room temperature for 3 hours. After the solvent in the reaction mixture was distilled off under reduced pressure, water and chloroform were added to the residue, and the chloroform layer was separated. The remaining aqueous layer was further extracted twice with chloroform. These chloroform solutions were combined, dried over sodium sulfate, and then chloroform was distilled off under reduced pressure to obtain triphenylsulfonium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonylimidate. (C-2) (1.580 g) was obtained (yield 90.4%).
¹ H NMR 7.62-7.78 ppm (m, 15H)
¹⁹ F NMR −119.86 ppm (s, 4F), −126.50 ppm (s, 2F)
When C-2 obtained by the above method was measured by ion chromatography, 0.6 ppm of bromide ions remained.

実施例１において、ビス（ペルフルオロエタンスルホニル）イミドリチウムの代わりに、ビス（１，２，２，２−テトラフルオロエタンスルホニル）イミドリチウム(1.619g, 4.61mmol)を用いた以外は、実施例１と同様の操作を行い、（４―フェニルチオフェニル）ジフェニルスルホニウム ビス（１，２，２，２−テトラフルオロエタンスルホニル）イミデート（Ｐ−７）(0.784g)を得た（収率96.9%）。
¹H NMR 7.87-8.36 ppm (m, 19H)、6.47 ppm (m, 2H)
¹⁹F NMR −72.05 ppm (m, 6F)、−192.48 ppm (m, 2F) [Example 7] Synthesis of (4-phenylthiophenyl) diphenylsulfonium bis (1,2,2,2-tetrafluoroethanesulfonyl) imidate (P-7)

In Example 1, Example 1 was used except that bis (1,2,2,2-tetrafluoroethanesulfonyl) imide lithium (1.619 g, 4.61 mmol) was used instead of bis (perfluoroethanesulfonyl) imide lithium. (4-phenylthiophenyl) diphenylsulfonium bis (1,2,2,2-tetrafluoroethanesulfonyl) imidate (P-7) (0.784 g) was obtained (yield 96.9%) .
¹ H NMR 7.87-8.36 ppm (m, 19H), 6.47 ppm (m, 2H)
¹⁹ F NMR −72.05 ppm (m, 6F), −192.48 ppm (m, 2F)

実施例１において、ビス（ペルフルオロエタンスルホニル）イミドリチウムの代わりに、ビス（１，１，２，２−テトラフルオロエタンスルホニル）イミドリチウム(1.619g, 4.61mmol)を用いた以外は、実施例１と同様の操作を行い、（４―フェニルチオフェニル）ジフェニルスルホニウム ビス（１，１，２，２−テトラフルオロエタンスルホニル）イミデート（Ｐ−８）(0.807g)を得た（収率99.9%）。
¹H NMR 7.87-8.78 ppm (m, 19H)、7.15 ppm (m, 2H)
¹⁹F NMR −121.43 ppm (m, 4F)、−134.94ppm (m, 4F) [Example 8] Synthesis of (4-phenylthiophenyl) diphenylsulfonium bis (1,1,2,2-tetrafluoroethanesulfonyl) imidate (P-8)

In Example 1, Example 1 was used except that bis (1,1,2,2-tetrafluoroethanesulfonyl) imide lithium (1.619 g, 4.61 mmol) was used instead of bis (perfluoroethanesulfonyl) imide lithium. (4-phenylthiophenyl) diphenylsulfonium bis (1,1,2,2-tetrafluoroethanesulfonyl) imidate (P-8) (0.807 g) was obtained (yield 99.9%) .
¹ H NMR 7.87-8.78 ppm (m, 19H), 7.15 ppm (m, 2H)
¹⁹ F NMR −121.43 ppm (m, 4F), −134.94 ppm (m, 4F)

実施例１において、ビス（ペルフルオロエタンスルホニル）イミドリチウムの代わりに、ビス（２，３，４，５，６−ペンタフルオロベンゼンスルホニル）イミドナトリウム(2.006g, 4.61mmol)を用いた以外は、実施例１と同様の操作を行い、（４―フェニルチオフェニル）ジフェニルスルホニウム ビス（２，３，４，５，６−ペンタフルオロベンゼンスルホニル）イミデート（Ｐ−９）(0.973g)を得た（収率99.8%）。
¹H NMR 7.89-8.36 ppm (m, 19H)、
¹⁹F NMR −137.69 ppm (m, 4F)、−150.63 ppm (m, 2F)、−161.96 ppm (m, 4F) [Example 9] Synthesis of (4-phenylthiophenyl) diphenylsulfonium bis (2,3,4,5,6-pentafluorobenzenesulfonyl) imidate (P-9)

In Example 1, except that bis (2,3,4,5,6-pentafluorobenzenesulfonyl) imide sodium (2.006 g, 4.61 mmol) was used instead of bis (perfluoroethanesulfonyl) imide lithium The same operation as in Example 1 was carried out to obtain (4-phenylthiophenyl) diphenylsulfonium bis (2,3,4,5,6-pentafluorobenzenesulfonyl) imidate (P-9) (0.973 g). Rate 99.8%).
¹ H NMR 7.89-8.36 ppm (m, 19H),
¹⁹ F NMR −137.69 ppm (m, 4F), −150.63 ppm (m, 2F), −161.96 ppm (m, 4F)

実施例１において、ビス（ペルフルオロエタンスルホニル）イミドリチウムの代わりに、１，１，２，２−テトラフルオロエタン−１，２−ジスルホニルイミドリチウム(1.148g, 4.61mmol)を用いた以外は、実施例１と同様の操作を行い、（４―フェニルチオフェニル）ジフェニルスルホニウム １，１，２，２−テトラフルオロエタン−１，２−ジスルホニルイミデート（Ｐ−１０）(1.154g)を得た（収率100%）。
¹H NMR 7.88-8.35 ppm (m, 19H)
¹⁹F NMR −114.66 ppm (s, 4F) [Example 10] Synthesis of (4-phenylthiophenyl) diphenylsulfonium 1,1,2,2-tetrafluoroethane-1,2-disulfonylimidate (P-10)

In Example 1, except that 1,1,2,2-tetrafluoroethane-1,2-disulfonylimide lithium (1.148 g, 4.61 mmol) was used instead of bis (perfluoroethanesulfonyl) imide lithium, The same operation as in Example 1 was performed to obtain (4-phenylthiophenyl) diphenylsulfonium 1,1,2,2-tetrafluoroethane-1,2-disulfonylimidate (P-10) (1.154 g). (Yield 100%).
¹ H NMR 7.88-8.35 ppm (m, 19H)
¹⁹ F NMR −114.66 ppm (s, 4F)

実施例１において、ビス（ペルフルオロエタンスルホニル）イミドリチウムの代わりに、 ビス（フルオロスルホニル）イミドカリウム (1.011g, 4.61mmol)を用いた以外は、実施例１と同様の操作を行い、（４―フェニルチオフェニル）ジフェニルスルホニウム ビス（フルオロスルホニル）イミデート（Ｐ−１１）(0.634g)を得た（収率99.9%）。
¹H NMR 7.87-8.35 ppm (m, 19H)
¹⁹F NMR 52.33 ppm (s, 2F) [Example 11] Synthesis of (4-phenylthiophenyl) diphenylsulfonium bis (fluorosulfonyl) imidate (P-11)

In Example 1, the same operation as in Example 1 was carried out except that bis (fluorosulfonyl) imide potassium (1.011 g, 4.61 mmol) was used instead of bis (perfluoroethanesulfonyl) imide lithium, and (4- Phenylthiophenyl) diphenylsulfonium bis (fluorosulfonyl) imidate (P-11) (0.634 g) was obtained (yield 99.9%).
^{1 H NMR 7.87-8.35 ppm (m,} 19H)
¹⁹ F NMR 52.33 ppm (s, 2F)

アセトニトリル(10mL)、水(2mL)が入った50mLの３口フラスコに、室温でビス（ペルフルオロエタンスルホニル）イミドリチウム (2.062g, 5.33mmol)を加えて均一に溶解させた。（１―ナフチル）ジフェニルスルホニウム トリフルオロメタンスルホネート(0.600g、1.33mmol)をアセトニトリル(10mL)に溶解させた溶液を、室温で３口フラスコの中に滴下し、滴下後、室温で３時間攪拌した。反応混合物中の溶媒を減圧留去後、残渣に水とクロロホルムを加えてクロロホルム層を分液した。さらに残った水層は、クロロホルムで２回抽出操作を行った。これらのクロロホルム溶液を一緒にした後、硫酸ナトリウムで乾燥後、クロロホルムを減圧留去して、（１―ナフチル）ジフェニルスルホニウム ビス（ペルフルオロエタンスルホニル）イミデート（Ｐ−１２）(0.796g)を得た（収率86.2%）。
¹H NMR 8.00-8.99 ppm (m, 17H)
¹⁹F NMR −78.49 ppm (s, 6F)、−117.33 ppm (s, 4F) [Example 12] Synthesis of (1-naphthyl) diphenylsulfonium bis (perfluoroethanesulfonyl) imidate (P-12)

Bis (perfluoroethanesulfonyl) imidolithium (2.062 g, 5.33 mmol) was added to a 50 mL three-necked flask containing acetonitrile (10 mL) and water (2 mL) at room temperature and dissolved uniformly. A solution prepared by dissolving (1-naphthyl) diphenylsulfonium trifluoromethanesulfonate (0.600 g, 1.33 mmol) in acetonitrile (10 mL) was dropped into a three-necked flask at room temperature, and the mixture was stirred at room temperature for 3 hours. After the solvent in the reaction mixture was distilled off under reduced pressure, water and chloroform were added to the residue, and the chloroform layer was separated. The remaining aqueous layer was extracted twice with chloroform. These chloroform solutions were combined, dried over sodium sulfate, and then chloroform was distilled off under reduced pressure to obtain (1-naphthyl) diphenylsulfonium bis (perfluoroethanesulfonyl) imidate (P-12) (0.796 g). (Yield 86.2%).
¹ H NMR 8.00-8.99 ppm (m, 17H)
¹⁹ F NMR −78.49 ppm (s, 6F), −117.33 ppm (s, 4F)

[Example 13] Synthesis of (4-phenylthiophenyl) diphenylsulfonium bis (perfluoroethanesulfonyl) imidate (P-1) In Example 1, instead of (4-phenylthiophenyl) diphenylsulfonium trifluoromethanesulfonate, ( 4-phenylthiophenyl) diphenylsulfonium The same procedure as in Example 1 was performed, except that 1,1,2,2-tetrafluoroethanesulfonate (0.635 g, 1.15 mmol) was used, and (4-phenylthiophenyl) Diphenylsulfonium bis (perfluoroethanesulfonyl) imidate (P-1) (0.856 g) was obtained (yield 99.1%).

  Since the sulfonium salt obtained in the present invention is free of halide ions, it can be used as a photoacid generator in various applications such as paints, coating agents, photo-curing adhesives, and semiconductor photolithography fields.

Claims (4)

The following general formula (1):

{Wherein R ¹ , R ² , and R ³ are each independently an alkyl group having 1 to 8 carbon atoms, a naphthyl group, or the following general formula (2):

(In the formula, A is any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenoxy group, an alkylthio group having 1 to 8 carbon atoms, or a phenylthio group. Wherein x is an integer of 1 to 8 and y is 0 or 1. } And the following general formula (3):

{Wherein M is Ma or Mb _1/2 , Ma is an alkali metal, Mb _1/2 is an alkaline earth metal, and Rf and Rf ′ are each independently F, C ₆ F ₅ or C _a F _{2a + 1-b} H _b (a is an integer of 1 to 8, and b is 0 or 1), or the following general formula (4):

(Wherein n is an integer of 1 to 5 and M is the same as described above). } Is contacted and mixed with a sulfonimide salt represented by the following general formula (5):

{Wherein R ¹ , R ² and R ³ are the same as those defined in the general formula (1), and Rf and Rf ′ are the same as those defined in the general formula (3). It is. } The manufacturing method of the sulfonium salt represented by this. In the general formula (1), R ¹ , R ² , and R ³ are each independently an alkyl group having 1 to 4 carbon atoms, a naphthyl group, or A in the formula is a hydrogen atom, a halogen atom, or a carbon number of 1 An aryl group represented by the above general formula (2), which is any one of -4 alkyl groups, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, an alkylthio group having 1 to 4 carbon atoms, or a phenylthio group; Yes, x is an integer of 1-4, and y is 0 or 1, The manufacturing method of the sulfonium salt represented by General formula (5) of Claim 1 characterized by the above-mentioned. In the general formula (3), Rf and Rf ′ are each independently F, C ₆ F ₅ or C _a F _{2a + 1-b} H _b (a is an integer of 1 to 6 and b is 0 or Or a structure represented by the general formula (4), wherein n is an integer of 1 to 4, in the general formula (5) according to claim 1, The manufacturing method of the sulfonium salt represented.   The manufacturing method of the sulfonium salt represented by General formula (5) of any one of Claims 1-3 whose M is an alkali metal in the said General formula (3).