JP4993462B2 - Method for producing fluorine compound - Google Patents

Description

  The present invention relates to a method for producing ω-fluorosulfonylperfluoroalkyl vinyl ether and a synthetic intermediate thereof, which are raw materials for fluorine-based solid electrolyte polymers useful for fuel cells and salt electrolysis processes.

しかしながら、電解フッ素化工程は副生成物が多く、ＦＣＯ（ＣＦ_２）_３ＳＯ_２Ｆの収率は低い。また、ＨＦＰＯ付加工程及びビニル化工程においても満足のいく収率が得られておらず、経済的に有利な製造法にするためには更なる生産効率の向上が必要である。The ω-fluorosulfonyl compound represented by the general formula (3) or the general formula (3 ′), which is a synthetic intermediate of the ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the general formula (2) or the general formula (2 ′) As an example of the production method, for example, in the case of FCO (CF ₂ ) ₂ SO ₂ F, a production method using tetrafluoroethylene, dimethyl carbonate and sodium ethyl mercaptide as starting materials is disclosed. This method has a problem that the reaction step is long and the yield is low (for example, see Patent Document 1).
As the formula (2) or the manufacturing method of the ω- fluorosulfonyl perfluoroalkyl vinyl ether of the formula (2 '), for example, in the case of _{CF 2 = CFO (CF 2)} 4 SO 2 F, in Scheme 1 As shown, methods using an sultone compound as a starting material and an electrolytic fluorination step, an addition step of hexafluoropropylene oxide (HFPO), and a vinylation step have been reported (see, for example, Patent Document 2 and Patent Document 3).

However, the electrolytic fluorination process has many by-products, and the yield of FCO (CF ₂ ) ₃ SO ₂ F is low. In addition, satisfactory yields have not been obtained in the HFPO addition step and the vinylation step, and further production efficiency needs to be improved in order to obtain an economically advantageous production method.

Further, as a method for producing ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1) or the general formula (1 ′), α, ω-dihaloperfluoroalkane is converted into dithione as shown in Scheme 2. A method of reacting with sodium acid and producing by chlorination and fluorination has been reported (for example, see Non-Patent Document 1). In this method, after the chlorination reaction, the target compound ω-haloperfluoroalkylsulfonyl chloride is isolated by distillation. However, it is difficult to separate by distillation, and the thermal stability of ω-haloperfluoroalkylsulfonyl chloride is further reduced. However, due to decomposition during distillation, the distillation yield was low, and it was difficult to produce the target compound advantageously industrially.

JP 56-90054 US Pat. No. 6,624,328 WO2004 / 60849 Weiming Qiu and Donald J. Burton, Journal of Fluorine Chemistry, 60: 93-100 (1993)

  In view of such a current situation, the present invention provides a method for producing ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the general formula (2) or the general formula (2 ′) and a synthetic intermediate thereof in a high yield. It is for the purpose.

As a result of intensive studies to solve the above problems, the present inventors have used ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1) or the general formula (1 ′) as a raw material. A method for efficiently producing ω-fluorosulfonylperfluoroalkyl vinyl ether represented by (2) or general formula (2 ′), and ω-haloperfluoro represented by general formula (1) or general formula (1 ′) The present invention was completed by developing a method for efficiently producing alkylsulfonyl fluoride or a synthetic intermediate thereof.
That is, the present invention is as follows.

1. As a raw material, the following general formula (1 ′)
X (CF ₂ ) _m SO ₂ F (1 ′)
(X is a halogen atom selected from I and Br, and m is an integer of 3 to 10.)
From ω-haloperfluoroalkylsulfonyl fluoride represented by the following general formula (2 ′)
CF ₂ = CFO (CF ₂ CF (CF ₃ ) O) _{n ′} (CF ₂ ) _m SO ₂ F (2 ′)
(N ′ is an integer of 0 to 2, and m is the same as in the general formula (1 ′).)
A method for producing ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the following method, which comprises the following steps (a ′) to (c ′):
(A ′) A step of producing an ω-fluorosulfonyl compound represented by the following general formula (3 ′) by treating the ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1 ′) with an oxidizing agent. ,
FCO (CF ₂ ) _m-1 SO ₂ F (3 ′)
(M is the same as in the general formula (1 ′).)
(B ′) An acid represented by the following general formula (4 ′) by reacting the ω-fluorosulfonyl compound represented by the general formula (3 ′) obtained in the step (a ′) with hexafluoropropylene oxide. Step of producing a fluoride compound, and CF ₃ CF (COF) O (CF ₂ CF (CF ₃ ) O) _{n ′} (CF ₂ ) _m SO ₂ F (4 ′)
(N ′ is the same as the general formula (2 ′), and m is the same as the general formula (1 ′).)
(C ′) A step of converting the acid fluoride compound represented by the general formula (4 ′) obtained in the step (b ′) to an ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the general formula (2 ′). .
2. 1. The oxidizing agent used in the step (a ′) is SO ₃ or fuming sulfuric acid. The method described in 1.
3. At least the ω-fluorosulfonyl compound represented by the above general formula (3 ′) obtained in the step (a ′) and the following general formula (5 ′) which is a by-product.
FSO ₂ O (CF ₂ ) _m SO ₂ F (5 ′)
(M is the same as in the general formula (1 ′).)
A reaction mixture containing a sulfonyl fluoride compound represented by
1 ′) A sulfonyl fluoride compound represented by the above general formula (5 ′) in the reaction mixture by contacting with an alkali metal salt, alkaline earth metal salt, or Lewis base is converted into the above general formula (3 ′). Converted to an ω-fluorosulfonyl compound represented by
2 ′) Subsequently, the ω-fluorosulfonyl compound represented by the general formula (3 ′) obtained by the operation of 1 ′) is used in the step (b ′).
2. The method described in 1.
4). At least the ω-fluorosulfonyl compound represented by the general formula (3 ′) obtained in the step (a ′) and the sulfonyl fluoride compound represented by the general formula (5 ′) as a by-product. From a reaction mixture comprising
3 ′) separating and removing the ω-fluorosulfonyl compound represented by the general formula (3 ′),
4 ′) The sulfonyl fluoride compound represented by the above general formula (5 ′) in the resulting reaction residue is brought into contact with an alkali metal salt, alkaline earth metal salt, or Lewis base, and the above general formula Converted to an ω-fluorosulfonyl compound represented by (3 ′),
5 ′) Next, the ω-fluorosulfonyl compound represented by the general formula (3 ′) obtained in the step 4 ′) is used in the step (b ′).
2. The method described in 1.
5). In the step (b ′), the ω-fluorosulfonyl compound represented by the general formula (3 ′) and hexafluoropropylene oxide are represented by the following general formula (6) in the presence of a fluorine ion-containing compound.
R ¹ O (R ² O) _p R ¹ (6)
(R ¹ is an alkyl group having 1 to 5 carbon atoms, R ² is C ₂ H ₄ or C ₃ H _6. P is an integer of 0 to 10)
The following general formula (4 ″) in which n ′ = 0 in the above general formula (4 ′), which comprises reacting in the presence of a mixed solvent of an ether solvent and a carboxylic acid dinitrile solvent
CF ₃ CF (COF) O (CF ₂ ) _m SO ₂ F (4 ″)
(M is the same as in the general formula (1 ′).)
1. A process for producing an acid fluoride compound represented by the above 1. The method described in 1.
6). 4. The mass ratio of the carboxylic acid dinitrile solvent in the mixed solvent of the ether solvent represented by the general formula (6) and the carboxylic acid dinitrile solvent is 30% by mass to 99% by mass. The method described.
7). In the step (c ′), the acid fluoride compound represented by the general formula (4 ″) is converted into a carboxylate, and then the carboxylate is thermally decomposed. In the general formula (2 ′), n A method for producing ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the following general formula (2 ″) in which “= 0”, wherein the target product is ω-fluoro represented by the following general formula (2 ″). When the number of moles of sulfonyl perfluoroalkyl vinyl ether formed is r and the number of moles of acid fluoride compound represented by the above general formula (4 ″) regenerated as a by-product is s, [s] / [r + s] The above-mentioned 1. is a step characterized in that the reaction is carried out at a production ratio of the by-product represented by 0.1 or less. The method described in 1.
CF ₂ = CFO (CF ₂ ) _m SO ₂ F (2 ″)
(M is the same as in the general formula (1 ′).)
8). The carboxylate salt derived from the acid fluoride compound represented by the general formula (4 ″) is a potassium salt represented by the following general formula (7), and thermal decomposition of the carboxylate is carried out without solvent. The method according to 7 above, which is performed.
CF ₃ CF (CO ₂ K) O (CF ₂ ) _m SO ₂ F (7)
(M is the same as in the general formula (1 ′).)
9. 6. The thermal decomposition of the carboxylate is performed while the carboxylate is kept in a solid state. Or 8. The method described in 1.
10. The ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1 ′) is obtained by the following steps (i) to (iv): Method described in:
(I) The following general formula (8)
X (CF ₂ ) _m X (8)
(X and m are the same as those in the general formula (1 ′).)
A dithionite selected from an alkali metal salt type, an alkaline earth metal salt type, a quaternary ammonium salt type, and a quaternary phosphonium salt type. After mixing and stirring, the following general formula (9)
X (CF ₂ ) _m SO ₂ M (9)
(In the formula, M is Ma, Mb _1/2 , a quaternary ammonium radical or a quaternary phosphonium radical, Ma is an alkali metal, and Mb is an alkaline earth metal. X and m are the above general formulas ( Same as 1 ').
A process for producing an ω-haloperfluoroalkylsulfinate represented by:
(Ii) separating the ω-haloperfluoroalkylsulfinate represented by the general formula (9) from the reaction mixture obtained in step (i),
(Iii) ω-haloperfluoroaurea represented by the above general formula (9) obtained in step (ii)
A ruchlorsulfinate is treated with a chlorinating agent to give the following general formula (10)
X (CF ₂ ) _m SO ₂ Cl (10)
(X and m are the same as those in the general formula (1 ′).)
A process for producing ω-haloperfluoroalkylsulfonyl chloride represented by:
(Iv) The ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) obtained in the step (iii) is treated with a fluorine ion-containing compound, and the ω represented by the general formula (1 ′) is obtained. -A step of producing haloperfluoroalkylsulfonyl fluoride.
11. The step (ii) is at least the ω-haloperfluoroalkylsulfinate represented by the general formula (9) obtained by the reaction of the step (i) and a by-product of the following general formula (11)
MO ₂ S (CF ₂ ) _m SO ₂ M (11)
(M is the same as the general formula (9), and m is the same as the general formula (1 ′).)
10. The operation of extracting and separating the ω-haloperfluoroalkylsulfinate represented by the general formula (9) from the reaction mixture containing the perfluoroalkyl-α, ω-bissulfinate represented by formula (9). The method described in 1.
12 10. The step 10. above wherein the step (ii) includes the following step (ii-1) and step (ii-2). The method described in 1.
(Ii-1) At least unreacted α, ω-dihaloperfluoroalkane obtained in the step (i) and represented by the general formula (9), which is the target compound. From the reaction mixture containing ω-haloperfluoroalkylsulfinate and perfluoroalkyl-α, ω-bissulfinate represented by the general formula (11) as a by-product, the above formula (8) Removing the represented α, ω-dihaloperfluoroalkane,
(Ii-2) At least the ω-haloperfluoroalkylsulfinate represented by the general formula (9) obtained in the step (ii-1) and the perfluoroalkyl-α represented by the general formula (11) Extracting and separating the ω-haloperfluoroalkylsulfinate represented by the general formula (9) from the mixture containing ω-bissulfinate.
13. The α, ω-di represented by the above general formula (8) is obtained by treating the reaction residue after separating and removing the ω-haloperfluoroalkylsulfinate represented by the general formula (9) with a chlorinating agent. 10. The haloperfluoroalkane and / or the ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) is produced, and these are reused in the step (i) and / or the step (iv). -12. The method as described in any one of.
14 After separating and removing the ω-haloperfluoroalkylsulfinate represented by the general formula (9), at least the perfluoroalkyl-α, ω-bissulfinate and the inorganic iodine represented by the general formula (11) are removed. An aqueous solution in which a reaction residue containing at least one inorganic salt selected from a chloride or an inorganic bromide is dissolved is treated with a chlorinating agent, and at least one of iodine or bromine and the following general formula (12):
ClO ₂ S (CF ₂ ) _m SO ₂ Cl (12)
(M is the same as in the general formula (1 ′).)
Perfluoroalkyl-α, ω-bissulfonyl chloride represented by the following formula, and then the reaction mixture is extracted with a poorly water-soluble organic solvent, whereby α, ω-diform represented by the general formula (8) is obtained. 10. The haloperfluoroalkane and / or the ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) is produced and separated, and these are reused in the step (i) and / or the step (iv). -12. The method as described in any one of.
15. By treating the reaction residue after separating and removing the ω-haloperfluoroalkylsulfinate represented by the general formula (9) with a chlorinating agent, the perfluoroalkyl-α represented by the general formula (12) is obtained. , Ω-bissulfonyl chloride, and then reacting the perfluoroalkyl-α, ω-bissulfonyl chloride with iodine or bromine to produce α, ω-dihaloperfluoroalkane represented by the general formula (8) and 10./. The ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) is produced and separated, and these are reused in the step (i) and / or the step (iv). -12. Any one of
The method described.
16. An α, ω-dihaloperfluoroalkane represented by the above general formula (8) comprising reacting the perfluoroalkyl-α, ω-bissulfonyl chloride represented by the general formula (12) with iodine or bromine; Alternatively, the ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) is produced, and these are reused in the step (i) and / or the step (iv). -12. The method as described in any one of.
17. In the compounds represented by the general formulas (1 ′) to (5 ′), (7) to (12), (2 ″), and (4 ″), m is an integer of 4 to 8. And 2. -16. The method as described in any one of these.
18. In the compounds represented by the general formulas (1 ′) to (5 ′), (7) to (12), (2 ″), and (4 ″), m is an integer of 4 to 6. And 2. -16. The method as described in any one of these.
19. In the compounds represented by the general formulas (2 ′) and (4 ′), n or n ′ is 0. ~ 4. 10. -15. And 17. -18. The method as described in any one of these. 20. In the compounds represented by the general formulas (1 ′) and (8) to (10), X is an iodine atom. ~ 4. And 10. -18. The method as described in any one of these.
21. 10. above. A process for producing ω-haloperfluoroalkylsulfonyl fluoride represented by the above general formula (1 ′), comprising the steps (i) to (iv) described in 1.
22. Above 11. -15. A process for producing an ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1 ′), comprising the step according to any one of the above.

  According to the present invention, there is provided a method for producing ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the above general formula (2) or general formula (2 ′) and a synthetic intermediate thereof in a high yield.

The present invention is described in detail below.
From steps (a) to (c), the ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1) is used as a raw material, and the ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the general formula (2) is obtained. By the manufacturing method and steps (a ′) to (c ′), the ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1 ′) is used as a raw material, and the general formula (2 ′) is used. The method for producing ω-fluorosulfonylperfluoroalkyl vinyl ether will be described.

で表されるω−ハロペルフルオロアルキルスルホニルフルオリドにおいて、Ｒ_ｆは炭素原子数１〜９の２価のペルフルオロカーボン基、ＸはＩ又はＢｒから選ばれるハロゲン原子、Ｙはフッ素原子、炭素原子数１〜３のペルフルオロアルキル基、又はＲ_ｆとの連結基（炭素原子数１〜３）を表す。以下、構造

を−ＣＦＹ−と表すこともある。−ＣＦＹ−Ｒ_ｆ−は炭素原子数３〜１０の２価のペルフルオロカーボン基である。
ＸとしてはＩ又はＢｒが好ましいが、反応性の面ではＩがより好ましい。
−ＣＦＹ−Ｒ_ｆ−は炭素原子数３〜１０の２価のペルフルオロカーボン基であるが、直鎖構造でも分岐構造でもよいし、環状構造を含んでもよい。
−ＣＦＹ−Ｒ_ｆ−の例としては、
−（ＣＦ_２）_ｍ− （ｍは３〜１０の範囲の整数）

等が挙げられ、特に−（ＣＦ_２）_ｍ−が好ましい。First, step (a) and step (a ′) will be described.
The following general formula (1) used in the present invention

In the ω-haloperfluoroalkylsulfonyl fluoride represented by the formula: R _f is a divalent perfluorocarbon group having 1 to 9 carbon atoms, X is a halogen atom selected from I or Br, Y is a fluorine atom, 1 to 3 perfluoroalkyl groups, or a linking group to R _f (1 to 3 carbon atoms). Below, the structure

May be represented as -CFY-. —CFY—R _f — is a divalent perfluorocarbon group having 3 to 10 carbon atoms.
X is preferably I or Br, but I is more preferable in terms of reactivity.
—CFY—R _f — is a divalent perfluorocarbon group having 3 to 10 carbon atoms, and may have a linear structure, a branched structure, or a cyclic structure.
_{-CFY-R f} - Examples of the
_{- (CF 2) m - (} m is in the range of 3-10 integer)

In particular, — (CF ₂ ) _m — is preferable.

（Ｒ_ｆ及びＹは上記一般式（１）と同じである。）
又は下記一般式（３’）
ＦＣＯ（ＣＦ_２）_ｍ−１ＳＯ_２Ｆ （３’）
（ｍは上記一般式（１’）と同じである。）
で表されるω−フルオロスルホニル化合物を得ることができる。上記一般式（３）で表されるω−フルオロスルホニル化合物において、Ｒ_ｆとＹは多様な組み合わせが可能であり、例えば

が挙げられる。In the ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1), the structure in which —CFY—R _f — is — (CF ₂ ) _m — has the following general formula (1 ′)
X (CF ₂ ) _m SO ₂ F (1 ′)
It corresponds to ω-haloperfluoroalkylsulfonyl fluoride represented by In the ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1 ′), m is preferably an integer in the range of 3 to 10. Easiness of synthesis and purification and ω- represented by the above general formula (2 ′) or general formula (2 ″) derived from ω-haloperfluoroalkylsulfonyl fluoride represented by the above general formula (1 ′) From the operability and functionality of fluorosulfonylperfluoroalkyl vinyl ether, m is more preferably 4-8, still more preferably 4-6, and particularly preferably 4.
The ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1) or the general formula (1 ′) is treated with an oxidant to give the following general formula (3).

(R _f and Y are the same as those in the general formula (1).)
Or the following general formula (3 ′)
FCO (CF ₂ ) _m-1 SO ₂ F (3 ′)
(M is the same as in the general formula (1 ′).)
Can be obtained. In the ω-fluorosulfonyl compound represented by the general formula (3), R _f and Y can be variously combined.

Is mentioned.

The ω-fluorosulfonyl compound represented by the general formula (3 ′) has high practicality and is particularly preferable. In the ω-fluorosulfonyl compound represented by the general formula (3 ′), m is more preferably 4 to 8 and still more preferably 4 to 6 for the same reason as the general formula (1 ′). Particularly preferably 4.
The oxidizing agent is not particularly limited as long as it can oxidize the X-CYF-group and convert it into an O = CY-group. Examples thereof include SO ₃ , fuming sulfuric acid, ClSO ₃ H, FSO ₃ H, NO ₂ , O ₂ , electrolytic oxidation and the like can be mentioned. Of these, SO ₃ or fuming sulfuric acid is preferred. Various catalysts and additives may be added to promote the reaction. For example, oxides such as HgO and P ₂ O ₅ and chlorides such as PCl ₅ and SbCl ₅ may be used as the catalyst.
When SO ₃ or fuming sulfuric acid is used as the oxidizing agent, the reaction temperature is preferably in the range of 20 ° C. to 150 ° C., more preferably in the range of 30 ° C. to 130 ° C., and particularly preferably in the range of 40 ° C. to 120 ° C. . When SO ₃ is used, it should be used in the range of 0.1 to 100 mol with respect to 1 mol of ω-haloperfluoroalkylsulfonyl fluoride represented by the above general formula (1) or general formula (1 ′). It is preferable to use in the range of 1 to 20 mol. In addition, when fuming sulfuric acid is used, various concentrations can be adopted as the concentration of SO _{3 in} the fuming sulfuric acid, but in terms of reaction rate, it is preferably 10% by mass or more, more preferably 30% by mass or more. is there. The fuming sulfuric acid is used in an amount of 0.1 to 100 mol as an effective SO ₃ amount of fuming sulfuric acid with respect to 1 mol of the ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1) or the general formula (1 ′). Preferably, it is used in the range of 1 to 20 mol.

The reaction time is not particularly limited, and it is sufficient that the reaction proceeds to some extent, for example, about 0.1 to 100 hours. Although the reaction method is not particularly limited, a mixture of ω-haloperfluoroalkylsulfonyl fluoride represented by the above general formula (1) or general formula (1 ′) and SO ₃ or fuming sulfuric acid is heated to reflux under normal pressure. Alternatively, SO ₃ or fuming sulfuric acid is added dropwise to the heated ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1) or general formula (1 ′), and the reaction product is distilled at the same time. You can take it. Further, a mixture of ω-haloperfluoroalkylsulfonyl fluoride represented by the above general formula (1) or general formula (1 ′) and SO ₃ or fuming sulfuric acid may be added to a pressurized container and heated.
When SO ₃ or fuming sulfuric acid is used as the oxidizing agent, the above general formula (1) or the above general formula (1) or the general formula (1 ′) represented by the general formula (1) 3) or the ω-fluorosulfonyl compound represented by the above general formula (3 ′) and the following general formula (5) as a by-product
_{FSO 2 O-CFY-R f} -SO 2 F (5)
(R _f and Y are the same as those in the general formula (1).)
Or the following general formula (5 ′)
FSO ₂ O (CF ₂ ) _m SO ₂ F (5 ′)
(M is the same as in the general formula (1 ′).)
Is included in the reaction mixture.

When the sulfonyl fluoride compound represented by the general formula (5) or the general formula (5 ′) is brought into contact with an alkali metal salt, an alkaline earth metal salt or a Lewis base, the general formula (3) Or an ω-fluorosulfonyl compound represented by the general formula (3 ′). For this reason, SO ₃ dissolved in the reaction mixture is washed and removed with concentrated sulfuric acid, and then directly contacted with an alkali metal salt, an alkaline earth metal salt, or a Lewis base, and the target compound is obtained by distillation operation. The ω-fluorosulfonyl compound represented by the general formula (3) or the general formula (3 ′) can be obtained. The SO ₃ dissolved in the reaction mixture is washed with concentrated sulfuric acid, removed, and then subjected to distillation operation to obtain the target compound ω-fluorosulfonyl represented by the general formula (3) or general formula (3 ′). After separating the compound, the distillation residue containing the sulfonyl fluoride compound represented by the general formula (5) or the general formula (5 ′) is contacted with an alkali metal salt, an alkaline earth metal salt, or a Lewis base, and distilled. The ω-fluorosulfonyl compound represented by the above general formula (3) or general formula (3 ′), which is the target compound, can also be obtained by the operation.
Alkali metal salts used in the above reaction include LiF, LiI, NaF, NaI, KF, KI, CsF, etc., alkaline earth metal salts such as MgF ₂ and CaF ₂ , Lewis bases such as trimethylamine, triethylamine, 1,8 -Diazabicyclo [5,4,0] undec-7-ene, 1,5-diazabicyclo [4,3,0] non-5-ene, N, N-diisopropylethylamine, etc., among which KF, N, N-diisopropylethylamine is preferred.
The amount of the alkali metal salt, alkaline earth metal salt, or Lewis base used is from 0.001 mol to 1 mol of the sulfonyl fluoride compound represented by the general formula (5) or the general formula (5 ′). It is preferably used in the range of 5 mol.

The reaction time is not particularly limited, and may be, for example, about 0.1 to 100 hours.
The reaction temperature is preferably in the range of 10 ° C to 220 ° C, more preferably in the range of 20 ° C to 200 ° C, and particularly preferably in the range of 30 ° C to 180 ° C.
Although the reaction method is not particularly limited, the above general formula (5) or general formula (5 ′) may be used for the alkali metal salt, alkaline earth metal salt, or Lewis base heated in the absence of solvent or in the presence of a solvent at normal pressure. The reaction product may be distilled simultaneously with the dropwise addition of the sulfonyl fluoride compound represented, or the sulfonyl fluoride compound represented by the general formula (5) or the general formula (5 ′) and the alkali metal salt, An alkaline earth metal salt or a mixture of Lewis bases may be heated to reflux. Alternatively, a mixture of the sulfonyl fluoride compound represented by the general formula (5) or the general formula (5 ′) and the above alkali metal salt, alkaline earth metal salt, or Lewis base may be added to a pressurized container and heated. Good.
When using a solvent, ether solvents such as diglyme, triglyme and tetraglyme,
Examples include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone, and polar solvents such as sulfolane. One type may be used, or a plurality of organic solvents may be combined. It doesn't matter.
After completion of the reaction, the ω-fluorosulfonyl compound represented by the above general formula (3) or general formula (3 ′), which is the target compound, can be obtained by distillation.

Next, the step (b) and the step (b ′) will be described.
By performing the reaction of the ω-fluorosulfonyl compound represented by the general formula (3) or the general formula (3 ′) obtained by the above method with hexafluoropropylene oxide (HFPO) by a known method, Formula (4)
_{CF 3 CF (COF) O (} CF 2 CF (CF 3) O) n -CFY-R f -SO 2 F (4)
(N is an integer of 0 to 2, and R _f and Y are the same as those in the general formula (1).)
Or the following general formula (4 ′)
CF ₃ CF (COF) O (CF ₂ CF (CF ₃ ) O) _{n ′} (CF ₂ ) _m SO ₂ F (4 ′)
(N ′ is an integer of 0 to 2, and m is the same as in the general formula (1 ′).)
The acid fluoride compound represented by this can be obtained.
Among the acid fluoride compounds represented by the general formula (4) or the general formula (4 ′), the present inventors have particularly high practicality, and the following n ′ = 0 in the general formula (4 ′). General formula (4 ")
CF ₃ CF (COF) O (CF ₂ ) _m SO ₂ F (4 ″)
(M is the same as in the general formula (1 ′).)
As a result of detailed investigation on the conditions for producing the acid fluoride compound represented by the formula (3 ′) from the ω-fluorosulfonyl compound represented by the above general formula (3 ′), an industrially advantageous production method was found. The method will be described.
In the acid fluoride compound represented by the general formula (4 ″), m is an integer of 3 to 10, and more preferably 4 to 8 for the same reason as the general formula (1 ′). More preferably, it is 4-6, and particularly preferably 4.

As a method for producing an acid fluoride compound (that is, CF ₃ CF (COF) O (CF ₂ ) ₄ SO ₂ F) in which m = 4 in the general formula (4 ″), diglyme is reacted in Patent Document 2. As a solvent, in the presence of KF, a method of reacting an equal amount of HFPO with an ω-fluorosulfonyl compound having m = 4 in the general formula (3 ′) (that is, with respect to 1 mol of FCO (CF ₂ ) ₃ SO ₂ F1 A method using 1 mol of HFPO is disclosed.The high-boiling compound in which the acid fluoride compound as the target product is obtained by the method described in Patent Document 2, but HFPO is further added as a by-product. In Patent Document 3, in order to suppress the formation of the by-product, ω-fluorosulfonate is used in the presence of KF using diglyme as a reaction solvent. A method is disclosed in which the amount of HFPO used is reduced with respect to the compound (ie, 0.77 mol of HFPO is used per 1 mol of FCO (CF ₂ ) ₃ SO ₂ F). In the method described in Document 3, although the production of the by-product is reduced, a large amount of the ω-fluorosulfonyl compound remains unreacted, so that the production efficiency is poor and it can be said to be an industrially advantageous production method. Absent.

As a result of studies on various reaction solvents, the present inventors have found that the following general formula (6)
R ¹ O (R ² O) _p R ¹ (6)
^{(R 1} is an alkyl group having 1 to 5 carbon atoms, ^{R 2} is .p is _C 2 _{H 4} or _C 3 _{H 6} is an integer of 0-10.)
In the presence of a mixed solvent of an ether solvent and a carboxylic acid dinitrile solvent, the ω-fluorosulfonyl compound (FCO (CF ₂ ) ₃ SO ₂ F) is reacted with an equal amount or more of HFPO. However, the acid fluoride compound (CF ₃ CF (COF) O (CF ₂ ) ₄ SO ₂ F), which is the target product, was obtained in a high yield and with high selectivity, and the above-mentioned by-product that was a problem in the above It was found that the amount of product produced and the residual amount of the ω-fluorosulfonyl compound were reduced.
Examples of the ether solvent represented by the general formula (6) include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, Examples include tetraethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, tolpropylene glycol dimethyl ether, and tetrapropylene glycol dimethyl ether. The carboxylic acid dinitrile solvent is a saturated aliphatic dicarboxylic acid having 3 to 8 carbon atoms, such as adiponitrile. The mass ratio of the carboxylic acid dinitrile in the mixed solvent of the ether solvent and the carboxylic acid dinitrile solvent is preferably 30% by mass to 99% by mass, more preferably 40% by mass to 97% by mass, and more preferably 50% by mass. It is particularly preferably 95% by mass or less.

In the above reaction, the amount of HFPO used is preferably 0.95 mol to 2 mol, more preferably 0.98 mol to 1.8 mol, and more preferably 1 mol to 1 mol of the ω-fluorosulfonyl compound. 1.5 mol is particularly preferred.
There is no restriction | limiting in particular about reaction pressure, For example, you may carry out under normal pressure or pressurization, but in order to make it react efficiently, the pressurization reaction in a pressurization container is preferable. The pressure in the pressure reaction is not limited, but it is preferable to introduce HFPO in a gauge pressure range of 0.01 MPa to 0.1 MPa.
In the above reaction, various fluorine ion-containing compounds such as alkali metal fluoride and quaternary ammonium fluoride are used as a catalyst, and among them, KF and CsF are more preferable. The amount of the fluorine ion-containing compound in the catalyst is not limited, but it may be usually about 0.001 mol to 1 mol with respect to 1 mol of the ω-fluorosulfonyl compound.
The reaction temperature is preferably in the range of -30 ° C to 50 ° C, more preferably in the range of -20 ° C to 30 ° C.
The reaction time is not particularly limited and depends on the time when HFPO is consumed, but is, for example, 0.5 to 72 hours.
After completion of the reaction, the contents are separated into two layers (the upper layer is a mixed solvent of an ether solvent and a carboxylic acid dinitrile solvent, and the lower layer is a reaction mixture containing an acid fluoride compound represented by the above general formula (4 ″)). Therefore, the acid fluoride compound represented by the general formula (4 ″) can be obtained by liquid separation and taking out the lower layer portion and performing a distillation operation.

Next, the step (c) and the step (c ′) will be described.
The acid fluoride compound represented by the above general formula (4), general formula (4 ′) or general formula (4 ″) obtained by the above method is represented by the following general formula (2).
_{CF 2 = CFO (CF 2 CF} (CF 3) O) n -CFY-R f -SO 2 F (2)
(N is an integer of 0 to 2, and R _f and Y are the same as in the general formula (1).)
Or the following general formula (2 ')
CF ₂ = CFO (CF ₂ CF (CF ₃ ) O) _{n ′} (CF ₂ ) _m SO ₂ F (2 ′)
(N ′ is an integer of 0 to 2, and m is the same as the general formula (1 ′).)
Or the following general formula (2 ")
CF ₂ = CFO (CF ₂ ) _m SO ₂ F (2 ″)
(M is the same as the above general formula (1 ′).)
To ω-fluorosulfonylperfluoroalkyl vinyl ether represented by The ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the general formula (2 ″) is particularly preferable because of its high practicality. Further, in the general formula (2 ″), m is preferably an integer in the range of 3 to 10. From the easiness of synthesis and purification, and operability / functionality, it is more preferably 4 to 8, still more preferably 4 to 6, and particularly preferably 4.
From the acid fluoride compound represented by the above general formula (4), general formula (4 ′) or general formula (4 ″), the above general formula (2), general formula (2 ′) or general formula (2 ″) As a method for obtaining the represented ω-fluorosulfonylperfluoroalkyl vinyl ether, a method of directly synthesizing from an acid fluoride compound, or an alkali metal salt, alkaline earth metal salt, alkyl ester of a carboxylic acid derived from the acid fluoride compound or There are known methods through various derivatives such as silyl esters, but the method of the vinylation step of the present invention is not particularly limited, and for example, any of these known methods can be adopted. Good.

More specific examples of the vinylation step will be described in the following a) to d).

a) From the acid fluoride compound represented by the general formula (4), the general formula (4 ′), or the general formula (4 ″), the general formula (2), the general formula (2 ′), or the general formula (2) )) Is obtained by supporting glass beads heated to 180 ° C. to 350 ° C., alkali metals such as KF, NaF, CsF, and CaF or alkaline earth metal fluorides. An acid fluoride compound represented by the above general formula (4), general formula (4 ′), or general formula (4 ″) is introduced into silica, alumina, etc. The ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the formula (2 ′) or the general formula (2 ″) can be obtained.

b) Next, the acid fluoride compound represented by the general formula (4), the general formula (4 ′) or the general formula (4 ″) is reacted with various basic compounds, and once alkali metal salt of carboxylic acid Alternatively, after converting to an alkaline earth metal salt, ω-fluorosulfonylperfluoro represented by the above general formula (2), general formula (2 ′), or general formula (2 ″) is obtained by heat decarboxylation of the carboxylate. A method for obtaining an alkyl vinyl ether will be described.
Examples of the basic compound used in the conversion reaction from the acid fluoride compound represented by the general formula (4), the general formula (4 ′), or the general formula (4 ″) to the carboxylate include alkali metals or Examples of the alkali metal or alkaline earth metal carbonate suitable for the reaction include, for example, lithium carbonate, carbonate, and the like. Sodium, potassium carbonate, cesium carbonate, rubidium carbonate, calcium carbonate, barium carbonate and the like can be mentioned, among which sodium carbonate, potassium carbonate, calcium carbonate and the like are preferable, sodium carbonate and potassium carbonate are more preferable, and potassium carbonate is particularly preferable.
When converting the acid fluoride compound represented by the general formula (4), the general formula (4 ′), or the general formula (4 ″) to the alkali metal salt or alkaline earth metal salt of the carboxylic acid, a solvent is used. For example, nitrile solvents such as acetonitrile and propionitrile, and ether solvents such as monoglyme, diglyme, triglyme, and tetraglyme are used. The reaction temperature is particularly preferably in the range of 0 ° C to 80 ° C.

From the alkali metal salt or alkaline earth metal salt of the carboxylic acid obtained by the neutralization reaction, the above general formula (2), general formula (2 ′), or general formula (2 ″) is obtained by a heat decarboxylation reaction. In the case of converting to the represented ω-fluorosulfonylperfluoroalkyl vinyl ether, a solvent may be used or the conversion may be performed without a solvent, but better reaction results are more easily achieved when the solvent is not used. It is more preferable.
As a condition for performing the decarboxylation reaction in the presence of a solvent, for example, by using an ether solvent such as diglyme, triglyme and tetraglyme, the decarboxylation reaction is performed in the range of 80 ° C. to 180 ° C. The ω-fluorosulfonylperfluoroalkyl vinyl ether represented by (2) or general formula (2 ′) or general formula (2 ″) can be produced.
When the decarboxylation reaction is performed without a solvent, the solvent used in the neutralization reaction is once distilled off by distillation or the like, and then decarboxylated in the range of 100 ° C to 250 ° C, preferably in the range of 150 ° C to 230 ° C. By carrying out the reaction, ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the above general formula (2), general formula (2 ′) or general formula (2 ″) can be obtained. Heating under solvent-free conditions In the decarboxylation reaction, it is desirable that the reaction product generated by the decarboxylation reaction be continuously and rapidly distilled out of the reaction system, and if the reaction product stays in the reactor, a by-product is generated. And the yield of the ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the general formula (2), the general formula (2 ′) or the general formula (2 ″), which is the target product, is low.

Regarding the conditions for producing ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the above general formula (2 ″), which is particularly practical, from the acid fluoride compound represented by the above general formula (4 ″). As a result of detailed examination, an industrially advantageous production method was found, and the method will be described below.
As a conventional technique, a sodium salt is once produced in Patent Document 2 from an acid fluoride compound (CF ₃ CF (COF) O (CF ₂ ) ₄ SO ₂ F) in which m = 4 in the general formula (4 ″). Then, ω-fluorosulfonylperfluoroalkyl vinyl ether (CF ₂ ═CFO (CF ₂ ) ₄ SO ₂ F) in which m = 4 in the general formula (2 ″) is produced by heat decarboxylation of the sodium salt. The method is shown.
The present inventors describe in Patent Document 2 a method for producing an ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the general formula (2 ″) from the acid fluoride compound represented by the general formula (4 ″). A wide range of considerations were also included, including As a result, it was found that the method via the sodium salt described in Patent Document 2 is not an industrially advantageous production method because many by-products that are difficult to separate are produced, while the specific reaction method according to the present invention. We have found that high quality products can be produced very efficiently with high yield.
First, the present inventors follow the method described in Patent Document 2, and the acid fluoride compound (CF ₃ CF (COF) O (CF ₂ ) ₄ SO ₂ in which m = 4 in the general formula (4 ″). F) is reacted with sodium carbonate to convert it to a sodium salt, and then the carboxylate is heated and decarboxylated in the absence of a solvent, and m = 4 in the above general formula (2 ″), which is the target product. - method of making a fluorosulfonyl perfluoroalkylvinylether _{(CF 2 = CFO (CF 2} ) 4 sO 2 F) was investigated in detail. As a result, in the heat decarboxylation reaction, an acid fluoride compound (CF ₃ CF (COF) O (CF ₂ ) ₄ SO ₂ F in which m = 4 in the general formula (4 ″) as a by-product in addition to the target product. ) Is produced in large quantities, and the yield of the target product is found to be low, and since the by-product has a boiling point close to that of the target product, it is difficult to separate them. Therefore, the method described in Patent Document 2 having these problems cannot be said to be an industrially advantageous production method.

When the present inventors closely observed the state of the sodium salt during the heat decarboxylation reaction in the method described in Patent Document 2, the sodium salt was melted at a temperature near the thermal decomposition temperature. Although the formation mechanism of the by-product at this time is not clear, an acid fluoride compound (CF ₃ CF) in which m = 4 in the above general formula (4 ″) is obtained by an intermolecular reaction of the molten sodium salt as described below. A reaction mechanism by which (COF) O (CF ₂ ) ₄ SO ₂ F) is easily formed was estimated.
-CO ₂ Na + -SO ₂ F → -COF + -SO ₃ Na
Therefore, as a result of intensive studies on the reaction method for suppressing the side reaction as much as possible, the present inventors have found that a salt that does not melt even during the heating decarboxylation reaction such as potassium salt exists. It has been found that in the decarboxylation reaction, the production of the acid fluoride compound represented by the above general formula (4 ″), which is a byproduct, is extremely reduced, and a high-purity target product can be obtained in a high yield.
As a result, the acid fluoride compound represented by the above general formula (4 ″) is converted into a carboxylate, and then the carboxylate is thermally decomposed to obtain an ω− represented by the above general formula (2 ″). In the production of fluorosulfonylperfluoroalkyl vinyl ether, r represents the number of moles of ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the above general formula (2 ″) as the target product, and the above general formula is regenerated as a by-product. When the number of moles of the acid fluoride compound represented by (4 ″) is s, the reaction is carried out with a by-product production ratio represented by [s] / [r + s] of 0.1 or less. The method for producing ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the general formula (2 ″), which is characterized by the above, has become possible. Here, the value of [s] / [r + s] is preferably 0.1 or less, more preferably 0.08 or less, still more preferably 0.06 or less, and particularly preferably 0.8. 04 or less. The lower limit of [s] / [r + s] is not particularly limited, but may be 0.001, 0.0001, or a detection limit of the measuring instrument or less.

As a specific method for carrying out the reaction at a by-product generation ratio represented by [s] / [r + s] as described above of 0.1 or less, “represented by the above general formula (4”) is used. The carboxylate salt derived from the acid fluoride compound is represented by the following general formula (7)
_{CF 3 CF (CO 2 K)} O (CF 2) m SO 2 F (7)
(M is the same as in the general formula (1 ′).)
In addition, the thermal decomposition of the carboxylate is carried out in the absence of a solvent, and as another method, the thermal decomposition of the carboxylate is carried out during the heat decarboxylation. This is performed while keeping the carboxylate in a solid phase.
Hereinafter, the acid fluoride compound (CF ₃ CF (COF) O (CF ₂ ) ₄ SO ₂ F) in which m = 4 in the general formula (4 ″) is converted into a carboxylate (sodium salt or potassium salt). The effect of the potassium salt will be described in detail by comparing the reaction results of sodium salt and potassium salt when the carboxylate is thermally decomposed without solvent. When the heating temperature is 180 ° C. or higher, the sodium salt is in a molten state during pyrolysis as described above, and a large amount of the acid fluoride compound represented by the above general formula (4 ″) is generated as a by-product. The ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the above general formula (2 ″) was obtained in a low yield, and the above [s] / [r + s] was 0.19. The carboxylate In the case of a potassium salt, as described above, the potassium salt is in a solid phase during thermal decomposition, and the acid fluoride compound represented by the above general formula (4 ″), which is the byproduct, is slightly produced. The target product ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the general formula (2 ″) was obtained in high yield, and [s] / [r + s] was 0.01.

c) The neutralization reaction by contacting the acid fluoride compound represented by the general formula (4), the general formula (4 ′) or the general formula (4 ″) with an alkali metal or alkaline earth metal carbonate at a high temperature. At the same time, as a method for carrying out the decarboxylation reaction, for example, by introducing the acid fluoride compound into a carbonate heated in the range of 200 ° C. to 350 ° C., the above general formula (2) or general formula (2 ′ ) Or ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the general formula (2 ″) can be obtained. Examples of the alkali metal or alkaline earth metal carbonate used include lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, rubidium carbonate, calcium carbonate, and barium carbonate. Of these, sodium carbonate, potassium carbonate, calcium carbonate and the like are more preferable, and potassium carbonate is particularly preferable.

d) A method of passing from the acid fluoride compound represented by the general formula (4), the general formula (4 ′) or the general formula (4 ″) through the silyl ester of carboxylic acid will be described below. A silyl ester of a carboxylic acid is produced by reacting the acid fluoride compound with an alkali metal silanolate compound such as Me ₃ SiOK, Me ₃ SiONa, Et ₃ SiOK and the like with a siloxane compound. Examples thereof include disiloxane compounds such as hexamethyldisiloxane, hexaethyldisiloxane, hexaphenyldisiloxane, siloxane polymers such as cyclic siloxane compounds, polymethylsiloxane, etc. The produced carboxylic acid silyl ester is converted to KF, NaF, etc. Of alkali metal fluoride as catalyst Then, it is subjected to a desilylation fluoride reaction in a liquid phase or gas phase, and ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the above general formula (2), general formula (2 ′) or general formula (2 ″) is obtained. Obtainable. The temperature at which the desilyl fluoride reaction is performed is, for example, in the range of 25 ° C. to 175 ° C. when the reaction is performed in the liquid phase, and in the range of 140 ° C. to 250 ° C. when the reaction is performed in the gas phase.
The ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the general formula (2), the general formula (2 ′) or the general formula (2 ″) obtained by the various methods described above can be purified by a method such as distillation. .

Next, the ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1 ′) used in the present invention will be described.
The ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1 ′), which is a synthesis raw material of the ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the general formula (2 ′), is produced by any method. Even those that have been prepared can be used in the method of the present invention. As a method for producing the ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1 ′), the production method shown in the above-mentioned scheme 2 has been reported. It has the above problems and is not an industrially advantageous production method. On the other hand, according to the steps (i) to (iv) of the present application described below, a highly pure ω-haloperfluoroalkylsulfonyl fluoride can be efficiently produced, which is particularly preferable practically.
Next, steps (i) to (iv) for producing ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1 ′) will be described.

First, step (i) will be described.
The following general formula (9)
X (CF ₂ ) _m SO ₂ M (9)
(In the formula, M is Ma, Mb _1/2 , a quaternary ammonium radical or a quaternary phosphonium radical, Ma is an alkali metal, Mb is an alkaline earth metal, and X and m are those represented by the general formula (1 Same as').)
The ω-haloperfluoroalkylsulfin salt represented by the formula is represented by the following general formula (8):
X (CF ₂ ) _m X (8)
(X and m are the same as those in the general formula (1 ′).)
A dithionite selected from an alkali metal salt type, an alkaline earth metal salt type, a quaternary ammonium salt type, and a quaternary phosphonium salt type. It can be obtained by mixing and stirring.
Examples of dithionite used in the production method of the present invention include alkali metal salt types such as Li ₂ S ₂ O ₄ , Na ₂ S ₂ O ₄ , K ₂ S ₂ O ₄ , and Cs ₂ S ₂ O ₄ , Alkaline earth metal salt types such as CaS ₂ O _4, quaternary ammonium salt types such as ((CH ₃ ) ₄ N) ₂ S ₂ O ₄ and ((n-Bu) ₄ N) ₂ S ₂ O ₄ , Quaternary phosphonium salt types such as ((CH ₃ ) ₄ P) ₂ S ₂ O ₄ and ((n-Bu) ₄ P) ₂ S ₂ O ₄ are mentioned, among which Na ₂ S ₂ O ₄ , K ₂ S ₂ O ₄ is preferred. The various dithionites described above may be used alone or in combination.

[Alpha], [omega] -dihaloperfluoroalkane represented by the general formula (8) and an alkali metal salt type, an alkaline earth metal salt type, a quaternary ammonium salt type, or a quaternary phosphonium salt type In addition to the ω-haloperfluoroalkylsulfinate represented by the above general formula (9), the dithionite reaction described below is a sulfinate salt of both α-position and ω-position as a by-product. Formula (11)
_{MO 2 S (CF 2) m} SO 2 M (11)
(M is the same as the general formula (9), and m is the same as the general formula (1 ′).)
Perfluoroalkyl-α, ω-bissulfinate is produced.
The amount of dithionite used is preferably 0.1 equivalents or more and 3 equivalents or less, more preferably 0.1 equivalents or more and 2.0 equivalents relative to the α, ω-dihaloperfluoroalkane represented by the general formula (8). The following is more preferable, and 0.2 equivalents or more and 1.5 equivalents or less are particularly preferable. The substrate reaction hardly progresses at 0.1 equivalents or less, and preferably at 3.0 equivalents or more because the amount of perfluoroalkyl-α, ω-bissulfinate represented by the general formula (11) increases. Absent.

Examples of the solvent used in the above reaction include ketone solvents such as acetone and methyl ethyl ketone, nitrile solvents such as acetonitrile and propionitrile, chain or cyclic ether solvents such as tetrahydrofuran, dioxane and diglyme, N, N- Examples include amide solvents such as dimethylformamide and N, N-dimethylacetamide, and various polar solvents such as dimethyl sulfoxide. Preferred are ketone solvents such as acetone and methyl ethyl ketone, and nitrile solvents such as acetonitrile and propionitrile, and more preferred are acetone and acetonitrile. These organic solvents are preferably used in a mixed solvent with water, and the organic solvent may be one kind or a combination of a plurality of organic solvents.
In the case of using water, the amount of the organic solvent used relative to water is preferably 0.1 to 100 times, more preferably 1 to 50 times, more preferably 2 or more times the volume of water. 20 times or less is particularly preferable. If the amount of water used is 100 times or more, the reaction of the substrate hardly proceeds, which is not preferable. The amount of water relative to the substrate is preferably 0.1 equivalents or more and 200 equivalents or less, more preferably 1 equivalents or more and 150 equivalents or less, and particularly preferably 5 equivalents or more and 100 equivalents or less.

From the α, ω-dihaloperfluoroalkane represented by the general formula (8) and any of alkali metal salt type, alkaline earth metal salt type, quaternary ammonium salt type, and quaternary phosphonium salt type In the reaction of the selected dithionite, a neutralizing agent or a buffer may be added. Examples of neutralizers include hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate, carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, hydrogen phosphates such as sodium hydrogen phosphate and potassium hydrogen phosphate Further, phosphates such as sodium phosphate and potassium phosphate, hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide can be used.
The reaction temperature is preferably in the range of -30 ° C to 90 ° C, more preferably in the range of -10 ° C to 60 ° C. The reaction time is not particularly limited as long as the dithionite is sufficiently consumed according to the reaction conditions, but is practically in the range of about 0.1 to 48 hours.

Next, process (ii) is demonstrated.
In the above step (i), the reaction between the α, ω-dihaloperfluoroalkane represented by the general formula (8) and the dithionite salt results in the ω- represented by the general formula (9) of the target product. In addition to the haloperfluoroalkylsulfinate, the unreacted α, ω-dihaloperfluoroalkane represented by the general formula (8) and the perfluoroalkyl-α, ω-bis represented by the general formula (11) Sulfinate is formed as a by-product. Further, inorganic iodide or inorganic bromide produced by the reaction is also present in the reaction system.
When a suspension in which inorganic iodide or inorganic bromide is precipitated and suspended is formed in the reaction system, separation and purification may be performed after removing inorganic iodide or inorganic bromide by filtration.
16. above. As the method for removing the α, ω-dihaloperfluoroalkane represented by the general formula (8) from the reaction mixture of the step (i) described in the step (ii-1), various removal methods may be used. Can be adopted. Specific examples of the removal method include, for example, distillation removal, extraction / removal with a fluorine atom-containing organic solvent, or ω-haloperfluoroalkylsulfinate represented by the above general formula (9) and the above general formula (11). And a method such as removal by phase separation from an aqueous medium containing a perfluoroalkyl-α, ω-bissulfinate represented by formula (1).
For example, in the removal method by distillation, the α, ω-dihaloperfluoroalkane represented by the above general formula (8) unreacted with the used organic solvent is removed from the solution or suspension after the reaction by distillation or the like. Can do.
As the removal method by phase separation, for example, when the organic solvent used is distilled off by distillation or the like and then water is added, it is separated into two layers, and α, ω-dihaloperfluoro represented by the above general formula (8) Since the alkane is separated into the lower layer, the α, ω-dihaloperfluoroalkane represented by the general formula (8) can be obtained by separating the lower layer.
The extraction / removal method using a fluorine atom-containing organic solvent is represented by the above general formula (8) by adding a fluorine atom-containing organic solvent such as HFC43-10mee or perfluorohexane to the reaction mixture obtained in step (i). A method for extracting α, ω-dihaloperfluoroalkane is mentioned.

The α, ω-dihaloperfluoroalkane represented by the above general formula (8) separated by the above method can be used again for the reaction with dithionite.
Next, from the mixture containing the ω-haloperfluoroalkylsulfinate represented by the general formula (9) and the perfluoroalkyl-α, ω-bissulfinate represented by the general formula (11), Various methods can be used in the step (ii-2) of extracting and separating the ω-haloperfluoroalkylsulfinate represented by (9). For example, an aqueous dispersion in which the ω-haloperfluoroalkylsulfinate represented by the general formula (9) and the perfluoroalkyl-α, ω-bissulfinate represented by the general formula (11) are dissolved, or both The ω-haloperfluoroalkylsulfinate represented by the general formula (9) can be extracted from the solid mixture containing the components.
From the reaction mixture in which the ω-haloperfluoroalkylsulfinate represented by the general formula (9) and the perfluoroalkyl-α, ω-bissulfinate represented by the general formula (11) are dissolved, As a method for extracting the ω-haloperfluoroalkylsulfinate represented by (9), for example, an organic solvent such as an ester solvent such as ethyl acetate or an ether solvent such as diethyl ether is added to form an organic solvent. A method of extracting the ω-haloperfluoroalkylsulfinate represented by the general formula (9) into the layer is mentioned. In this case, the perfluoroalkyl-α, ω-bissulfinate represented by the general formula (11) and the inorganic salt such as inorganic iodide or inorganic bromide which is a by-product generated in the step (i) are: Separated to the water layer side. After separating the organic layer containing the ω-haloperfluoroalkylsulfinate represented by the general formula (9), when the organic solvent is distilled off, the high purity ω- represented by the general formula (9) is obtained. The haloperfluoroalkylsulfinate can be isolated. The organic layer contains almost no perfluoroalkyl-α, ω-bissulfinate represented by the general formula (11).
From a solid mixture containing both components of the ω-haloperfluoroalkylsulfinate represented by the general formula (9) and the perfluoroalkyl-α, ω-bissulfinate represented by the general formula (11), Examples of a method for separating the ω-haloperfluoroalkylsulfinate represented by the general formula (9) include an organic solvent such as an ester solvent such as ethyl acetate and an ether solvent such as diethyl ether, and the solid mixture. The method of extracting the (omega) -halo perfluoroalkyl sulfinate represented by the said General formula (9) from said is mentioned. The perfluoroalkyl-α, ω-bissulfinate represented by the general formula (11), which is a solid insoluble in the organic solvent, and inorganic salts such as inorganic iodide or inorganic bromide can be removed by filtration. it can. On the other hand, when the organic solvent is distilled off from the filtrate by distillation or the like, a high purity ω-haloperfluoroalkylsulfinate represented by the above general formula (9) is obtained in a high yield.

Next, process (iii) is demonstrated.
The ω-haloperfluoroalkylsulfinate represented by the general formula (9) obtained in the step (ii) is treated with a chlorinating agent to give the following general formula (10).
X (CF ₂ ) _m SO ₂ Cl (10)
(X and m are the same as those in the general formula (1 ′).)
Ω-haloperfluoroalkylsulfonyl chloride represented by the following formula can be obtained. Specifically, the ω-haloperfluoroalkylsulfinate represented by the general formula (9) is dissolved or dispersed in water, an organic solvent or a mixed solvent thereof, and then chlorinated by adding a chlorinating agent. The reaction can be performed.
Although the said process can be implemented in various media, when the ease of reaction operation, safety | security, etc. are considered, it is preferable to use the aqueous solution containing water or an acid as a solvent.
The chlorinating agent is not particularly limited as long as it can convert the -SO 2 _M in -SO 2 _Cl, it is possible to use various known chlorinating agents. For example, chlorine, sulfuryl chloride or the like can be used as the chlorinating agent, but chlorine is particularly preferable. When chlorination reaction is carried out in water using chlorine, the object ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) is insoluble in water, so that it can be easily separated from water. Thus, industrial implementation is particularly advantageous.
The conditions for the chlorination reaction are not particularly limited, and may be determined as appropriate so that the desired chlorinated product is produced according to the type of chlorinating agent used. For example, when chlorine is used as the chlorinating agent, a chlorination reaction may be performed by supplying chlorine gas into an aqueous solution in which the ω-haloperfluoroalkylsulfinate of the general formula (9) is dissolved. Is preferably 0 to 50 ° C., and the amount of chlorine charged is preferably about 1 to 5 moles per mole of the ω-haloperfluoroalkylsulfinate of the above general formula (9), more preferably in the range of 1.2 to 3 moles. preferable. The concentration of the ω-haloperfluoroalkylsulfinate of the above general formula (9) in the aqueous solution is not particularly limited, but is usually about 0.5 to 50% by mass.

Next, process (iv) is demonstrated.
The ω-haloperfluoro represented by the general formula (1 ′) is obtained by treating the ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) obtained in the step (iii) with a fluorine ion-containing compound. Alkylsulfonyl fluoride can be obtained.
The reaction with the fluorine ion-containing compound can be carried out according to a known method. If the ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) is reacted with the fluorine ion-containing compound in a solvent or in the absence of a solvent. Good. There is no restriction | limiting in particular as a solvent, A various solvent can be used, Polar organic solvents, such as acetonitrile, a sulfolane, a dimethylsulfoxide, N, N- dimethylformamide, water, or these mixed solvents etc. can be used.
The fluoride ion-containing compound to be used is not particularly limited as long as it can convert the -SO 2 _Cl into -SO 2 _F, may be a known fluoride ion-containing compound. Examples thereof include alkali metal fluorides such as NaF and KF.
The reaction temperature is in the range of 0 to 200 ° C., and the reaction time may be about 0.1 to 48 hours. The amount of the fluorine ion-containing compound used is preferably 1 mol or more and 10 mol or less and more preferably 1 mol or more and 5 mol or less with respect to 1 mol of the ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10). . The concentration of ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) is not particularly limited, but is usually 10 to 100% by mass.

スキーム３で示すように、本発明の工程（ｉ）から（ｉｖ）の工程を経ることによって、不安定な上記一般式（１０）で表されるω−ハロペルフルオロアルキルスルホニルクロリドを蒸留等の熱履歴をかけることなく、高収率、高選択的に、上記一般式（１’）で表されるω−ハロペルフルオロアルキルスルホニルフルオリドに変換できる。The method for separating the ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1 ′) obtained by the above method may be appropriately changed depending on the solvent used for the reaction. For example, the ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1 ′) can be separated by distillation, and depending on the type of the solvent, water can be added to represent the general formula (1 ′). The ω-haloperfluoroalkylsulfonyl fluoride can be separated as an organic layer.
A specific example of steps (i) to (iv) of the present application described above is shown in Scheme 3.

As shown in Scheme 3, the unstable ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) is heated by distillation or the like through the steps (i) to (iv) of the present invention. It can be converted into ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1 ′) with high yield and high selectivity without applying a history.

Next, it is represented by the general formula (8) from the perfluoroalkyl-α, ω-bissulfinate represented by the general formula (11) which is a by-product separated by the step (ii-2). A method for producing α, ω-dihaloperfluoroalkane and / or ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) will be described.
The treatment liquid or purification residue separated in step (ii-2) includes a perfluoroalkyl-α, ω-bissulfinate represented by the above general formula (11) and an inorganic iodide or inorganic bromine, which are by-products. At least one inorganic salt selected from the group of compounds. In the first step of reacting the treatment liquid or the purified residue with a chlorinating agent, the perfluoroalkyl-α, ω-bissulfinate represented by the general formula (11) is represented by the general formula (12). Perfluoroalkyl-α, ω-bissulfonyl chloride is produced, while iodine or bromine is produced from inorganic iodide or inorganic bromide. Next, in the second step, α, ω-dihaloperfluoro represented by the above general formula (8) is obtained by reaction of perfluoroalkyl-α, ω-bissulfonyl chloride represented by the above general formula (12) with iodine or bromine. Alkane and / or ω-haloperfluoroalkylsulfonyl chloride represented by the above general formula (10) can be obtained. The production ratio of the α, ω-dihaloperfluoroalkane represented by the general formula (8) and the ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) is as follows. It depends on the ratio of the perfluoroalkyl-α, ω-bissulfonyl chloride represented and the coexisting iodine or bromine.

In the second step, by adding a solvent capable of simultaneously dissolving both iodine or bromine and the perfluoroalkyl-α, ω-bissulfonyl chloride represented by the general formula (12), the above general formula (8) The conversion reaction to α, ω-dihaloperfluoroalkane represented by the above formula and / or ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) can be promoted. Examples of solvents for simultaneously dissolving iodine or bromine and perfluoroalkyl-α, ω-bissulfonyl chloride represented by the above general formula (12) include ester solvents such as ethyl acetate and butyl acetate, Examples include polar solvents such as ether solvents such as monoglyme and diglyme, nitrile solvents such as acetonitrile and propionitrile, and ketone solvents such as acetone and methyl ethyl ketone. In addition, when a poorly water-soluble organic solvent such as ethyl acetate or butyl acetate is used as the solvent, it is more preferable because the product can be extracted simultaneously with the reaction.
In the first step, the treatment liquid or the purified residue is reacted with a chlorinating agent to produce perfluoroalkyl-α, ω-bissulfonyl chloride represented by the general formula (12), and the acid chloride is filtered. Or α, ω-dihaloperfluoroalkane represented by the above general formula (8) and / or the above general formula (10) by reacting with iodine or bromine in a solvent after isolation by solvent extraction or the like. The represented ω-haloperfluoroalkylsulfonyl chloride can also be obtained. In this case, the kind of α, ω-dihaloperfluoroalkane represented by the general formula (8) and / or the ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) and the production ratio thereof are Or it determines with the addition amount of a bromine. Examples of the solvent in this step include ester solvents such as ethyl acetate and butyl acetate, ether solvents such as monoglyme and diglyme, nitrile solvents such as acetonitrile and propionitrile, and ketone solvents such as acetone and methyl ethyl ketone. It is done.

There is no restriction | limiting in particular as a chlorinating agent used at the said 1st step, It is possible to use a well-known chlorinating agent. For example, chlorine, sulfuryl chloride or the like can be used as a chlorinating agent, and chlorine is particularly preferable.
The α, ω-dihaloperfluoroalkane represented by the general formula (8) obtained by the above operation can be reused in the reaction with the dithionite in the step (i). The ω-haloperfluoroalkylsulfonyl chloride represented by the above general formula (10) obtained by the above operation is reused in the reaction with the fluorine ion-containing compound in the above step (iv), and the above general formula (1) It can be converted into ω-haloperfluoroalkylsulfonyl fluoride represented by ').

The ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the general formula (2) or the general formula (2 ′) by the production method of the present invention is used as a monomer component for polymers used in various solid electrolyte materials or ion exchange membranes. It is a useful substance.
This solid electrolyte polymer is, for example, an electrolyte membrane of a solid polymer electrolyte fuel cell, a catalyst binder, a membrane for a lithium battery, a membrane for salt electrolysis, a membrane for water electrolysis, a membrane for hydrohalic acid electrolysis, a membrane for an oxygen concentrator, Used as a temperature sensor film, a gas sensor film, and the like.
As described above, according to the present invention, the ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the general formula (2) or the general formula (2 ′) and a synthetic intermediate thereof can be produced in high yield.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely in detail, this invention is not limited to these.
In the examples and comparative examples, various physical properties were measured by the following methods.
1. Fluorine-19 nuclear magnetic resonance ⁽¹⁹ F-NMR) spectrum
^{For the 19} F-NMR spectrum, a JSX-400 nuclear magnetic resonance apparatus manufactured by JEOL Ltd. was used as a measuring apparatus, deuterated chloroform as a solvent, and Freon-11 (CFCl ₃ ) as a reference substance.
2. Gas chromatography (GC)
The following apparatus and conditions were used.
Device: GC-2010 manufactured by Shimadzu Corporation, Japan
Column: Capillary column RTX-200 manufactured by RESTEK, USA
(Inner diameter 0.25mm, length 60m, film thickness 1μm)
-Capillary column DB-1 manufactured by J & WS Scientific, USA
(Inner diameter 0.25mm, length 30m, film thickness 1μm)
Carrier gas: He
Detection: FID
3. Gas chromatography mass spectrum (GC-MS)
The following apparatus and conditions were used.
Equipment: Automass-Sun (trade name) manufactured by JEOL, Japan
Column: Capillary column RTX-200 manufactured by RESTEK, USA
(Inner diameter 0.25mm, length 60m, film thickness 1μm)
-Capillary column DB-1 manufactured by J & WS Scientific, USA
(Inner diameter 0.25mm, length 30m, film thickness 1μm)
Carrier gas: He

Example 1
(Synthesis of CF ₂ = CFO (CF ₂ ) ₄ SO ₂ F from I (CF ₂ ) ₄ I)
A 5 L reactor was charged with 2250 mL of acetone, 750 mL of water, and 1000 g of I (CF ₂ ) ₄ I, and the reactor was cooled in an ice bath. To this reactor, 287 g of Na ₂ S ₂ O ₄ was added in 5 portions over 15 minutes, and the mixture was stirred at room temperature for 2 hours. According to ¹⁹ F-NMR, 57 mol% of I (CF ₂ ) ₄ I remained, 36 mol% of I (CF ₂ ) ₄ SO ₂ Na, and 7 mol% of NaO ₂ S (CF ₂ ) ₄ SO ₂ Na were formed from ¹⁹ F-NMR. Was. Acetone and I (CF ₂ ) ₄ I were distilled off from the reaction mixture under reduced pressure to obtain a solid residue. Water was added to the residue, and the mixture was extracted 3 times with ethyl acetate. These ethyl acetate extracts were concentrated under reduced pressure to obtain 445 g of a brown solid.
This solid was found to contain 0.79 mol (yield 36%) of I (CF ₂ ) ₄ SO ₂ Na by ¹⁹ F-NMR (internal standard: CF ₃ CO ₂ Na). The aqueous layer after the extraction operation contains 0.15 mol (yield 7%) of NaO ₂ S (CF ₂ ) ₄ SO ₂ Na by ¹⁹ F-NMR (internal standard: CF ₃ CO ₂ Na). I understood it.
I (CF ₂ ) ₄ SO ₂ Na
¹⁹ F-NMR -61.9 ppm (2F), -114.2 ppm (2F), -122.2 ppm (2F), -131.1 ppm (2F)
NaO ₂ S (CF ₂ ) ₄ SO ₂ Na
¹⁹ F-NMR -123.0 ppm (4F), -130.6 ppm (4F)
Four-necked flask 2L equipped with a gas blowing tube, _{I (CF} 2) 4 _SO 2 brown solid 445g containing Na _{(I (CF} 2) 0.79mol containing 4 _SO 2 Na), and water 1000mL Added and stirred. The flask was cooled in an ice bath and blown with chlorine until separated into two layers. When the lower layer was separated, 336 g of liquid was obtained. This liquid was found to contain 0.787 mol (yield 99.7%) of I (CF ₂ ) ₄ SO ₂ Cl by ¹⁹ F-NMR (internal standard: C ₆ F ₆ ).
¹⁹ F-NMR -61.6 ppm (2F), -105.8 ppm (2F), -114.3 ppm (2F), -120.0 ppm (2F)
To a 2 L four-necked flask equipped with a dropping funnel and a reflux condenser, 187.8 g of KF and 700 mL of acetonitrile were added and heated to 50 ° C. 665 g of I (CF ₂ ) ₄ SO ₂ Cl was added dropwise to the flask over 2 hours. After the dropping, the mixture was further stirred at 50 ° C. for 2 hours, and completion of the reaction was confirmed by ¹⁹ F-NMR. When water was added to the reaction mixture, it was separated into two layers. After liquid separation of the lower layer, distillation purification (bp92 ° C., 26.6 kPa) yielded 606.8 g of I (CF ₂ ) ₄ SO ₂ F (yield 94.9%).
¹⁹ F-NMR 44.0 ppm (1F), -61.6 ppm (2F), -109.6 ppm (2F), -114.6 ppm (2F), -121.1 ppm (2F)
To a 10 L three-necked flask equipped with a reflux tower and a thermometer, 7.2 kg of 65 mass% fuming sulfuric acid was added to 5.26 kg of I (CF ₂ ) ₄ SO ₂ F, and heated under reflux for 40 hours under normal pressure. The reaction mixture was separated into two layers and the conversion reached 98%. The upper layer was separated, and further washed three times with concentrated sulfuric acid.

The liquid obtained was purified by distillation (bp 54 ° C., 40 kPa) to obtain 2.67 kg (yield 74.4%) of FOC (CF ₂ ) ₃ SO ₂ F, and ¹⁹ F-NMR ( internal _standard: C _{6 F} 6) from _{FSO 2 O (CF 2) 4} SO 2 F was found to contain 78.5% by weight.
FOC (CF ₂ ) ₃ SO ₂ F
¹⁹ F-NMR 44.3 ppm (1F), 22.5 ppm (1F), -109.8 ppm (2F), -119.5 ppm (2F), -122.4 ppm (2F)
FSO ₂ O (CF ₂ ) ₄ SO ₂ F
¹⁹ F-NMR 48.5 ppm (1F), 43.6 ppm (1F), −85.0 ppm (2F), −109.8 ppm (2F), −122.0 ppm (2F), −126.2 ppm (2F)
A 2 L autoclave was charged with 1000 g of FOC (CF ₂ ) ₃ SO ₂ F, 40 g of tetraglyme, 400 g of adiponitrile, and 27.2 g of KF, and 654 g of hexafluoropropylene oxide (HFPO) was introduced over 6 hours while stirring at 0 ° C. did. After the reaction, excess HFPO was released, the contents were separated, and the lower layer portion was taken out to obtain 1588 g of liquid. According to GC and ¹⁹ F-NMR (internal standard: C ₆ F ₆ ), this liquid was 3.354 mol (yield 94.0%) of CF ₃ CF (COF) O (CF ₂ ) ₄ SO ₂ F, CF ₃ CF (COF) OCF ₂ CF (CF ₃ ) O (CF ₂ ) ₄ SO ₂ F is 0.036 mol (1.0% yield), and unreacted FOC (CF ₂ ) ₃ SO ₂ F is 0. It was found to contain 157 mol. The obtained liquid was 1449 g of CF ₃ CF (COF) O (CF ₂ ) ₄ SO ₂ F (yield 91.0%) by distillation purification (bp 105 ° C., 40 kPa).
¹⁹ F-NMR 44.0 ppm (1F), 23.8 ppm (1F), -79.9 ppm (1F), -84.4 ppm (3F), -87.2 ppm (1F), -110.0 ppm (2F), -122.1 ppm (2F), -126.8 ppm (2F), -132.4 ppm (1F)
102 g of dried potassium carbonate and 135 g of anhydrous ethylene glycol dimethyl ether are placed in a 1 L four-necked flask equipped with a dropping funnel and a distillation tower, and CF ₃ CF (COF) O ( 300 g of CF ₂ ) ₄ SO ₂ F was slowly added dropwise. After the foaming stopped, the mixture was further stirred at 50 ° C. for 2 hours, and ¹⁹ F-NMR confirmed that the raw material was completely neutralized and converted to CF ₃ CF (CO ₂ K) O (CF ₂ ) ₄ SO ₂ F. did. From this reaction mixture, ethylene glycol dimethyl ether was distilled off under reduced pressure, and the residue was further heated to 140 ° C. and dried under reduced pressure. When the residue containing dried CF ₃ CF (CO ₂ K) O (CF ₂ ) ₄ SO ₂ F was heated to 190 ° C. under reduced pressure, decarboxylation reaction occurred, and 222 g of liquid was distilled. The distilled liquid was 0.572 mol (yield: 85.0%) of the target product CF ₂ = CFO (CF ₂ ) ₄ SO ₂ F by GC and ¹⁹ F-NMR (internal standard: C ₆ F ₆ ). In addition, 0.007 mol of CF ₃ CF (COF) O (CF ₂ ) ₄ SO ₂ F regenerated as a by-product was contained, and [s] / [r + s] was 0.01. Liquid obtained above, purification by distillation (bp92 ℃, 40kPa) _{gave CF 2 = CFO (CF 2)} 4 SO 2 F210g (82.2% yield).
¹⁹ F-NMR: 43.8 ppm (1F), -87.0 ppm (2F), -110.0 ppm (2F), -116.9 ppm (1F), -122.2 ppm (2F), -124.4 ppm (1F) ), -127.0 ppm (2F), -138.4 ppm (1F)
EI-MS: m / z 380, 283, 100, 97, 81

Comparative Example 1
Three-neck flask _{500mL I (CF 2) 4 I50g} , put acetone 150 mL, and water 50 mL, The flask was immersed in an ice _bath, it was added to Na ₂ S ₂ O 4 19 g portions and allowed to stir at room temperature for 2 hours It was. When measuring the reaction mixture with _{^{19 F-NMR, I (CF}} 2) 4 it is left _{38mol%, I (CF 2)} 4 SO 2 Na is _{44mol%, NaO 2 S (CF} 2) 4 SO 2 Na is 18mol % Was produced. Solids in the reaction mixture were removed by filtration, and acetone was distilled off from the filtrate to obtain a residue. The residue was transferred to a 500 mL three-necked flask equipped with a gas blowing tube, and 200 mL of water was further added. The flask was placed in an ice bath and blown with chlorine until separated into two layers. When the lower layer was separated, a mixture containing I (CF ₂ ) ₄ I, I (CF ₂ ) ₄ SO ₂ Cl, and ClO ₂ S (CF ₂ ) ₄ SO ₂ Cl was obtained in the lower layer. These mixtures were subjected to distillation operation, and were obtained by mixing I (CF ₂ ) ₄ I, I (CF ₂ ) ₄ SO ₂ Cl, ClO ₂ S (CF ₂ ) ₄ SO ₂ Cl, and ¹⁹ F- According to NMR (internal standard: C ₆ F ₆ ), I (CF ₂ ) ₄ SO ₂ Cl contained 0.011 mol (yield 10%).

Comparative Example 2
A 200 mL autoclave was charged with 100 g of FOC (CF ₂ ) ₃ SO ₂ F, 45 g of tetraglyme, and 2.72 g of KF obtained in Example 1, and stirred at 0 ° C. for 59. 3 g was introduced over 6 hours. After the reaction, the content was separated, and the lower layer portion was taken out to obtain 136.2 g of liquid. This liquid was measured by GC, ¹⁹ F-NMR (internal standard: C ₆ F ₆ ), CF ₃ CF (COF) O (CF ₂ ) ₄ SO ₂ F, 0.186 mol (yield 52.2%), CF ₃ CF (COF) OCF ₂ CF (CF ₃ ) O (CF ₂ ) ₄ SO ₂ F 0.055 mol (yield 15.3%), CF ₃ CF (COF) O (CF ₂ CF (CF ₃ ) O) _It contained 0.006 mol (yield 1.8%) of ₂ (CF ₂ ) ₄ SO ₂ F and 0.039 mol of unreacted FOC (CF ₂ ) ₃ SO ₂ F.

Comparative Example 3
A 200 mL four-necked flask equipped with a dropping funnel and a distillation tower was charged with 16.4 g of dried sodium carbonate and 15 ml of anhydrous ethylene glycol dimethyl ether at 70 ° C. and 30 g of CF ₃ CF (COF) obtained in Example 1. ) O (CF ₂ ) ₄ SO ₂ F was slowly added dropwise. After the foaming stopped, the mixture was further stirred at 70 ° C. for 2 hours, and ¹⁹ F-NMR confirmed that the raw material was completely neutralized and converted to CF ₃ CF (CO ₂ Na) O (CF ₂ ) ₄ SO ₂ F. did. From this reaction mixture, ethylene glycol dimethyl ether was distilled off under reduced pressure, and the residue was further heated to 120 ° C. and dried under reduced pressure. When the dried residue containing CF ₃ CF (CO ₂ Na) O (CF ₂ ) ₄ SO ₂ F was heated to 200 ° C., 18.9 g of liquid was distilled by decarboxylation reaction. The distilled liquid was analyzed by ¹⁹ F-NMR (internal standard: C ₆ F ₆ ), and CF ₂ = CFO (CF ₂ ) ₄ SO ₂ F was 0.038 mol (yield 56.1%), CF ₃ CF (COF ) O (CF ₂ ) ₄ SO ₂ F contained 0.009 mol, and [s] / [r + s] was 0.19.

Example 2
In a 200 mL three-necked flask equipped with a distillation column and a dropping funnel, 33.2 g of sulfolane and 6.05 g of KF were put, and while heating to 50 ° C., the FSO ₂ O (CF ₂ ) ₄ SO obtained in Example 1 was used. the ₂ F was added dropwise distillation residue 100g containing 78.5 wt%. After the dropwise addition, the mixture was further heated and stirred at 50 ° C. for 2 hours, and then purified by distillation to obtain 54.7 g (yield 95.1%) of FCO (CF ₂ ) ₃ SO ₂ F.

Example 3
(Synthesis of CF ₂ = CFO (CF ₂ ) ₃ SO ₂ F from I (CF ₂ ) ₃ I)
A 1 L three-necked flask equipped with a reflux tower and a stirrer was charged with 300 g of I (CF ₂ ) ₃ I, 900 mL of acetone and 300 mL of water, the flask was placed in an ice bath, and 96.9 g of Na ₂ S ₂ O ₄ was added little by little. . After stirring for 2 hours, when the reaction mixture was measured by ¹⁹ F-NMR, 36.6 mol% of I (CF ₂ ) ₃ SO ₂ Na and 8.4 mol% of NaO ₂ S (CF ₂ ) ₃ SO ₂ Na were produced. It was. After acetone was distilled off from the reaction mixture, 300 mL of water was added to separate the two layers, and the lower layer was separated to recover 159 g of I (CF ₂ ) ₃ I. The upper layer was extracted three times with ethyl acetate, and then the ethyl acetate solution was concentrated under reduced pressure to obtain a viscous liquid. This liquid was found to contain 0.272 mol of I (CF ₂ ) ₃ SO ₂ Na by ¹⁹ F-NMR (internal standard: CF ₃ CO ₂ Na) (yield 36.6%).
The liquid containing I (CF ₂ ) ₃ SO ₂ Na was transferred to a 1 L three-necked flask equipped with a gas blowing tube, and 300 mL of water was further added. The flask was placed in an ice bath and chlorine was blown into two layers. When the lower layer was separated, 97.7 g of liquid was obtained. This liquid was found to be I (CF ₂ ) ₃ SO ₂ Cl by ¹⁹ F-NMR (yield 92.8%).
To a 500 mL flask equipped with a reflux tower, 97.7 g of I (CF ₂ ) ₃ SO ₂ Cl obtained above, 45.3 g of KF, and 200 mL of acetonitrile were added and stirred at 50 ° C. for 2 hours. After completion of the reaction, water was added to the reaction mixture to separate into two layers. When the lower layer was separated, 86.1 g of liquid was obtained, and it was found by ¹⁹ F-NMR that it was I (CF ₂ ) ₃ SO ₂ F (yield 92.0%).
When 255 g of 60% by mass of fuming sulfuric acid was added to 86.1 g of I (CF ₂ ) ₃ SO ₂ F obtained above and heated at 60 ° C. for 19 hours under normal pressure, the reaction mixture was separated into two layers, and the conversion rate was 91 % Reached. The upper layer was separated, washed with concentrated sulfuric acid, and then purified by distillation to obtain 34.1 g of liquid.

This liquid was found to be FOC (CF ₂ ) ₂ SO ₂ F by ¹⁹ F-NMR (yield 62.0%).
¹⁹ F-NMR 44.3 ppm (1F), 22.5 ppm (1F), -109.8 ppm (2F), -119.5 ppm (2F)
A 100 mL autoclave is charged with 40 g of FOC (CF ₂ ) ₂ SO ₂ F, 5 g of tetraglyme, 15 g of adiponitrile, and 1.8 g of potassium fluoride. While stirring at 0 ° C., 38.5 g of HFPO is added over 2 hours. Introduced. After the reaction, excess HFPO was released, the contents were separated, and the lower layer portion was taken out. The obtained liquid was distilled to obtain 50.9 g (yield 74%) of CF ₃ CF (COF) O (CF ₂ ) ₃ SO ₂ F.
A 200 mL three-necked flask equipped with a dropping funnel and a distillation tower is charged with 19.5 g of dried potassium carbonate and 50 mL of anhydrous acetonitrile, and the above CF ₃ CF (COF) O (CF _{2) 3} was slowly added dropwise SO ₂ F50.9g. After the foaming stopped, after further stirring at 40 ° C. for 2 hours, it was confirmed by ¹⁹ F-NMR that the raw material was completely neutralized and converted to CF ₃ CF (CO ₂ K) O (CF ₂ ) ₃ SO ₂ F. did. Acetonitrile was distilled off from the reaction mixture under reduced pressure, and the residue was heated to 140 ° C. and dried under reduced pressure. When the residue containing dried CF ₃ CF (CO ₂ K) O (CF ₂ ) ₃ SO ₂ F was heated to 220 ° C. under normal pressure, a decarboxylation reaction occurred and a liquid was distilled. Further, the obtained liquid was purified by distillation to obtain 35.2 g of CF ₂ ═CFO (CF ₂ ) ₃ SO ₂ F (yield 83%).
¹⁹ F-NMR 43.8 ppm (1F), -86.7 ppm (2F), -110.0 ppm (2F), -116.6 ppm (1F), -124.1 ppm (1F), -125.6 ppm (2F) -138.5 ppm (1F)

Example 4
(Synthesis of CF ₂ = CFO (CF ₂ ) ₆ SO ₂ F from I (CF ₂ ) ₆ I)
Reflux tower, _I 3-neck 2L flask equipped with a stirrer _(CF 2) 6 I122g and acetone 450 mL, containing water 50 mL, with a flask in an ice _bath, was added to Na ₂ S ₂ O 4 48g slightly, Stir at 25 ° C. for 2 hours. When measuring the reaction mixture with ^{_{19 F-NMR, I (CF}} 2) 6 SO 2 Na is _{68mol%, NaO 2 S (CF} 2) 6 SO 2 Na was produced 6 mol%. After acetone and water were distilled off from the reaction mixture, 300 mL of HFC43-10mee was added to the residue, and the solid was filtered. When HFC43-10mee was distilled off from the filtrate under reduced pressure, 31.6 g of I (CF ₂ ) ₆ I was recovered. On the other hand, 500 mL of water was added to the solid, and extracted three times with ethyl acetate, and then the ethyl acetate solution was concentrated under reduced pressure to obtain a solid. This solid was found to contain 0.150 mol of I (CF ₂ ) ₆ SO ₂ Na by ¹⁹ F-NMR (internal standard: CF ₃ CO ₂ Na) (yield 68%).
The above I (CF ₂ ) ₆ SO ₂ Na was transferred to a 1 L three-necked flask equipped with a gas blowing tube, 300 mL of water was added, the flask was placed in an ice bath, and chlorine was blown into it, and the two layers were separated. . When the lower layer was separated, 75.1 g of liquid was obtained. This liquid was found to be I (CF ₂ ) ₆ SO ₂ Cl by ¹⁹ F-NMR (yield 95.3%).
In a 500 mL flask equipped with a reflux tower, 24.8 g of KF and 150 mL of acetonitrile were added to 75.1 g of I (CF ₂ ) ₆ SO ₂ Cl obtained above, and the mixture was stirred at 50 ° C. for 2 hours. After completion of the reaction, water was added to the reaction mixture to separate into two layers. When the lower layer was separated, 66.8 g of liquid was obtained. This liquid was found to be I (CF ₂ ) ₆ SO ₂ F by ¹⁹ F-NMR (yield 91.9%).
When 269 g of 60 wt% fuming sulfuric acid was added to 129 g of I (CF ₂ ) ₆ SO ₂ F and heated at 60 ° C. for 12 hours and further at 80 ° C. for 13.5 hours, the reaction mixture was separated into two layers and converted The rate reached 100%. The upper layer was separated and washed with concentrated sulfuric acid to obtain 89 g of liquid.

This liquid was found to be FOC (CF ₂ ) ₅ SO ₂ F by ¹⁹ F-NMR (yield 93%).
¹⁹ F-NMR 44.3 ppm (1F), 22.5 ppm (1F), −109.7 ppm (2F), −120.0 ppm (2F), −121.8 ppm (2F), −122.5 ppm (2F), -124.1 ppm (2F)
A 200 mL autoclave is charged with 79 g of FOC (CF ₂ ) ₅ SO ₂ F, 7 g of tetraglyme, 35 g of adiponitrile, and 1.45 g of potassium fluoride, and 41.4 g of HFPO is added over 7 hours while stirring at 0 ° C. Introduced. After the reaction, excess HFPO was released, the contents were separated, and the lower layer portion was taken out. The obtained liquid was distilled to obtain 91.6 g (yield 81%) of CF ₃ CF (COF) O (CF ₂ ) ₆ SO ₂ F.
In a nitrogen stream, 31.9 g of dried potassium carbonate and 200 mL of anhydrous ethylene glycol dimethyl ether are placed in a 500 mL three-necked flask equipped with a dropping funnel and a distillation tower, and the above CF ₃ CF (COF) O (CF ₂ ) is added at room temperature. the ₆ SO ₂ F120g was slowly added dropwise. The mixture was stirred at room temperature for 1 hour and further stirred at 50 ° C. for 1 hour, and then the raw material was completely neutralized by ¹⁹ F-NMR and converted to CF ₃ CF (CO ₂ K) O (CF ₂ ) ₆ SO ₂ F. It was confirmed. Ethylene glycol dimethyl ether was distilled off from the reaction mixture under reduced pressure, and the residue was heated to 100 ° C. and dried, and then heated to 200 ° C. under reduced pressure to cause decarboxylation and liquid was distilled. Further, 94.3 g of CF ₂ ═CFO (CF ₂ ) ₆ SO ₂ F was obtained from the obtained liquid by distillation purification (yield 89%).
¹⁹ F-NMR 43.8 ppm (1F), -86.9 ppm (2F), -110.0 ppm (2F), -117.1 ppm (1F), -121.9 ppm (2F), -123.4 ppm (2F) -122.0 ppm (2F), -124.7 ppm (1F), -127.3 ppm (2F), -138.4 ppm (1F)
EI-MS: m / z 480, 100, 97, 81

Example 5
The reaction was performed in the same manner as in Example 1 except that the separation and purification method after the reaction of I (CF ₂ ) ₄ I and Na ₂ S ₂ O ₄ was changed as follows. That is, after completion of the reaction of I (CF ₂ ) ₄ I and Na ₂ S ₂ O ₄ , acetone was distilled off from the reaction mixture, and then water was added to separate the two layers. When the lower layer was separated, I (CF ₂ ) 546 g of ₄ I was recovered. In addition, ethyl acetate was added to the upper layer, followed by extraction three times with ethyl acetate, and then the ethyl acetate solution was concentrated under reduced pressure to obtain a brown solid. By ¹⁹ F-NMR (internal standard: CF ₃ CO ₂ Na), It was found that 0.79 mol (yield 36%) of I (CF ₂ ) ₄ SO ₂ Na was contained.

Example 6
A 1 L four-necked flask equipped with a gas blowing tube is charged with 900 g of an aqueous solution containing 0.15 mol of NaO ₂ S (CF ₂ ) ₄ SO ₂ Na and NaI separated in Example 1, and chlorine is blown in an ice bath. A solid was formed and became a suspended state. It was confirmed by ¹⁹ F-NMR that the produced solid was iodine and ClO ₂ S (CF ₂ ) ₄ SO ₂ Cl. When ethyl acetate was added to this suspension, iodine and ClO ₂ S (CF ₂ ) ₄ SO ₂ Cl were dissolved and then separated into two layers. This ethyl acetate layer was confirmed to be I (CF ₂ ) ₄ I by ¹⁹ F-NMR. After separating the ethyl acetate layer, distillation purification was performed under normal pressure to obtain 65.7 g of I (CF ₂ ) ₄ I (when NaO ₂ S (CF ₂ ) ₄ SO ₂ Na was used as a starting material, 94%).
ClO ₂ S (CF ₂ ) ₄ SO ₂ Cl
¹⁹ F-NMR -105.6 ppm (4F), -120.3 ppm (4F)

Example 7
A 100 mL three-necked flask was charged with 3.2 g (8.06 mmol) of ClO ₂ S (CF ₂ ) ₄ SO ₂ Cl obtained in Example 6, 2.05 g (8.06 mmol) of iodine, and 10 mL of ethyl acetate. And stirred at room temperature for 3 hours. By ¹⁹ F-NMR in the reaction mixture, I _{(CF 2) 4} I is included _{8mol%, I (CF 2)} 4 SO 2 Cl is _{64mol%, ClO 2 S (CF} 2) 4 SO 2 Cl is 20 mol% I found out.

Example 8
A 100 mL three-necked flask was charged with 3.2 g (8.06 mmol) of ClO ₂ S (CF ₂ ) ₄ SO ₂ Cl obtained in Example 6, 4.10 g (16.1 mmol) of iodine, and 10 mL of ethyl acetate. And stirred at room temperature for 3 hours. This reaction mixture was confirmed by ¹⁹ F-NMR to be converted to I (CF ₂ ) ₄ I at a conversion rate of 100%.

Industrial applicability

  The ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the general formula (2) or the general formula (2 ′) obtained by the production method of the present invention and its synthetic intermediate are fluorine-based compounds useful for fuel cells and salt electrolysis processes. Used as a raw material for solid electrolyte polymers.

Claims (22)

As a raw material, the following general formula (1 ′)
X (CF ₂ ) _m SO ₂ F (1 ′)
(X is a halogen atom selected from I and Br, and m is an integer of 3 to 10.)
From ω-haloperfluoroalkylsulfonyl fluoride represented by the following general formula (2 ′)
CF ₂ = CFO (CF ₂ CF (CF ₃ ) O) _{n ′} (CF ₂ ) _m SO ₂ F (2 ′)
(N ′ is an integer of 0 to 2, and m is the same as in the general formula (1 ′).)
A method for producing ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the following method, which comprises the following steps (a ′) to (c ′):
(A ′) A step of producing an ω-fluorosulfonyl compound represented by the following general formula (3 ′) by treating the ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1 ′) with an oxidizing agent. ,
FCO (CF ₂ ) _m-1 SO ₂ F (3 ′)
(M is the same as in the general formula (1 ′).)
(B ′) An acid represented by the following general formula (4 ′) by reacting the ω-fluorosulfonyl compound represented by the general formula (3 ′) obtained in the step (a ′) with hexafluoropropylene oxide. Step of producing a fluoride compound, and CF ₃ CF (COF) O (CF ₂ CF (CF ₃ ) O) _{n ′} (CF ₂ ) _m SO ₂ F (4 ′)
(N ′ is the same as the general formula (2 ′), and m is the same as the general formula (1 ′).)
(C ′) A step of converting the acid fluoride compound represented by the general formula (4 ′) obtained in the step (b ′) to an ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the general formula (2 ′). . The method according to claim 1, wherein the oxidizing agent used in step (a ′) is SO ₃ or fuming sulfuric acid. At least the ω-fluorosulfonyl compound represented by the above general formula (3 ′) obtained in the step (a ′) and the following general formula (5 ′) which is a by-product.
FSO ₂ O (CF ₂ ) _m SO ₂ F (5 ′)
(M is the same as in the general formula (1 ′).)
A reaction mixture containing a sulfonyl fluoride compound represented by
1 ′) A sulfonyl fluoride compound represented by the above general formula (5 ′) in the reaction mixture by contacting with an alkali metal salt, alkaline earth metal salt, or Lewis base is converted into the above general formula (3 ′). Converted to an ω-fluorosulfonyl compound represented by
The method according to claim 2, wherein the ω-fluorosulfonyl compound represented by the general formula (3 ′) obtained by the operation 2 ′) and 1 ′) is used in the step (b ′). At least the ω-fluorosulfonyl compound represented by the general formula (3 ′) obtained in the step (a ′) and the sulfonyl fluoride compound represented by the general formula (5 ′) as a by-product. From a reaction mixture comprising
3 ′) separating and removing the ω-fluorosulfonyl compound represented by the general formula (3 ′),
4 ′) The sulfonyl fluoride compound represented by the above general formula (5 ′) in the resulting reaction residue is brought into contact with an alkali metal salt, alkaline earth metal salt, or Lewis base, and the above general formula Converted to an ω-fluorosulfonyl compound represented by (3 ′),
5 ′) Next, the ω-fluorosulfonyl compound represented by the general formula (3 ′) obtained in the step 4 ′) is used in the step (b ′).
The method of claim 2. In the step (b ′), the ω-fluorosulfonyl compound represented by the general formula (3 ′) and hexafluoropropylene oxide are represented by the following general formula (6) in the presence of a fluorine ion-containing compound.
R ¹ O (R ² O) _p R ¹ (6)
(R ¹ is an alkyl group having 1 to 5 carbon atoms, R ² is C ₂ H ₄ or C ₃ H _6. P is an integer of 0 to 10)
The following general formula (4 ″) in which n ′ = 0 in the above general formula (4 ′), which comprises reacting in the presence of a mixed solvent of an ether solvent and a carboxylic acid dinitrile solvent
CF ₃ CF (COF) O (CF ₂ ) _m SO ₂ F (4 ″)
(M is the same as in the general formula (1 ′).)
The method of Claim 1 which is a process of manufacturing the acid fluoride compound represented by these.   The mass ratio of the carboxylic acid dinitrile solvent in the mixed solvent of the ether solvent and the carboxylic acid dinitrile solvent represented by the general formula (6) is 30% by mass or more and 99% by mass or less. Method. In the step (c ′), the acid fluoride compound represented by the general formula (4 ″) is converted into a carboxylate, and then the carboxylate is thermally decomposed. In the general formula (2 ′), n A method for producing ω-fluorosulfonylperfluoroalkyl vinyl ether represented by the following general formula (2 ″) in which “= 0”, wherein the target product is ω-fluoro represented by the following general formula (2 ″). When the number of moles of sulfonyl perfluoroalkyl vinyl ether formed is r and the number of moles of acid fluoride compound represented by the above general formula (4 ″) regenerated as a by-product is s, [s] / [r + s] The method according to claim 1, wherein the reaction is carried out at a production ratio of the by-product represented by 0.1 or less.
CF ₂ = CFO (CF ₂ ) _m SO ₂ F (2 ″)
(M is the same as in the general formula (1 ′).) The carboxylate salt derived from the acid fluoride compound represented by the general formula (4 ″) is a potassium salt represented by the following general formula (7), and thermal decomposition of the carboxylate is carried out without solvent. The method of claim 7, wherein the method is performed.
CF ₃ CF (CO ₂ K) O (CF ₂ ) _m SO ₂ F (7)
(M is the same as in the general formula (1 ′).)   The method according to claim 7 or 8, wherein the thermal decomposition of the carboxylate is carried out while keeping the carboxylate in a solid phase. The method according to claim 1, wherein the ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1 ') is obtained by the following steps (i) to (iv):
(I) The following general formula (8)
X (CF ₂ ) _m X (8)
(X and m are the same as those in the general formula (1 ′).)
A dithionite selected from an alkali metal salt type, an alkaline earth metal salt type, a quaternary ammonium salt type, and a quaternary phosphonium salt type. After mixing and stirring, the following general formula (9)
X (CF ₂ ) _m SO ₂ M (9)
(In the formula, M is Ma, Mb _1/2 , a quaternary ammonium radical or a quaternary phosphonium radical, Ma is an alkali metal, and Mb is an alkaline earth metal. X and m are the above general formulas ( Same as 1 ').
A process for producing an ω-haloperfluoroalkylsulfinate represented by:
(Ii) separating the ω-haloperfluoroalkylsulfinate represented by the general formula (9) from the reaction mixture obtained in step (i),
(Iii) The ω-haloperfluoroalkylsulfinate represented by the above general formula (9) obtained in step (ii) is treated with a chlorinating agent to give the following general formula (10)
X (CF ₂ ) _m SO ₂ Cl (10)
(X and m are the same as those in the general formula (1 ′).)
A step of producing ω-haloperfluoroalkylsulfonyl chloride represented by formula (iv), and (iv) a fluorinated ion-containing compound of ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) obtained in step (iii) The process of manufacturing omega-haloperfluoroalkyl sulfonyl fluoride represented by the said General formula (1 ') by processing by. The step (ii) is at least the ω-haloperfluoroalkylsulfinate represented by the general formula (9) obtained by the reaction of the step (i) and a by-product of the following general formula (11)
MO ₂ S (CF ₂ ) _m SO ₂ M (11)
(M is the same as the general formula (9), and m is the same as the general formula (1 ′).)
The method comprises the step of extracting and separating the ω-haloperfluoroalkylsulfinate represented by the general formula (9) from the reaction mixture containing the perfluoroalkyl-α, ω-bissulfinate represented by formula (9): The method described. The method according to claim 10, wherein the step (ii) includes the following step (ii-1) and step (ii-2).
(Ii-1) At least unreacted α, ω-dihaloperfluoroalkane obtained in the step (i) and represented by the general formula (9), which is the target compound. From the reaction mixture containing ω-haloperfluoroalkylsulfinate and perfluoroalkyl-α, ω-bissulfinate represented by the general formula (11) as a by-product, the above formula (8) Removing the represented α, ω-dihaloperfluoroalkane,
(Ii-2) At least the ω-haloperfluoroalkylsulfinate represented by the general formula (9) obtained in the step (ii-1) and the perfluoroalkyl-α represented by the general formula (11) Extracting and separating the ω-haloperfluoroalkylsulfinate represented by the general formula (9) from the mixture containing ω-bissulfinate. The α, ω-di represented by the above general formula (8) is obtained by treating the reaction residue after separating and removing the ω-haloperfluoroalkylsulfinate represented by the general formula (9) with a chlorinating agent. A haloperfluoroalkane and / or an ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) is produced and reused in the step (i) and / or the step (iv). The method as described in any one of. After separating and removing the ω-haloperfluoroalkylsulfinate represented by the general formula (9), at least the perfluoroalkyl-α, ω-bissulfinate and the inorganic iodine represented by the general formula (11) are removed. An aqueous solution in which a reaction residue containing at least one inorganic salt selected from a chloride or an inorganic bromide is dissolved is treated with a chlorinating agent, and at least one of iodine or bromine and the following general formula (12):
ClO ₂ S (CF ₂ ) _m SO ₂ Cl (12)
(M is the same as in the general formula (1 ′).)
Perfluoroalkyl-α, ω-bissulfonyl chloride represented by the following formula, and then the reaction mixture is extracted with a poorly water-soluble organic solvent, whereby α, ω-diform represented by the general formula (8) is obtained. The haloperfluoroalkane and / or the ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) is produced and separated, and these are reused in the step (i) and / or the step (iv). The method as described in any one of -12.   By treating the reaction residue after separating and removing the ω-haloperfluoroalkylsulfinate represented by the general formula (9) with a chlorinating agent, the perfluoroalkyl-α represented by the general formula (12) is obtained. , Ω-bissulfonyl chloride, and then reacting the perfluoroalkyl-α, ω-bissulfonyl chloride with iodine or bromine to produce α, ω-dihaloperfluoroalkane represented by the general formula (8) and The omega-haloperfluoroalkyl sulfonyl chloride represented by the said General formula (10) is manufactured, isolate | separated, and these are reused for process (i) and / or process (iv). The method according to claim 1. An α, ω-dihaloperfluoroalkane represented by the above general formula (8) comprising reacting the perfluoroalkyl-α, ω-bissulfonyl chloride represented by the general formula (12) with iodine or bromine; Alternatively, ω-haloperfluoroalkylsulfonyl chloride represented by the above general formula (10) is produced , and these are reused in the step (i) and / or the step (iv). The method according to item .   2. In the compounds represented by the general formulas (1 ′) to (5 ′), (7) to (12), (2 ″), and (4 ″), m is an integer of 4 to 8. And the method according to any one of claims 2 to 16.   2. In the compounds represented by the general formulas (1 ′) to (5 ′), (7) to (12), (2 ″), and (4 ″), m is an integer of 4 to 6. And the method according to any one of claims 2 to 16.   The method according to any one of claims 1 to 4, 10 to 15, and 17 to 18, wherein n or n 'is 0 in the compounds represented by the general formulas (2') and (4 '). .   The method according to any one of claims 1 to 4 and 10 to 18, wherein in the compounds represented by the general formulas (1 ') and (8) to (10), X is an iodine atom.   A method for producing an ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1 '), comprising the steps (i) to (iv) according to claim 10.   A method for producing an ω-haloperfluoroalkylsulfonyl fluoride represented by the general formula (1 '), comprising the step according to any one of claims 11 to 15.