WO2005085187A1 - Method for producing fluorine compound - Google Patents

Method for producing fluorine compound Download PDF

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Publication number
WO2005085187A1
WO2005085187A1 PCT/JP2005/003888 JP2005003888W WO2005085187A1 WO 2005085187 A1 WO2005085187 A1 WO 2005085187A1 JP 2005003888 W JP2005003888 W JP 2005003888W WO 2005085187 A1 WO2005085187 A1 WO 2005085187A1
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Prior art keywords
general formula
represented
above general
fluoride
reaction
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PCT/JP2005/003888
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French (fr)
Japanese (ja)
Inventor
Hideo Saito
Nobuyuki Uematsu
Masanori Ikeda
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Asahi Kasei Kabushiki Kaisha
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Priority to JP2006510769A priority Critical patent/JP4993462B2/en
Publication of WO2005085187A1 publication Critical patent/WO2005085187A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/78—Halides of sulfonic acids
    • C07C309/79—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms
    • C07C309/80—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/78—Halides of sulfonic acids
    • C07C309/79—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms
    • C07C309/82—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms of a carbon skeleton substituted by singly-bound oxygen atoms

Definitions

  • the present invention relates to a method for producing ⁇ -fluorosulfol perfluoroalkyl alkyl ether, which is a raw material of a fluorine-based solid electrolyte polymer useful for a fuel cell and a salt electrolysis process, and a synthetic intermediate thereof.
  • Patent Document 1 JP-A-56-90054
  • Patent Document 2 US Pat. No. 6,624,328
  • Patent Document 3 WO2004Z60849
  • Non-Patent Document 1 Weiming Qiu and Donald J. Burton, Journal of Fluorine
  • the present invention relates to a novel ⁇ -fluorosulfol-perperfluoroalkylbutyl ether represented by the general formula (2) or (2 ′) and a synthetic intermediate thereof. It is an object of the present invention to provide a method for producing the compound in a high yield.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the general formula (1) or Starting from the ⁇ -no, perfluoroalkylsulfur fluoride represented by the general formula (1,) as a raw material, the ⁇ -fluorosulfol-fluorofluoride represented by the general formula (2) or (2 ′) is used as a raw material.
  • Method for efficiently producing alkyl vinyl ether, and method for efficiently producing ⁇ -haloperfluoroalkylsulfur fluoride represented by the general formula (1) or (1 ′) or a synthetic intermediate thereof And completed the present invention.
  • the present invention is as follows.
  • R is a divalent perfluorocarbon group having 1 to 9 carbon atoms
  • X is selected from I or Br.
  • a halogen atom, Y is a fluorine atom, a perfluoroalkyl group having 1 to 3 carbon atoms, or
  • —CFY— R— is a divalent perfluorocarbon group having 3 to 10 carbon atoms.
  • Step (b ′) obtained by the above general formula (4 ′) Fluoride-sulfide compound represented by the above general formula (2) is converted to an ⁇ -fluorosulfol-perfluoroalkylbutyl ether represented by the general formula (2). Converting to.
  • R 1 is an alkyl group having 115 carbon atoms
  • R 2 is CH or CH.
  • P is 0-10
  • the mass ratio of the carboxylic acid di-tolyl solvent in the mixed solvent of the ether solvent represented by the general formula (6) and the carboxylic acid di-tolyl solvent is 30% by mass or more and 99% by mass.
  • This is a method for producing ⁇ -fluorosulfol-perfluoroalkyl ether represented by the following general formula (2 "), wherein ⁇ is a target product represented by the following general formula (2") —R is the number of moles of fluorosulfol-perfluoroalkylbutyl ether formed, and s is the number of moles of the acid fluoride conjugate represented by the above general formula (4 ′′) regenerated as a by-product.
  • the method is characterized in that the reaction is carried out at a production ratio of a by-product represented by [s] Z [r + s] of 0.1 or less.
  • Acid fluoride compound represented by the above general formula (4 ) The derived carboxylate is a potassium salt represented by the following general formula (7), and the carboxylate does not undergo thermal decomposition. 12. The method according to 11 above, which is performed in a solvent.
  • alkali metal salt type alkaline earth metal salt type, quaternary ammonium salt type, or quaternary phospho-dimethyl salt type
  • quaternary ammonium salt type quaternary phospho-dimethyl salt type
  • M is Ma, Mb, a quaternary ammo-radical or a quaternary phospho-dimethyl
  • Ma is an alkali metal and Mb is an alkaline earth metal.
  • X and m are the same as those in the general formula (1 ′).
  • step (ii) is at least the ⁇ - haloperfluoroalkylsulfinic acid salt represented by the general formula (9) obtained by the reaction of the step (i) and a by-product (1
  • step (ii) includes the following steps (ii 1) and (ii 2).
  • ⁇ -haloperfluoroalkylsulfinate represented by the general formula (9) is separated and removed, and then the reaction residue is treated with a chlorinating agent to represent the general formula (8).
  • a, ⁇ Dihaloperfluoroalkane and Z or ⁇ -C-perfluoroalkylsulfoylc chloride represented by the above general formula (10) are produced, and these are subjected to step (i) and Z or 14.
  • reaction mixture represented by the general formula (8) ⁇ Dihaloperfluoroalkane and Z or ⁇ -haloperfluoroalkylsulfol-chloride represented by the above general formula (10) are produced, separated and subjected to step (i) and step (iv). ).
  • Oc ⁇ dihalo perflur represented by the above general formula (8), which comprises reacting perfluoroalkyl a, ⁇ bissulfol chloride represented by the above general formula (12) with iodine or bromine.
  • n or n is SO. 21. — Method described in item 1 of 22.
  • the ⁇ -fluorosulfol-leperfluoroalkylbutyl ether represented by the general formula (2) or (2 ′) and a synthetic intermediate thereof are produced in high yield.
  • a method is provided.
  • Steps (a)-(c) From the above, ⁇ -fluoroperfluoroalkylsulfur fluoride represented by the above general formula (1) is used as a raw material to obtain ⁇ -fluorosulfur-fluoride represented by the above general formula (2). According to the method for producing perfluoroalkylbutyl ether and the steps (a), (c), the ⁇ -noperoperfluoroalkylsulfurfluoride represented by the general formula (1) is used as a raw material. A method for producing ⁇ -fluorosulfol-perfluoroalkyl vinyl ether represented by the general formula (2) will be described.
  • step (a) and the step (a ') will be described.
  • R is a divalent perfluorocarbon group having 19 carbon atoms
  • X is a halogen atom selected from I or Br
  • Y represents a fluorine atom, a perfluoroalkyl group having 13 to 13 carbon atoms, or an f group linked to R (1 to 13 carbon atoms).
  • CF— is sometimes referred to as CFY—.
  • CFY— R— is a divalent perfluoro with 3-10 carbon atoms f
  • X is preferably I or Br, but I is more preferred in terms of reactivity! /.
  • CFY—R— is a divalent perfluorocarbon group having 3 to 10 carbon atoms.
  • It may have a structure, a branched structure, or a cyclic structure.
  • Synthesis and easiness of purification and represented by the above general formula (2) or general formula (2 ") derived from ⁇ -haloperfluoroalkylsulfur fluoride represented by the above general formula (1 ') M is more preferably 418, further preferably 416, and particularly preferably 4, from the viewpoint of the operability and functionality of the ⁇ -fluorosulfol-perfluoroalkyl vinyl ether to be obtained.
  • the ⁇ -fluorosulholi-rui dyad product represented by the following formula can be obtained.
  • R and ⁇ can be variously combined. Yes, for example
  • the ⁇ -fluorosulfonylui conjugate represented by the above general formula (3 ') is particularly preferable because of its high practicality.
  • m is more preferably 418, more preferably 416, for the same reason as in the above general formula (1 ′). And particularly preferably 4.
  • SO fuming sulfuric acid
  • C1SOH C1SOH
  • FSOH NO , O
  • catalysts and additives may be added to promote the reaction.
  • catalysts such as HgO and PO
  • chlorides such as pentaoxide, PC1, and SbCl may be used.
  • reaction temperature should be between 20 ° C and 150 ° C.
  • the concentration of SO in fuming sulfuric acid may vary.
  • the amount of fuming sulfuric acid is 0.1 mol based on the effective SO amount of fuming sulfuric acid per 1 mol of ⁇ - haloperfluoroalkylsulfur fluoride represented by the above general formula (1) or (1 ′). Preferred to use in the range from 1 to 100 moles 1 mole force 20
  • the reaction time is not particularly limited, and may be, for example, about 0.1 to 100 hours as long as the reaction proceeds to some extent.
  • the reaction method is not particularly limited.
  • the mixture of ⁇ -haloperfluoroalkylsulfur fluoride represented by the general formula (1) or (1 ′) and SO or fuming sulfuric acid may be heated to reflux,
  • a sulfol fluoride conjugate represented by the formula is contained in the reaction mixture.
  • the sulfonyl fluoride compound represented by the general formula (5) or (5 ′) is a target compound when brought into contact with an alkali metal salt, an alkaline earth metal salt, or a Lewis base. It can be converted to an ⁇ -fluorosulfonyl compound represented by (3) or the general formula (3 ′). Therefore, the SO dissolved in the reaction mixture is washed and removed with concentrated sulfuric acid.
  • the mixture After removal, the mixture is directly brought into contact with an alkali metal salt, an alkaline earth metal salt, or a Lewis base, and subjected to a distillation operation to obtain a target compound represented by the above general formula (3) or (3 ′) represented by the general formula (3 ′).
  • -Fluorosulfonyl ligated products can be obtained.
  • the target compound After washing and removing the SO dissolved in the reaction mixture with concentrated sulfuric acid, the target compound,
  • the sulfonylfluoride represented by the above general formula (5) or (5 ′) is separated.
  • the distillation residue containing the Doi-Dai-Gai product is brought into contact with an alkali metal salt, an alkaline earth metal salt, or a Lewis base to perform a distillation operation.
  • the ⁇ -fluorosulfonyl compound represented by the above general formula (3) or (3 ′) which is the target compound, can also be obtained.
  • Triethynoleamine, 1,8-diazabicyclo [5,4,0] indene, 1,5-diazabicyclo [4,3,0] non-5-ene, N, N-diisopropylethyla KF and N, N-diisopropylethylamine are preferable among the powers including min.
  • the amount of the alkali metal salt, alkaline earth metal salt or Lewis base to be used is 0.001 mol based on 1 mol of the sulfol fluoride compound represented by the general formula (5) or (5 ′). It is preferred to use in the range of from 5 to 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, particularly preferably in the range of 30 ° C to 180 ° C.
  • the reaction method is not particularly limited, the alkali metal salt, alkaline earth metal salt, or Lewis base heated under normal pressure in the absence of a solvent or in the presence of a solvent may be added to the above-mentioned general formula (5) or (5 ′)
  • the reaction product may be distilled off at the same time as the dropwise addition of the sulfolfluoride conjugate represented by the general formula (5), or the sulfolfluoride conjugate represented by the above general formula (5) or (5 ′)
  • a mixture of the above-mentioned alkali metal salt, alkaline earth metal salt or Lewis base may be heated to reflux.
  • a mixture of the sulfonylfluoride conjugate represented by the general formula (5) or (5 ′) and the above alkali metal salt, alkaline earth metal salt, or Lewis base is added to a pressurized container. You can heat it.
  • ether solvents such as diglyme, triglyme and tetraglyme
  • amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone
  • polar solvents such as sulfolane A solvent
  • one kind may be used or a plurality of organic solvents may be combined.
  • m is an integer of 3-10, but more preferably 418 for the same reason as in the general formula (1 '). Yes, more preferably 416, and particularly preferably 4.
  • Patent Document 2 discloses that diglyme is used as a reaction solvent.
  • R 1 is an alkyl group having 115 carbon atoms
  • R 2 is CH or CH.
  • P is 0-10
  • Examples of the ether-based solvent represented by the general formula (6) include diethylene glycol dimethyl enoate, diethylene glycol olenoethyl enoate, diethylene glycol propylene dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyole enoate, Ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, toluene propylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether And the like.
  • Examples of the carboxylic acid di-tolyl-based solvent include saturated aliphatic dicarboxylic acids having 3 to 8 carbon atoms, such as adipo-tolyl.
  • the mass ratio of di-tolyl carboxylate in the mixed solvent of the ether-based solvent and di-tolyl carboxylate is preferably from 30% by mass to 99% by mass, more preferably from 40% by mass to 97% by mass. More preferred 50% by mass or more and 95% by mass or less is particularly preferred.
  • the amount of HFPO used depends on the amount of the ⁇ -fluorosulfol compound From 0.95 monoreca to HFPOi, 2 monoreca S is preferred, and from 0.98 monoreca to 1.8 monoreca is more preferably 1 mol to 1.5 mol.
  • reaction pressure there is no particular restriction on the reaction pressure.
  • the reaction may be performed under normal pressure or under pressure.
  • a pressurized reaction in a pressurized vessel is preferred.
  • the pressure in the pressurized reaction is not limited, but it is preferable to introduce HFPO within a range of 0.1 OlMPa force to 0.1 IMPa gauge pressure.
  • various fluoride ion-containing compounds such as alkali metal fluoride and quaternary ammonium fluoride are used as catalysts, and among them, KF and CsF are more preferable.
  • the amount of the fluorine ion-containing conjugate of the catalyst is not limited, it is usually about 0.001 to 1 mol per 1 mol of the ⁇ -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 during which HFPO is consumed, and is, for example, 0.5 hour and 72 hours.
  • the contents are divided into two layers (the upper layer is a mixed solvent of an ether-based solvent and a carboxylic acid dinitrile-based solvent, and the lower layer is a reaction mixture containing the acid fluoride conjugate represented by the above general formula (4 ")).
  • the lower layer portion is taken out, and the acid fluoride conjugate represented by the above general formula (4 ") can be obtained by a distillation operation.
  • ⁇ -fluorosulfol-perfluoroalkyl ethers Can be converted into ⁇ -fluorosulfol-perfluoroalkyl ethers, respectively.
  • the ⁇ -fluorosulfol-perperfluoroalkylbutyl ether represented by the general formula (2 ") has high practicability and is particularly preferable.
  • m is preferably an integer in the range of 3 to 10, but is more preferably 418, and still more preferably 416, from the viewpoint of ease of synthesis and purification and operability. Yes, especially 4
  • An acid fluoride compound represented by the above general formula (4) or the general formula (4 ') or the general formula (4 ") is introduced into silica or alumina or the like supporting an alkali metal or alkaline earth metal fluoride, By contacting, ⁇ -fluorosulfol-perfluorofluoroalkyl ether represented by the general formula (2), (2 ′) or (2 ′′) can be obtained.
  • the acid fluoride compound represented by the general formula (4) or (4 ′) or (4 ′′) is reacted with various basic compounds to form an alkali metal salt of carboxylic acid.
  • the carboxylate After being converted into a salt or an alkaline earth metal salt, the carboxylate is subjected to a heat decarboxylation reaction, whereby ⁇ -fluorosulfo- represented by the above general formula (2) or (2 ′) or (2 ′′) is obtained.
  • the method for obtaining ruperfluoroalkylbutyl ether will be described.
  • Examples of the basic compound used in the conversion reaction from the acid fluoride conjugate represented by the general formula (4) or (4 ′) or (4 ′′) to the carboxylate include: Alkali metal or alkaline earth metal carbonates and hydroxides are preferred, especially carbonates because of their good operability. Examples include lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, rubidium carbonate, calcium carbonate, barium carbonate, etc., and among them, sodium carbonate, potassium carbonate, and the like are preferred, such as sodium carbonate, potassium carbonate, and calcium carbonate. Particularly preferred is potassium carbonate.
  • a solvent When converting the acid fluoride conjugate represented by the general formula (4), (4 ′) or (4 ′′) into an alkali metal salt or an alkaline earth metal salt of the carboxylic acid, a solvent is required.
  • a solvent for example, a solvent such as acetonitrile or propio-tolyl, or a tolyl solvent or an ether such as monoglyme, diglyme, triglyme, or tetraglyme may be used.
  • a system solvent is used, and a reaction temperature in the range of 0 ° C to 80 ° C is particularly preferred!
  • the above-mentioned general formula (2) or general formula (2 ′) or general formula (2 ′′) is obtained by heat decarboxylation reaction.
  • the conversion may be carried out with or without a solvent, but it is better to carry out the conversion without a solvent. Easy to achieve reaction grade! /, So more preferred.
  • Conditions for performing the decarboxylation reaction in the presence of a solvent include, for example, performing the decarboxylation reaction in the range of 80 ° C to 180 ° C using an ethereal solvent such as diglyme, triglyme, or tetraglyme.
  • the ⁇ -fluorosulfol-perperfluoroalkylbutyl ether represented by the general formula (2), (2 ′) or (2 ′′) can be produced.
  • the solvent used in the neutralization reaction is once distilled off by distillation or the like, and then the decarboxylation reaction is performed in the range of 100 ° C to 250 ° C, preferably in the range of 150 ° C to 230 ° C.
  • the ⁇ -fluorosulfol-perfluorofluoroalkyl ether represented by the general formula (2), (2 ′) or (2 ′′) can be obtained.
  • the reaction products It is desirable to carry out the reaction while continuously and quickly distilling the product out of the reaction system. If the reaction product stays in the reactor, by-products are likely to be generated, and the ⁇ full represented by the above-mentioned general formula (2), general formula (2 ′) or general formula (2 ′′), which is the target product, The yield of olosulfonyl perfluoroalkyl butyl ether is reduced.
  • the present inventors have converted the particularly useful ⁇ -fluorosulfol-leperfluoroalkylbutyl ether represented by the above general formula (2 ′′) to the acid fluoridyl ether represented by the above general formula (4 ′′).
  • the acid fluoridyl ether represented by the above general formula (4 ′′).
  • the present inventors have proposed a method for producing an acid fluoridation compound represented by the above general formula (4 ") and a method for producing ⁇ -fluorosulfol perfluoroalkyl alkyl ether represented by the above general formula (2"). , Including the method described in Patent Document 2.
  • the method via sodium salt described in Patent Document 2 is not an industrially advantageous production method due to the generation of many difficult-to-separate by-products. It has been found that high quality products can be produced with high yield by employing the method very efficiently.
  • Patent Document 2 having these problems cannot be said to be an industrially advantageous production method.
  • the present inventors have conducted intensive studies on a reaction method for minimizing the side reaction as described above. As a result, there are salts such as potassium salts which do not melt even during the heating decarboxylation reaction. In the thermal decarboxylation reaction, it was found that the amount of the by-product acid fluoride compound represented by the above general formula (4 ") was extremely reduced, and the target product of high purity was obtained in high yield.
  • the value of [s] Z [r + s] is preferably 0.1 or less, more preferably 0.08 or less, further preferably 0.06 or less, and particularly preferably. 0.04 or less.
  • the lower limit of [s] Z [r + s] is not particularly limited, but may be 0.001 or 0.0001, or may be lower than the detection limit of the measuring instrument.
  • the carboxylate derived from the acid fluoride compound represented by ") is represented by the following general formula (7)
  • thermal decomposition of the carboxylate is carried out without a solvent.
  • the thermal decomposition of the carboxylate is carried out during decarboxylation by heating. This is performed while keeping the carboxylate in a solid phase state.
  • the effect of the potassium salt will be specifically described by comparing the reaction results of the sodium salt and the potassium salt when the carboxylate is thermally decomposed with a medium.
  • the carboxylate is a sodium salt
  • the heating temperature is set to 180 ° C. or higher
  • the sodium salt is in a molten state at the time of thermal decomposition as described above, and is represented by the above general formula (4 ′′) as a by-product.
  • the acid fluoride compound is produced in a large amount, and the desired product, ⁇ -fluorosulfol-perfluoroalkylalkyl ether represented by the above general formula (2 ′′), is obtained in low yield, and the [ s ] Z [r + s] was 0.19.
  • the carboxylate is a potassium salt
  • the potassium salt is in a solid phase upon thermal decomposition, and is an acid fluoride represented by the general formula (4 "), which is a by-product described above.
  • the formation of the compound was slight, and the desired product, ⁇ -fluorosulfol-perperfluoroalkylbutyl ether represented by the above general formula (2 "), was obtained in high yield, and [s] Z [r + s] was 0.01.
  • alkali metal or alkaline earth metal carbonates used include lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, and carbonate. Rubidium, calcium carbonate, barium carbonate and the like can be mentioned. Among them, potassium carbonate, which is more preferably sodium carbonate, potassium carbonate, calcium carbonate and the like, is particularly preferable.
  • a silyl ester of carboxylic acid is produced by reacting the silanol compound with a siloxane compound using the catalyst as a catalyst.
  • siloxane conjugates include, for example, disiloxane conjugates such as hexamethinoresisiloxane, hexethinoresisiloxane, and hexafeninoresisiloxane, and siloxane polymers such as cyclic siloxane compounds and polymethylsiloxane.
  • the silyl ester of the carboxylic acid thus produced is subjected to a desilyl fluoride reaction in a liquid or gaseous phase using an alkali metal fluoride such as KF or NaF as a catalyst to obtain the above general formula (2) or general formula (2 ′)
  • ⁇ -fluorosulfonylperfluoroalkylbutyl ether represented by the general formula (2 ") can be obtained.
  • the temperature at which the desilyl fluoride reaction is performed is, for example, a reaction in a liquid phase. In this case, the reaction temperature is in the range of 25 ° C to 175 ° C, and when the reaction is performed in the gas phase, it is in the range of 140 ° C to 250 ° C.
  • the ⁇ -fluorosulfol-perperfluoroalkylbutyl ether represented by the general formula (2), (2 ′) or (2 ′′) obtained by the above-mentioned various methods is obtained by a method such as distillation. Can be purified.
  • ⁇ -haloperfluoroalkylsulfonylfluoride represented by the above general formula (1) which is a raw material for synthesizing ⁇ -fluorosulfol-perperfluoroalkylbutyl ether represented by the above general formula (2).
  • the metal can be used in the method of the present invention whatever is manufactured by any method.
  • the production method shown in the above scheme 2 has been reported. However, it is not an industrially advantageous production method.
  • highly pure ⁇ -haloperfluoroalkylsulfur fluoride is efficiently produced. It is practically particularly preferable because it can be manufactured.
  • step (i) will be described.
  • M is Ma, Mb, quaternary ammom-radical or quaternary phospho-mradica
  • Ma is an alkali metal and Mb is an alkaline earth metal.
  • X and m are the same as those in the above general formula (1 ′).
  • Alkali metal salt type such as O, KSO, CsSO, alkaline earth metal salt type such as CaSO
  • Quaternary ammonium salt forms such as ((CH) N) SO and ((n-Bu) N) SO, ((CH) P
  • a, ⁇ -dihaloperfluoroalkane represented by the above general formula (8) and an alkali metal salt type, an alkaline earth metal salt type, a quaternary ammonium salt type, or a quaternary ammonium salt type In the reaction of dithionite selected from any of the lower phospho-dum salt forms, in addition to the ⁇ -haloperfluoroalkylsulfinate represented by the general formula (9), by-products
  • the amount of the dithionite used is preferably from 0.1 to 3 equivalents to the a, ⁇ dihaloperfluoroalkane represented by the general formula (8). 0.1 to 2.0 equivalents Is more preferably 0.2 to 1.5 equivalents. At less than 0.1 equivalent, the reaction of the substrate hardly progresses, and at more than 3.0 equivalent, the amount of perfluoroalkyl ⁇ , ⁇ bissulfinate represented by the above general formula (11) increases. This is not preferred.
  • Solvents used in the above reaction include, for example, ketone solvents such as acetone and methyl ethyl ketone, -tolyl solvents such as acetonitrile and propio-tolyl, and linear or cyclic solvents such as tetrahydrofuran, dioxane and diglyme.
  • Ether solvents amide solvents such as ⁇ , ⁇ -dimethylformamide and ⁇ , ⁇ -dimethylacetamide, and various polar solvents such as dimethyl sulfoxide.
  • ketone solvents such as acetone and methyl ethyl ketone
  • -tolyl solvents such as acetonitrile and propio-tolyl
  • acetone and acetonitrile are preferred.
  • These organic solvents are preferably used as a mixed solvent with water, and one kind of organic solvent may be used, or a combination of a plurality of organic solvents may be used.
  • the amount of the organic solvent to be used with respect to water is preferably 0.1 times or more and 100 times or less, more preferably 1 time or more and 50 times or less with respect to the volume of water. It is particularly preferable that the ratio be from 20 to 20 times. If the amount of water used is more than 100 times, the reaction of the substrate hardly proceeds, which is not preferable.
  • the amount of water relative to the substrate is preferably from 0.1 to 200 equivalents, more preferably from 1 to 150 equivalents, particularly preferably from 5 to 100 equivalents, based on the substrate.
  • a neutralizing agent or a buffer may be added.
  • the neutralizing agent include hydrogen carbonate such as lithium hydrogen carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate; carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; and phosphorus such as sodium hydrogen phosphate and potassium hydrogen phosphate.
  • Hydrogen salts, phosphates such as sodium phosphate and potassium phosphate, and hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and the like can be used. It comes out.
  • Reaction temperatures are 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 depending on the reaction conditions, but practically, the range is about 0.1 to 48 hours. .
  • step (ii) will be described.
  • the target compound represented by the above general formula (9) is obtained by reacting a, ⁇ dihaloperfluoroalkane represented by the above general formula (8) with dithionite.
  • a, ⁇ dihaloperfluoroalkane represented by the above general formula (8) with dithionite.
  • Oroalkyl ⁇ , ⁇ bissulfinates are formed as by-products.
  • an inorganic iodide or an inorganic bromide generated by the reaction also exists in the reaction system.
  • inorganic iodide or inorganic bromide When a suspension in which inorganic iodide or inorganic bromide is precipitated and formed in the reaction system is formed, inorganic iodide or inorganic bromide may be removed by filtration and separation and purification may be performed. .
  • the removal method can be adopted.
  • Specific examples of the removal method include, for example, removal by distillation, extraction and removal with a fluorine atom-containing organic solvent, or ⁇ -haloperfluoroalkylsulfinate represented by the general formula (9) and Examples of the method include removal by phase separation from an aqueous medium containing a perfluoroalkyl ⁇ , ⁇ bissulfinate represented by the general formula (11).
  • the unreacted a, ⁇ dihaloperfluoroalkane represented by the above general formula (8) is reacted with the used organic solvent by distillation or the like from the solution or suspension after the reaction. Can be excluded.
  • a removal method by phase separation for example, after distilling off the organic solvent used by a method such as distillation, water is added to separate into two layers, and a, ⁇ dihalo perfluoro represented by the above general formula (8) is obtained. Since the lower alkane is separated into the lower layer, the lower layer The a, ⁇ dihaloperfluoroalkane represented by the general formula (8) can be obtained.
  • the method of extraction and removal using a fluorine atom-containing organic solvent is as follows.
  • the reaction mixture obtained in step (i) is mixed with a fluorine atom-containing organic solvent such as HFC43-10mee and perfluorohexane, and the above formula (8) is used.
  • a fluorine atom-containing organic solvent such as HFC43-10mee and perfluorohexane
  • an aqueous dispersion in which the ⁇ -haloperfluoroalkylsulfinate represented by the general formula (9) and the perfluoroalkyl ⁇ , ⁇ bissulfinate represented by the general formula (11) are dissolved From the liquid or the solid mixture containing both components, the ⁇ -haloperfluoroalkylsulfinate represented by the above general formula (9) can be extracted.
  • Reaction mixture in which the ⁇ -haloperfluoroalkyl sulfinate represented by the general formula (9) and the perfluoroalkyl a, ⁇ bis sulfinate represented by the general formula (11) are dissolved As a method for extracting the ⁇ -haloperfluoroalkyl sulfinate represented by the above general formula (9), for example, ester solvents such as ethyl acetate, ether solvents such as ethyl ether, etc. And extracting the ⁇ -noperoperfluoroalkylsulfinate represented by the above general formula (9) into the organic layer by adding the poorly water-soluble organic solvent.
  • ester solvents such as ethyl acetate
  • ether solvents such as ethyl ether
  • the perfluoroalkyl ⁇ , ⁇ -bissulfinate represented by the general formula (11) and the inorganic iodide or inorganic bromide such as an inorganic iodide or an inorganic bromide generated in the step (i) are used.
  • the salt is separated on the aqueous layer side.
  • the organic solvent is distilled off to obtain a highly pure compound represented by the above general formula (9).
  • ⁇ -haloperfluoroalkyl sulfinate can be isolated.
  • the organic layer contains almost no perfluoroalkyl a, ⁇ bissulfinate represented by the general formula (11)! /.
  • an ester solvent such as ethyl acetate or an ether solvent such as getyl ether is used.
  • the perfluoroalkyl ⁇ , ⁇ bissulfinate represented by the general formula (11) and inorganic salts such as inorganic iodide or inorganic bromide, which are insoluble in the organic solvent, are removed by filtration. be able to.
  • the organic solvent is distilled off from the filtrate by distillation or the like, a high-purity ⁇ -no, perfluoroalkylsulfinate represented by the above general formula (9) is obtained in a high yield.
  • step (iii) will be described.
  • the ⁇ -haloperfluoroalkylsulfojuruku mouth represented by the formula can be obtained. Specifically, after dissolving or dispersing the ⁇ -haloperfluoroalkylsulfinate represented by the general formula (9) in water, an organic solvent or a mixed solvent thereof, a chlorinating agent is added. With this, a chlorination reaction can be performed.
  • This step can be carried out in various media, but considering the ease and safety of the reaction operation, it is preferable to use water or an aqueous solution containing an acid as the solvent.
  • the chloridizing agent is not particularly limited as long as it can convert —SO M to SO C1.
  • chloridizing agents For example, the ability to use chlorine, sulfuryl chloride or the like as a chlorine-containing agent, particularly preferably chlorine.
  • chlorine sulfuryl chloride or the like
  • the target compound ⁇ -haloperfluoroalkylsulfuric acid mouth lid represented by the above general formula (10)
  • the conditions for the chlorination reaction are not particularly limited, and may be appropriately determined depending on the type of the chlorinating agent to be used so that the desired chlorinated product is produced.
  • chlorine gas is supplied to an aqueous solution in which the ⁇ -noperoperfluoroalkyl sulfinate of the above general formula (9) is dissolved to perform the chlorination reaction.
  • the reaction temperature is preferably 0-50 ° C, and the amount of chlorine charged is preferably about 115 mol per mol of ⁇ - haloperfluoroalkyl sulfinic acid salt of the above general formula (9).
  • the range of 1.2 to 3 moles is more preferable.
  • the concentration of the ⁇ -noperoperfluoroalkyl sulfinate of the above general formula (9) in the aqueous solution is not particularly limited, but may be usually about 0.5 to 50% by mass.
  • the compound represented by the general formula (1 ′) is obtained.
  • ⁇ -haloperfluoroalkylsulfur fluoride can be obtained.
  • the reaction with the fluoride ion-containing compound can be carried out according to a known method, and in a solvent or without a solvent, the ⁇ -haloperfluoroalkylsulfonyl chloride represented by the above general formula (10) and fluorine ion What is necessary is just to make the contained dangling product react.
  • the solvent is not particularly limited, and various solvents can be used.
  • a polar organic solvent such as acetonitrile, sulfolane, dimethyl sulfoxide, ⁇ , ⁇ -dimethylformamide, water, or a mixed solvent thereof can be used. .
  • the fluorine ion-containing compound used is one that can convert SO C1 to SO F.
  • Any known fluorine ion-containing conjugate can be used without particular limitation.
  • Examples include alkali metal fluorides such as NaF and KF.
  • the reaction temperature may be in the range of 0 to 200 ° C, and the reaction time may be about 0.1 hour, about 48 hours.
  • the amount of the fluoride ion-containing compound to be used is preferably 1 mol or more and 10 mol or less with respect to 1 mol of the ⁇ -halofluoroalkylsulfonyl chloride represented by the above general formula (10). It is more preferably at least 5 mol and at most 5 mol.
  • the concentration of ⁇ -haloperfluoroalkylsulfol chloride represented by the above general formula (10) is not particularly limited, but is usually 10 to 100% by mass.
  • the method for separating the ⁇ -haloperfluoroalkylsulfonyl fluoride represented by the above general formula (1 ′) obtained by the above method may be appropriately changed depending on the solvent used in the reaction.
  • ⁇ -noperoperfluoroalkylsulfonyl fluoride represented by the above general formula (1 ′) can be separated by distillation, and the above general formula can be obtained by removing water depending on the type of solvent.
  • the ⁇ -haloperfluoroalkylsulfur-fluoride represented by the formula (1) can be separated as an organic layer.
  • step (ii 2) the by-product perfluoroalkyl a, ⁇ bissulfinate represented by the above general formula (11), which is separated by the above step (ii 2), is converted into the above general formula (8)
  • a method for producing the ⁇ , ⁇ dihaloperfluoroalkane and ⁇ or the ⁇ -haloperfluoroalkylsulfol-chloride represented by the general formula (10) will be described.
  • the processing solution or purified residue separated in step (ii 2) contains by-products perfluoroalkyl a, ⁇ bissulfinate represented by the general formula (11) and inorganic iodide or Inorganic bromide power Contains at least one selected inorganic salt.
  • the perfluoroalkyl, ⁇ bissulfinate represented by the general formula (11) is represented by the general formula (12)
  • Perfluoroalkyl ⁇ , ⁇ -bissulfol-chloride is formed, while inorganic iodide or inorganic bromide forms iodine or bromine.
  • the reaction of the perfluoroalkyl a, ⁇ bissulfol chloride represented by the above general formula (12) with iodine or bromine causes ⁇ , ⁇ represented by the above general formula (8).
  • Dihaloperfluoroalkanes and ⁇ -haloperfluoroalkyl sulfides represented by the general formula (10) can be obtained.
  • the formation ratio of the ⁇ , ⁇ dihalo perfluoroalkane represented by the general formula (8) and the ⁇ -haloperfluoroalkyl sulfonyl chloride represented by the general formula (10) is determined by the above-mentioned general formula It is determined by the ratio of perfluoroalkylalkyl ⁇ , ⁇ -bissulfoyl chloride represented by (12) and coexisting iodine or bromine.
  • a solvent capable of simultaneously dissolving iodine or bromine and both the perfluoroalkyl ⁇ , ⁇ bissulfoulyl chloride compound represented by the general formula (12) is added, whereby the compound represented by the general formula (8) is added.
  • Examples of the solvent for simultaneously dissolving iodine or bromine and both the perfluoroalkyl ⁇ , ⁇ -bissulfoyl chloride compound represented by the above general formula (12) include, for example, ethyl acetate, butyl acetate and the like.
  • Examples include polar solvents such as ester solvents, ether solvents such as monoglyme and diglyme, -tolyl solvents such as acetonitrile and propio-tolyl, and ketone solvents such as acetone and methyl ethyl ketone. It is more preferable to use a poorly water-soluble organic solvent such as ethyl acetate or butyl acetate as the solvent, because the product can be extracted simultaneously with the reaction.
  • polar solvents such as ester solvents, ether solvents such as monoglyme and diglyme, -tolyl solvents such as acetonitrile and propio-tolyl, and ketone solvents such as acetone and methyl ethyl ketone.
  • polar solvents such as ester solvents, ether solvents such as monoglyme and diglyme, -tolyl solvents such as acetonitrile and propio-tolyl, and ketone solvent
  • the treatment solution or the purified residue is reacted with a chlorinating agent to form a perfluoroalkyl a, ⁇ bissulfol chloride represented by the general formula (12), and the acid chloride is converted to Isolation by filtration, solvent extraction, or the like, followed by reaction with iodine or bromine in a solvent, gives ⁇ , ⁇ dihaloperfluoroalkane represented by the above general formula (8) and Z or ⁇ -haloperfluoroalkylsulfoyl chloride represented by the above general formula (10) can also be obtained.
  • the ratio is determined by the amount of iodine or bromine added.
  • the solvent in this step include ester solvents such as ethyl acetate and butyl acetate, ether solvents such as monodalaim and diglyme, -tolyl solvents such as acetonitrile and propio-tolyl, acetone, and methyl ethyl ketone. And the like.
  • chlorinating agent used in the first step a publicly known chlorinating agent without particular limitation can be used.
  • a publicly known chlorinating agent without particular limitation can be used.
  • chlorine, sulfuryl chloride and the like can be used as a chlorinating agent, and chlorine is particularly preferred.
  • the a, ⁇ -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 ⁇ -haloperfluoroalkylsulfonyl chloride represented by the above general formula (10) obtained by the above operation is reused in the reaction with the fluorine ion-containing conjugate in the above step (iv).
  • it can be used after being converted to ⁇ -no and perfluoroalkylsulfur fluoride represented by the above general formula (1,).
  • the ⁇ -fluorosulfonylperfluoroalkylvinyl ether represented by the above general formula (2) or (2 ′) according to the production method of the present invention can be used for various solid electrolyte materials or ion exchange membranes. It is a useful substance as a monomer component for polymers.
  • the solid electrolyte polymer examples include an electrolyte membrane for 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, and a membrane for oxygen concentrator. It is used as a film for temperature sensors and films for gas sensors.
  • the ⁇ -fluorosulfo-leperfluoroalkylbutyl ether represented by the general formula (2) or (2 ′) and a synthetic intermediate thereof can be produced at a high yield. Can be manufactured.
  • the 19 F-NMR spectrum was measured using a GSX-400 nuclear magnetic resonance device manufactured by JEOL Japan as a measuring device, double-mouthed form as a solvent, and Freon 11 (CFC1) as a reference material.
  • the test was performed under the following apparatus and conditions.
  • the test was performed under the following apparatus and conditions.
  • the vessel was cooled in an ice bath.
  • 287 g of Na 2 S O is calorie divided into 5 times in 15 minutes.
  • reaction mixture was 19 F-NMR, 57 mol I (CF) I % Remaining, 36 mol% of I (CF) SONa and 7 mol% of NaOS (CF) SONa
  • the obtained liquid was purified by distillation (bp 54 ° C, 40 kPa) to obtain FOC (CF) SO F 2.67 kg
  • the flask was placed in an ice bath, 19 g of Na 2 S 2 O was added little by little, and the mixture was stirred at room temperature for 2 hours.
  • Recol dimethyl ether was distilled off under reduced pressure, and the residue was further heated to 120 ° C. and dried under reduced pressure. Dried residue containing CF CF (CO Na) 0 (CF) SO F to 200 ° C
  • Example 1 In a 200 mL three-necked flask equipped with a distillation tower and a dropping funnel, 33.2 g of sulfolane and 6.05 g of KF were placed, and while heating to 50 ° C, the FSO 0 (CF) SOF obtained in Example 1 was heated.
  • reaction mixture Upon heating at 60 ° C. for 19 hours, the reaction mixture separated into two layers and reached a conversion of 91%. After separating the upper layer and washing with concentrated sulfuric acid, distillation and purification yielded 34.lg of liquid.
  • reaction mixture power is also ethylene glyco
  • the reaction was carried out in the same manner as in Example 1. That is, after the reaction of I (CF) I and NaSO is completed, After acetone was distilled off from the mixture, water was added to separate the mixture into two layers. When the lower layer was separated, 546 g of I (CF) I was recovered. Ethyl acetate is added to the upper layer and extracted three times with ethyl acetate.
  • Example 1 In a 1 L four-necked flask equipped with a gas injection tube, NaO S (CF) separated in Example 1 was placed.
  • the solid formed is iodine and CIO S (CF) SOCI.

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Abstract

Disclosed is a method for producing an ω-fluorosulfonyl perfluoroalkyl vinyl ether represented by the general formula (2) below through specific steps (a)-(c) from an ω-haloperfluoroalkyl sulfonyl fluoride represented by the general formula (1) below used as the raw material. (1) (In the formula, Rf represents a divalent perfluorocarbon group having 1-9 carbon atoms; X represents a halogen atom selected from I and Br; Y represents a fluorine atom, a perfluoroalkyl group having 1-3 carbon atoms or a linking group with Rf (having 1-3 carbon atoms; and -CFY-Rf- represents a divalent perfluorocarbon group having 3-10 carbon atoms.). (2): CF2=CFO(CF2CF(CF3)O)n-CFY-Rf-SO2F (In the formula, n is an integer of 0-2, and Rf and Y are as defined in the general formula (1) above.)

Description

フッ素化合物の製造方法  Method for producing fluorine compound
技術分野  Technical field
[0001] 本発明は燃料電池や食塩電解プロセスに有用なフッ素系固体電解質ポリマーの原 料である、 ω—フルォロスルホ-ルペルフルォロアルキルビュルエーテル及びその合 成中間体の製造方法に関する。  The present invention relates to a method for producing ω-fluorosulfol perfluoroalkyl alkyl ether, which is a raw material of a fluorine-based solid electrolyte polymer useful for a fuel cell and a salt electrolysis process, and a synthetic intermediate thereof.
背景技術  Background art
[0002] 一般式（2)又は一般式（2，）で表される ω—フルォロスルホ-ルペルフルォロアルキ ルビ-ルエーテルの合成中間体である一般式（3)又は一般式（3 ' )で表される ω—フ ルォロスルホ -ル化合物の製造方法の例としては、例えば FCO (CF ) SO Fの場  [0002] General formula (3) or general formula (3 '), which is a synthetic intermediate of ω-fluorosulfol-perperfluoroalkylvinyl ether represented by general formula (2) or (2,) An example of a method for producing an ω-fluorosulfur compound represented by the following formula:
2 2 2 合、テトラフルォロエチレンとジメチルカーボネートとナトリウムェチルメル力プチドを 出発原料とした製造方法が開示されている。この方法は、反応工程が長ぐかつ収率 が低いという問題があった (例えば、特許文献 1参照)。  In the case of 222, 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).
また、一般式（2)又は一般式（2' )で表される ω—フルォロスルホ-ルペルフルォロ アルキルビュルエーテルの製造方法としては、例えば CF =CFO (CF ) SO Fの場  Further, a method for producing ω-fluorosulfol-perperfluoroalkylbutyl ether represented by the general formula (2) or (2 ′) includes, for example, the case of CF = CFO (CF) SOF.
2 2 4 2 合、スキーム 1に示されるようにスルトン化合物を出発原料として、電解フッ素化工程 、へキサフルォロプロピレンォキシド（HFPO)の付カ卩工程、ビュル化工程による方法 が報告されている (例えば、特許文献 2、特許文献 3参照)。  As shown in Scheme 1, a method involving the use of a sultone compound as a starting material, an electrolytic fluorination process, a process of adding hexafluoropropylene oxide (HFPO), and a process of forming a butyl compound were reported. (For example, see Patent Documents 2 and 3).
<スキーム 1 > <Scheme 1>
C 電解フッ素化 HFpo Na2C03 C electrolytic fluorinated HFpo Na 2 C0 3
^ FCO(CF2)jS02F ^ CFjCFOiCFiJiSOiF CF2=CFO(CF2)4S02F s y.28% y.65% 0F y.74 し力しながら、電解フッ素化工程は副生成物が多ぐ FCO (CF ) SO Fの収率は ^ FCO (CF 2 ) jS0 2 F ^ CFjCFOiCFiJiSOiF CF 2 = CFO (CF 2 ) 4 S0 2 F s y.28% y.65% 0F y.74 FCO (CF) SO F
2 3 2  2 3 2
低い。また、 HFPO付カ卩工程及びビニルイ匕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。  Low. In addition, satisfactory yields have not been obtained in the kneading process with HFPO and the vinyl iridescence process, and further improvement in production efficiency is required to make the production method economically advantageous.
[0003] さらに、一般式（1)又は一般式（1，）で表される ω—ノ、口ペルフルォロアルキルスル ホ-ルフルオリドの製造方法として、スキーム 2に示されるように、 α , ω—ジハロペル フルォロアルカンを亜ジチオン酸ナトリウムと反応させ、塩素化、フッ素化により製造 する方法が報告されている（例えば非特許文献 1参照)。この方法では塩素化反応後 、蒸留操作により目的化合物である ω—ノヽロペルフルォロアルキルスルホユルクロリド を単離している力 蒸留による分離が困難であるうえ、さらに ω—ノヽロペルフルォロア ルキルスルホユルク口リドの熱安定性が悪いため、蒸留時の分解により、蒸留収率が 低くなり、工業的に有利に目的化合物を製造することは困難であった。 くスキーム 2 > I(CF2)mI [0003] Further, as shown in Scheme 2, as a method for producing ω-no, perfluoroalkylsulfur fluoride represented by the general formula (1) or (1,), α, ω —Dihaloper A method of producing a fluoroalkane by reacting it with sodium dithionite and chlorinating and fluorinating it has been reported (for example, see Non-Patent Document 1). In this method, after the chlorination reaction, the target compound ω-noperoperfluoroalkylsulfuryl chloride is isolated by a distillation operation, separation by force distillation is difficult, and furthermore, ω-noperoperfluoroalkylsulfurylc Since the thermal stability of the lid was poor, the distillation yield was reduced due to decomposition during distillation, and it was difficult to produce the target compound industrially advantageously. Scheme 2> I (CF 2 ) m I
KCF2)mI I(CF2)mS02ClKCF 2 ) m II (CF 2 ) m S0 2 Cl
Figure imgf000004_0001
ClO2S(CF2)mS02CI
Figure imgf000004_0001
ClO 2 S (CF 2 ) m S0 2 CI
： Θ : Θ
I(CF2)mS02Cl i(CF2)mS02F I (CF 2 ) m S0 2 Cl i (CF 2 ) m S0 2 F
*1  * 1
蒸留による I(CF2)mS02CI の単離が困難。 Distillation with I (CF 2) m S0 2 CI isolation difficult.
I(CF2)mS02CI が不安定なため蒸留収率が低い I (CF 2) m S0 is low distillation yields for unstable 2 CI
[0004] 特許文献 1：特開昭 56— 90054号 [0004] Patent Document 1: JP-A-56-90054
特許文献 2：米国特許第 6624328号  Patent Document 2: US Pat. No. 6,624,328
特許文献 3： WO2004Z60849号  Patent Document 3: WO2004Z60849
非特干文献 1： Weiming Qiu and Donald J. Burton, Journal of Fluorine  Non-Patent Document 1: Weiming Qiu and Donald J. Burton, Journal of Fluorine
Chemistry,60卷 93— 100頁 （1993年）  Chemistry, Vol. 60, pp. 93-100 (1993)
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0005] 本発明は、このような現状に鑑み、一般式（2)又は一般式（2' )で表される ω—フル ォロスルホ-ルペルフルォロアルキルビュルエーテル及びその合成中間体を高収率 で製造する方法を提供することを目的とするものである。 [0005] In view of the above-mentioned circumstances, the present invention relates to a novel ω-fluorosulfol-perperfluoroalkylbutyl ether represented by the general formula (2) or (2 ′) and a synthetic intermediate thereof. It is an object of the present invention to provide a method for producing the compound in a high yield.
課題を解決するための手段  Means for solving the problem
[0006] 本発明者らは、上記問題を解決すベぐ鋭意研究を行った結果、一般式（1)又は 一般式（ 1，）で表される ω—ノ、口ペルフルォロアルキルスルホ-ルフルオリドを原料と して、一般式（2)又は一般式（2' )で表される ω—フルォロスルホ-ルペルフルォロア ルキルビニルエーテルを効率的に製造する方法、及び一般式（1)又は一般式（1 ' ) で表される ω—ハロペルフルォロアルキルスルホ-ルフルオリド又はその合成中間体 を効率的に製造する方法を開発し、本発明を完成させた。 The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the general formula (1) or Starting from the ω-no, perfluoroalkylsulfur fluoride represented by the general formula (1,) as a raw material, the ω-fluorosulfol-fluorofluoride represented by the general formula (2) or (2 ′) is used as a raw material. Method for efficiently producing alkyl vinyl ether, and method for efficiently producing ω-haloperfluoroalkylsulfur fluoride represented by the general formula (1) or (1 ′) or a synthetic intermediate thereof And completed the present invention.
すなわち、本発明は以下のとおりである。  That is, the present invention is as follows.
1.原料として、下記一般式（1) 1. As a raw material, the following general formula (1)
Υ Υ
X— CF— Rf— S02F X— CF— R f — S0 2 F
(Rは炭素原子数 1一 9の 2価のペルフルォロカーボン基、 Xは I又は Brから選ばれる f (R is a divalent perfluorocarbon group having 1 to 9 carbon atoms, X is selected from I or Br.
ハロゲン原子、 Yはフッ素原子、炭素原子数 1一 3のペルフルォロアルキル基、又はA halogen atom, Y is a fluorine atom, a perfluoroalkyl group having 1 to 3 carbon atoms, or
Rとの連結基 (炭素原子数 1一 3)を表す Represents a linking group to R (1-3 carbon atoms)
f  f
Y  Y
(― CF—は以下一 C F Y—とも表す） 。  (-CF- is also referred to below as C CF Y-).
—CFY— R—は炭素原子数 3— 10の 2価のペルフルォロカーボン基である。） —CFY— R— is a divalent perfluorocarbon group having 3 to 10 carbon atoms. )
f  f
で表される ω—ハロペルフルォロアルキルスルホ-ルフルオリドから下記一般式（2) CF =CFO (CF CF (CF ) θ) — CFY— R—SO F (2) From the ω-haloperfluoroalkylsulfur fluoride represented by the following formula (2) CF = CFO (CF CF (CF) θ) — CFY— R—SO F (2)
2 2 3 n f 2  2 2 3 n f 2
(nは 0— 2の整数であり、 R及び Yは上記一般式（1)と同じである。 )  (n is an integer of 0-2, and R and Y are the same as in the general formula (1).)
f  f
で表される ω—フルォロスルホ-ルペルフルォロアルキルビュルエーテルを製造する 方法であって、以下の工程 (a)—（c)を含む上記方法： A method for producing ω-fluorosulfol-perfluoroalkyl ether represented by the formula, comprising the following steps (a) to (c):
(a)上記一般式 (1)で表される ω—ハロペルフルォロアルキルスルホ-ルフルオリドを 酸化剤で処理して下記一般式（3)で表される ω -フルォロスルホニル化合物を製造 する工程、  (a) An ω-haloperfluoroalkylsulfur fluoride represented by the above general formula (1) is treated with an oxidizing agent to produce an ω-fluorosulfonyl compound represented by the following general formula (3). The process of
Υ Υ
I ( 3 )  I (3)
0=C— Rf— S02F 0 = C— Rf— S0 2 F
(R及び Yは上記一般式（1)と同じである。 ) (b)工程 (a)で得られた上記一般式（3)で表される ω—フルォロスルホニル化合物と へキサフルォロプロピレンォキシドを反応させて下記一般式 (4)で表される酸フルォ リド化合物を製造する工程、及び (R and Y are the same as in the above general formula (1).) (b) reacting the ω-fluorosulfonyl compound represented by the above general formula (3) obtained in the step (a) with hexafluoropropylene oxide and represented by the following general formula (4) Producing an acid fluoride compound,
CF CF(COF)0(CF CF(CF )θ)— CFY— R— SO F (4)  CF CF (COF) 0 (CF CF (CF) θ) — CFY— R— SO F (4)
3 2 3 n f 2  3 2 3 n f 2
(nは上記一般式（2)と同じであり、 R及び Yは上記一般式（1)と同じである。 )  (n is the same as in the general formula (2), and R and Y are the same as in the general formula (1).)
f  f
(c)工程 (b)で得られた上記一般式 (4)で表される酸フルオリドィ匕合物を上記一般式 (2)で表される ω—フルォロスルホ-ルペルフルォロアルキルビュルエーテルに変換 する工程。  (c) converting the acid fluoride conjugate represented by the general formula (4) obtained in the step (b) into the ω-fluorosulfol-perfluoroalkyl ether represented by the general formula (2); The process of converting.
2.原料として、下記一般式（1') 2. As a raw material, the following general formula (1 ')
X(CF ) SO F (1，）  X (CF) SO F (1,)
2 m 2  2 m 2
(Xは I又は Brから選ばれるハロゲン原子、 mは 3— 10の整数である。 ) で表される ω—ハロペルフルォロアルキルスルホ-ルフルオリドから下記一般式（2，） CF =CFO(CF CF(CF )θ) (CF ) SO F (2，）  (X is a halogen atom selected from I or Br, and m is an integer of 3-10.) From the ω-haloperfluoroalkylsulfur fluoride represented by the following general formula (2,) CF = CFO ( CF CF (CF) θ) (CF) SO F (2,)
2 2 3 n' 2 m 2  2 2 3 n '2 m 2
(n'は 0— 2の整数であり、 mは上記一般式（1')と同じである。 )  (n 'is an integer of 0-2, and m is the same as in the above general formula (1').)
で表される ω—フルォロスルホ-ルペルフルォロアルキルビュルエーテルを製造する 方法であって、以下の工程 (a')—（ ）を含む上記方法： A method for producing an ω-fluorosulfol-perfluoroalkyl ether represented by the formula, comprising the following steps (a ′) — ():
(a， )上記一般式（ 1，）で表される ω—ハロペルフルォロアルキルスルホ-ルフルオリ ドを酸化剤で処理して下記一般式（3 ' )で表される ω—フルォロスルホニル化合物を 製造する工程、  (a,) The ω-haloperfluoroalkylsulfur fluoride represented by the general formula (1,) is treated with an oxidizing agent, and the ω-fluoro represented by the following general formula (3 ′) is treated. A step of producing a sulfonyl compound,
FCO(CF ) SO F (3，）  FCO (CF) SO F (3,)
2 m-1 2  2 m-1 2
(mは上記一般式（1')と同じである。 )  (m is the same as in the above general formula (1 ′).)
(b ' )工程（a ' )で得られた上記一般式（3 ' )で表される ω—フルォロスルホニル化合 物とへキサフルォロプロピレンォキシドを反応させて下記一般式 (4' )で表される酸フ ルオリドィ匕合物を製造する工程、及び (b ′) The ω-fluorosulfonyl compound represented by the above general formula (3 ′) obtained in the step (a ′) is reacted with hexafluoropropylene oxide to give the following general formula (4) ') A process for producing an acid fluoride compound represented by
CF CF(C0F)0(CF CF(CF )θ) (CF ) SO F (4，）  CF CF (C0F) 0 (CF CF (CF) θ) (CF) SO F (4,)
3 2 3 n' 2 m 2  3 2 3 n '2 m 2
(nは上記一般式（2' )と同じであり、 mは上記一般式（ )と同じである。 ) (c ' )工程 (b ' )で得られた上記一般式 (4 ' )で表される酸フルオリドィ匕合物を上記一 般式（2，）で表される ω—フルォロスルホ-ルペルフルォロアルキルビュルエーテル に変換する工程。 (n is the same as the above general formula (2 ′), m is the same as the above general formula ().) (c ′) Step (b ′) obtained by the above general formula (4 ′) Fluoride-sulfide compound represented by the above general formula (2) is converted to an ω-fluorosulfol-perfluoroalkylbutyl ether represented by the general formula (2). Converting to.
[0009] 3.前記工程 (a)で使用される酸化剤が SO又は発煙硫酸である、上記 1.に記載の  3. The method according to 1 above, wherein the oxidizing agent used in the step (a) is SO or fuming sulfuric acid.
3  Three
方法。  Method.
4.前記工程 (a)で得られた少なくとも上記一般式（3)で表される ω—フルォロスルホ ニル化合物、及び副生成物である下記一般式 (5)  4. The ω-fluorosulfonyl compound represented by at least the general formula (3) obtained in the step (a) and the following general formula (5) which is a by-product
FSO O-CFY-R -SO F (5)  FSO O-CFY-R -SO F (5)
2 f 2  2 f 2
(R及び Yは上記一般式（1)と同じである。 )  (R and Y are the same as in the above general formula (1).)
f  f
で表されるスルホ-ルフルオリド化合物を含む反応混合物を、  A reaction mixture containing a sulfol fluoride compound represented by
1)アルカリ金属塩、アルカリ土類金属塩、又はルイス塩基と接触させて、該反応混合 物中の上記一般式（5)で表されるスルホニルフルオリドィ匕合物を、上記一般式（3)で 表される ω—フルォロスルホ-ル化合物に変換し、  1) The sulfonylfluoride conjugate represented by the general formula (5) in the reaction mixture is brought into contact with an alkali metal salt, an alkaline earth metal salt, or a Lewis base, and ) Is converted to a ω-fluorosulfol compound represented by
2)次いで、 1)の操作で得られた、上記一般式（3)で表される ω—フルォロスルホニル 化合物を、工程 (b)に使用する、  2) Then, the ω-fluorosulfonyl compound represented by the general formula (3) obtained by the operation of 1) is used in the step (b),
上記 3.に記載の方法。  The method described in 3. above.
5.前記工程 (a)で得られた、少なくとも上記一般式（3)で表される ω—フルォロスル ホニル化合物、及び副生成物である上記一般式（5)で表されるスルホニルフルオリド 化合物を含む反応混合物から、  5. At least the ω-fluorosulfonyl compound represented by the general formula (3) and the sulfonyl fluoride compound represented by the general formula (5), which is a by-product, obtained in the step (a) From the reaction mixture containing
3)上記一般式（3)で表される ω—フルォロスルホ-ルイ匕合物を分離除去し、 3) Separate and remove the ω-fluorosulholi-luid conjugate represented by the general formula (3),
4)その結果得られた反応残渣中の上記一般式（5)で表されるスルホ-ルフルオリド 化合物を、アルカリ金属塩、アルカリ土類金属塩、又はルイス塩基と接触させて、上 記一般式（3)で表される ω—フルォロスルホ-ルイ匕合物に変換し、 4) The sulfol fluoride compound represented by the above general formula (5) in the resulting reaction residue is brought into contact with an alkali metal salt, an alkaline earth metal salt, or a Lewis base to obtain the above-mentioned general formula ( 3) converted to ω-fluorosulho-rui-dani compound represented by
5)次いで、上記工程 4)で得られた、上記一般式（3)で表される ω—フルォロスルホ- ル化合物を、前記工程 (b)に使用する、  5) Next, the ω-fluorosulfur compound represented by the general formula (3) obtained in the above step 4) is used in the above step (b),
上記 3.に記載の方法。  The method described in 3. above.
[0010] 6.前記工程 (a' )で使用される酸化剤が SO又は発煙硫酸である、上記 2.に記載 [0010] 6. The method according to the above item 2, wherein the oxidizing agent used in the step (a ′) is SO or fuming sulfuric acid.
3  Three
の方法。  the method of.
7.前記工程 (a' )で得られた、少なくとも上記一般式（3 ' )で表される ω—フルォロス ルホニル化合物、及び副生成物である下記一般式（5' ) FSO 0 (CF ) SO F (5，） 7. At least the ω-fluorosulfonyl compound represented by the general formula (3 ′) obtained in the step (a ′) and the following general formula (5 ′) which is a by-product FSO 0 (CF) SO F (5,)
2 2 m 2  2 2 m 2
(mは上記一般式（1 ' )と同じである。 )  (m is the same as in the above general formula (1 ′).)
で表されるスルホ-ルフルオリド化合物を含む反応混合物を、 A reaction mixture containing a sulfol fluoride compound represented by
1 ' )アルカリ金属塩、アルカリ土類金属塩、又はルイス塩基と接触させて、該反応混 合物中の上記一般式（5 ' )で表されるスルホニルフルオリドィ匕合物を、上記一般式（3 ' )で表される ω—フルォロスルホ-ル化合物に変換し、 1 ′) The sulfonylfluoride compound represented by the above general formula (5 ′) in the reaction mixture is contacted with an alkali metal salt, an alkaline earth metal salt, or a Lewis base, and Converted to the ω-fluorosulfol compound represented by the formula (3 ′),
2 ' )次いで、 1 ' )の操作で得られた上記一般式（3 ' )で表される ω—フルォロスルホ- ルイ匕合物を工程 (b' )に使用する  2 ′) Then, the ω-fluorosulholi- Louis conjugate represented by the general formula (3 ′) obtained by the operation of 1 ′) is used in the step (b ′).
上記 6.に記載の方法。 The method described in 6. above.
8.前記工程 (a' )で得られた、少なくとも上記一般式（3 ' )で表される ω—フルォロス ルホニル化合物、及び副生成物である上記一般式（5 ' )で表されるスルホニルフルォ リド化合物を含む反応混合物から、  8. The ω-fluorosulfonyl compound represented by at least the above general formula (3 ′) obtained in the above step (a ′), and the sulfonylfuran represented by the above general formula (5 ′) which is a by-product From the reaction mixture containing the
3 ' )上記一般式（3 ' )で表される ω—フルォロスルホ-ルイ匕合物を分離除去し、 3 ′) Separating and removing the ω-fluorosulholi-rui compound represented by the general formula (3 ′),
4' )その結果得られた反応残渣中の上記一般式（5' )で表されるスルホ-ルフルオリ ド化合物を、アルカリ金属塩、アルカリ土類金属塩、又はルイス塩基と接触させて、上 記一般式（3 ' )で表される ω—フルォロスルホニル化合物に変換し、 4 ′) The sulfol fluoride compound represented by the above general formula (5 ′) in the resulting reaction residue is brought into contact with an alkali metal salt, an alkaline earth metal salt, or a Lewis base, and Converted to an ω-fluorosulfonyl compound represented by the general formula (3 ′),
5 ' )次!、で、上記工程 4 ' )で得られた上記一般式（3 ' )で表される ω—フルォロスルホ ニル化合物を、前記工程 (b' )に使用する、  5 ′) Next, the ω-fluorosulfonyl compound represented by the above general formula (3 ′) obtained in the above step 4 ′) is used in the above step (b ′),
上記 6.に記載の方法。 The method described in 6. above.
9.上記一般式（3' )で表される ω—フルォロスルホ-ル化合物とへキサフルォロプロ ピレンォキシドをフッ素イオン含有ィ匕合物の存在下、下記一般式 (6) 9. An ω-fluorosulfol compound represented by the above general formula (3 ′) and hexafluoropropylene oxide are present in the presence of a fluoride ion-containing compound of the following general formula (6)
RxO (R20) R1 (6) R x O (R 2 0) R 1 (6)
P  P
(R1は炭素数 1一 5のアルキル基であり、 R2は C H又は C Hである。 pは 0— 10 (R 1 is an alkyl group having 115 carbon atoms, R 2 is CH or CH. P is 0-10
2 4 3 6  2 4 3 6
の整数である。 ) Is an integer. )
で表されるエーテル系溶媒とカルボン酸ジ-トリル系溶媒の混合溶媒存在下で反応 させることを含む、上記一般式 (4' )において n' =0である下記一般式 (4") Wherein the reaction is performed in the presence of a mixed solvent of an ether-based solvent and a carboxylic acid di-tolyl-based solvent represented by the following general formula (4 ") wherein n '= 0 in the above general formula (4').
CF CF (COF) 0 (CF ) SO F (4")  CF CF (COF) 0 (CF) SO F (4 ")
3 2 m 2  3 2 m 2
(mは上記一般式（1 ' )と同じである。 ) で表される酸フルオリド化合物を製造する方法。 (m is the same as in the above general formula (1 ′).) A method for producing an acid fluoride compound represented by the formula:
10.上記一般式 (6)で表されるエーテル系溶媒とカルボン酸ジ-トリル系溶媒の混 合溶媒中に占める該カルボン酸ジ-トリル系溶媒の質量割合が 30質量％以上 99質 量％以下である上記 9.記載の方法。  10. The mass ratio of the carboxylic acid di-tolyl solvent in the mixed solvent of the ether solvent represented by the general formula (6) and the carboxylic acid di-tolyl solvent is 30% by mass or more and 99% by mass. 9. The method according to 9. above, wherein:
11.上記一般式 (4")で表される酸フルオリド化合物をカルボン酸塩に変換し、次い で該カルボン酸塩を熱分解して、上記一般式（2' )において n' =0である下記一般式 (2")で表される ω—フルォロスルホ-ルペルフルォロアルキルビュルエーテルを製 造する方法であって、目的生成物である下記一般式（2")で表される ω—フルォロス ルホ-ルペルフルォロアルキルビュルエーテルの生成モル数を r、副生成物として再 生成した上記一般式 (4")で表される酸フルオリドィ匕合物の生成モル数を sとした場合 、 [s]Z[r+s]で表される副生成物の生成割合が 0. 1以下で反応を実施することを特徴 とする、上記方法。  11. The acid fluoride compound represented by the above general formula (4 ″) is converted into a carboxylate, and then the carboxylate is thermally decomposed, and when n ′ = 0 in the above general formula (2 ′), This is a method for producing ω-fluorosulfol-perfluoroalkyl ether represented by the following general formula (2 "), wherein ω is a target product represented by the following general formula (2") —R is the number of moles of fluorosulfol-perfluoroalkylbutyl ether formed, and s is the number of moles of the acid fluoride conjugate represented by the above general formula (4 ″) regenerated as a by-product. In this case, the method is characterized in that the reaction is carried out at a production ratio of a by-product represented by [s] Z [r + s] of 0.1 or less.
CF =CFO (CF ) SO F (2")  CF = CFO (CF) SO F (2 ")
2 2 m 2  2 2 m 2
(mは上記一般式（1 ' )と同じである。 )  (m is the same as in the above general formula (1 ′).)
12.上記一般式 (4")で表される酸フルオリド化合物力 誘導されるカルボン酸塩が 下記一般式 (7)で表されるカリウム塩であり、かつ、該カルボン酸塩の熱分解を無溶 媒で行う、上記 11.に記載の方法。 12. Acid fluoride compound represented by the above general formula (4 ") The derived carboxylate is a potassium salt represented by the following general formula (7), and the carboxylate does not undergo thermal decomposition. 12. The method according to 11 above, which is performed in a solvent.
CF CF (CO K) 0 (CF ) SO F (7)  CF CF (CO K) 0 (CF) SO F (7)
3 2 2 m 2  3 2 2 m 2
(mは上記一般式（1 ' )と同じである。 )  (m is the same as in the above general formula (1 ′).)
13.カルボン酸塩の熱分解を、該カルボン酸塩を固相状態に保ちながら行う、上記 1 1.又は 12.に記載の方法。  13. The method according to 11. or 12. above, wherein the thermal decomposition of the carboxylate is carried out while keeping the carboxylate in a solid state.
14.上記一般式（1， )で表される ω—ノヽロペルフルォロアルキルスルホ-ルフルオリド 力 下記工程 (i)一（iv)により得られる、上記 2.に記載の方法：  14. The ω-noperoperfluoroalkylsulfur fluoride force represented by the above general formula (1), the method described in the above item 2, obtained by the following step (i)-(iv):
(i)下記一般式 (8)  (i) The following general formula (8)
X (CF ) X (8)  X (CF) X (8)
2 m  2 m
(X及び mは上記一般式（1 ' )と同じである。 )  (X and m are the same as in the above general formula (1 ′).)
で表される a , ω—ジハロペルフルォロアルカンをアルカリ金属塩型、アルカリ土類金 属塩型、第 4級アンモ-ゥム塩型、又は第 4級ホスホ-ゥム塩型の何れ力から選ばれ る亜ジチオン酸塩と混合、攪拌して、下記一般式 (9) A, ω-dihaloperfluoroalkane represented by the following formula: alkali metal salt type, alkaline earth metal salt type, quaternary ammonium salt type, or quaternary phospho-dimethyl salt type Will be chosen from any strength And mixed with dithionite and stirred to obtain the following general formula (9)
X (CF ) SO M (9)  X (CF) SO M (9)
2 m 2  2 m 2
(式中、 Mは、 Ma、 Mb 、第 4級アンモ -ゥムラジカル又は第 4級ホスホ-ゥムラジ  (Wherein, M is Ma, Mb, a quaternary ammo-radical or a quaternary phospho-dimethyl
1/2  1/2
カルであり、 Maはアルカリ金属、 Mbはアルカリ土類金属である。 X及び mは上記一 般式（1 ' )と同じである。） Ma is an alkali metal and Mb is an alkaline earth metal. X and m are the same as those in the general formula (1 ′). )
で表される ωーハロペルフルォロアルキルスルフィン酸塩を製造する工程、A process for producing an ω-haloperfluoroalkylsulfinate represented by:
(ii)工程 (i)で得られた反応混合物から上記一般式（9)で表される ω -ハロペルフル ォロアルキルスルフィン酸塩を分離する工程、 (ii) separating the ω-haloperfluoroalkylsulfinate represented by the general formula (9) from the reaction mixture obtained in the step (i),
(iii)工程（ii)で得られた上記一般式（9)で表される ω ノヽロペルフルォロアルキルス ルフィン酸塩を塩素化剤で処理して下記一般式（10)  (iii) treating the ω-noperoperfluoroalkyl sulfinate represented by the above general formula (9) obtained in the step (ii) with a chlorinating agent to obtain the following general formula (10)
X (CF ) SO CI ( 10)  X (CF) SO CI (10)
2 m 2  2 m 2
(X及び mは上記一般式（1 ' )と同じである。 )  (X and m are the same as in the above general formula (1 ′).)
で表される ω—ハロペルフルォロアルキルスルホ-ルクロリドを製造する工程、及びA process of producing ω-haloperfluoroalkylsulfol-chloride represented by
(iv)工程（iii)で得られた上記一般式（10)で表される ω—ハロペルフルォロアルキル スルホニルクロリドをフッ素イオン含有ィ匕合物で処理して、上記一般式（1 ' )で表され る ω—ハロペルフルォロアルキルスルホ-ルフルオリドを製造する工程。 (iv) treating the ω-haloperfluoroalkyl sulfonyl chloride represented by the general formula (10) obtained in the step (iii) with a fluoride ion-containing conjugate, ) it expresses in omega - halo pel full O b alkylsulfonyl - the process of manufacturing the Rufuruorido.
15.前記工程 (ii)が、工程 (i)の反応で得られた少なくとも上記一般式 (9)で表され る ω—ハロペルフルォロアルキルスルフィン酸塩及び副生成物である下記一般式（1 15. The following general formula wherein the step (ii) is at least the ω- haloperfluoroalkylsulfinic acid salt represented by the general formula (9) obtained by the reaction of the step (i) and a by-product (1
1) 1)
MO S (CF ) SO M ( 1 1)  MO S (CF) SO M (1 1)
2 2 m 2  2 2 m 2
(Mは上記一般式（9)と同じであり、 mは上記一般式（1 ' )と同じである。 ) で表されるペルフルォロアルキル α , ω ビススルフィン酸塩を含む反応混合物か ら上記一般式（9)で表される ω—ハロペルフルォロアルキルスルフィン酸塩を抽出分 離する操作を含む、上記 14.に記載の方法。  (M is the same as in the above general formula (9), m is the same as in the above general formula (1 ′).) A reaction mixture containing a perfluoroalkyl α, ω bissulfinate represented by the following formula: 15. The method according to the above 14, which comprises an operation of extracting and separating the ω-haloperfluoroalkylsulfinate represented by the general formula (9).
16.前記工程 (ii)が、下記工程 (ii 1)及び工程 (ii 2)を含む工程である上記 14. に記載の方法。  16. The method according to the above 14, wherein the step (ii) includes the following steps (ii 1) and (ii 2).
(ii 1)前記工程 (i)で得られた少なくとも未反応の上記一般式 (8)で表される ex , ω -ジハ口ペルフルォロアルカン、目的化合物である上記一般式（9)で表される ω -ハ 口ペルフルォロアルキルスルフィン酸塩、及び副生成物である上記一般式（11)で表 されるペルフルォロアルキル α , ω ビススルフィン酸塩を含む反応混合物から、上 記一般式（8)で表される a , ω ジハロペルフルォロアルカンを除去する工程、 (ii-2)上記工程 (ii-1)で得られた少なくとも上記一般式（9)で表される ω—ハロペル フルォロアルキルスルフィン酸塩及び上記一般式（11)で表されるペルフルォロアル キル a , ω ビススルフィン酸塩を含む混合物から、上記一般式（9)で表される ω - ノ、口ペルフルォロアルキルスルフィン酸塩を抽出分離する工程。 (ii 1) at least the unreacted ex, ω-diha-mouth perfluoroalkane represented by the general formula (8) obtained in the step (i), and the compound represented by the general formula (9) Expressed ω-c From the reaction mixture containing the perfluoroalkyl sulfinic acid salt and the perfluoroalkyl α, ω bissulfinate represented by the above general formula (11), which is a by-product, from the above general formula (8 A), a step of removing a, ω dihaloperfluoroalkane represented by the formula (ii-2): ω-haloper represented by at least the general formula (9) obtained in the step (ii-1) From a mixture containing a fluoroalkylsulfinate and a perfluoroalkyl a, ω bissulfinate represented by the above general formula (11), ω -no represented by the above general formula (9) A step of extracting and separating a loalkylsulfinic acid salt;
17.上記一般式（9)で表される ω—ハロペルフルォロアルキルスルフィン酸塩を分離 除去した後の反応残渣を塩素化剤で処理する操作により上記一般式 (8)で表される a , ω ジハロペルフルォロアルカン及び Z又は上記一般式（10)で表される ω—ハ 口ペルフルォロアルキルスルホユルク口リドを製造し、これらを工程（i)及び Z又はェ 程 (iv)に再使用する、上記 14.一 16.のいずれか一項に記載の方法。  17. The ω-haloperfluoroalkylsulfinate represented by the general formula (9) is separated and removed, and then the reaction residue is treated with a chlorinating agent to represent the general formula (8). a, ω Dihaloperfluoroalkane and Z or ω-C-perfluoroalkylsulfoylc chloride represented by the above general formula (10) are produced, and these are subjected to step (i) and Z or 14. The method according to any one of 14.-1 16. above, which is reused in step (iv).
18.上記一般式（9)で表される ω—ハロペルフルォロアルキルスルフィン酸塩を分離 除去した後の、少なくとも上記一般式（11)で表されるペルフルォロアルキル α , ω ビススルフィン酸塩及び無機沃化物又は無機臭化物カゝら選ばれる少なくとも一方の 無機塩を含有する反応残渣を溶解した水溶液を塩素化剤で処理し、沃素又は臭素 の少なくとも一方と下記一般式（ 12) 18. After separating and removing the ω-haloperfluoroalkylsulfinate represented by the above general formula (9), at least the perfluoroalkyl α, ωbis represented by the above general formula (11) An aqueous solution in which a reaction residue containing a sulfinate and at least one inorganic salt selected from inorganic iodides and inorganic bromides is dissolved is treated with a chlorinating agent, and at least one of iodine or bromine is added to the following general formula (12)
CIO S (CF ) SO CI (12)  CIO S (CF) SO CI (12)
2 2 m 2  2 2 m 2
(mは上記一般式（1 ' )と同じである。 )  (m is the same as in the above general formula (1 ′).)
で表されるペルフルォロアルキル α , ω—ビススルホ-ルクロリドを生成させ、次い で、当該反応混合物を水難溶性有機溶媒で抽出処理することにより、上記一般式 (8 )で表される , ω ジハロペルフルォロアルカン及び Z又は上記一般式（10)で表 される ω—ハロペルフルォロアルキルスルホ-ルクロリドを製造'分離し、これらを工程 (i)及び Ζ又は工程 (iv)に再使用する、上記 14.一 16.のいずれか一項に記載の 方法。 By producing a perfluoroalkyl α, ω-bissulfol-chloride represented by the following formula, and then subjecting the reaction mixture to an extraction treatment with a poorly water-soluble organic solvent, the reaction mixture represented by the general formula (8) ω Dihaloperfluoroalkane and Z or ω-haloperfluoroalkylsulfol-chloride represented by the above general formula (10) are produced, separated and subjected to step (i) and step (iv). ). The method according to any one of 14.1-1.
19.上記一般式（9)で表される ω—ハロペルフルォロアルキルスルフィン酸塩を分離 除去した後の反応残渣を、塩素化剤で処理することにより上記一般式（12)で表され るペルフルォロアルキル α , ω—ビススルホ-ルクロリドを製造し、次いで当該ペル フルォロアルキル α , ω—ビススルホユルク口リドを沃素又は臭素と反応させて、上 記一般式（8)で表される a , ω ジハロペルフルォロアルカン及び Ζ又は上記一般 式（10)で表される ω ノヽロペルフルォロアルキルスルホユルク口リドを製造、分離し、 これらを工程 (i)及び Ζ又は工程 (iv)に再使用する、上記 14. 一 16.のいずれか一 項に記載の方法。 19. The reaction residue obtained after separating and removing the ω-haloperfluoroalkylsulfinate represented by the general formula (9) is treated with a chlorinating agent to thereby represent the general formula (12). To produce perfluoroalkyl α, ω-bissulfol-chloride A fluoroalkyl α , ω-bissulfoylucide is reacted with iodine or bromine to give a, ω dihaloperfluoroalkane represented by the above general formula (8) and Ζ or the above general formula (10). Ω 製造 14. 14. 製造 製造 製造 製造 製造 製造 製造 製造 製造 製造 製造 製造 製造 製造 製造 製造 製造 製造 に 製造 製造 記載 記載 記載 に にthe method of.
20.上記一般式 ( 12)で表されるペルフルォロアルキル a , ω ビススルホ-ルクロ リドを沃素又は臭素と反応させることを含む上記一般式 (8)で表される oc , ω ジハロ ペルフルォロアルカン及び Ζ又は上記一般式（10)で表される ω—ハロペルフルォロ アルキルスルホニルクロリドを製造する方法。  20. Oc, ω dihalo perflur represented by the above general formula (8), which comprises reacting perfluoroalkyl a, ω bissulfol chloride represented by the above general formula (12) with iodine or bromine. A method for producing o-alkanes and ω-haloperfluoroalkylsulfonyl chlorides represented by the general formula (10).
[0015] 21.上記一般式（1 ' )一（5' )、（7)—（12)、（2")、及び (4")で表される化合物にお いて、 mは 4一 8の整数である上記 2.及び 6. — 20.のいずれ力 1項に記載の方法。[0015] 21. In the compounds represented by the general formulas (1 ')-(5'), (7)-(12), (2 "), and (4"), m is 418 2. The method according to any one of clauses 1 and 2 above, which is an integer of
22.上記一般式（1 ' )一（5' )、 (7)—（12)、（2")、及び (4")で表される化合物にお いて、 mは 4一 6の整数である上記 2.及び 6. — 20.のいずれ力 1項に記載の方法。22. In the compounds represented by the above general formulas (1 ')-(5'), (7)-(12), (2 "), and (4"), m is an integer of 4-16. There is a method described in paragraphs 1 and 2 above.
23.上記一般式（2)、（2' )、（4)、及び (4 ' )で表される化合物において、 n又は n 力 SOである上記 1. 一 8. 、 14. 一 19.及び 21. — 22.のいずれ力 1項に記載の方法 23. In the compounds represented by the above general formulas (2), (2 ′), (4), and (4 ′), n or n is SO. 21. — Method described in item 1 of 22.
24.上記一般式（1)、（1 ' )、及び (8)—（10)で表される化合物において、 Xが沃素 原子である上記 1. 一 8.及び 14. 一 22.のいずれ力 1項に記載の方法。 24. In the compounds represented by the above general formulas (1), (1 ′), and (8)-(10), any one of the above 1.1-1. The method of paragraph 1.
25.上記 14.に記載の工程 (i)一（iv)を含む、上記一般式（1 ' )で表される ω—ハロ ペルフルォロアルキルスルホ-ルフルオリドを製造する方法。  25. A method for producing an ω-halo perfluoroalkylsulfur fluoride represented by the general formula (1 ′), comprising the step (i)-(iv) described in the above 14.
26.上記 15. — 19.のいずれ力 1項に記載の工程を含む、上記一般式（1 ' )で表さ れる ω—ノ、口ペルフルォロアルキルスルホ-ルフルオリドを製造する方法。  26. A method for producing an ω-no, perfluoroalkylsulfur fluoride represented by the above general formula (1 ′), which comprises the step of any one of the above 15. to 19.
発明の効果  The invention's effect
[0016] 本発明によれば、上記一般式（2)又は一般式（2 ' )で表される ω フルォロスルホ -ルペルフルォロアルキルビュルエーテル及びその合成中間体を高収率で製造す る方法が提供される。  According to the present invention, the ω-fluorosulfol-leperfluoroalkylbutyl ether represented by the general formula (2) or (2 ′) and a synthetic intermediate thereof are produced in high yield. A method is provided.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0017] 以下に本発明を詳細に説明する。 工程（a)—（c)〖こより、上記一般式（1)で表される ω ノヽロペルフルォロアルキルス ルホ-ルフルオリドを原料として、上記一般式（2)で表される ω フルォロスルホ-ル ペルフルォロアルキルビュルエーテルを製造する方法、及び工程（a，）一（c，）により 、上記一般式（ 1，）で表される ω ノヽロペルフルォロアルキルスルホ-ルフルオリドを 原料として、上記一般式（2，）で表される ω フルォロスルホ-ルペルフルォロアルキ ルビニルエーテルを製造する方法について説明をする。 Hereinafter, the present invention will be described in detail. Steps (a)-(c) From the above, ω-fluoroperfluoroalkylsulfur fluoride represented by the above general formula (1) is used as a raw material to obtain ω-fluorosulfur-fluoride represented by the above general formula (2). According to the method for producing perfluoroalkylbutyl ether and the steps (a), (c), the ω-noperoperfluoroalkylsulfurfluoride represented by the general formula (1) is used as a raw material. A method for producing ω-fluorosulfol-perfluoroalkyl vinyl ether represented by the general formula (2) will be described.
まず、工程 (a)及び工程 (a' )について説明をする。  First, the step (a) and the step (a ') will be described.
本発明に使用される下記一般式（1)
Figure imgf000013_0001
で表される ω—ハロペルフルォロアルキルスルホ-ルフルオリドにおいて、 Rは炭素 f 原子数 1一 9の 2価のペルフルォロカーボン基、 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 1一 3のペルフルォロアルキル基、又は Rとの連結 f 基 (炭素原子数 1一 3)を表す。以下、構造 Y The following general formula (1) used in the present invention
Figure imgf000013_0001
In the ω-haloperfluoroalkylsulfur fluoride represented by the formula, R is a divalent perfluorocarbon group having 19 carbon atoms, X is a halogen atom selected from I or Br, Y Represents a fluorine atom, a perfluoroalkyl group having 13 to 13 carbon atoms, or an f group linked to R (1 to 13 carbon atoms). Below, structure Y
— CF— を CFY—と表すこともある。—CFY— R—は炭素原子数 3— 10の 2価のペルフルォロ f  — CF— is sometimes referred to as CFY—. —CFY— R— is a divalent perfluoro with 3-10 carbon atoms f
カーボン基である。 It is a carbon group.
Xとしては I又は Brが好まし 、が、反応性の面では Iがより好まし!/、。  X is preferably I or Br, but I is more preferred in terms of reactivity! /.
CFY— R—は炭素原子数 3— 10の 2価のペルフルォロカーボン基である力 直鎖 f  CFY—R— is a divalent perfluorocarbon group having 3 to 10 carbon atoms.
構造でも分岐構造でもよいし、環状構造を含んでもよい。 It may have a structure, a branched structure, or a cyclic structure.
-CFY-R—の例としては、  -CFY-R—
f  f
-(CF ) 一 （mは 3— 10の範囲の整数）  -(CF) one (m is an integer in the range of 3-10)
2 m -CFCF2CF2CF2 — CF2CF2CFCF2 2 m -CFCF 2 CF 2 CF 2 — CF 2 CF 2 CFCF2
CF3 CF3 CF 3 CF 3
Figure imgf000014_0001
等が挙げられ、特に- (CF ) —が好ましい。
Figure imgf000014_0001
And-(CF 2) — is particularly preferable.
2 m  2 m
上記一般式（1)で表される ω—ノ、口ペルフルォロアルキルスルホ-ルフルオリドに おいて、—CFY— R—が—(CF ) 一である構造は、下記一般式（1 ' )  In the ω-no, perfluoroalkylsulfur fluoride represented by the above general formula (1), the structure where —CFY—R— is — (CF 2) is represented by the following general formula (1 ′)
f 2 m  f 2 m
X (CF ) SO F (1，）  X (CF) SO F (1,)
2 m 2  2 m 2
で表される ω—ハロペルフルォロアルキルスルホ-ルフルオリドに相当する。上記一 般式（ 1，）で表される ω—ノヽロペルフルォロアルキルスルホ-ルフルオリドにお 、て、 mは 3— 10の範囲の整数が好ま 、。合成 ·精製の容易性及び上記一般式（ 1 ' )で 表される ω—ハロペルフルォロアルキルスルホ-ルフルオリドから誘導される上記一 般式（2，）又は一般式（2")で表される ω—フルォロスルホ-ルペルフルォロアルキル ビニルエーテルの操作性'機能性から、 mはより好ましくは 4一 8であり、さらに好ましく は 4一 6であり、特に好ましくは 4である。 It corresponds to ω-haloperfluoroalkylsulfur fluoride represented by In the ω-noperoperfluoroalkylsulfur fluoride represented by the general formula (1), m is preferably an integer in the range of 3-10. Synthesis and easiness of purification and represented by the above general formula (2) or general formula (2 ") derived from ω-haloperfluoroalkylsulfur fluoride represented by the above general formula (1 ') M is more preferably 418, further preferably 416, and particularly preferably 4, from the viewpoint of the operability and functionality of the ω-fluorosulfol-perfluoroalkyl vinyl ether to be obtained.
上記一般式（1)又は上記一般式（1 ' )で表される ω—ハロペルフルォロアルキルス ルホニルフルオリドは酸化剤で処理することによって、下記一般式（3)  The ω-haloperfluoroalkylsulfonyl fluoride represented by the above general formula (1) or the above general formula (1 ′) is treated with an oxidizing agent to give the following general formula (3)
Υ Υ
I ― ( 3 )  I ― (3)
0=C— Rf— S02F 0 = C— Rf— S0 2 F
(R及び Yは上記一般式（1)と同じである。 ) (R and Y are the same as in the above general formula (1).)
f  f
又は下記一般式（3 ' ) Or the following general formula (3 ')
FCO (CF ) SO F (3，）  FCO (CF) SO F (3,)
2 m-1 2  2 m-1 2
(mは上記一般式（1 ' )と同じである。 )  (m is the same as in the above general formula (1 ′).)
で表される ω—フルォロスルホ-ルイ匕合物を得ることができる。上記一般式（3)で表さ れる ω—フルォロスルホ-ル化合物において、 Rと Υは多様な組み合わせが可能で あり、例えば The ω-fluorosulholi-rui dyad product represented by the following formula can be obtained. In the ω-fluorosulfol compound represented by the general formula (3), R and Υ can be variously combined. Yes, for example
Figure imgf000015_0001
が挙げられる。
Figure imgf000015_0001
Is mentioned.
[0020] 上記一般式（3' )で表される ω—フルォロスルホニルイ匕合物は、実用性が高ぐ特に 好ましい。上記一般式（3' )で表される ω—フルォロスルホ-ル化合物において、 mは 上記一般式（1 ' )と同様の理由により、より好ましくは 4一 8であり、さらに好ましくは 4 一 6であり、特に好ましくは 4である。  [0020] The ω-fluorosulfonylui conjugate represented by the above general formula (3 ') is particularly preferable because of its high practicality. In the ω-fluorosulfol compound represented by the above general formula (3 ′), m is more preferably 418, more preferably 416, for the same reason as in the above general formula (1 ′). And particularly preferably 4.
酸化剤としては、 X— CYF—基を酸ィ匕して 0 = CY—基に変換できるものであれば特 にそれ以上の制限はなぐ例として SO、発煙硫酸、 C1SO H、 FSO H、 NO、 O、  The oxidizing agent is not particularly limited as long as it can convert the X—CYF— group into 0 = CY—group by oxidizing it. Examples of SO, fuming sulfuric acid, C1SOH, FSOH, NO , O,
3 3 3 2 2 電解酸化等が挙げられる。中でも so 3又は発煙硫酸が好ましい。当該反応を促進す るために各種の触媒や添加剤を加えてもよぐ例えば触媒として HgO、 P O等の酸  3 3 3 2 2 electrolytic oxidation and the like. Among them, so 3 or fuming sulfuric acid is preferable. Various catalysts and additives may be added to promote the reaction.For example, catalysts such as HgO and PO
2 5 化物、 PC1、 SbCl等の塩化物を用いても構わない。  Alternatively, chlorides such as pentaoxide, PC1, and SbCl may be used.
5 5  5 5
酸化剤として SO又は発煙硫酸を用いる場合は、反応温度は 20°Cから 150°Cの範  When using SO or fuming sulfuric acid as the oxidizing agent, the reaction temperature should be between 20 ° C and 150 ° C.
3  Three
囲で行うことが好ましぐ 30°Cから 130°Cの範囲がより好ましぐ 40°Cから 120°Cの範 囲が特に好ましい。 SOを使用する場合は、上記一般式（1)又は一般式（1 ' )で表さ  It is preferable to perform the reaction in the range of 30 ° C. to 130 ° C. More preferably, the range of 40 ° C. to 120 ° C. is particularly preferable. When SO is used, it is expressed by the above general formula (1) or general formula (1 ').
3  Three
れる ω—ノヽロペルフルォロアルキルスルホ-ルフルオリド 1モルに対して 0. 1モルから 100モルの範囲で用いることが好ましぐ 1モルから 20モルの範囲で用いることがより 好ましい。また、発煙硫酸を使用する場合、発煙硫酸中の SOの濃度としては、各種  It is preferably used in the range of 0.1 to 100 mol per 1 mol of ω-noperoperfluoroalkylsulfur fluoride, more preferably in the range of 1 to 20 mol. When fuming sulfuric acid is used, the concentration of SO in fuming sulfuric acid may vary.
3  Three
の濃度が採用可能である力 反応速度の面では 10質量％以上が好ましぐより好ま しくは 30質量％以上である。発煙硫酸は、上記一般式（1)又は一般式（1 ' )で表され る ω—ハロペルフルォロアルキルスルホ-ルフルオリド 1モルに対して、発煙硫酸の実 効 SO量として 0. 1モルから 100モルの範囲で用いることが好ましぐ 1モル力ら 20In terms of the reaction rate at which the concentration can be adopted, 10% by mass or more is more preferable than 30% by mass. The amount of fuming sulfuric acid is 0.1 mol based on the effective SO amount of fuming sulfuric acid per 1 mol of ω- haloperfluoroalkylsulfur fluoride represented by the above general formula (1) or (1 ′). Preferred to use in the range from 1 to 100 moles 1 mole force 20
3 Three
モルの範囲で用いることがより好まし!/、。  More preferred to use in the molar range! / ,.
[0021] 反応時間は特に限定的ではなぐ反応がある程度進行すればよぐ例えば 0. 1時 間から 100時間程度とすればよい。反応方法は特に限定的ではないが、常圧下、上 記一般式（1)又は一般式（1 ' )で表される ω—ハロペルフルォロアルキルスルホ-ル フルオリドと SO又は発煙硫酸の混合物を加熱還流させてもよいし、加熱した上記 [0021] The reaction time is not particularly limited, and may be, for example, about 0.1 to 100 hours as long as the reaction proceeds to some extent. The reaction method is not particularly limited. The mixture of ω-haloperfluoroalkylsulfur fluoride represented by the general formula (1) or (1 ′) and SO or fuming sulfuric acid may be heated to reflux,
3 一 般式（1)又は一般式（ 1，）で表される ω—ハロペルフルォロアルキルスルホ-ルフル オリドに SO又は発煙硫酸を滴下と同時に反応生成物を留出させる形態をとつても  3 SO or fuming sulfuric acid is added dropwise to ω-haloperfluoroalkylsulfur fluoride represented by the general formula (1) or (1,), and the reaction product is distilled off at the same time. Also
3  Three
構わない。また、加圧容器に上記一般式（1)又は一般式（1 ' )で表される ω—ハロぺ ルフルォロアルキルスルホ-ルフルオリドと SO又は発煙硫酸の混合物を加えてカロ I do not care. In addition, a mixture of ω-halogenfluoroalkylsulfur fluoride represented by the above general formula (1) or (1 ′) and SO or fuming sulfuric acid is added to a pressurized container, and calorie is added.
3  Three
熱させてもよい。 It may be heated.
酸化剤として、 SO又は発煙硫酸を使用した場合、上記一般式（1)又は上記一般  When SO or fuming sulfuric acid is used as the oxidizing agent, the above general formula (1) or the above general formula (1)
3  Three
式（1 ' )で表される ω—ノヽロペルフルォロアルキルスルホ-ルフルオリドから、 目的化 合物である上記一般式（3)又は上記一般式（3 ' )で表される ω—フルォロスルホニル 化合物と共に、副生成物である下記一般式 (5) From the ω-noperoperfluoroalkylsulfur fluoride represented by the formula (1 ′), the ω-furo represented by the above-mentioned general formula (3) or the above-mentioned general formula (3 ′) is obtained. Together with the olosulfonyl compound, a by-product represented by the following general formula (5)
FSO O-CFY-R -SO F (5)  FSO O-CFY-R -SO F (5)
2 f 2  2 f 2
(R及び Yは上記一般式（1)と同じである。 )  (R and Y are the same as in the above general formula (1).)
f  f
又は下記一般式（5 ' ) Or the following general formula (5 ')
FSO 0 (CF ) SO F (5，）  FSO 0 (CF) SO F (5,)
2 2 m 2  2 2 m 2
(mは上記一般式（1 ' )と同じである。 )  (m is the same as in the above general formula (1 ′).)
で表されるスルホ-ルフルオリドィ匕合物が反応混合物中に含まれる。 A sulfol fluoride conjugate represented by the formula is contained in the reaction mixture.
上記一般式（5)又は一般式（5' )で表されるスルホニルフルオリド化合物は、アル力 リ金属塩、アルカリ土類金属塩、又はルイス塩基と接触させると、 目的化合物である 上記一般式（3)又は一般式（3 ' )で表される ω -フルォロスルホニル化合物に変換す ることができる。このため、当該反応混合物に溶解している SOを濃硫酸で洗浄、除  The sulfonyl fluoride compound represented by the general formula (5) or (5 ′) is a target compound when brought into contact with an alkali metal salt, an alkaline earth metal salt, or a Lewis base. It can be converted to an ω-fluorosulfonyl compound represented by (3) or the general formula (3 ′). Therefore, the SO dissolved in the reaction mixture is washed and removed with concentrated sulfuric acid.
3  Three
去した後、そのまま、アルカリ金属塩、アルカリ土類金属塩、又はルイス塩基と接触さ せ、蒸留操作により、 目的化合物である上記一般式 (3)又は一般式 (3' )で表される ω—フルォロスルホニルイ匕合物を得ることができる。なお、当該反応混合物に溶解し ている SOを濃硫酸で洗浄、除去した後、蒸留操作により目的化合物である上記 After removal, the mixture is directly brought into contact with an alkali metal salt, an alkaline earth metal salt, or a Lewis base, and subjected to a distillation operation to obtain a target compound represented by the above general formula (3) or (3 ′) represented by the general formula (3 ′). -Fluorosulfonyl ligated products can be obtained. After washing and removing the SO dissolved in the reaction mixture with concentrated sulfuric acid, the target compound,
3 一 般式（3)又は一般式（3 ' )で表される ω -フルォロスルホニルイヒ合物を分離後、上記 一般式 (5)又は一般式 (5 ' )で表されるスルホニルフルオリドィ匕合物を含有する蒸留 残渣をアルカリ金属塩、アルカリ土類金属塩、又はルイス塩基と接触させ、蒸留操作 により目的化合物である上記一般式（3)又は一般式（3 ' )で表される ω フルォロス ルホニル化合物を得ることもできる。 3 After separating the ω-fluorosulfonyluic compound represented by the general formula (3) or (3 ′), the sulfonylfluoride represented by the above general formula (5) or (5 ′) is separated. The distillation residue containing the Doi-Dai-Gai product is brought into contact with an alkali metal salt, an alkaline earth metal salt, or a Lewis base to perform a distillation operation. Thus, the ω-fluorosulfonyl compound represented by the above general formula (3) or (3 ′), which is the target compound, can also be obtained.
上記反応で使用するアルカリ金属塩としては LiF、 Lil、 NaF、 Nal、 KF、 KI、 CsF 等、アルカリ土類金属塩としては MgF、 CaF等、ルイス塩基としてはトリメチルァミン  LiF, Lil, NaF, Nal, KF, KI, CsF, etc. as alkali metal salts used in the above reaction, MgF, CaF, etc. as alkaline earth metal salts, trimethylamine as Lewis base
2 2  twenty two
、トリエチノレアミン、 1, 8—ジァザビシクロ [5, 4, 0]ゥンデクー 7 ェン、 1, 5—ジァザビ シクロ [4, 3, 0]ノン 5—ェン、 N, N—ジイソプロピルェチルァミン等が挙げられる力 中でも KF、 N, N—ジイソプロピルェチルァミンが好ましい。  , Triethynoleamine, 1,8-diazabicyclo [5,4,0] indene, 1,5-diazabicyclo [4,3,0] non-5-ene, N, N-diisopropylethyla KF and N, N-diisopropylethylamine are preferable among the powers including min.
上記アルカリ金属塩、アルカリ土類金属塩、又はルイス塩基の使用量は、上記一般 式（5)又は一般式（5' )で表されるスルホ-ルフルオリド化合物 1モルに対して 0. 00 1モルから 5モルの範囲で用いることが好まし!/、。  The amount of the alkali metal salt, alkaline earth metal salt or Lewis base to be used is 0.001 mol based on 1 mol of the sulfol fluoride compound represented by the general formula (5) or (5 ′). It is preferred to use in the range of from 5 to 5 mol! / ,.
[0023] 反応時間は特に限定はなぐ例えば 0. 1時間から 100時間程度とすればよい。 The reaction time is not particularly limited, and may be, for example, about 0.1 to 100 hours.
反応温度は 10°Cから 220°Cの範囲が好ましぐ 20°Cから 200°Cの範囲がより好ま しぐ 30°Cから 180°Cの範囲が特に好ましい。  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, particularly preferably in the range of 30 ° C to 180 ° C.
反応方法は特に限定されないが、無溶媒又は溶媒存在下、常圧下で、加熱したァ ルカリ金属塩、アルカリ土類金属塩、又はルイス塩基に、上記一般式 (5)又は一般式 (5' )で表されるスルホ-ルフルオリドィ匕合物を滴下すると同時に反応生成物を留出 させてもょ 、し、上記一般式（5)又は一般式（5 ' )で表されるスルホ-ルフルオリドィ匕 合物と上記アルカリ金属塩、アルカリ土類金属塩、又はルイス塩基の混合物を加熱 還流させても構わない。また、加圧容器に一般式（5)又は一般式（5 ' )で表されるス ルホニルフルオリドィ匕合物と上記アルカリ金属塩、アルカリ土類金属塩、又はルイス 塩基の混合物を加えて加熱してもよ 、。  Although the reaction method is not particularly limited, the alkali metal salt, alkaline earth metal salt, or Lewis base heated under normal pressure in the absence of a solvent or in the presence of a solvent may be added to the above-mentioned general formula (5) or (5 ′) The reaction product may be distilled off at the same time as the dropwise addition of the sulfolfluoride conjugate represented by the general formula (5), or the sulfolfluoride conjugate represented by the above general formula (5) or (5 ′) And a mixture of the above-mentioned alkali metal salt, alkaline earth metal salt or Lewis base may be heated to reflux. Also, a mixture of the sulfonylfluoride conjugate represented by the general formula (5) or (5 ′) and the above alkali metal salt, alkaline earth metal salt, or Lewis base is added to a pressurized container. You can heat it.
溶媒を使用する場合、ジグライム、トリグライム、テトラグライム等のエーテル系溶媒、 N, N—ジメチルホルムアミド、 N, N—ジメチルァセトアミド、 N—メチルー 2—ピロリドン等 のアミド系溶媒、スルホラン等の極性溶媒が挙げられ、 1種類でもよいし、又は複数の 有機溶媒を組み合わせても構わな ヽ。  When a solvent is used, ether solvents such as diglyme, triglyme and tetraglyme, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and polar solvents such as sulfolane A solvent may be used, and one kind may be used or a plurality of organic solvents may be combined.
反応終了後、蒸留操作により目的化合物である上記一般式 (3)又は一般式 (3 ' ) で表される ω フルォロスルホ-ル化合物を得ることができる。  After completion of the reaction, the desired compound ω-fluorosulfol compound represented by the above general formula (3) or (3 ′) can be obtained by distillation.
[0024] 次に、工程 (b)及び工程 (b' )について説明する。 上記の方法で得られた上記一般式（3)又は一般式（3 ' )で示される ω—フルォロス ルホ-ル化合物とへキサフルォロプロピレンォキシド（HFPO)の反応を、公知の方 法で行うことにより、下記一般式 (4) Next, the step (b) and the step (b ′) will be described. The reaction between the ω-fluorosulfur compound represented by the above general formula (3) or (3 ′) obtained by the above method and hexafluoropropylene oxide (HFPO) is carried out by a known method. The following general formula (4)
CF CF (COF) 0 (CF CF (CF ) θ)— CFY— R— SO F (4)  CF CF (COF) 0 (CF CF (CF) θ) — CFY— R— SO F (4)
3 2 3 n f 2  3 2 3 n f 2
(nは 0— 2の整数であり、 R及び Yは上記一般式（1)と同じである。 )  (n is an integer of 0-2, and R and Y are the same as in the general formula (1).)
f  f
又は下記一般式 (4 ' ) Or the following general formula (4 ')
CF CF (C0F) 0 (CF CF (CF ) θ) (CF ) SO F (4，）  CF CF (C0F) 0 (CF CF (CF) θ) (CF) SO F (4,)
3 2 3 n' 2 m 2  3 2 3 n '2 m 2
(nは 0— 2の整数であり、 mは上記一般式（1 ' )と同じである。 )  (n is an integer of 0-2, and m is the same as in the above general formula (1 ′).)
で表される酸フルオリドィ匕合物を得ることができる。 Can be obtained.
本発明者らは、上記一般式 (4)又は一般式 (4 ' )で表される酸フルオリド化合物の 中でも、特に実用性の高い、上記一般式 (4' )において n =0である下記一般式 (4" )  The present inventors have found that among the acid fluoride compounds represented by the above general formula (4) or (4 ′), the following general formula, in which n = 0 in the above general formula (4 ′), is particularly highly practical. Expression (4 ")
CF CF (C0F) 0 (CF ) SO F (4")  CF CF (C0F) 0 (CF) SO F (4 ")
3 2 m 2  3 2 m 2
(mは上記一般式（1 ' )と同じである。 )  (m is the same as in the above general formula (1 ′).)
で表される酸フルオリド化合物を、上記一般式（3 ' )で表される ω—フルォロスルホニ ル化合物から製造する条件について詳細な検討を行い、工業的に有利な製造方法 を見出したので、以下にその方法について説明する。 A detailed study was conducted on the conditions for producing the acid fluoride compound represented by the formula (3 ′) from the ω-fluorosulfonyl compound represented by the general formula (3 ′), and an industrially advantageous production method was found. The method will be described.
なお、上記一般式 (4")で表される酸フルオリド化合物において、 mは 3— 10の整 数であるが、上記一般式（1 ' )と同様の理由により、より好ましくは 4一 8であり、さらに 好ましくは 4一 6であり、特に好ましくは 4である。  In the acid fluoride compound represented by the general formula (4 "), m is an integer of 3-10, but more preferably 418 for the same reason as in the general formula (1 '). Yes, more preferably 416, and particularly preferably 4.
上記一般式 (4")にお!/、て m=4である酸フルオリド化合物（すなわち、 CF CF (CO In the general formula (4 "), the acid fluoride compound having! / And m = 4 (ie, CF CF (CO
3  Three
F) 0 (CF ) SO F)を製造する方法としては、特許文献 2に、ジグライムを反応溶媒と  As a method for producing F) 0 (CF) SO F), Patent Document 2 discloses that diglyme is used as a reaction solvent.
2 4 2  2 4 2
して、 KF存在下、上記一般式（3，）において m=4である ω—フルォロスルホニル化 合物と等量の HFPOを反応させる方法（すなわち、 FCO (CF ) SO F1モルに対し Then, in the presence of KF, a method of reacting an equivalent amount of HFPO with an ω-fluorosulfonyl compound where m = 4 in the above general formula (3) (that is, with respect to 1 mole of FCO (CF) SO F
2 3 2  2 3 2
、 1モルの HFPOを使用する方法）が開示されている。この特許文献 2に記載の方法 により、目的物である該酸フルオリドィ匕合物は得られる力 副生成物として HFPOが さらに付加した高沸点化合物が多く生成するという問題がある。特許文献 3では、該 副生成物の生成を抑えるため、ジグライムを反応溶媒として、 KF存在下、該 ω—フル ォロスルホニル化合物に対して HFPOの使用量を減らして反応させる方法 (すなわ ち、 FCO (CF ) SO Flモルに対し、 0. 77モルの HFPOを使用する方法）が開示さ Using 1 mole of HFPO). According to the method described in Patent Document 2, the acid fluoride conjugate, which is the target, has a problem that a large number of high-boiling compounds to which HFPO is further added as an by-product are obtained. In Patent Document 3, in order to suppress the generation of the by-product, the ω-full A method of reducing the amount of HFPO used to react with an olosulfonyl compound (ie, a method of using 0.77 mol of HFPO per mol of FCO (CF) SOFl) is disclosed.
2 3 2  2 3 2
れている。この特許文献 3に記載の方法では、該副生成物の生成は少なくなるものの 、該 ω—フルォロスルホニルイ匕合物が未反応のまま多く残存するため、生産効率が悪 ぐ工業的に有利な製造方法とは言えない。  It is. In the method described in Patent Document 3, although the generation of the by-products is reduced, the ω-fluorosulfonyl conjugate remains unreacted in a large amount, so that the production efficiency is poor in industrial production. It is not an advantageous manufacturing method.
[0026] 本発明者らは、様々な反応溶媒につ!、て検討を行った結果、下記一般式 (6) The present inventors have conducted studies on various reaction solvents and found that the following general formula (6)
RxO (R20) R1 (6) R x O (R 2 0) R 1 (6)
P  P
(R1は炭素数 1一 5のアルキル基であり、 R2は C H又は C Hである。 pは 0— 10 (R 1 is an alkyl group having 115 carbon atoms, R 2 is CH or CH. P is 0-10
2 4 3 6  2 4 3 6
の整数である。 )  Is an integer. )
で表されるエーテル系溶媒とカルボン酸ジ-トリル系溶媒の混合溶媒の存在下では In the presence of a mixed solvent of an ether solvent represented by and a di-tolyl carboxylate solvent
、該 ω—フルォロスルホニル化合物（FCO (CF ) SO F)に対して、等量以上の HFP More than an equal amount of HFP to the ω-fluorosulfonyl compound (FCO (CF) SO F)
2 3 2  2 3 2
Oと反応させても、 目的物である該酸フルオリドィ匕合物（CF CF (COF) 0 (CF ) SO  Even when reacted with O, the desired acid fluoride conjugate (CF CF (COF) 0 (CF) SO
3 2 4 3 2 4
F)が高収率、高選択的に得られ、上記で問題となっていた該副生成物の生成量及F) can be obtained with high yield and high selectivity, and the amount of by-products
2 2
び該 ω—フルォロスルホニルイ匕合物の残存量は少なくなることを見出した。  And the residual amount of the ω-fluorosulfonyl ligated product was found to be reduced.
上記一般式 (6)で表されるエーテル系溶媒の例としては、ジエチレングリコールジメ チノレエーテノレ、ジエチレングリコーノレジェチノレエーテノレ、ジエチレングリコーノレジプロ ピルエーテル、ジエチレングリコールジブチルエーテル、トリエチレングリコールジメチ ノレエーテノレ、トリエチレングリコールジェチルエーテル、テトラエチレングリコールジメ チルエーテル、テトラエチレングリコールジェチルエーテル、プロピレングリコールジメ チルエーテル、プロピレングリコールジェチルエーテル、ジプロピレングリコールジメ チノレエ一テル、トルプロピレングリコールジメチノレエーテル、テトラプロピレングリコー ルジメチルエーテル等が挙げられる。また、カルボン酸ジ-トリル系溶媒としては、炭 素数 3— 8個を有する飽和脂肪族ジカルボン酸であり、例えばアジポ-トリル等が挙 げられる。上記エーテル系溶媒とカルボン酸ジ-トリル系溶媒の混合溶媒中に占め るカルボン酸ジ-トリルの質量割合は、 30質量％以上 99質量％以下が好ましぐ 40 質量％以上 97質量％以下がより好ましぐ 50質量％以上 95質量％以下が特に好ま しい。  Examples of the ether-based solvent represented by the general formula (6) include diethylene glycol dimethyl enoate, diethylene glycol olenoethyl enoate, diethylene glycol propylene dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyole enoate, Ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, toluene propylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether And the like. Examples of the carboxylic acid di-tolyl-based solvent include saturated aliphatic dicarboxylic acids having 3 to 8 carbon atoms, such as adipo-tolyl. The mass ratio of di-tolyl carboxylate in the mixed solvent of the ether-based solvent and di-tolyl carboxylate is preferably from 30% by mass to 99% by mass, more preferably from 40% by mass to 97% by mass. More preferred 50% by mass or more and 95% by mass or less is particularly preferred.
[0027] 上記反応において HFPOの使用量は、上記該 ω—フルォロスルホ-ル化合物 1モ ノレに対して、 HFPOiま 0. 95モノレカら 2モノレカ S好ましく、 0. 98モノレカら 1. 8モノレカ ^よ り好ましぐ 1モルから 1. 5モルが特に好ましい。 [0027] In the above reaction, the amount of HFPO used depends on the amount of the ω-fluorosulfol compound From 0.95 monoreca to HFPOi, 2 monoreca S is preferred, and from 0.98 monoreca to 1.8 monoreca is more preferably 1 mol to 1.5 mol.
反応圧力については特に制約はなぐ例えば常圧下でも加圧下でもよいが、効率 的に反応させるためには加圧容器中の加圧反応が好ま 、。加圧反応での圧力に は制限はないが、ゲージ圧で 0. OlMPa力ら 0. IMPaの範囲で HFPOを導入して いくことが好ましい。  There is no particular restriction on the reaction pressure. For example, the reaction may be performed under normal pressure or under pressure. For efficient reaction, a pressurized reaction in a pressurized vessel is preferred. The pressure in the pressurized reaction is not limited, but it is preferable to introduce HFPO within a range of 0.1 OlMPa force to 0.1 IMPa gauge pressure.
上記反応には、アルカリ金属フルオリドゃ 4級アンモ-ゥムフルオリド等の各種のフ ッ素イオン含有化合物が触媒として用いられ、その中でも KFや CsFがより好ま 、。 触媒のフッ素イオン含有ィ匕合物の量は限定的ではないが、通常、上記該 ω フルォ ロスルホニル化合物 1モルに対して 0. 001モルから 1モル程度とすればよ!/、。  In the above reaction, various fluoride ion-containing compounds such as alkali metal fluoride and quaternary ammonium fluoride are used as catalysts, and among them, KF and CsF are more preferable. Although the amount of the fluorine ion-containing conjugate of the catalyst is not limited, it is usually about 0.001 to 1 mol per 1 mol of the ω-fluorosulfonyl compound!
反応温度は 30°Cから 50°Cの範囲が好ましぐ— 20°Cから 30°Cの範囲がより好ま しい。  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.
反応時間は特に制限はなぐ HFPOが消費される時間によるが、例えば、 0. 5時間 力 72時間である。  The reaction time is not particularly limited, and depends on the time during which HFPO is consumed, and is, for example, 0.5 hour and 72 hours.
反応終了後、内容物は 2層（上層はエーテル系溶媒とカルボン酸ジニトリル系溶媒 の混合溶媒、下層は上記一般式 (4")で表される酸フルオリドィ匕合物を含有する反応 混合物）に分離するため、分液して下層部分を取り出し、蒸留操作により、上記一般 式 (4")で表される酸フルオリドィ匕合物を得ることができる。  After the completion of the reaction, the contents are divided into two layers (the upper layer is a mixed solvent of an ether-based solvent and a carboxylic acid dinitrile-based solvent, and the lower layer is a reaction mixture containing the acid fluoride conjugate represented by the above general formula (4 ")). In order to separate, the lower layer portion is taken out, and the acid fluoride conjugate represented by the above general formula (4 ") can be obtained by a distillation operation.
次に、工程 (c)及び工程 (c' )について説明する。  Next, the step (c) and the step (c ′) will be described.
上記の方法で得られた、上記一般式 (4)又は一般式 (4 ' )又は一般式 (4")で表さ れる酸フルオリド化合物は、下記一般式（2)  The acid fluoride compound represented by the general formula (4), (4 ′) or (4 ″) obtained by the above method is represented by the following general formula (2)
CF =CFO (CF CF (CF ) θ) CFY— R— SO F (2)  CF = CFO (CF CF (CF) θ) CFY— R— SO F (2)
2 2 3 n f 2  2 2 3 n f 2
(nは 0— 2の整数であり、 R及び Yは上記一般式（1)と同じ。 )  (n is an integer of 0-2, and R and Y are the same as in the general formula (1).)
f  f
又は下記一般式（2 ' ) Or the following general formula (2 ')
CF =CFO (CF CF (CF ) θ) (CF ) SO F (2，）  CF = CFO (CF CF (CF) θ) (CF) SO F (2,)
2 2 3 n' 2 m 2  2 2 3 n '2 m 2
(n は 0— 2の整数であり、 mは上記一般式（1 ' )と同じ。 )  (n is an integer from 0 to 2 and m is the same as in the above general formula (1 ′).)
又は下記一般式（2") Or the following general formula (2 ")
CF =CFO (CF ) SO F (2") (mは上記一般式（1 ' )と同じ。） CF = CFO (CF) SO F (2 ") (m is the same as in the above general formula (1 ′).)
で表される ω—フルォロスルホ-ルペルフルォロアルキルビュルエーテルに、それぞ れ変換することができる。上記一般式（2")で表される ω—フルォロスルホ-ルペルフ ルォロアルキルビュルエーテルは実用性が高く特に好ましい。さらに、上記一般式（Can be converted into ω-fluorosulfol-perfluoroalkyl ethers, respectively. The ω-fluorosulfol-perperfluoroalkylbutyl ether represented by the general formula (2 ") has high practicability and is particularly preferable.
2")において、 mは 3— 10の範囲の整数が好ましいが、合成'精製の容易性、及び操 作性'機能性から、より好ましくは 4一 8であり、さらに好ましくは 4一 6であり、特に好ま しくは 4である。 In 2 "), m is preferably an integer in the range of 3 to 10, but is more preferably 418, and still more preferably 416, from the viewpoint of ease of synthesis and purification and operability. Yes, especially 4
上記一般式 (4)又は一般式 (4 ' )又は一般式 (4")で表される酸フルオリドィ匕合物か ら、上記一般式（2)又は一般式（2' )又は一般式（2")で表される ω—フルォロスルホ -ルペルフルォロアルキルビュルエーテルを得る方法としては、酸フルオリド化合物 から直接合成する方法、ある!ヽは該酸フルオリド化合物から誘導されるカルボン酸の アルカリ金属塩、アルカリ土類金属塩、アルキルエステル又はシリルエステル等の各 種の誘導体を経る方法が知られている力 S、本発明のビュルィ匕工程の方法には特に 制約は無ぐ例えば、これらの公知の方法の中のいずれの方法を採用してもよい。 当該ビニルイ匕工程のより具体的な例を以下の a)— d)で説明する。 From the acid fluoride conjugate represented by the general formula (4), the general formula (4 ′) or the general formula (4 ″), the general formula (2) or the general formula (2 ′) or the general formula (2) As a method for obtaining ω-fluorosulfur-fluorofluoroalkyl ether represented by "), there is a method of directly synthesizing from an acid fluoride compound, and! Is an alkali metal of a carboxylic acid derived from the acid fluoride compound. There are no particular restrictions on the method of passing through various types of derivatives such as salts, alkaline earth metal salts, alkyl esters or silyl esters, and there are no particular restrictions on the method of the buliding process of the present invention. Any of the above methods may be adopted. More specific examples of the vinyli-dani process will be described in a ) to d) below.
a)上記一般式 (4)又は一般式 (4 ' )又は一般式 (4")で表される酸フルオリド化合物 から、直接上記一般式（2)又は一般式（2' )又は一般式（2")で表される ω—フルォロ スルホ-ルペルフルォロアルキルビュルエーテルを得る方法としては、 180°C力ら 35 0°Cに加熱したガラスビーズや、 KF、 NaF、 CsF、 CaF等のアルカリ金属又はアル力 リ土類金属フルオリドを担持したシリカ又はアルミナ等に、上記一般式 (4)又は一般 式 (4' )又は一般式 (4")で表される酸フルオリド化合物を導入し、接触させることによ つて上記一般式（2)又は一般式（2' )又は一般式（2")で表される ω—フルォロスルホ -ルペルフルォロアルキルビュルエーテルを得ることができる。 a) From the acid fluoride compound represented by the general formula (4), the general formula (4 ′), or the general formula (4 ″), directly from the general formula (2), the general formula (2 ′), or the general formula (2) The method for obtaining ω-fluoro sulfol perfluoroalkyl butyl ether represented by ") is as follows: glass beads heated to 180 ° C at 350 ° C, KF, NaF, CsF, CaF, etc. An acid fluoride compound represented by the above general formula (4) or the general formula (4 ') or the general formula (4 ") is introduced into silica or alumina or the like supporting an alkali metal or alkaline earth metal fluoride, By contacting, ω-fluorosulfol-perfluorofluoroalkyl ether represented by the general formula (2), (2 ′) or (2 ″) can be obtained.
b)次に、上記一般式 (4)又は一般式 (4' )又は一般式 (4")で表される酸フルオリド 化合物を各種の塩基性化合物と反応させて、ー且カルボン酸のアルカリ金属塩又は アルカリ土類金属塩にした後、該カルボン酸塩の加熱脱炭酸反応により、上記一般 式（2)又は一般式（2' )又は一般式（2")で表される ω—フルォロスルホ-ルペルフル ォロアルキルビュルエーテルを得る方法について説明する。 上記一般式 (4)又は一般式 (4 ' )又は一般式 (4")で表される酸フルオリドィ匕合物か ら該カルボン酸塩への変換反応で使用する塩基性化合物の例としては、アルカリ金 属又はアルカリ土類金属の炭酸塩や水酸ィ匕物が挙げられる。特に炭酸塩は、操作 性が良いので好ましい。当該反応に適したアルカリ金属又はアルカリ土類金属の炭 酸塩としては、例えば炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸セシウム、炭 酸ルビジウム、炭酸カルシウム、炭酸バリウム等が挙げられるが、中でも炭酸ナトリウ ム、炭酸カリウム、炭酸カルシウム等が好ましぐ炭酸ナトリウム、炭酸カリウムがより好 ましぐ炭酸カリウムが特に好ましい。 b) Next, the acid fluoride compound represented by the general formula (4) or (4 ′) or (4 ″) is reacted with various basic compounds to form an alkali metal salt of carboxylic acid. After being converted into a salt or an alkaline earth metal salt, the carboxylate is subjected to a heat decarboxylation reaction, whereby ω-fluorosulfo- represented by the above general formula (2) or (2 ′) or (2 ″) is obtained. The method for obtaining ruperfluoroalkylbutyl ether will be described. Examples of the basic compound used in the conversion reaction from the acid fluoride conjugate represented by the general formula (4) or (4 ′) or (4 ″) to the carboxylate include: Alkali metal or alkaline earth metal carbonates and hydroxides are preferred, especially carbonates because of their good operability. Examples include lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, rubidium carbonate, calcium carbonate, barium carbonate, etc., and among them, sodium carbonate, potassium carbonate, and the like are preferred, such as sodium carbonate, potassium carbonate, and calcium carbonate. Particularly preferred is potassium carbonate.
上記一般式 (4)又は一般式 (4 ' )又は一般式 (4")で表される酸フルオリドィ匕合物か ら該カルボン酸のアルカリ金属塩又はアルカリ土類金属塩に変換する場合、溶媒を 使用しても構わないし、無溶媒で変換を実施しても構わない。溶媒を使用する場合、 例えばァセトニトリル、プロピオ-トリル等の-トリル系溶媒やモノグライム、ジグライム 、トリグライム、テトラグライム等のエーテル系溶媒が使用される。反応温度としては 0 °Cから 80°Cの範囲が特に好まし!/、。  When converting the acid fluoride conjugate represented by the general formula (4), (4 ′) or (4 ″) into an alkali metal salt or an alkaline earth metal salt of the carboxylic acid, a solvent is required. When a solvent is used, for example, a solvent such as acetonitrile or propio-tolyl, or a tolyl solvent or an ether such as monoglyme, diglyme, triglyme, or tetraglyme may be used. A system solvent is used, and a reaction temperature in the range of 0 ° C to 80 ° C is particularly preferred!
上記の中和反応で得られた該カルボン酸のアルカリ金属塩又はアルカリ土類金属 塩から、加熱脱炭酸反応により上記一般式 (2)又は一般式 (2' )又は一般式 (2")で 表される ω—フルォロスルホ-ルペルフルォロアルキルビュルエーテルに変換する場 合、溶媒を使用しても構わないし無溶媒で変換を実施しても構わないが、無溶媒で 実施するほうが良好な反応成績を実現しやす!/、のでより好ま 、。  From the alkali metal salt or alkaline earth metal salt of the carboxylic acid obtained in the above neutralization reaction, the above-mentioned general formula (2) or general formula (2 ′) or general formula (2 ″) is obtained by heat decarboxylation reaction. When converting to the expressed ω-fluorosulfol-perfluoroalkyl alkyl ether, the conversion may be carried out with or without a solvent, but it is better to carry out the conversion without a solvent. Easy to achieve reaction grade! /, So more preferred.
溶媒存在下で脱炭酸反応を行う場合の条件としては、例えばジグライム、トリグライ ム、テトラグライム等のエーテル系溶媒を使って、 80°Cから 180°Cの範囲で脱炭酸反 応を行うことにより、上記一般式（2)又は一般式（2' )又は一般式（2")で表される ω— フルォロスルホ-ルペルフルォロアルキルビュルエーテルを製造することができる。 無溶媒で脱炭酸反応を行う場合は、中和反応の際に使用した溶媒を一旦蒸留等 により留去した後、 100°Cから 250°Cの範囲、好ましくは 150°Cから 230°Cの範囲で 脱炭酸反応を行うことにより、上記一般式 (2)又は一般式 (2' )又は一般式 (2")で表 される ω—フルォロスルホ-ルペルフルォロアルキルビュルエーテルを得ることができ る。無溶媒条件下での加熱脱炭酸反応においては、脱炭酸反応で生成した反応生 成物は連続的に速やかに反応系外に留去させながら反応を行うことが望ましい。反 応生成物が反応器内で滞留すると、副生成物が生じやすくなり、目的物である上記 一般式（2)又は一般式（2' )又は一般式（2")で表される ω フルォロスルホニルぺ ルフルォロアルキルビュルエーテルの収率が低くなる。 Conditions for performing the decarboxylation reaction in the presence of a solvent include, for example, performing the decarboxylation reaction in the range of 80 ° C to 180 ° C using an ethereal solvent such as diglyme, triglyme, or tetraglyme. The ω-fluorosulfol-perperfluoroalkylbutyl ether represented by the general formula (2), (2 ′) or (2 ″) can be produced. When performing the neutralization reaction, the solvent used in the neutralization reaction is once distilled off by distillation or the like, and then the decarboxylation reaction is performed in the range of 100 ° C to 250 ° C, preferably in the range of 150 ° C to 230 ° C. By doing so, the ω-fluorosulfol-perfluorofluoroalkyl ether represented by the general formula (2), (2 ′) or (2 ″) can be obtained. In thermal decarboxylation under solvent-free conditions, the reaction products It is desirable to carry out the reaction while continuously and quickly distilling the product out of the reaction system. If the reaction product stays in the reactor, by-products are likely to be generated, and the ω full represented by the above-mentioned general formula (2), general formula (2 ′) or general formula (2 ″), which is the target product, The yield of olosulfonyl perfluoroalkyl butyl ether is reduced.
本発明者らは、特に実用性の高い上記一般式（2")で表される ω フルォロスルホ -ルペルフルォロアルキルビュルエーテルを、上記一般式（4")で表される酸フルォ リドィ匕合物から製造する条件について詳細に検討した結果、工業的に有利な製造方 法を見出したので、以下にその方法について説明する。  The present inventors have converted the particularly useful ω-fluorosulfol-leperfluoroalkylbutyl ether represented by the above general formula (2 ″) to the acid fluoridyl ether represented by the above general formula (4 ″). As a result of a detailed study of the conditions for manufacturing from the compound, an industrially advantageous manufacturing method was found. The method is described below.
従来技術としては、特許文献 2に、上記一般式 (4")において m= 4である酸フルォ リドィ匕合物（CF CF (COF) 0 (CF ) SO F)から、ー且ナトリウム塩を製造し、次いで  As a prior art, Patent Document 2 discloses that sodium salt is produced from an acid fluoride compound (CF CF (COF) 0 (CF) SO F) in which m = 4 in the above general formula (4 ″). And then
3 2 4 2  3 2 4 2
当該ナトリウム塩の加熱脱炭酸反応により、上記一般式（2")において m=4である ω フルォロスルホ-ルペルフルォロアルキルビュルエーテル（CF =CFO (CF ) SO By the heat decarboxylation reaction of the sodium salt, ω-fluorosulfol-perfluoroalkylbutyl ether (CF = CFO (CF) SO) in which m = 4 in the above general formula (2 ″)
2 2 4 2 2 4
F)を製造する方法が示されて!/ヽる。 The method of manufacturing F) is shown!
2  2
本発明者等は、上記一般式 (4")で表される酸フルオリドィ匕合物力 上記一般式 (2 ")で表される ω フルォロスルホ-ルペルフルォロアルキルビュルエーテルを製造す る方法について、特許文献 2に記載の方法も含めて幅広く検討した。その結果、特許 文献 2に記載のナトリウム塩を経由する方法は分離困難な副生成物が多く生成する ため工業的に有利な製造方法ではないことが判明し、一方、本発明による特定の反 応方法を採用すると極めて効率的に高品質の製品を高収率で製造できることを見出 した。  The present inventors have proposed a method for producing an acid fluoridation compound represented by the above general formula (4 ") and a method for producing ω-fluorosulfol perfluoroalkyl alkyl ether represented by the above general formula (2"). , Including the method described in Patent Document 2. As a result, it has been found that the method via sodium salt described in Patent Document 2 is not an industrially advantageous production method due to the generation of many difficult-to-separate by-products. It has been found that high quality products can be produced with high yield by employing the method very efficiently.
先ず最初に、本発明者らは、特許文献 2に記載の方法に従って、上記一般式 (4") において m=4である酸フルオリドィ匕合物（CF CF (COF) 0 (CF ) SO F)を炭酸ナ  First, the present inventors have proposed, according to the method described in Patent Document 2, an acid fluoride conjugate (CF CF (COF) 0 (CF) SO F) wherein m = 4 in the above general formula (4 ″). The carbonate
3 2 4 2 トリウムと反応させてナトリウム塩に変換した後、無溶媒下で当該カルボン酸塩を加熱 脱炭酸反応させて、目的物である上記一般式（2")において m=4である ω フルォ ロスルホ -ルペルフルォロアルキルビュルエーテル（CF =CFO (CF ) SO F)を製  After reacting with 3242 thorium to convert to sodium salt, the carboxylate is heated and decarboxylated in the absence of a solvent to obtain ω with m = 4 in the above-mentioned general formula (2 ″) as the target compound. Fluorosulfo-leperfluoroalkyl butyl ether (CF = CFO (CF) SOF)
2 2 4 2 造する方法について詳細に検討した。その結果、加熱脱炭酸反応において、目的物 の他に副生成物として上記一般式 (4")において m=4である酸フルオリド化合物（C F CF (COF) 0 (CF ) SO F)が大量に生成するため、目的物の収率が低下するこ とがわかった。さらに該副生成物は、目的物と沸点が近いため、両者を分離するのが 困難であり、高純度の目的物を得るために繁雑な精製操作が必要となる。したがってThe method of fabrication was studied in detail. As a result, in the thermal decarboxylation reaction, in addition to the target substance, a large amount of acid fluoride compound (CF CF (COF) 0 (CF) SO F) in which m = 4 in the above general formula (4 ") as a by-product The yield of the target product may decrease due to I understood. Furthermore, since the by-product has a boiling point close to that of the target product, it is difficult to separate the two, and a complicated purification operation is required to obtain a high-purity target product. Therefore
、これらの問題点を抱えている特許文献 2に記載の方法は、工業的に有利な製造方 法とは言えない。 However, the method described in Patent Document 2 having these problems cannot be said to be an industrially advantageous production method.
本発明者等が、特許文献 2に記載の方法における加熱脱炭酸反応時のナトリウム 塩の状態を詳細に観察したところ、ナトリウム塩は熱分解温度付近の温度で溶融して いた。この際の副生成物の生成機構は明らかではないが、下記のような溶融状態の ナトリウム塩の分子間反応により、上記一般式 (4")において m=4である酸フルオリド 化合物 (CF CF (COF) 0 (CF ) SO F)が容易に生成する反応機構が推定された  The present inventors have observed in detail the state of the sodium salt during the thermal decarboxylation reaction in the method described in Patent Document 2, and found that the sodium salt was melted at a temperature near the thermal decomposition temperature. Although the formation mechanism of the by-products at this time is not clear, the acid fluoride compound (CF CF (m) in which m = 4 in the above general formula (4 ") is obtained by an intermolecular reaction of a sodium salt in a molten state as described below. The reaction mechanism for easily producing (COF) 0 (CF) SO F) was estimated.
3 2 4 2  3 2 4 2
-CO Na H—— SO F → C〇F + -SO Na -CO Na H—— SO F → C〇F + -SO Na
2 2 3  2 2 3
そこで、本発明者らは、上記のような副反応を極力抑制する反応方法を鋭意検討し た結果、カリウム塩のように加熱脱炭酸反応時にも溶融しない塩が存在し、そのような 塩の加熱脱炭酸反応では副生成物である上記一般式 (4")で表される酸フルオリド 化合物の生成が極めて少なくなり、高純度の目的物が高収率で得られることを見出 した。  Accordingly, the present inventors have conducted intensive studies on a reaction method for minimizing the side reaction as described above. As a result, there are salts such as potassium salts which do not melt even during the heating decarboxylation reaction. In the thermal decarboxylation reaction, it was found that the amount of the by-product acid fluoride compound represented by the above general formula (4 ") was extremely reduced, and the target product of high purity was obtained in high yield.
その結果、「上記一般式 (4")で表される酸フルオリドィ匕合物をカルボン酸塩に変換 し、次いで当該カルボン酸塩を熱分解して、上記一般式（2")で表される ω フルォ ロスルホ -ルペルフルォロアルキルビュルエーテルを製造するにあたって、目的生 成物である上記一般式（2")で表される ω フルォロスルホ-ルペルフルォロアルキ ルビ-ルエーテルの生成モル数を r、副生成物として再生成する上記一般式 (4")で 表される酸フルオリドィ匕合物の生成モル数を sとした場合、 [s]Z[r+s]で表される副生 成物の生成割合を 0. 1以下で反応を実施することを特徴とする、上記一般式 (2")で 表される ω フルォロスルホ-ルペルフルォロアルキルビュルエーテルを製造する方 法」が可能になった。ここで、 [s]Z[r+s]の値は、好ましくは 0. 1以下であり、より好まし くは 0. 08以下であり、さらに好ましくは 0. 06以下であり、特に好ましくは 0. 04以下 である。また、 [s]Z[r+s]の下限値は特に制約はないが、 0. 001、又は 0. 0001、又 は測定機器の検出限界以下の場合もあり得る。 [0033] 上記のような [s]Z[r+s]で表される副生成物の生成割合を 0. 1以下で反応を実施す る具体的な方法としては、「上記一般式 (4")で表される酸フルオリド化合物から誘導 されるカルボン酸塩が下記一般式（7) As a result, "the acid fluoride conjugate represented by the above general formula (4") is converted into a carboxylate, and then the carboxylate is thermally decomposed to obtain the compound represented by the above general formula (2 ") In the production of ω-fluorosulfol-leperfluoroalkylbutyl ether, the number of moles of the desired product ω-fluorosulfol-leperfluoroalkylalkyl ether represented by the above general formula (2 ") Where r is the number of moles of the acid fluoride conjugate represented by the above general formula (4 ″) that is regenerated as a by-product, and s is the by-product represented by [s] Z [r + s] A method for producing an ω-fluorosulfol-perperfluoroalkylbutyl ether represented by the general formula (2 "), characterized in that the reaction is carried out at a production rate of 0.1 or less." Is now possible. Here, the value of [s] Z [r + s] is preferably 0.1 or less, more preferably 0.08 or less, further preferably 0.06 or less, and particularly preferably. 0.04 or less. The lower limit of [s] Z [r + s] is not particularly limited, but may be 0.001 or 0.0001, or may be lower than the detection limit of the measuring instrument. [0033] As a specific method for carrying out the reaction at a production ratio of the by-product represented by [s] Z [r + s] of 0.1 or less, as described in the above general formula (4) The carboxylate derived from the acid fluoride compound represented by ") is represented by the following general formula (7)
CF CF (CO K) 0 (CF ) SO F (7)  CF CF (CO K) 0 (CF) SO F (7)
3 2 2 m 2  3 2 2 m 2
(mは上記一般式（1 ' )と同じである。 )  (m is the same as in the above general formula (1 ′).)
で表されるカリウム塩であり、かつ、当該カルボン酸塩の熱分解を無溶媒で行うことで あり、さらに別の方法としては、加熱脱炭酸の際に、カルボン酸塩の熱分解を、当該 カルボン酸塩を固相状態に保ちながら行うことである。  And thermal decomposition of the carboxylate is carried out without a solvent.As another method, the thermal decomposition of the carboxylate is carried out during decarboxylation by heating. This is performed while keeping the carboxylate in a solid phase state.
以下に、上記一般式 (4")において m=4である酸フルオリドィ匕合物（CF CF (COF  In the following, the acid fluoride conjugate (CF CF (COF
3  Three
) 0 (CF ) SO F)をカルボン酸塩 (ナトリウム塩又はカリウム塩）に変換した後、無溶 ) After converting 0 (CF) SO F) to carboxylate (sodium salt or potassium salt),
2 4 2 2 4 2
媒で当該カルボン酸塩を熱分解させた場合の、ナトリウム塩とカリウム塩の反応成績 を比較して、カリウム塩の効果を具体的に説明する。該カルボン酸塩がナトリウム塩の 場合、加熱温度を 180°C以上にすると、上記のようにナトリウム塩は熱分解時に溶融 状態であり、副生成物として上記一般式 (4")で表される酸フルオリド化合物が多量 に生成し、 目的物である上記一般式（2")で表される ω—フルォロスルホ-ルペルフ ルォロアルキルビュルエーテルは低収率で得られ、上記の [s]Z[r+s]は 0. 19であつ た。一方、当該カルボン酸塩がカリウム塩の場合、上記のように、カリウム塩は熱分解 時に固相状態であり、上記の副生成物である上記一般式 (4")で表される酸フルオリ ド化合物の生成はわずかであり、 目的物である上記一般式（2")で表される ω—フル ォロスルホ-ルペルフルォロアルキルビュルエーテルは高収率で得られ、 [s]Z[r+s] は 0. 01であった。 The effect of the potassium salt will be specifically described by comparing the reaction results of the sodium salt and the potassium salt when the carboxylate is thermally decomposed with a medium. When the carboxylate is a sodium salt, when the heating temperature is set to 180 ° C. or higher, the sodium salt is in a molten state at the time of thermal decomposition as described above, and is represented by the above general formula (4 ″) as a by-product. The acid fluoride compound is produced in a large amount, and the desired product, ω-fluorosulfol-perfluoroalkylalkyl ether represented by the above general formula (2 ″), is obtained in low yield, and the [ s ] Z [r + s] was 0.19. On the other hand, when the carboxylate is a potassium salt, as described above, the potassium salt is in a solid phase upon thermal decomposition, and is an acid fluoride represented by the general formula (4 "), which is a by-product described above. The formation of the compound was slight, and the desired product, ω-fluorosulfol-perperfluoroalkylbutyl ether represented by the above general formula (2 "), was obtained in high yield, and [s] Z [r + s] was 0.01.
[0034] c)上記一般式 (4)又は一般式 (4 ' )又は一般式 (4")で表される酸フルオリド化合物 とアルカリ金属又はアルカリ土類金属の炭酸塩を高温で接触させて、中和反応と同 時に脱炭酸反応を行う方法としては、例えば 200°Cから 350°Cの範囲に加熱した炭 酸塩の中に、上記酸フルオリド化合物を導入することで、上記一般式（2)又は一般式 (2' )又は一般式 (2")で表される ω—フルォロスルホ-ルペルフルォロアルキルビ- ルエーテルを得ることができる。使用されるアルカリ金属又はアルカリ土類金属の炭 酸塩の例としては、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸セシウム、炭酸 ルビジウム、炭酸カルシウム、炭酸バリウム等が挙げられる。中でも炭酸ナトリウム、炭 酸カリウム、炭酸カルシウム等がより好ましぐ炭酸カリウムが特に好ましい。 C) contacting the acid fluoride compound represented by the general formula (4) or (4 ′) or the general formula (4 ″) with an alkali metal or alkaline earth metal carbonate at a high temperature, As a method of performing the decarboxylation reaction at the same time as the neutralization reaction, for example, by introducing the above acid fluoride compound into a carbonate heated to a temperature in the range of 200 ° C to 350 ° C, the above general formula (2) ) Or the general formula (2 ′) or the general formula (2 ″), to obtain an ω-fluorosulfol-perperfluoroalkyl vinyl ether. Examples of the alkali metal or alkaline earth metal carbonates used include lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, and carbonate. Rubidium, calcium carbonate, barium carbonate and the like can be mentioned. Among them, potassium carbonate, which is more preferably sodium carbonate, potassium carbonate, calcium carbonate and the like, is particularly preferable.
[0035] d)上記一般式 (4)又は一般式 (4' )又は一般式 (4")で表される酸フルオリド化合物 力 カルボン酸のシリルエステルを経由する方法を以下に説明する。例えば、先ず最 初に該酸フルオリド化合物と、 Me SiOK 等のアルカリ金属  D) An acid fluoride compound represented by the above general formula (4) or (4 ′) or (4 ″) A method via a silyl ester of a carboxylic acid is described below. First, the acid fluoride compound and an alkali metal such as Me SiOK
3 、 Me SiONa  3, Me SiONa
3 、 Et SiOK  3, Et SiOK
3  Three
シラノレ一トイ匕合物を触媒として、シロキサン化合物と反応させることによって、カルボ ン酸のシリルエステルを製造する。シロキサンィ匕合物の例としては、例えばへキサメ チノレジシロキサン、へキサェチノレジシロキサン、へキサフエニノレジシロキサン等のジ シロキサンィ匕合物、環状シロキサン化合物、ポリメチルシロキサン等のシロキサンポリ マーが挙げられる。製造したカルボン酸のシリルエステルを、 KFや NaF等のアルカリ 金属フルオリドを触媒として、液相又は気相で脱シリルフルオリド反応に付し、上記一 般式（2)又は一般式（2' )又は一般式（2")で表される ω—フルォロスルホニルペルフ ルォロアルキルビュルエーテルを得ることができる。脱シリルフルオリド反応を行う温 度としては、例えば、液相で反応を行う場合、 25°Cから 175°Cの範囲、気相で反応を 行う場合は 140°Cから 250°Cの範囲である。  A silyl ester of carboxylic acid is produced by reacting the silanol compound with a siloxane compound using the catalyst as a catalyst. Examples of siloxane conjugates include, for example, disiloxane conjugates such as hexamethinoresisiloxane, hexethinoresisiloxane, and hexafeninoresisiloxane, and siloxane polymers such as cyclic siloxane compounds and polymethylsiloxane. No. The silyl ester of the carboxylic acid thus produced is subjected to a desilyl fluoride reaction in a liquid or gaseous phase using an alkali metal fluoride such as KF or NaF as a catalyst to obtain the above general formula (2) or general formula (2 ′) Alternatively, ω-fluorosulfonylperfluoroalkylbutyl ether represented by the general formula (2 ") can be obtained. The temperature at which the desilyl fluoride reaction is performed is, for example, a reaction in a liquid phase. In this case, the reaction temperature is in the range of 25 ° C to 175 ° C, and when the reaction is performed in the gas phase, it is in the range of 140 ° C to 250 ° C.
上記の各種方法で得られた上記一般式（2)又は一般式（2 ' )又は一般式（2")で表 される ω—フルォロスルホ-ルペルフルォロアルキルビュルエーテルは蒸留等の方 法で精製することができる。  The ω-fluorosulfol-perperfluoroalkylbutyl ether represented by the general formula (2), (2 ′) or (2 ″) obtained by the above-mentioned various methods is obtained by a method such as distillation. Can be purified.
[0036] 次に、本発明に使用される上記一般式（1 ' )で表される ω—ハロペルフルォロアル キルスルホ-ルフルオリドにつ 、て説明する。 Next, the ω-haloperfluoroalkylsulfur fluoride represented by the above general formula (1 ′) used in the present invention will be described.
上記一般式（2，）で表される ω—フルォロスルホ-ルペルフルォロアルキルビュル エーテルの合成原料である上記一般式（1， )で表される ω—ハロペルフルォロアルキ ルスルホニルフルオリドは、どのような方法で製造されたものでも本発明の方法に使 用することができる。上記一般式（1，）で表される ω—ハロペルフルォロアルキルスル ホニルフルオリドの製造方法としては、上記スキーム 2に示される製造法が報告され ているが、この方法は前記のように各種の合成上の問題点を抱えており、工業的に 有利な製造方法ではない。それに対して、以下に説明する本願の工程 (i)一 (iv)に よると、効率的に高純度の ω—ハロペルフルォロアルキルスルホ-ルフルオリドを製 造することができるので、実用的に特に好ましい。 Ω-haloperfluoroalkylsulfonylfluoride represented by the above general formula (1), which is a raw material for synthesizing ω-fluorosulfol-perperfluoroalkylbutyl ether represented by the above general formula (2). The metal can be used in the method of the present invention whatever is manufactured by any method. As a method for producing the ω-haloperfluoroalkylsulfonyl fluoride represented by the above general formula (1), the production method shown in the above scheme 2 has been reported. However, it is not an industrially advantageous production method. On the other hand, according to the process (i)-(iv) of the present invention described below, highly pure ω-haloperfluoroalkylsulfur fluoride is efficiently produced. It is practically particularly preferable because it can be manufactured.
次に、上記一般式（1，）で表される ω—ハロペルフルォロアルキルスルホ-ルフルォ リドを製造する工程 (i)一 (iv)につ 、て説明する。  Next, the steps (i)-(iv) for producing the ω-haloperfluoroalkylsulfur-fluoride represented by the general formula (1) will be described.
[0037] 最初に工程 (i)につ 、て説明する。 First, the step (i) will be described.
下記一般式 (9)  The following general formula (9)
X(CF ) SO M (9)  X (CF) SO M (9)
2 m 2  2 m 2
(式中、 Mは Ma、 Mb 、第 4級アンモ -ゥムラジカル又は第 4級ホスホ-ゥムラジカ  (Wherein, M is Ma, Mb, quaternary ammom-radical or quaternary phospho-mradica
1/2  1/2
ルであり、 Maはアルカリ金属、 Mbはアルカリ土類金属である。 X及び mは上記一般 式（1 ' )と同じである。）  Ma is an alkali metal and Mb is an alkaline earth metal. X and m are the same as those in the above general formula (1 ′). )
で表される ω—ハロペルフルォロアルキルスルフィン塩は、下記一般式（8)  The ω-haloperfluoroalkylsulfine salt represented by the following general formula (8)
X(CF ) X (8)  X (CF) X (8)
2 m  2 m
(X、 mは上記一般式（1 ' )と同じである。 )  (X and m are the same as in the general formula (1 ′).)
で表される a , ω—ジハロペルフルォロアルカンをアルカリ金属塩型、アルカリ土類金 属塩型、第 4級アンモ-ゥム塩型、又は第 4級ホスホ-ゥム塩型の何れ力から選ばれ る亜ジチオン酸塩と混合、攪拌させること〖こより得られる。  A, ω-dihaloperfluoroalkane represented by the following formula: alkali metal salt type, alkaline earth metal salt type, quaternary ammonium salt type, or quaternary phospho-dimethyl salt type It can be obtained by mixing and stirring with a dithionite selected from any force.
本発明の製造方法において使用される亜ジチオン酸塩としては、 Li S O  As the dithionite used in the production method of the present invention, Li S O
2 2 4、 Na S  2 2 4, Na S
2 2 twenty two
O、 K S O、 Cs S O等のアルカリ金属塩型、 CaS O等のアルカリ土類金属塩型Alkali metal salt type such as O, KSO, CsSO, alkaline earth metal salt type such as CaSO
4 2 2 4 2 2 4 2 4 4 2 2 4 2 2 4 2 4
、 ( (CH ) N) S Oや（（n - Bu) N) S O等の第 4級アンモニゥム塩型、（（CH ) P Quaternary ammonium salt forms such as ((CH) N) SO and ((n-Bu) N) SO, ((CH) P
3 4 2 2 4 4 2 2 4 3 43 4 2 2 4 4 2 2 4 3 4
) S Oや（（n— Bu) P) S O等の第 4級ホスホ-ゥム塩型が挙げられる力 中でも N) S O and ((n-Bu) P) S O and other quaternary phospho-pium salt forms.
2 2 4 4 2 2 4 2 2 4 4 2 2 4
a S O、 K S Oが好ましい。なお、上記の各種の亜ジチオン酸塩は単独で用いて a S O and K S O are preferred. The above various dithionite salts are used alone.
2 2 4 2 2 4 2 2 4 2 2 4
も混合で用いても構わない。  May be used as a mixture.
[0038] 上記一般式（8)で表される a , ω—ジハロペルフルォロアルカンとアルカリ金属塩型 、アルカリ土類金属塩型、第 4級アンモ-ゥム塩型、又は第 4級ホスホ-ゥム塩型の何 れカから選ばれる亜ジチオン酸塩の反応では、上記一般式（9)で表される ω—ハロ ペルフルォロアルキルスルフィン酸塩の他に、副生成物として α位、 ω位の両方がス ルフィン酸塩化された下記一般式（11)  [0038] a, ω-dihaloperfluoroalkane represented by the above general formula (8) and an alkali metal salt type, an alkaline earth metal salt type, a quaternary ammonium salt type, or a quaternary ammonium salt type In the reaction of dithionite selected from any of the lower phospho-dum salt forms, in addition to the ω-haloperfluoroalkylsulfinate represented by the general formula (9), by-products The following general formula (11) in which both the α-position and the ω-position are sulfinated
MO S(CF ) SO M (11)  MO S (CF) SO M (11)
2 2 m 2  2 2 m 2
(Mは上記一般式（9)と同じであり、 mは上記一般式（1 ' )と同じである。 ) で表されるペルフルォロアルキル α , ω—ビススルフィン酸塩が生成する。 (M is the same as the general formula (9), and m is the same as the general formula (1 ′).) The perfluoroalkyl α, ω-bissulfinate represented by the formula is formed.
亜ジチオン酸塩の使用量は、上記一般式（8)で表される a , ω ジハロペルフルォ ロアルカンに対して 0. 1当量以上 3当量以下が好ましぐ 0. 1当量以上 2. 0当量以 下がさらに好ましぐ 0. 2当量以上 1. 5当量以下が特に好ましい。 0. 1当量以下で は基質の反応がほとんど進まず、 3. 0当量以上では、上記一般式（11)で表される ペルフルォロアルキル α , ω ビススルフィン酸塩の生成量が多くなるため好ましく ない。  The amount of the dithionite used is preferably from 0.1 to 3 equivalents to the a, ω dihaloperfluoroalkane represented by the general formula (8). 0.1 to 2.0 equivalents Is more preferably 0.2 to 1.5 equivalents. At less than 0.1 equivalent, the reaction of the substrate hardly progresses, and at more than 3.0 equivalent, the amount of perfluoroalkyl α, ω bissulfinate represented by the above general formula (11) increases. This is not preferred.
[0039] 上記反応に使用する溶媒としては、例えばアセトン、メチルェチルケトン等のケトン 系溶媒、ァセトニトリル、プロピオ-トリル等の-トリル系溶媒、テトラヒドロフラン、ジォ キサン、ジグライム等の鎖状又は環状のエーテル系溶媒、 Ν, Ν—ジメチルホルムアミ ド、 Ν, Ν—ジメチルァセトアミド等のアミド系溶媒、ジメチルスルホキシド等の各種の極 性溶媒が挙げられる。好ましくはアセトン、メチルェチルケトン等のケトン系溶媒、ァセ トニトリル、プロピオ-トリル等の-トリル系溶媒であり、更に好ましくはアセトン、ァセト 二トリルである。これらの有機溶媒は水との混合溶媒で用いられるのが好ましぐ有機 溶媒は 1種類でもよいし、又は複数の有機溶媒の組み合わせでも構わない。  [0039] Solvents used in the above reaction include, for example, ketone solvents such as acetone and methyl ethyl ketone, -tolyl solvents such as acetonitrile and propio-tolyl, and linear or cyclic solvents such as tetrahydrofuran, dioxane and diglyme. Ether solvents, amide solvents such as Ν, Ν-dimethylformamide and Ν, Ν-dimethylacetamide, and various polar solvents such as dimethyl sulfoxide. Preferred are ketone solvents such as acetone and methyl ethyl ketone, and -tolyl solvents such as acetonitrile and propio-tolyl, and more preferred are acetone and acetonitrile. These organic solvents are preferably used as a mixed solvent with water, and one kind of organic solvent may be used, or a combination of a plurality of organic solvents may be used.
水を使用する場合には、水に対する上記有機溶媒の使用量としては、水の体積量 に対して 0. 1倍以上 100倍以下が好ましぐ 1倍以上 50倍以下がさらに好ましぐ 2倍 以上 20倍以下が特に好ましい。水の使用量が 100倍以上であると基質の反応がほ とんど進まなくなるため好ましくない。また、基質に対する水の量としては、基質に対 して 0. 1当量以上 200当量以下が好ましぐ 1当量以上 150当量以下がさらに好まし く、 5当量以上 100当量以下が特に好ましい。  When water is used, the amount of the organic solvent to be used with respect to water is preferably 0.1 times or more and 100 times or less, more preferably 1 time or more and 50 times or less with respect to the volume of water. It is particularly preferable that the ratio be from 20 to 20 times. If the amount of water used is more than 100 times, the reaction of the substrate hardly proceeds, which is not preferable. The amount of water relative to the substrate is preferably from 0.1 to 200 equivalents, more preferably from 1 to 150 equivalents, particularly preferably from 5 to 100 equivalents, based on the substrate.
[0040] 上記一般式（8)で表される α , ω ジハロペルフルォロアルカンと、アルカリ金属塩 型、アルカリ土類金属塩型、第 4級アンモ-ゥム塩型、又は第 4級ホスホ-ゥム塩型の 何れカゝから選ばれる亜ジチオン酸塩の反応では中和剤や緩衝剤を入れても構わな い。中和剤としては炭酸水素リチウム、炭酸水素ナトリウム、炭酸水素カリウム等の炭 酸水素塩、炭酸リチウム、炭酸ナトリウム、炭酸カリウム等の炭酸塩、リン酸水素ナトリ ゥム、リン酸水素カリウム等のリン酸水素塩、リン酸ナトリウム、リン酸カリウム等のリン 酸塩、水酸化リチウム、水酸化ナトリウム、水酸ィ匕カリウム等の水酸ィ匕物等を用いるこ とがでさる。 The α, ω 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 ammonium salt type In the reaction of dithionite selected from any of the lower phospho-dimethyl salts, a neutralizing agent or a buffer may be added. Examples of the neutralizing agent include hydrogen carbonate such as lithium hydrogen carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate; carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; and phosphorus such as sodium hydrogen phosphate and potassium hydrogen phosphate. Hydrogen salts, phosphates such as sodium phosphate and potassium phosphate, and hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and the like can be used. It comes out.
反応温度は 30°Cから 90°Cの範囲が好ましぐ— 10°Cから 60°Cの範囲がさらに好 ましい。反応時間は、反応条件に応じて、亜ジチオン酸塩が十分に消費される時間 であればよぐ特に制約はないが、実用的には 0. 1時間から 48時間程度の範囲が好 ましい。  Reaction temperatures are 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 depending on the reaction conditions, but practically, the range is about 0.1 to 48 hours. .
次に、工程 (ii)について説明する。  Next, the step (ii) will be described.
上記の工程 (i)で、上記一般式（8)で表される a , ω ジハロペルフルォロアルカン と亜ジチオン酸塩の反応により、目的物の上記一般式（9)で表される ω—ハロペルフ ルォロアルキルスルフィン酸塩の他に、上記一般式（8)で表される未反応の α , ω— ジハロペルフルォロアルカンと上記一般式（11)で表されるペルフルォロアルキル α , ω ビススルフィン酸塩が副生成物として生成する。さらに当該反応により生成す る無機沃化物又は無機臭化物も反応系に存在する。  In the above step (i), the target compound represented by the above general formula (9) is obtained by reacting a, ω dihaloperfluoroalkane represented by the above general formula (8) with dithionite. In addition to the ω-haloperfluoroalkyl sulfinic acid salt, unreacted α, ω-dihaloperfluoroalkane represented by the above general formula (8) and perfluuyl represented by the above general formula (11) Oroalkyl α, ω bissulfinates are formed as by-products. Further, an inorganic iodide or an inorganic bromide generated by the reaction also exists in the reaction system.
当該反応系で無機沃化物又は無機臭化物が析出 '懸濁した懸濁液が形成される 場合には、無機沃化物又は無機臭化物を濾過により除去してカゝら分離精製を行って も構わない。  When a suspension in which inorganic iodide or inorganic bromide is precipitated and formed in the reaction system is formed, inorganic iodide or inorganic bromide may be removed by filtration and separation and purification may be performed. .
上記 16.の工程 (ii 1)に記載されている工程 (i)の反応混合物から上記一般式 (8 )で表される a , ω ジハロペルフルォロアルカンを除去する方法としては、各種の除 去方法を採用することができる。その除去方法の具体例としては、例えば、蒸留によ る除去、フッ素原子含有有機溶媒による抽出 '除去、又は上記一般式 (9)で表される ωーハロペルフルォロアルキルスルフィン酸塩及び上記一般式（11)で表されるペル フルォロアルキル α , ω ビススルフィン酸塩を含む水系媒体からの相分離による 除去等の方法が挙げられる。 There are various methods for removing the a, ω dihaloperfluoroalkane represented by the general formula (8) from the reaction mixture of the step (i) described in the step (ii 1) of the above 16. The removal method can be adopted. Specific examples of the removal method include, for example, removal by distillation, extraction and removal with a fluorine atom-containing organic solvent, or ω-haloperfluoroalkylsulfinate represented by the general formula (9) and Examples of the method include removal by phase separation from an aqueous medium containing a perfluoroalkyl α , ω bissulfinate represented by the general formula (11).
例えば、蒸留による除去方法では、反応後の溶液又は懸濁液から蒸留等により、 使用した有機溶媒と未反応の上記一般式 (8)で表される a , ω ジハロペルフルォロ アルカンを除くことができる。  For example, in the removal method by distillation, the unreacted a, ω dihaloperfluoroalkane represented by the above general formula (8) is reacted with the used organic solvent by distillation or the like from the solution or suspension after the reaction. Can be excluded.
相分離による除去方法としては、例えば蒸留等の方法によって使用した有機溶媒 を留去した後に水を加えると 2層に分離し、上記一般式 (8)で表される a , ω ジハロ ペルフルォロアルカンが下層に分離されるので、下層を分液することにより、上記一 般式（8)で表される a , ω ジハロペルフルォロアルカンを得ることができる。 As a removal method by phase separation, for example, after distilling off the organic solvent used by a method such as distillation, water is added to separate into two layers, and a, ω dihalo perfluoro represented by the above general formula (8) is obtained. Since the lower alkane is separated into the lower layer, the lower layer The a, ω dihaloperfluoroalkane represented by the general formula (8) can be obtained.
フッ素原子含有有機溶媒による抽出 ·除去方法は、工程 (i)で得られた反応混合物 に、 HFC43— 10mee、ペルフルォ口へキサン等のフッ素原子含有有機溶媒をカロえ て上記一般式（8)で表される a , ω ジハロペルフルォロアルカンを抽出する方法が 挙げられる。  The method of extraction and removal using a fluorine atom-containing organic solvent is as follows. The reaction mixture obtained in step (i) is mixed with a fluorine atom-containing organic solvent such as HFC43-10mee and perfluorohexane, and the above formula (8) is used. There is a method for extracting the a, ω dihaloperfluoroalkane represented.
以上の方法で分離した上記一般式（8)で表される a , ω ジハロペルフルォロアル カンは、再度、亜ジチオン酸塩との反応に使用することができる。  The a, ω dihaloperfluoroalkane represented by the above general formula (8) separated by the above method can be used again for the reaction with dithionite.
次に上記一般式（9)で表される ω—ハロペルフルォロアルキルスルフィン酸塩と上 記一般式（11)で表されるペルフルォロアルキル a , ω ビススルフィン酸塩を含む 混合物から、上記一般式（9)で表される ω—ハロペルフルォロアルキルスルフィン酸 塩を抽出分離する工程 (ii - 2)では、各種方法が使用できる。例えば上記一般式 (9) で表される ω—ハロペルフルォロアルキルスルフィン酸塩と上記一般式（ 11)で表され るペルフルォロアルキル α , ω ビススルフィン酸塩が溶解した水性分散液、又は 両成分を含有する固体混合物から、上記一般式（9)で表される ω—ハロペルフルォ 口アルキルスルフィン酸塩を抽出することができる。  Next, a mixture containing the ω-haloperfluoroalkylsulfinate represented by the above general formula (9) and the perfluoroalkyl a, ω bissulfinate represented by the above general formula (11) In the step (ii-2) of extracting and separating the ω-haloperfluoroalkylsulfinate represented by the general formula (9) from the above, various methods can be used. 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 From the liquid or the solid mixture containing both components, the ω-haloperfluoroalkylsulfinate represented by the above general formula (9) can be extracted.
上記一般式（9)で表される ω—ハロペルフルォロアルキルスルフィン酸塩と上記一 般式（11)で表されるペルフルォロアルキル a , ω ビススルフィン酸塩が溶解した 反応混合物から、上記一般式（9)で表される ω—ハロペルフルォロアルキルスルフィ ン酸塩を抽出する方法としては、例えば、酢酸ェチル等のエステル系溶媒やジェチ ルエーテル等のエーテル系溶媒等の水難溶性有機溶媒を加えて、有機層に上記一 般式（9)で表される ω ノヽロペルフルォロアルキルスルフィン酸塩を抽出する方法が 挙げられる。この場合、上記一般式（11)で表されるペルフルォロアルキル α , ω - ビススルフィン酸塩及び、上記工程 (i)で生成した副生成物である無機沃化物又は 無機臭化物等の無機塩は水層側に分離される。上記一般式 (9)で表される ω—ハロ ペルフルォロアルキルスルフィン酸塩を含む有機層を分液した後、有機溶媒を留去 すると、高純度の上記一般式（9)で表される ω—ハロペルフルォロアルキルスルフィ ン酸塩を単離することができる。なお、当該有機層には、上記一般式（11)で表され るペルフルォロアルキル a , ω ビススルフィン酸塩はほとんど含まれな！/、。 上記一般式（9)で表される ω—ハロペルフルォロアルキルスルフィン酸塩と上記一 般式（11)で表されるペルフルォロアルキル a , ω ビススルフィン酸塩の両成分を 含有する固体混合物から、上記一般式（9)で表される ω—ハロペルフルォロアルキル スルフィン酸塩を分離する方法としては、例えば酢酸ェチル等のエステル系溶媒や ジェチルエーテル等のエーテル系溶媒等の有機溶媒で、当該固体混合物から上記 一般式（9)で表される ω ノヽロペルフルォロアルキルスルフィン酸塩を抽出する方法 が挙げられる。当該有機溶媒に不溶な固形物である上記一般式（11)で表されるぺ ルフルォロアルキル α , ω ビススルフィン酸塩、及び無機沃化物又は無機臭化物 等の無機塩は濾過により除去することができる。一方、濾液は蒸留等により有機溶媒 を留去すると、高純度の上記一般式（9)で表される ω—ノ、口ペルフルォロアルキルス ルフィン酸塩が高収率で得られる。 Reaction mixture in which the ω-haloperfluoroalkyl sulfinate represented by the general formula (9) and the perfluoroalkyl a, ω bis sulfinate represented by the general formula (11) are dissolved. As a method for extracting the ω-haloperfluoroalkyl sulfinate represented by the above general formula (9), for example, ester solvents such as ethyl acetate, ether solvents such as ethyl ether, etc. And extracting the ω-noperoperfluoroalkylsulfinate represented by the above general formula (9) into the organic layer by adding the poorly water-soluble organic solvent. In this case, the perfluoroalkyl α, ω-bissulfinate represented by the general formula (11) and the inorganic iodide or inorganic bromide such as an inorganic iodide or an inorganic bromide generated in the step (i) are used. The salt is separated on the aqueous layer side. After separating the organic layer containing the ω-halo perfluoroalkylsulfinate represented by the above general formula (9), the organic solvent is distilled off to obtain a highly pure compound represented by the above general formula (9). Ω-haloperfluoroalkyl sulfinate can be isolated. The organic layer contains almost no perfluoroalkyl a, ω bissulfinate represented by the general formula (11)! /. Contains both the ω-haloperfluoroalkylsulfinate represented by the above general formula (9) and the perfluoroalkyl a, ωbissulfinate expressed by the above general formula (11) As a method for separating the ω-haloperfluoroalkyl sulfinate represented by the general formula (9) from the solid mixture to be produced, for example, an ester solvent such as ethyl acetate or an ether solvent such as getyl ether is used. A method of extracting the ω-noperoperfluoroalkylsulfinate represented by the general formula (9) from the solid mixture with an organic solvent such as the above. The perfluoroalkyl α , ω bissulfinate represented by the general formula (11) and inorganic salts such as inorganic iodide or inorganic bromide, which are insoluble in the organic solvent, are removed by filtration. be able to. On the other hand, when the organic solvent is distilled off from the filtrate by distillation or the like, a high-purity ω-no, perfluoroalkylsulfinate represented by the above general formula (9) is obtained in a high yield.
次に、工程 (iii)について説明する。  Next, the step (iii) will be described.
上記の工程 (ii)で得られた上記一般式（9)で表される ω—ハロペルフルォロアルキ ルスルフィン酸塩は塩素ィ匕剤で処理することによって下記一般式（10)  The ω-haloperfluoroalkylsulfinate represented by the above general formula (9) obtained in the above step (ii) is treated with a chloridizing agent to give the following general formula (10)
X(CF ) SO CI (10)  X (CF) SO CI (10)
2 m 2  2 m 2
(X及び mは上記一般式（1 ' )と同じである。 )  (X and m are the same as in the above general formula (1 ′).)
で表される ω—ハロペルフルォロアルキルスルホユルク口リドを得ることができる。具体 的には上記一般式（9)で表される ω—ハロペルフルォロアルキルスルフィン酸塩を水 、有機溶媒又はそれらの混合溶媒に溶解又は分散させた後、塩素化剤を添加するこ とにより塩素化反応を行うことができる。 The ω-haloperfluoroalkylsulfojuruku mouth represented by the formula can be obtained. Specifically, after dissolving or dispersing the ω-haloperfluoroalkylsulfinate represented by the general formula (9) in water, an organic solvent or a mixed solvent thereof, a chlorinating agent is added. With this, a chlorination reaction can be performed.
当該工程は、各種の媒体中で実施できるが、反応操作の容易性や安全性等を考 慮すると、水又は酸を含む水溶液を溶媒とすることが好まし ヽ。  This step can be carried out in various media, but considering the ease and safety of the reaction operation, it is preferable to use water or an aqueous solution containing an acid as the solvent.
塩素ィ匕剤としては、—SO Mを SO C1に変換できるものであれば特に制限はなぐ  The chloridizing agent is not particularly limited as long as it can convert —SO M to SO C1.
2 2  twenty two
各種の公知の塩素ィ匕剤を用いることが可能である。例えば、塩素、塩化スルフリル等 を塩素ィ匕剤として用いることができる力 特に塩素が好ましい。塩素を用いて水中で 塩素化反応を行う場合は、 目的物である上記一般式（10)で表される ω—ハロペルフ ルォロアルキルスルホユルク口リドは水に不溶であるため、水との分離操作が容易と なり、工業的実施が特に有利となる。 塩素化反応の条件については、特に制限はなぐ使用する塩素化剤の種類に応じ て、 目的とする塩素化物が生成するように適宜決めればよい。例えば、塩素化剤とし て塩素を用いる場合には、上記一般式（9)の ω ノヽロペルフルォロアルキルスルフィ ン酸塩を溶解した水溶液中に塩素ガスを供給して塩素化反応を行えばよぐ反応温 度は 0— 50°C、塩素の仕込み量は上記一般式（9)の ω—ハロペルフルォロアルキル スルフィン酸塩 1モルに対して 1一 5モル程度が好ましぐ 1. 2モルから 3モルの範囲 がより好ましい。水溶液中の上記一般式（9)の ω ノヽロペルフルォロアルキルスルフ イン酸塩の濃度については、特に限定はないが、通常 0. 5— 50質量％程度とすれ ばよい。 It is possible to use various well-known chloridizing agents. For example, the ability to use chlorine, sulfuryl chloride or the like as a chlorine-containing agent, particularly preferably chlorine. When chlorination reaction is carried out in water using chlorine, the target compound, ω-haloperfluoroalkylsulfuric acid mouth lid represented by the above general formula (10), is insoluble in water, so it must be separated from water. The operation is easier and industrial implementation is particularly advantageous. The conditions for the chlorination reaction are not particularly limited, and may be appropriately determined depending on the type of the chlorinating agent to be used so that the desired chlorinated product is produced. For example, when chlorine is used as the chlorinating agent, chlorine gas is supplied to an aqueous solution in which the ω-noperoperfluoroalkyl sulfinate of the above general formula (9) is dissolved to perform the chlorination reaction. The reaction temperature is preferably 0-50 ° C, and the amount of chlorine charged is preferably about 115 mol per mol of ω- haloperfluoroalkyl sulfinic acid salt of the above general formula (9). The range of 1.2 to 3 moles is more preferable. The concentration of the ω-noperoperfluoroalkyl sulfinate of the above general formula (9) in the aqueous solution is not particularly limited, but may be usually about 0.5 to 50% by mass.
次に、工程 (iv)について説明する。  Next, the step (iv) will be described.
工程（iii)で得られた上記一般式（10)で表される ω—ハロペルフルォロアルキルス ルホニルクロリドをフッ素イオン含有ィ匕合物で処理することによって、一般式（1 ' )で 表される ω—ハロペルフルォロアルキルスルホ-ルフルオリドを得ることができる。 フッ素イオン含有ィ匕合物による反応は公知の方法に従って行うことができ、溶媒中 又は無溶媒下で上記一般式（10)で表される ω—ハロペルフルォロアルキルスルホ二 ルクロリドとフッ素イオン含有ィ匕合物を反応させればよい。溶媒としては、特に制限は なく多様な溶媒が使用可能であり、ァセトニトリル、スルホラン、ジメチルスルホキシド 、 Ν, Ν—ジメチルホルムアミド等の極性有機溶媒、水又はこれらの混合溶媒などを用 いることがでさる。  By treating the ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) obtained in the step (iii) with the fluoride-containing compound, the compound represented by the general formula (1 ′) is obtained. Ω-haloperfluoroalkylsulfur fluoride can be obtained. The reaction with the fluoride ion-containing compound can be carried out according to a known method, and in a solvent or without a solvent, the ω-haloperfluoroalkylsulfonyl chloride represented by the above general formula (10) and fluorine ion What is necessary is just to make the contained dangling product react. The solvent is not particularly limited, and various solvents can be used.A polar organic solvent such as acetonitrile, sulfolane, dimethyl sulfoxide, Ν, Ν-dimethylformamide, water, or a mixed solvent thereof can be used. .
使用するフッ素イオン含有ィ匕合物としては、 SO C1を SO Fに変換できるもので  The fluorine ion-containing compound used is one that can convert SO C1 to SO F.
2 2  twenty two
あれば特に限定はなぐ公知のフッ素イオン含有ィ匕合物を用いることができる。例え ば、 NaF、 KF等のアルカリ金属フルオリドが挙げられる。 Any known fluorine ion-containing conjugate can be used without particular limitation. Examples include alkali metal fluorides such as NaF and KF.
反応温度は 0— 200°Cの範囲で、反応時間は 0. 1時間力 48時間程度であれば よい。フッ素イオン含有ィ匕合物の使用量は、上記一般式（10)で表される ω ハロぺ ルフルォロアルキルスルホ-ルクロリド 1モルに対して、 1モル以上 10モル以下が好 ましぐ 1モル以上 5モル以下がより好ましい。また、上記一般式（10)で表される ω— ハロペルフルォロアルキルスルホ-ルクロリドの濃度は特に制限はな 、が、通常 10 一 100質量％である。 [0045] 上記の方法で得られた上記一般式（ 1 ' )で表される ω—ハロペルフルォロアルキル スルホニルフルオリドを分離する方法は、反応に使用する溶媒によって適宜変えれ ばよ 、。例えば蒸留で上記一般式（ 1 ' )で表される ω ノヽロペルフルォロアルキルス ルホニルフルオリドを分離することもできるし、また溶媒の種類によっては水をカ卩える ことによって上記一般式（1， )で表される ω—ハロペルフルォロアルキルスルホ -ルフ ルオリドを有機層として分離することができる。 The reaction temperature may be in the range of 0 to 200 ° C, and the reaction time may be about 0.1 hour, about 48 hours. The amount of the fluoride ion-containing compound to be used is preferably 1 mol or more and 10 mol or less with respect to 1 mol of the ω-halofluoroalkylsulfonyl chloride represented by the above general formula (10). It is more preferably at least 5 mol and at most 5 mol. The concentration of ω-haloperfluoroalkylsulfol chloride represented by the above general formula (10) is not particularly limited, but is usually 10 to 100% by mass. The method for separating the ω-haloperfluoroalkylsulfonyl fluoride represented by the above general formula (1 ′) obtained by the above method may be appropriately changed depending on the solvent used in the reaction. For example, ω-noperoperfluoroalkylsulfonyl fluoride represented by the above general formula (1 ′) can be separated by distillation, and the above general formula can be obtained by removing water depending on the type of solvent. The ω-haloperfluoroalkylsulfur-fluoride represented by the formula (1) can be separated as an organic layer.
以上で説明した本願の工程 (i)一 (iv)の具体例をスキーム 3に示す。 くスキ一ム 3 > 本発明の方法の例  A specific example of the steps (i)-(iv) of the present invention described above is shown in Scheme 3. Scheme 3> Examples of the method of the present invention
工程 ( i)  Process (i)
Na2S20, Na 2 S 2 0,
KCF2)mI I(CF2)mS02Na
Figure imgf000033_0001
 KCF 2) m II (CF 2 ) m S0 2 Na
Figure imgf000033_0001
：程 (iv)  : About (iv)
F〇  F〇
l(CF2)mS02CI KCF2) l (CF 2 ) m S0 2 CI KCF 2 )
* 2 ：高選択的に分離が可能。 * 2: Highly selective separation is possible.
* 3 ：不安定な I(CF,)mSO,Cl は熱履歴かけずに I(CF2)mS02F * 3: Unstable I (CF,) m SO, I (CF 2) Cl is without applying thermal history m S0 2 F
に高収率で変 できる。 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—ノ、口ペルフルォロアルキルスルホ-ルクロリドを 蒸留等の熱履歴をかけることなぐ高収率、高選択的に、上記一般式（1 ' )で表され る ω—ハロペルフルォロアルキルスルホ-ルフルオリドに変換できる。 It can be changed at a high yield. As shown in Scheme 3, through the steps (i) to (iv) of the present invention, the unstable ω-no, perfluoroalkylsulfo-formula represented by the above general formula (10) is obtained. Luchloride can be converted into ω- haloperfluoroalkylsulfur-fluoride represented by the above general formula (1 ′) with high yield and high selectivity without applying a heat history such as distillation.
[0046] 次に上記工程 (ii 2)によって分離された副生成物である上記一般式（11)で表さ れるペルフルォロアルキル a , ω ビススルフィン酸塩から上記一般式（8)で表され る α , ω ジハロペルフルォロアルカン及び Ζ又は上記一般式（10)で表される ω— ハロペルフルォロアルキルスルホ-ルクロリドを製造する方法について説明する。 工程 (ii 2)によって分離された処理液又は精製残渣には副生成物である上記一 般式（11)で表されるペルフルォロアルキル a , ω ビススルフィン酸塩及び無機沃 素化物又は無機臭素化物力 選ばれる少なくとも一方の無機塩を含んでいる。この 処理液又は精製残渣を塩素化剤と反応させる第 1ステップでは、上記一般式（11)で 表されるペルフルォロアルキル , ω ビススルフィン酸塩からは、上記一般式（ 12 )で表されるペルフルォロアルキル α , ω—ビススルホ-ルクロリドが生成し、一方、 無機沃素化物又は無機臭素化物力 は、沃素又は臭素が生成する。次いで第 2ステ ップでは上記一般式（ 12)で表されるペルフルォロアルキル a , ω ビススルホ-ル クロリドと沃素又は臭素の反応により、上記一般式 (8)で表される α , ω ジハロペル フルォロアルカン及び Ζ又は上記一般式（10)で表される ω—ハロペルフルォロアル キルスルホユルク口リドを得ることができる。上記一般式（8)で表される α , ω ジハロ ペルフルォロアルカンと上記一般式（10)で表される ω—ハロペルフルォロアルキル スルホニルクロリドの生成比は、生成した上記一般式（12)で表されるペルフルォロア ルキルー α , ω—ビススルホユルクロリドと、共存する沃素又は臭素の割合によつて決 まる。 Next, the by-product perfluoroalkyl a, ω bissulfinate represented by the above general formula (11), which is separated by the above step (ii 2), is converted into the above general formula (8) A method for producing the α, ω dihaloperfluoroalkane and Ζ or the ω-haloperfluoroalkylsulfol-chloride represented by the general formula (10) will be described. The processing solution or purified residue separated in step (ii 2) contains by-products perfluoroalkyl a, ω bissulfinate represented by the general formula (11) and inorganic iodide or Inorganic bromide power Contains at least one selected inorganic salt. this In the first step of reacting the treatment liquid or the purified residue with a chlorinating agent, the perfluoroalkyl, ω bissulfinate represented by the general formula (11) is represented by the general formula (12) Perfluoroalkyl α, ω-bissulfol-chloride is formed, while inorganic iodide or inorganic bromide forms iodine or bromine. Next, in the second step, the reaction of the perfluoroalkyl a, ω bissulfol chloride represented by the above general formula (12) with iodine or bromine causes α, ω represented by the above general formula (8). Dihaloperfluoroalkanes and ω-haloperfluoroalkyl sulfides represented by the general formula (10) can be obtained. The formation ratio of the α, ω dihalo perfluoroalkane represented by the general formula (8) and the ω-haloperfluoroalkyl sulfonyl chloride represented by the general formula (10) is determined by the above-mentioned general formula It is determined by the ratio of perfluoroalkylalkyl α , ω -bissulfoyl chloride represented by (12) and coexisting iodine or bromine.
第 2ステップにおいて、沃素又は臭素と、上記一般式（12)で表されるペルフルォロ アルキル α , ω ビススルホユルクロリドの両化合物を同時に溶解させる溶媒を添 カロさせることによって、上記一般式（8)で表される α , ω ジハロペルフルォロアルカ ン及び Ζ又は上記一般式（10)で表される ω—ハロペルフルォロアルキルスルホ-ル クロリドへの変換反応を促進させることができる。沃素又は臭素と、上記一般式（12) で表されるペルフルォロアルキル α , ω—ビススルホユルクロリドの両化合物を同時 に溶解させる溶媒の例としては、例えば酢酸ェチル、酢酸ブチル等のエステル系溶 媒、モノグライム、ジグライム等のエーテル系溶媒、ァセトニトリル、プロピオ-トリル等 の-トリル系溶媒、アセトン、メチルェチルケトン等のケトン系溶媒等の極性溶媒が挙 げられる。なお、溶媒として、酢酸ェチルや酢酸ブチルのような水難溶性有機溶媒を 使用した場合には、反応と同時に生成物の抽出も同時に実施できるのでより好まし い。 In the second step, a solvent capable of simultaneously dissolving iodine or bromine and both the perfluoroalkyl α , ω bissulfoulyl chloride compound represented by the general formula (12) is added, whereby the compound represented by the general formula (8) is added. And ω -haloperfluoroalkylsulfonyl chloride represented by the general formula (10). . Examples of the solvent for simultaneously dissolving iodine or bromine and both the perfluoroalkyl α, ω-bissulfoyl chloride compound represented by the above general formula (12) include, for example, ethyl acetate, butyl acetate and the like. Examples include polar solvents such as ester solvents, ether solvents such as monoglyme and diglyme, -tolyl solvents such as acetonitrile and propio-tolyl, and ketone solvents such as acetone and methyl ethyl ketone. It is more preferable to use a poorly water-soluble organic solvent such as ethyl acetate or butyl acetate as the solvent, because the product can be extracted simultaneously with the reaction.
また、上記第 1ステップで、処理液又は精製残渣を塩素化剤と反応させて上記一般 式（ 12)で表されるペルフルォロアルキル a , ω ビススルホ-ルクロリドを生成させ 、当該酸クロリドをろ過や溶媒抽出等で単離してから、溶媒中で沃素又は臭素と反応 させることより、上記一般式（8)で表される α , ω ジハロペルフルォロアルカン及び Z又は上記一般式（10)で表される ω—ハロペルフルォロアルキルスルホユルクロリド を得ることもできる。この場合、上記一般式（8)で表される α , ω—ジノヽ口ペルフルォ ロアルカン及び Ζ又は上記一般式（10)で表される ω—ハロペルフルォロアルキルス ルホニルクロリドの種類とその生成割合は、沃素又は臭素の添加量で決定される。当 該工程の溶媒の例としては、酢酸ェチル、酢酸ブチル等のエステル系溶媒、モノダラ ィム、ジグライム等のエーテル系溶媒、ァセトニトリル、プロピオ-トリル等の-トリル系 溶媒、アセトン、メチルェチルケトン等のケトン系溶媒が挙げられる。 In the first step, the treatment solution or the purified residue is reacted with a chlorinating agent to form a perfluoroalkyl a, ω bissulfol chloride represented by the general formula (12), and the acid chloride is converted to Isolation by filtration, solvent extraction, or the like, followed by reaction with iodine or bromine in a solvent, gives α, ω dihaloperfluoroalkane represented by the above general formula (8) and Z or ω-haloperfluoroalkylsulfoyl chloride represented by the above general formula (10) can also be obtained. In this case, the types of α, ω-dino-perfluoroalkane and Ζ represented by the general formula (8) and ω-haloperfluoroalkylsulfonyl chloride represented by the general formula (10) and their production The ratio is determined by the amount of iodine or bromine added. Examples of the solvent in this step include ester solvents such as ethyl acetate and butyl acetate, ether solvents such as monodalaim and diglyme, -tolyl solvents such as acetonitrile and propio-tolyl, acetone, and methyl ethyl ketone. And the like.
[0048] 上記第 1ステップで使用される塩素化剤としては、特に制限はなぐ公知の塩素化 剤を用いることが可能である。例えば、塩素、塩化スルフリル等を塩素化剤として用い ることができ、特に塩素が好ましい。 [0048] As the chlorinating agent used in the first step, a publicly known chlorinating agent without particular limitation can be used. For example, chlorine, sulfuryl chloride and the like can be used as a chlorinating agent, and chlorine is particularly preferred.
上記の操作で得られた上記一般式（8)で表される a , ω—ジハロペルフルォロアル カンは、上記工程 (i)の亜ジチオン酸塩との反応に再使用することができる。また上 記の操作で得られた上記一般式（10)で表される ω—ハロペルフルォロアルキルスル ホニルクロリドは上記工程 (iv)のフッ素イオン含有ィ匕合物との反応に再使用されて、 上記一般式（ 1，）で表される ω—ノ、口ペルフルォロアルキルスルホ-ルフルオリドに変 換して使用することができる。  The a, 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 conjugate in the above step (iv). Thus, it can be used after being converted to ω-no and perfluoroalkylsulfur fluoride represented by the above general formula (1,).
[0049] 本発明の製造方法によって上記一般式 (2)又は一般式 (2 ' )で表される ω—フルォ ロスルホニルペルフルォロアルキルビニルエーテルは、各種の固体電解質材料又は イオン交換膜等に用 、るポリマー用のモノマー成分として有用な物質である。 The ω-fluorosulfonylperfluoroalkylvinyl ether represented by the above general formula (2) or (2 ′) according to the production method of the present invention can be used for various solid electrolyte materials or ion exchange membranes. It is a useful substance as a monomer component for polymers.
この固体電解質ポリマーは、例えば固体高分子電解質型燃料電池の電解質膜、 触媒バインダーや、リチウム電池用膜、食塩電解用膜、水電解用膜、ハロゲン化水 素酸電解用膜、酸素濃縮器用膜、温度センサー用膜、ガスセンサー用膜等として使 用される。  Examples of the solid electrolyte polymer include an electrolyte membrane for 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, and a membrane for oxygen concentrator. It is used as a film for temperature sensors and films for gas sensors.
以上の通り、本発明によれば、上記一般式（2)又は一般式（2' )で表される ω -フ ルォロスルホ -ルペルフルォロアルキルビュルエーテル及びその合成中間体を高収 率で製造することができる。  As described above, according to the present invention, the ω-fluorosulfo-leperfluoroalkylbutyl ether represented by the general formula (2) or (2 ′) and a synthetic intermediate thereof can be produced at a high yield. Can be manufactured.
実施例  Example
[0050] 以下、実施例及び比較例により本発明を具体的に詳細に説明するが、本発明はこ れらに限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. It is not limited to these.
実施例及び比較例にぉ 、て種々の物性は次の方法により測定した。  Various physical properties were measured by the following methods in Examples and Comparative Examples.
1.フッ素— 19核磁気共鳴（19F— NMR)スペクトル 1. Fluorine - 19 nuclear magnetic resonance (19 F- NMR) spectrum
19F - NMRスペクトルは、測定装置として日本電子日本国製 GSX - 400型核磁気共 鳴装置、溶媒として重クロ口ホルム、基準物質としてフレオン 11 (CFC1 )を使用した The 19 F-NMR spectrum was measured using a GSX-400 nuclear magnetic resonance device manufactured by JEOL Japan as a measuring device, double-mouthed form as a solvent, and Freon 11 (CFC1) as a reference material.
3  Three
2.ガスクロマトグラフィー（GC) 2. Gas chromatography (GC)
以下の装置及び条件で行った。  The test was performed under the following apparatus and conditions.
装置：日本国島津製作所社製 GC-2010 Apparatus: GC-2010 manufactured by Shimadzu Corporation of Japan
カラム：'米国 RESTEK社製 キヤビラリ一力ラム RTX— 200 Column: 'Risk One-Ray Ram RTX—200 manufactured by RESTEK, USA
(内径 0. 25mm,長さ 60m、膜厚 1 μ m)  (Inner diameter 0.25mm, length 60m, film thickness 1μm)
'米酣 &WScientific社製 キヤビラリ一力ラム DB— 1  'American & WScientific's Kirabari Ichiram Lamb DB-1
(内径 0. 25mm,長さ 30m、膜厚 1 μ m)  (0.25mm inner diameter, 30m length, 1μm film thickness)
キャリアガス： He Carrier gas: He
検出: FID Detection: FID
3.ガスクロマトグラフィーマススペクトル（GC— MS)  3. Gas chromatography mass spectrum (GC-MS)
以下の装置及び条件で行った。  The test was performed under the following apparatus and conditions.
装置：日本国日本電子製 Automass— Sun (商品名） Equipment: Automass—Sun (trade name) manufactured by JEOL of Japan
カラム：'米国 RESTEK社製 キヤビラリ一力ラム RTX— 200 Column: 'Risk One-Ray Ram RTX—200 manufactured by RESTEK, USA
(内径 0. 25mm,長さ 60m、膜厚 1 μ m)  (Inner diameter 0.25mm, length 60m, film thickness 1μm)
'米酣 &WScientific社製 キヤビラリ一力ラム DB— 1  'American & WScientific's Kirabari Ichiram Lamb DB-1
(内径 0. 25mm,長さ 30m、膜厚 1 μ m)  (0.25mm inner diameter, 30m length, 1μm film thickness)
キャリアガス： He Carrier gas: He
実施例 1 Example 1
(I (CF ) Iから CF =CFO (CF ) SO Fの合成）  (Synthesis of CF = CFO (CF) SO F from I (CF) I)
2 4 2 2 4 2  2 4 2 2 4 2
5L反応器に、ァセ卜ン 2250mL、水 750mL、及び I (CF ) IlOOOgを入れ、反応  In a 5 L reactor, put 2250 mL of acetone, 750 mL of water, and I (CF)
2 4  twenty four
器を氷浴で冷却した。この反応器に、 Na S O 287gを 15分間で 5回に分けてカロえ The vessel was cooled in an ice bath. In this reactor, 287 g of Na 2 S O is calorie divided into 5 times in 15 minutes.
2 2 4  2 2 4
た後、室温で 2時間攪拌させた。反応混合物は19 F— NMRより、 I (CF ) Iが 57mol %残存し、 I (CF ) SO Naが 36mol%、 NaO S (CF ) SO Naが 7mol%生成してThen, the mixture was stirred at room temperature for 2 hours. Reaction mixture was 19 F-NMR, 57 mol I (CF) I % Remaining, 36 mol% of I (CF) SONa and 7 mol% of NaOS (CF) SONa
2 4 2 2 2 4 2 2 4 2 2 2 4 2
いた。該反応混合物からアセトンと I (CF ) Iを減圧留去すると、固体状の残渣が得ら Was. Acetone and I (CF) I were distilled off from the reaction mixture under reduced pressure to give a solid residue.
2 4  twenty four
れた。この残渣に水をカ卩え、酢酸ェチルで 3回抽出し、これらの酢酸ェチル抽出溶液 を減圧濃縮すると茶色固体 445gが得られた。 It was. Water was added to the residue, extracted three times with ethyl acetate, and these ethyl acetate extracted solutions were concentrated under reduced pressure to obtain 445 g of a brown solid.
この固体は、 19F— NMR (内部標準： CF CO Na)により I (CF ) SO Naを 0. 79m This solid was converted to I (CF) SO Na by 0.79 m by 19 F-NMR (internal standard: CF CO Na).
3 2 2 4 2  3 2 2 4 2
ol (収率 36%)含有することがわ力つた。また、上記抽出操作後の水層には、 19F-N MR (内部標準： CF CO Na)により NaO S (CF ) SO Naを 0. 15mol (収率 7%) ol (36% yield). In the aqueous layer after the above-mentioned extraction operation, 0.15 mol of NaOS (CF) SONa was obtained by 19 FN MR (internal standard: CFCONa) (yield: 7%).
3 2 2 2 4 2  3 2 2 2 4 2
含有することがわ力つた。 It was strong to contain.
I (CF ) SO Na  I (CF) SO Na
2 4 2  2 4 2
19F— NMR -61. 9ppm (2F)、— 114. 2ppm (2F)、— 122. 2ppm(2F)、— 13 1. lppm (2F) 19 F—NMR -61.9 ppm (2F), —114.2 ppm (2F), —122.2 ppm (2F), —13 1. lppm (2F)
NaO S (CF ) SO Na NaO S (CF) SO Na
2 2 4 2  2 2 4 2
19F— NMR -123. 0ppm (4F)、— 130. 6ppm (4F) 19 F—NMR -123.0 ppm (4F), 130.6 ppm (4F)
ガス吹き込み管を備えた 2Lの 4つ口フラスコに、上記 I (CF ) SO Naを含む茶色  In a 2L four-necked flask equipped with a gas injection tube, put the brown containing I (CF) SONa
2 4 2  2 4 2
固体 445g (I (CF ) SO Naを 0. 79mol含有）、及び水 lOOOmLを加えて攪拌した 445 g of solid (containing 0.79 mol of I (CF) SONa) and 100 mL of water were added and stirred.
2 4 2  2 4 2
。このフラスコを氷浴で冷却し、 2層に分離するまで塩素を吹き込んだ。下層を分液 すると、 336gの液体が得られた。この液体は、 19F— NMR (内部標準： C F )により 1 ( . The flask was cooled in an ice bath and blown with chlorine until it separated into two layers. When the lower layer was separated, 336 g of a liquid was obtained. The liquid was analyzed by 19 F-NMR (internal standard: CF) to give 1 (
6 6  6 6
CF ) SO C1を 0. 787mol (収率 99. 7%)含有していることがわかった。  CF) SO C1 was found to contain 0.787 mol (99.7% yield).
2 4 2  2 4 2
19F— NMR -61. 6ppm (2F)、— 105. 8ppm (2F)、— 114. 3ppm(2F)、— 12 0. 0ppm (2F) 19 F—NMR -61.6 ppm (2F), —105.8 ppm (2F), —114.3 ppm (2F), —120.0 ppm (2F)
滴下ロート、還流冷却管を備えた 2Lの 4つ口フラスコに、 KF187. 8gとァセトニトリ ノレ 700mLをカロ免、 50oCにカロ熱した。このフラス に I (CF ) SO C1665gを 2時間力 A 2 L four-necked flask equipped with a dropping funnel and a reflux condenser was charged with 187.8 g of KF and 700 mL of acetonitrile in a calorie-free manner and heated to 50 ° C. by calo. Add 1665g of I (CF) SO C to this frus for 2 hours
2 4 2  2 4 2
けて滴下した。滴下後、さらに 50°Cで 2時間攪拌し、 19F— NMRで反応終了を確認し た。反応混合物に水を加えると 2層に分離した。下層を分液後、蒸留精製 (bp92°C、 26. 6kPa)すると、 606. 8gの I (CF ) SO F力 S得られた（収率 94. 9%) 0 And dropped. After the addition, the mixture was further stirred at 50 ° C. for 2 hours, and the completion of the reaction was confirmed by 19 F-NMR. Water was added to the reaction mixture to separate into two layers. After the lower layer was separated, purified by distillation (bp92 ° C, 26. 6kPa) Then, obtained I (CF) SO F force S of 606. 8g (yield: 94.9%) 0
2 4 2  2 4 2
19F— NMR 44. 0ppm (lF)、— 61. 6ppm(2F)、— 109. 6ppm (2F)、— 114. 6ppm (2F)、— 121. lppm(2F) 19 F—NMR 44.0 ppm (lF), —61.6 ppm (2F), —109.6 ppm (2F), —114.6 ppm (2F), —121. Lppm (2F)
還流塔と温度計を備えた 10Lの 3つ口フラスコに、 I (CF ) SO F5. 26kgに 65質 量％の発煙硫酸 7.2kgを加えて、常圧下、 40時間加熱還流すると、反応混合物は 2 層に分離し、転ィ匕率は 98%に到達した。上層を分液後、さらに濃硫酸で 3回洗浄し た。 I (CF) SO F 5.26 kg in a 10-liter three-necked flask equipped with a reflux tower and a thermometer. The mixture was heated and refluxed at normal pressure for 40 hours, and the reaction mixture was separated into two layers, and the conversion ratio reached 98%. After separating the upper layer, it was further washed three times with concentrated sulfuric acid.
得られた液体は、蒸留精製 (bp54°C、 40kPa)により、 FOC(CF ) SO F2.67kg  The obtained liquid was purified by distillation (bp 54 ° C, 40 kPa) to obtain FOC (CF) SO F 2.67 kg
2 3 2  2 3 2
(収率 74.4%)が得られ、 570gの蒸留残渣には19 F— NMR (内部標準: C F )より F (Yield: 74.4%), and 570 g of the distillation residue was analyzed by 19 F-NMR (internal standard: CF) to obtain F
6 6 6 6
SO 0(CF ) SO Fが 78.5質量％含まれていることが分かった。 It was found that SO 0 (CF) SO F was contained at 78.5% by mass.
2 2 4 2  2 2 4 2
FOC (CF ) SO F  FOC (CF) SO F
2 3 2  2 3 2
19F— NMR 44.3ppm(lF)、22.5ppm(lF)、— 109.8ppm(2F)、— 119.5pp m(2F)、— 122.4ppm(2F) 19 F—NMR 44.3 ppm (1F), 22.5 ppm (1F), — 109.8 ppm (2F), — 119.5 ppm (2F), — 122.4 ppm (2F)
FSO 0(CF ) SO F FSO 0 (CF) SO F
2 2 4 2  2 2 4 2
19F— NMR 48.5ppm(lF)、43.6ppm(lF)、— 85.0ppm(2F)、— 109.8pp m(2F)、— 122.0ppm(2F)、— 126.2ppm(2F) 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)
2Lのオートクレーブに、 FOC(CF ) SO F1000g、テトラグライム 40g、アジポ-ト  In a 2L autoclave, FOC (CF) SO F1000g, tetraglyme 40g, adipate
2 3 2  2 3 2
リル 400g、及び KF27.2gを入れ、 0°Cで攪拌しながら、へキサフルォロプロピレン ォキシド (HFPO)654gを 6時間かけて導入した。反応後、過剰の HFPOを放圧し、 内容物を分液して下層部分を取り出すと、 1588gの液体が得られた。この液体は、 G C、及び19 F— NMR (内部標準： C F )により、 CF CF(COF)0(CF ) SO Fを 3.3 400 g of ril and 27.2 g of KF were added, and 654 g of hexafluoropropylene oxide (HFPO) was introduced over 6 hours while stirring at 0 ° C. After the reaction, excess HFPO was released, the contents were separated, and the lower layer was taken out to obtain 1588 g of a liquid. This liquid was converted to 3.3 CF CF (COF) 0 (CF) SO F by GC and 19 F-NMR (internal standard: CF).
6 6 3 2 4 2  6 6 3 2 4 2
54mol (収率 94.0%)、 CF CF(COF)OCF CF(CF )0(CF ) SO Fを 0.036m  54mol (Yield 94.0%), CF CF (COF) OCF CF (CF) 0 (CF) SOF 0.036m
3 2 3 2 4 2  3 2 3 2 4 2
ol(収率 1.0%)、未反応の FOC(CF ) SO Fを 0.157mol含有することがわかつ ol (1.0% yield) and 0.157mol of unreacted FOC (CF) SOF
2 3 2  2 3 2
た。得られた液体は、蒸留精製 (bpl05°C、 40kPa)により、 1449gの CF CF(COF It was. The obtained liquid was purified by distillation (bpl05 ° C, 40 kPa) to obtain 1449 g of CF CF (COF
3  Three
)0(CF ) SO F (収率 91.0%)であった。  ) 0 (CF) SO F (yield 91.0%).
2 4 2  2 4 2
19F— NMR 44.0ppm(lF)、 23.8ppm(lF)、— 79.9ppm(lF)、— 84.4ppm( 3F)、— 87.2ppm(lF)、— 110.0ppm(2F)、— 122. lppm(2F)、— 126.8ppm( 2F)、— 132.4ppm(lF) 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. lppm (2F ),-126.8 ppm (2F),-132.4 ppm (lF)
滴下ロートと蒸留塔を備えた 1Lの 4つ口フラスコに乾燥した炭酸カリウム 102gと、 無水エチレングリコールジメチルエーテル 135gを入れ、フラスコの内温が 50°C以内 になるように CF CF(COF)0(CF ) SO F300gをゆっくり滴下した。発泡が止まつ  In a 1-L four-necked flask equipped with a dropping funnel and a distillation tower, put 102 g of dried potassium carbonate and 135 g of anhydrous ethylene glycol dimethyl ether, and put CF CF (COF) 0 ( 300 g of CF) SO F were slowly added dropwise. Stop foaming
3 2 4 2  3 2 4 2
て力 さらに 50°Cで 2時間攪拌後、 19F— NMRにより完全に原料が中和され、 CF C F(CO K)0(CF ) SO Fに変換したことを確認した。この反応混合物力 エチレンAfter stirring at 50 ° C for 2 hours, the raw material was completely neutralized by 19 F-NMR, It was confirmed that it was converted to F (CO K) 0 (CF) SO F. This reaction mixture power ethylene
2 2 4 2 2 2 4 2
グリコールジメチルエーテルを減圧留去し、さらに残渣を 140°Cに加熱して減圧下で 乾燥させた。乾燥させた CF CF(CO K)0(CF ) SO Fを含む残渣を減圧下 190  Glycol dimethyl ether was distilled off under reduced pressure, and the residue was heated to 140 ° C. and dried under reduced pressure. The residue containing dried CF CF (CO K) 0 (CF) SO F
3 2 2 4 2  3 2 2 4 2
°Cに加熱すると脱炭酸反応が起こり、 222gの液体が留出した。留出した液体は GC 、 19F— NMR (内部標準： C F )により、目的物である CF =CFO(CF ) SO Fが 0. When heated to ° C, a decarboxylation reaction occurred, and 222 g of liquid was distilled. The distilled liquid was analyzed by GC and 19 F-NMR (internal standard: CF) to find that the target compound, CF = CFO (CF) SO F, was 0.
6 6 2 2 4 2 6 6 2 2 4 2
572mol (収率 85.0%)、副生成物として再生成した CF CF(COF)0(CF ) SO 572mol (yield 85.0%), regenerated as a by-product CF CF (COF) 0 (CF) SO
3 2 4 2 3 2 4 2
Fが 0.007mol含有しており、 [s]Z[r+s]は、 0.01であった。上記で得られた液体は 、蒸留精製（bp92。C、 40kPa)により、 CF =CFO(CF ) SO F210g (収率 82.2 The content of F was 0.007 mol, and [s] Z [r + s] was 0.01. The liquid obtained above was purified by distillation (bp 92; C, 40 kPa) to obtain 210 g of CF = CFO (CF 3) SO F (yield: 82.2
2 2 4 2  2 2 4 2
%)を得た。  %).
19F— NMR: 43.8ppm(lF)、— 87.0ppm(2F)、— 110.0ppm(2F)、— 116.9 ppm(lF)、— 122.2ppm(2F)、— 124.4ppm(lF)、— 127.0ppm(2F)、— 138. 4ppm(lF) 19 F NMR: 43.8 ppm (lF), 87.0 ppm (2F), 110.0 ppm (2F), 116.9 ppm (lF), 122.2 ppm (2F), 124.4 ppm (lF), 127.0 ppm 2F), 138.4 ppm (lF)
EI-MS:m/z 380, 283, 100, 97, 81  EI-MS: m / z 380, 283, 100, 97, 81
[0053] 比較例 1 [0053] Comparative Example 1
500mLの 3つ口フラスコに I(CF ) I50g、アセトン 150mL、及び水 50mLを入れ、  In a 500 mL three-necked flask, put 50 g of I (CF) I, 150 mL of acetone, and 50 mL of water,
2 4  twenty four
フラスコを氷浴につけ、 Na S O 19gを少しずつ加えた後、室温で 2時間攪拌させた  The flask was placed in an ice bath, 19 g of Na 2 S 2 O was added little by little, and the mixture was stirred at room temperature for 2 hours.
2 2 4  2 2 4
。反応混合物を19 F - NMRで測定すると、 I(CF ) Iが 38mol%残存し、 l(CF ) SO . When the reaction mixture was measured by 19 F-NMR, 38 mol% of I (CF) I remained and l (CF) SO
2 4 2 4 2 2 4 2 4 2
Naが 44mol%、 NaO S(CF ) SO Naが 18mol%生成していた。反応混合物中の 44 mol% of Na and 18 mol% of NaOS (CF) SONa were produced. In the reaction mixture
2 2 4 2  2 2 4 2
固形物をろ過で取り除き、さらにろ液力 アセトンを留去し、残渣を得た。該残渣をガ ス吹き込み管を備えた 500mLの 3つ口フラスコに移し、さらに水 200mLを加えた。フ ラスコを氷浴につけ、 2層に分離するまで塩素を吹き込んだ。下層を分液すると、下 層には I(CF ) I、 I(CF ) SO Cl、 CIO S(CF ) SO CIを含む混合物が得られた。  The solid was removed by filtration, and the filtrate acetone was distilled off to obtain a residue. The residue was transferred to a 500 mL three-necked flask equipped with a gas injection tube, and 200 mL of water was further added. The flask was immersed in an ice bath and chlorine was blown in until it separated into two layers. When the lower layer was separated, a mixture containing I (CF) I, I (CF) SOCl, and CIOS (CF) SOCI was obtained in the lower layer.
2 4 2 4 2 2 2 4 2  2 4 2 4 2 2 2 4 2
これらの混合物は蒸留操作を行ったが、 I (CF ) I、 I(CF ) SO Cl、 CIO S(CF )  These mixtures were subjected to a distillation operation, but I (CF) I, I (CF) SOCl, CIOS (CF)
2 4 2 4 2 2 2 4 2 4 2 4 2 2 2 4
SO CIが混在して得られ、 19F— NMR (内部標準： C F )により I(CF ) SO CIは 0. SO CI is obtained by mixing, 19 F- NMR (internal standard: CF) by I (CF) SO CI 0.
2 6 6 2 4 2  2 6 6 2 4 2
Ollmol (収率 10%)含有して!/、た。  Ollmol (10% yield)!
[0054] 比較例 2 Comparative Example 2
200mLのオートクレーブに、実施例 1で得られた、 FOC(CF ) SO F100g、テトラ  In a 200 mL autoclave, 100 g of FOC (CF) SO F obtained in Example 1 was added.
2 3 2  2 3 2
グライム 45g、及び KF2.72gを入れ、 0°Cで攪拌しながら、へキサフルォロプロピレ ンォキシド (HFPO)59. 3gを 6時間かけて導入した。反応後、内容物を分液して下 層部分を取り出すと、 136. 2gの液体が得られた。この液体は GC、 19F— NMR (内部 標準： C F )により、 CF CF(COF)0(CF ) SO Fを 0. 186mol (収率 52. 2%)、Add 45 g of glime and 2.72 g of KF, and stir at 0 ° C. 59.3 g of oxoxide (HFPO) was introduced over 6 hours. After the reaction, the content was separated and the lower layer was taken out to obtain 136.2 g of a liquid. This liquid was analyzed by GC and 19 F-NMR (internal standard: CF) to obtain 0.186 mol (yield 52.2%) of CF CF (COF) 0 (CF) SO F,
6 6 3 2 4 2 6 6 3 2 4 2
CF CF(COF)OCF CF(CF )0(CF ) SO Fを 0.055mol (収率 15. 3%)、 CF CF CF (COF) OCF CF (CF) 0 (CF) SOF 0.055mol (15.3% yield), CF
3 2 3 2 4 2 33 2 3 2 4 2 3
CF(COF)0(CF CF(CF ) O) (CF ) SO Fを 0.006mol (収率 1.8%)、未反応 0.006mol (1.8% yield) of CF (COF) 0 (CF CF (CF) O) (CF) SOF, unreacted
2 3 2 2 4 2  2 3 2 2 4 2
の FOC(CF ) SO Fを 0.039mol含有していた。  0.039 mol of FOC (CF 3) 2 SO F.
2 3 2  2 3 2
[0055] 比較例 3  [0055] Comparative Example 3
滴下ロートと蒸留塔を備えた 200mLの 4つ口フラスコに乾燥した炭酸ナトリウム 16 .4gと、無水エチレングリコールジメチルエーテル 15mlを入れ、 70°Cで、実施例 1で 得られた 30gの CF CF(COF)0(CF ) SO Fをゆっくり滴下した。発泡が止まって  In a 200 mL four-necked flask equipped with a dropping funnel and a distillation column, 16.4 g of dried sodium carbonate and 15 mL of anhydrous ethylene glycol dimethyl ether were placed, and at 70 ° C, 30 g of the CF CF (COF ) 0 (CF) SO F was slowly added dropwise. Foaming stops
3 2 4 2  3 2 4 2
力もさらに 70°Cで 2時間攪拌後、 19F— NMRにより完全に原料が中和され、 CF CF( After further stirring at 70 ° C for 2 hours, the raw material was completely neutralized by 19 F-NMR, and CF CF (
3 Three
CO Na)0(CF ) SO Fに変換したことを確認した。この反応混合物からエチレングIt was confirmed that it was converted to CONa) 0 (CF) SOF. Ethylene oxide is obtained from this reaction mixture.
2 2 4 2 2 2 4 2
リコールジメチルエーテルを減圧留去し、さらに残渣を 120°Cに加熱して減圧下で乾 燥させた。乾燥させた CF CF(CO Na)0(CF ) SO Fを含む残渣を 200°Cまでカロ  Recol dimethyl ether was distilled off under reduced pressure, and the residue was further heated to 120 ° C. and dried under reduced pressure. Dried residue containing CF CF (CO Na) 0 (CF) SO F to 200 ° C
3 2 2 4 2  3 2 2 4 2
熱させると脱炭酸反応により 18. 9gの液体が留出した。留出した液体は19 F— NMR( 内部標準： C F )により、 CF =CFO(CF ) SO Fが 0.038mol (収率 56. 1%)、 C Upon heating, 18.9 g of liquid was distilled out by the decarboxylation reaction. The distillate was analyzed by 19 F-NMR (internal standard: CF). CF = CFO (CF) SOF 0.038 mol (yield 56.1%), C
6 6 2 2 4 2  6 6 2 2 4 2
F CF(COF)0(CF ) SO Fが 0.009mol含有しており、 [s]Z[r+s]は、 0. 19であ 0.009 mol of FCF (COF) 0 (CF) SOF is contained, and [s] Z [r + s] is 0.19.
3 2 4 2 3 2 4 2
つた o  I
[0056] 実飾 12  [0056] Decoration 12
蒸留塔と滴下ロートを備えた 200mLの 3つ口フラスコにスルホラン 33. 2g、及び K F6.05gを入れ、 50°Cに加熱しながら、実施例 1で得られた FSO 0(CF ) SO Fを  In a 200 mL three-necked flask equipped with a distillation tower and a dropping funnel, 33.2 g of sulfolane and 6.05 g of KF were placed, and while heating to 50 ° C, the FSO 0 (CF) SOF obtained in Example 1 was heated. To
2 2 4 2 2 2 4 2
78. 5質量％含有する蒸留残渣 100gを滴下した。滴下後、さらに 50°Cで 2時間加熱 攪拌した後、蒸留精製を行うと、 FCO(CF ) SO Fが 54. 7g (収率 95. 1%)得られ 100 g of a distillation residue containing 78.5% by mass was added dropwise. 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 of FCO (CF) SOF (yield: 95.1%).
2 3 2  2 3 2
た。  It was.
[0057] 実施例 3  Example 3
(I(CF ) Iから CF =CFO(CF ) SO Fの合成）  (Synthesis of CF = CFO (CF) SOF from I (CF) I)
2 3 2 2 3 2  2 3 2 2 3 2
還流塔及び攪拌機を備えた 1Lの 3つ口フラスコに I(CF ) I300gとアセトン 900mL  In a 1 L three-necked flask equipped with a reflux tower and stirrer, 300 g of I (CF) I and 900 mL of acetone
2 3  twenty three
及び水 300mLを入れ、フラスコを氷浴につけ、 Na S O 96. 9gを少しずつ加えた。 2時間攪拌した後、反応混合物を19 F— NMRで測定すると、 I (CF ) SO Naが 36. 6 And 300 mL of water, the flask was placed in an ice bath, and 96.9 g of NaSO was added little by little. After stirring for 2 hours, the reaction mixture was measured by 19 F-NMR to show that I (CF) SO Na was 36.6.
2 3 2 mol%、 NaO S (CF ) SO Naが 8· 4mol%生成していた。該反応混合物からァセ  232 mol% and 8.4 mol% of NaOS (CF) SONa were produced. From the reaction mixture
2 2 3 2  2 2 3 2
トンを留去した後、水 300mLをカ卩えると 2層に分離し、下層を分液すると I (CF ) Iが After distilling off tons, 300 mL of water is separated into two layers when sifted, and I (CF) I is separated when the lower layer is separated.
2 3 twenty three
159g回収された。また、上層は酢酸ェチルで 3回抽出した後、酢酸ェチル溶液を減 圧濃縮すると粘稠な液体が得られた。この液体は19 F— NMR (内部標準: CF CO N 159 g were recovered. The upper layer was extracted three times with ethyl acetate, and the ethyl acetate solution was concentrated under reduced pressure to obtain a viscous liquid. This liquid has 19 F-NMR (internal standard: CF CO N
3 2 a)により、 I (CF ) SO Naを 0· 272mol含むことがわかった（収率 36· 6%)。  According to 32a), it was found that 0.272 mol of I (CF) SONa was contained (yield: 36.6%).
2 3 2  2 3 2
ガス吹き込み管を備えた 1Lの 3つ口フラスコに、上記 I (CF ) SO Naを含む液体を  In a 1-L three-necked flask equipped with a gas injection tube, the liquid containing I (CF) SONa was placed.
2 3 2  2 3 2
移し、さらに、水 300mLをカ卩えた。フラスコを氷浴につけ、塩素を吹き込んでいくと、 2層に分離した。下層を分液すると 97. 7gの液体が得られた。この液体は、 19F— NM Rにより、 I (CF ) SO CIであることがわかった（収率 92. 8%)。 Then, 300 mL of water was added. The flask was immersed in an ice bath, and chlorine was blown into the flask to separate into two layers. Separation of the lower layer yielded 97.7 g of liquid. This liquid was determined to be I (CF) SOCI by 19 F—NMR (yield 92.8%).
2 3 2  2 3 2
還流塔を備えた 500mLフラスコに、上記で得られた I (CF ) SO C197. 7gと KF4  In a 500 mL flask equipped with a reflux tower, 19 g of I (CF) SOC 197.7 obtained above and KF4
2 3 2  2 3 2
5. 3gとァセトニトリル 200mLを加え、 50°Cで 2時間攪拌した。反応終了後、反応混 合物に水を加えると 2層に分離した。下層を分液すると、 86. lgの液体が得られ、 19F NMRにより I (CF ) SO Fであることがわかった（収率 92. 0%)。 5.3 g and 200 mL of acetonitrile were added, and the mixture was stirred at 50 ° C for 2 hours. After the reaction was completed, water was added to the reaction mixture to separate into two layers. Separation of the lower layer yielded 86.lg of liquid, which was found to be I (CF) SOF by 19 F NMR (yield 92.0%).
2 3 2  2 3 2
上記で得られた I (CF ) SO F86. lgに 60質量0 /0の発煙硫酸 255gを加え、常圧 Obtained above I (CF) SO F86. 60 mass 0/0 oleum 255g added to lg, normal pressure
2 3 2  2 3 2
下、 60°Cで 19時間加熱すると、反応混合物は 2層に分離し、転化率 91%に到達し た。上層を分液後、濃硫酸で洗浄した後、蒸留精製を行うと 34. lgの液体が得られ た。 Upon heating at 60 ° C. for 19 hours, the reaction mixture separated into two layers and reached a conversion of 91%. After separating the upper layer and washing with concentrated sulfuric acid, distillation and purification yielded 34.lg of liquid.
この液体は19 F— NMRにより、 FOC (CF ) SO Fであることがわかった（収率 62. 0 This liquid was found to be FOC (CF) SOF by 19 F-NMR (yield 62.0).
2 2 2  2 2 2
%)。  %).
19F— NMR 44. 3ppm(lF)、 22. 5ppm(lF)、— 109. 8ppm (2F)、— 119. 5pp m (2F) 19 F—NMR 44.3 ppm (lF), 22.5 ppm (lF), — 109.8 ppm (2F), — 119.5 ppm (2F)
lOOmLのオートクレーブに、 FOC (CF ) SO F40g、テトラグライム 5g、アジポニト  lOOmL autoclave, FOC (CF) SO F40g, tetraglyme 5g, adiponito
2 2 2  2 2 2
リル 15g、及びフッ化カリウム 1. 8gを入れ、 0°Cで攪拌しながら、 38. 5gの HFPOを 、 2時間かけて導入した。反応後、過剰の HFPOを放圧し、内容物を分液して下層部 分を取り出した。得られた液体を蒸留して、 CF CF (COF) 0 (CF ) SO F50. 9g ( 15 g of ril and 1.8 g of potassium fluoride were added, and 38.5 g of HFPO was introduced over 2 hours while stirring at 0 ° C. After the reaction, excess HFPO was released, the contents were separated, and the lower layer was taken out. The obtained liquid is distilled to obtain CF CF (COF) 0 (CF) SO F50.9 g (
3 2 3 2 収率 74%)を得た。  32 3 2 yield 74%).
滴下ロートと蒸留塔を備えた 200mLの 3つ口フラスコに乾燥した炭酸カリウム 19. 5 gと、無水ァセトニトリル 50mLを入れ、 40°Cのオイルバスで加熱しながら、上記 CF Dried potassium carbonate in a 200 mL three-necked flask equipped with a dropping funnel and distillation tower 19.5 g and 50 mL of anhydrous acetonitrile, and heat in a 40 ° C oil bath.
3 Three
CF (COF) 0 (CF ) SO F50. 9gをゆっくり滴下した。発泡が止まってからさらに 40 9 g of CF (COF) 0 (CF) SO F 5 was slowly added dropwise. 40 more after foaming stops
2 3 2  2 3 2
°Cで 2時間攪拌後、 19F— NMRより完全に原料が中和され、 CF CF (CO K) 0 (CF After stirring at ° C for 2 hours, the raw material was completely neutralized by 19 F-NMR, and CF CF (CO K) 0 (CF
3 2 2 3 2 2
) SO Fに変換したことを確認した。この反応混合物力 ァセトニトリルを減圧留去し、) It was confirmed that it was converted to SOF. The reaction mixture, acetonitrile, was distilled off under reduced pressure.
3 2 3 2
残渣を 140°Cに加熱して減圧下で乾燥させた。乾燥させた CF CF (CO K) 0 (CF ) The residue was heated to 140 ° C and dried under reduced pressure. Dried CF CF (CO K) 0 (CF)
3 2 2 3 2 2
SO Fを含む残渣を常圧下 220°Cまで加熱すると、脱炭酸反応が起こり、液体が留When the residue containing SO F is heated to 220 ° C under normal pressure, a decarboxylation reaction occurs and the liquid evaporates.
3 2 3 2
出した。さらに得られた液体は蒸留精製により、 35. 2gの CF =CFO (CF ) SO F Issued. The obtained liquid was purified by distillation to obtain 35.2 g of CF = CFO (CF) SO F
2 2 3 2 を得た (収率 83%)。  2 232 was obtained (yield 83%).
19F— NMR 43. 8ppm(lF)、— 86. 7ppm (2F)、— 110. 0ppm (2F)、— 116. 6p pm (lF)、— 124. lppm (lF)、— 125. 6ppm (2F)、— 138. 5ppm(lF) 19 F—NMR 43.8 ppm (1F), 86.7 ppm (2F), 111.0 ppm (2F), 116.6 ppm (lF), 124.lppm (lF), 125.6 ppm (2F ), 138.5 ppm (lF)
実施例 4 Example 4
(I (CF ) Iから CF =CFO (CF ) SO Fの合成）  (Synthesis of CF = CFO (CF) SO F from I (CF) I)
2 6 2 2 6 2  2 6 2 2 6 2
還流塔、攪拌機を備えた 2Lの 3つ口フラスコに I (CF ) I122gとアセトン 450mL、  In a 2 L three-necked flask equipped with a reflux tower and a stirrer, 122 g of I (CF) I and 450 mL of acetone,
2 6  2 6
水 50mLを入れ、フラスコを氷浴につけ、 Na S O 48gを少しずつ加えた後、 25°Cで Add 50 mL of water, place the flask in an ice bath, add 48 g of Na S O little by little, and then at 25 ° C.
2 2 4  2 2 4
2時間攪拌した。反応混合物を19 F-NMRで測定すると、 I (CF ) SO Naが 68mol Stir for 2 hours. When the reaction mixture was measured by 19 F-NMR, I (CF) SO Na was 68 mol
2 6 2  2 6 2
%、 NaO S (CF ) SO Naが 6mol%生成していた。反応混合物力もアセトンと水を  %, NaOS (CF) SONa was produced at 6 mol%. The reaction mixture power also uses acetone and water
2 2 6 2  2 2 6 2
留去した後、残渣に HFC43— 10mee300mLをカ卩え、固形物をろ過した。ろ液から HFC43— lOmeeを減圧留去させると、 I (CF ) Iが 31. 6g回収された。一方、固形 After distillation, 300 mL of HFC43-10mee was added to the residue, and the solid was filtered. When HFC43-lOmee was distilled off from the filtrate under reduced pressure, 31.6 g of I (CF) I was recovered. Meanwhile, solid
2 6  2 6
物に 500mLの水をカ卩えた後、酢酸ェチルで 3回抽出した後、酢酸ェチル溶液を減 圧濃縮すると固体が得られた。この固体は、 19F— NMR (内部標準: CF CO Na)に After 500 mL of water was added to the product and extracted three times with ethyl acetate, the ethyl acetate solution was concentrated under reduced pressure to obtain a solid. This solid was analyzed by 19 F-NMR (internal standard: CF CO Na).
3 2 より I (CF ) SO Naを 0· 150mol含有していることがわかった（収率 68%)。  From 32, it was found that it contained 0.150 mol of I (CF) SONa (yield: 68%).
2 6 2  2 6 2
ガス吹き込み管を備えた 1Lの 3つ口フラスコに、上記 I (CF ) SO Naを移し、水 30  The above I (CF) SO Na was transferred to a 1 L three-necked flask equipped with a gas injection tube,
2 6 2  2 6 2
OmLをカ卩え、フラスコを氷浴につけ、塩素を吹き込んでいくと、 2層に分離した。下層 を分液すると、 75. lgの液体が得られた。この液体は19 F— NMRにより、 I (CF ) SO OmL was added, the flask was placed in an ice bath, and chlorine was blown into the flask to separate into two layers. Separation of the lower layer yielded 75.lg of liquid. This liquid was analyzed by 19 F-NMR for I (CF) SO
2 6 2 6
CIであることがわかった（収率 95. 3%)。 It was found to be CI (yield 95.3%).
2  2
還流塔を備えた 500mLフラスコに、上記で得られた I (CF ) SO C175. lgに KF2  In a 500 mL flask equipped with a reflux tower, add I (CF) SO C175.lg obtained above to KF2
2 6 2  2 6 2
4. 8gとァセトニトリル 150mLを加え、 50°Cで 2時間攪拌した。反応終了後、反応混 合物に水を加えると 2層に分離した。下層を分液すると、 66. 8gの液体が得られた。 この液体は F— NMRにより、 I(CF ) SO Fであることがわかった（収率 91.9%)。 4.8 g and 150 mL of acetonitrile were added, and the mixture was stirred at 50 ° C for 2 hours. After the reaction was completed, water was added to the reaction mixture to separate into two layers. When the lower layer was separated, 66.8 g of a liquid was obtained. This liquid was found to be I (CF) SO F by F-NMR (yield 91.9%).
2 6 2  2 6 2
I(CF ) SO F129gに 60質量0 /0の発煙硫酸 269gを加え、常圧下、 60°Cで 12時I (CF) SO F129g 60 wt 0/0 oleum 269g addition, under normal pressure, 12 o'clock at 60 ° C
2 6 2 2 6 2
間、さらに 80°Cで 13.5時間加熱すると、反応混合物は 2層に分離し、転化率は 100 %に到達した。上層を分液後、濃硫酸で洗浄すると 89gの液体が得られた。  Upon further heating at 80 ° C for 13.5 hours, the reaction mixture separated into two layers and the conversion reached 100%. After separating the upper layer, washing with concentrated sulfuric acid gave 89 g of a liquid.
[0060] この液体は、 19F— NMRにより、 FOC(CF ) SO Fであることがわかった（収率 93 This liquid was found to be FOC (CF 2) SO F by 19 F-NMR (yield 93
2 5 2  2 5 2
%)。  %).
19F— NMR 44.3ppm(lF)、 22.5ppm(lF)、— 109.7ppm(2F)、— 120. Opp m(2F)、— 121.8ppm(2F)、— 122.5ppm(2F)、— 124. lppm(2F) 19 F—NMR 44.3 ppm (1F), 22.5 ppm (1F), — 109.7 ppm (2F), — 120. Opp m (2F), — 121.8 ppm (2F), — 122.5 ppm (2F), — 124. lppm (2F)
200mLのオートクレーブに、 FOC(CF ) SO F79g、テトラグライム 7g、アジポニト  In a 200 mL autoclave, 79 g of FOC (CF) SO F, 7 g of tetraglyme, adiponito
2 5 2  2 5 2
リル 35g、及び 1.45gのフッ化カリウムを入れ、 0°Cで攪拌しながら、 41.4gの HFP Oを 7時間かけて導入した。反応後、過剰の HFPOを放圧し、内容物を分液して下層 部分を取り出した。得られた液体を蒸留して、 CF CF(COF)0(CF ) SO F91.6g  35 g of ril and 1.45 g of potassium fluoride were added, and 41.4 g of HFP O was introduced over 7 hours while stirring at 0 ° C. After the reaction, excess HFPO was released, the contents were separated, and the lower layer was taken out. Distill the obtained liquid, CF CF (COF) 0 (CF) SO F 91.6 g
3 2 6 2 3 2 6 2
(収率 81%)を得た。 (81% yield).
窒素気流中、滴下ロートと蒸留塔を備えた 500mLの 3つ口フラスコに乾燥した炭酸 カリウム 31.9gと、無水エチレングリコールジメチルエーテル 200mLを入れ、室温で 上記 CF CF(COF)0(CF ) SO F120gをゆっくり滴下した。そのまま室温で 1時間 In a nitrogen stream, 31.9 g of dried potassium carbonate and 200 mL of anhydrous ethylene glycol dimethyl ether were placed in a 500 mL three-necked flask equipped with a dropping funnel and a distillation tower, and the above CF CF (COF) 0 (CF) SO F 120 g was added at room temperature. It was dripped slowly. 1 hour at room temperature
3 2 6 2 3 2 6 2
攪拌し、さらに 50°Cで 1時間攪拌後、 19F— NMRより完全に原料が中和され、 CF C After stirring at 50 ° C for 1 hour, the raw material was completely neutralized by 19 F-NMR.
3 Three
F(CO K)0(CF ) SO Fに変換したことを確認した。反応混合物力もエチレングリコIt was confirmed that it was converted to F (CO K) 0 (CF) SO F. Reaction mixture power is also ethylene glyco
2 2 6 2 2 2 6 2
ールジメチルエーテルを減圧留去し、残渣を 100°Cに加熱して乾燥させた後、減圧 下 200°Cに加熱すると脱炭酸反応が起こり液体が留出した。さらに得られた液体は 蒸留精製により、 94.3gの CF =CFO(CF ) SO Fを得た（収率 89%)。  The residue was heated to 100 ° C and dried. After heating to 200 ° C under reduced pressure, a decarboxylation reaction occurred and the liquid was distilled off. Further, the obtained liquid was purified by distillation to obtain 94.3 g of CF = CFO (CF) SOF (89% yield).
2 2 6 2  2 2 6 2
19F— NMR 43.8ppm(lF)、— 86.9ppm(2F)、— 110.0ppm(2F)、— 117. lp pm(lF)、— 121.9ppm(2F)、— 123.4ppm(2F)、— 124.0ppm(2F)、— 124.7 ppm(lF)、— 127.3ppm(2F)、— 138.4ppm(lF) 19 F—NMR 43.8 ppm (1F), 86.9 ppm (2F), 110.0 ppm (2F), 117.lp pm (1F), 121.9 ppm (2F), 123.4 ppm (2F), 124.0 ppm (2F),-124.7 ppm (lF),-127.3 ppm (2F),-138.4 ppm (lF)
EI-MS:m/z 480, 100, 97, 81  EI-MS: m / z 480, 100, 97, 81
[0061] 実施例 5 Example 5
KCF ) Iと Na S Oの反応後の分離精製方法を以下のように変更した以外は実施 (KCF) I carried out except that the method of separation and purification after the reaction of I and NaSO was changed as follows
2 4 2 2 4 2 4 2 2 4
例 1と同様にして反応を行った。すなわち、 I(CF ) Iと Na S Oの反応終了後、反応 混合物からアセトンを留去した後、水を加えると 2層に分離し、下層を分液すると I (C F ) Iが 546g回収された。また、上層に酢酸ェチルをカ卩えて、酢酸ェチルで 3回抽出The reaction was carried out in the same manner as in Example 1. That is, after the reaction of I (CF) I and NaSO is completed, After acetone was distilled off from the mixture, water was added to separate the mixture into two layers. When the lower layer was separated, 546 g of I (CF) I was recovered. Ethyl acetate is added to the upper layer and extracted three times with ethyl acetate.
2 4 twenty four
した後、これらの酢酸ェチル溶液を減圧濃縮すると茶色固体が得られ、 19F— NMR( 内部標準： CF CO Na)により、 I (CF ) SO Naが 0. 79mol (収率 36%)含有して After that, these ethyl acetate solutions were concentrated under reduced pressure to give a brown solid, which contained 0.79 mol (36% yield) of I (CF) SONa by 19 F-NMR (internal standard: CF CO Na). hand
3 2 2 4 2  3 2 2 4 2
いることがわかった。  I knew it was there.
[0062] 実施例 6  Example 6
ガス吹き込み管を備えた 1Lの 4つ口フラスコに、実施例 1で分離した NaO S (CF )  In a 1 L four-necked flask equipped with a gas injection tube, NaO S (CF) separated in Example 1 was placed.
2 2 twenty two
SO NaO. 15molと Nalを含む 900gの水溶液を入れ、氷浴中で塩素を吹き込むとSO NaO. Pour 900g aqueous solution containing 15mol and Nal and blow chlorine in ice bath.
4 2 4 2
固体が生成し懸濁状態となった。生成した固体は、沃素と CIO S (CF ) SO CIであ  A solid formed and became suspended. The solid formed is iodine and CIO S (CF) SOCI.
2 2 4 2 ることが19 F— NMRで確認された。この懸濁液に酢酸ェチルをカ卩えると沃素と CIO S 2 242 was confirmed by 19 F-NMR. When ethyl acetate is added to this suspension, iodine and CIO S
2 2
(CF ) SO C1は溶解した後、 2層に分離した。この酢酸ェチル層は19 F-NMRにより(CF) SO C1 was dissolved and then separated into two layers. This ethyl acetate layer was analyzed by 19 F-NMR.
2 4 2 2 4 2
KCF ) Iであることが確認された。酢酸ェチル層を分離した後、常圧下で蒸留精製 KCF) I. After separating the ethyl acetate layer, purify by distillation under normal pressure
2 4 twenty four
を行い、 I (CF ) Iが 65. 7g得られた（NaO S (CF ) SO Naを出発原料とした場合  And 65.7 g of I (CF) I was obtained (when NaO S (CF) SO Na was used as a starting material).
2 4 2 2 4 2  2 4 2 2 4 2
、収率 94%)。  , Yield 94%).
CIO S (CF ) SO C1  CIO S (CF) SO C1
2 2 4 2  2 2 4 2
19F— NMR -105. 6ppm (4F)、— 120. 3ppm (4F) 19 F—NMR -105.6 ppm (4F), —120.3 ppm (4F)
[0063] 施例 7 [0063] Example 7
lOOmLの 3つ口フラスコに、実施例 6で得られた CIO S (CF ) SO C13. 2g (8. 0  In a 100 mL three-necked flask, 13.2 g of CIO S (CF 2) SO C obtained in Example 6 (8.0
2 2 4 2  2 2 4 2
6mmol)、沃素 2. 05g (8. 06mmol)、及び酢酸ェチル lOmLを入れ、室温 3時間 攪拌した。この反応混合物には19 F— NMRにより、 I (CF ) Iが 8mol%、 I (CF ) SO 6 mmol), 2.55 g (8.06 mmol) of iodine and 10 mL of ethyl acetate were added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was analyzed by 19 F-NMR for 8 mol% of I (CF) I and I (CF) SO
2 4 2 4 2 2 4 2 4 2
CIが 64mol%、 CIO S (CF ) SO CIが 20mol%含まれていることがわかった。 It was found that 64 mol% of CI and 20 mol% of CIO S (CF) SOCI were contained.
2 2 4 2  2 2 4 2
[0064] 実施例 8  Example 8
lOOmLの 3つ口フラスコに、実施例 6で得られた CIO S (CF ) SO C13. 2g (8. 0  In a 100 mL three-necked flask, 13.2 g of CIO S (CF 2) SO C obtained in Example 6 (8.0
2 2 4 2  2 2 4 2
6mmol)、沃素 4. 10g (16. lmmol)、及び酢酸ェチル lOmLを入れ、室温 3時間 攪拌した。この反応混合物は19 F— NMRにより、転化率 100%で I (CF ) Iに変換し 6 mmol), 4.10 g (16. lmmol) of iodine and 10 mL of ethyl acetate were added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was converted to I (CF) I by 19 F-NMR at 100% conversion.
2 4  twenty four
ていることが確認された。  It was confirmed that.
産業上の利用の可能性  Industrial potential
[0065] 本発明の製造方法により得られる上記一般式 (2)又は一般式 (2 ' )で表される ω— フルォロスルホ-ルペルフルォロアルキルビュルエーテル及びその合成中間体は、 燃料電池や食塩電解プロセスに有用なフッ素系固体電解質ポリマーの原料として用 いられる。 The ω— represented by the above general formula (2) or (2 ′) obtained by the production method of the present invention Fluorosulfol perfluoroalkylbutyl ether and its synthetic intermediates are used as raw materials for fluorine-based solid electrolyte polymers useful for fuel cells and salt electrolysis processes.

Claims

請求の範囲 原料として、下記一般式（1) Y X— CF— Rf― S02F (Rは炭素原子数 1一 9の 2価のペルフルォロカーボン基、 Xは I又は Brから選ばれる f ハロゲン原子、 Yはフッ素原子、炭素原子数 1一 3のペルフルォロアルキル基、又はRとの連結基 (炭素原子数 1 f 一 3)を表す Y (― CF—は以下一 C F Y—とも表す） 。 —CFY— R—は炭素原子数 3— 10の 2価のペルフルォロカーボン基である。） f で表される ω—ハロペルフルォロアルキルスルホ-ルフルオリドから下記一般式（2) CF =CFO (CF CF (CF ) θ) — CFY— R—SO F (2) 2 2 3 n f 2 (nは 0— 2の整数であり、 R及び Yは上記一般式（1)と同じである。 ) f で表される ω—フルォロスルホ-ルペルフルォロアルキルビュルエーテルを製造する 方法であって、以下の工程 (a)—（c)を含む上記方法： (a)上記一般式 (1)で表される ω—ハロペルフルォロアルキルスルホ-ルフルオリドを 酸化剤で処理して下記一般式（3)で表される ω -フルォロスルホニル化合物を製造 する工程、 Υ I η ( 3 ) 0=C— Rf— S02F Claims As a raw material, the following general formula (1): YX—CF—Rf—S02F (R is a divalent perfluorocarbon group having 1 to 19 carbon atoms, X is an f halogen atom selected from I or Br Y represents a fluorine atom, a perfluoroalkyl group having 13 to 13 carbon atoms, or a linking group to R (1 f to 13 carbon atoms). Y (—CF— is also referred to as 1 CFY—) —CFY—R— is a divalent perfluorocarbon group having 3 to 10 carbon atoms.) From the ω-haloperfluoroalkylsulfur fluoride represented by f, the following general formula (2) CF = CFO (CF CF (CF) θ) — CFY— R—SO F (2) 2 2 3 nf 2 (n is an integer of 0—2, and R and Y are the same as in the above general formula (1). A method for producing ω-fluorosulfol-perfluoroalkylbutyl ether represented by f, comprising the following steps (a) to (c): (a) the above-mentioned general formula ( Ω expressed by 1) A step of treating haloperfluoroalkylsulfurfluoride with an oxidizing agent to produce an ω-fluorosulfonyl compound represented by the following general formula (3), ΥIη (3) 0 = C—Rf— S02F
(R及び Yは上記一般式（1)と同じである。 ) (R and Y are the same as in the above general formula (1).)
f  f
(b)工程 (a)で得られた上記一般式（3)で表される ω—フルォロスルホニル化合物と へキサフルォロプロピレンォキシドを反応させて下記一般式 (4)で表される酸フルォ リド化合物を製造する工程、及び  (b) reacting the ω-fluorosulfonyl compound represented by the general formula (3) obtained in the step (a) with hexafluoropropylene oxide and represented by the following general formula (4) Producing an acid fluoride compound,
CF CF (COF) 0 (CF CF (CF ) θ) —CFY— R—SO F (4)  CF CF (COF) 0 (CF CF (CF) θ) —CFY— R—SO F (4)
3 2 3 n f 2  3 2 3 n f 2
(nは上記一般式（2)と同じであり、 R及び Yは上記一般式（1)と同じである。 ) (c)工程 (b)で得られた上記一般式 (4)で表される酸フルオリドィ匕合物を上記一般式 (2)で表される ω—フルォロスルホ-ルペルフルォロアルキルビュルエーテルに変換 する工程。 (n is the same as in the general formula (2), and R and Y are the same as in the general formula (1).) (c) converting the acid fluoride conjugate represented by the general formula (4) obtained in the step (b) into the ω-fluorosulfol-perfluoroalkyl ether represented by the general formula (2); The process of converting.
[2] 原料として、下記一般式 (1 ' ) [2] As a raw material, the following general formula (1 ')
X(CF ) SO F (1，）  X (CF) SO F (1,)
2 m 2  2 m 2
(Xは I又は Brから選ばれるハロゲン原子、 mは 3— 10の整数である。 ) で表される ω—ハロペルフルォロアルキルスルホ-ルフルオリドから下記一般式（2，） CF =CFO (CF CF (CF ) θ) (CF ) SO F (2，）  (X is a halogen atom selected from I or Br, and m is an integer of 3-10.) From the ω-haloperfluoroalkylsulfur fluoride represented by the following general formula (2,) CF = CFO ( CF CF (CF) θ) (CF) SO F (2,)
2 2 3 n' 2 m 2  2 2 3 n '2 m 2
(n'は 0— 2の整数であり、 mは上記一般式（1 ' )と同じである。 )  (n 'is an integer of 0-2, and m is the same as in the above general formula (1').)
で表される ω—フルォロスルホ-ルペルフルォロアルキルビュルエーテルを製造する 方法であって、以下の工程 (a' )—（ ）を含む上記方法：  A method for producing an ω-fluorosulfol-perfluoroalkylbutyl ether represented by the above formula, comprising the following steps (a ′) — ():
(a， )上記一般式（ 1，）で表される ω—ハロペルフルォロアルキルスルホ-ルフルオリ ドを酸化剤で処理して下記一般式（3 ' )で表される ω—フルォロスルホニル化合物を 製造する工程、  (a,) The ω-haloperfluoroalkylsulfur fluoride represented by the general formula (1,) is treated with an oxidizing agent, and the ω-fluoro represented by the following general formula (3 ′) is treated. A step of producing a sulfonyl compound,
FCO (CF ) SO F (3，）  FCO (CF) SO F (3,)
2 m-1 2  2 m-1 2
(mは上記一般式（1 ' )と同じである。 )  (m is the same as in the above general formula (1 ′).)
(b ' )工程（a ' )で得られた上記一般式（3 ' )で表される ω—フルォロスルホニル化合 物とへキサフルォロプロピレンォキシドを反応させて下記一般式 (4' )で表される酸フ ルオリドィ匕合物を製造する工程、及び  (b ′) The ω-fluorosulfonyl compound represented by the above general formula (3 ′) obtained in the step (a ′) is reacted with hexafluoropropylene oxide to give the following general formula (4) ') A process for producing an acid fluoride compound represented by
CF CF (C0F) 0 (CF CF (CF ) θ) (CF ) SO F (4，）  CF CF (C0F) 0 (CF CF (CF) θ) (CF) SO F (4,)
3 2 3 n' 2 m 2  3 2 3 n '2 m 2
(nは上記一般式（2' )と同じであり、 mは上記一般式（ )と同じである。 ) (c ' )工程 (b ' )で得られた上記一般式 (4 ' )で表される酸フルオリドィ匕合物を上記一 般式（2，）で表される ω—フルォロスルホ-ルペルフルォロアルキルビュルエーテル に変換する工程。  (n is the same as the above general formula (2 ′), m is the same as the above general formula ().) (c ′) Step (b ′) obtained by the above general formula (4 ′) Converting the acid fluoridation compound obtained into the ω-fluorosulfol-perfluoroalkylbutyl ether represented by the general formula (2).
[3] 前記工程 (a)で使用される酸化剤が SO又は発煙硫酸である、請求項 1に記載の  [3] The method according to claim 1, wherein the oxidizing agent used in the step (a) is SO or fuming sulfuric acid.
3  Three
方法。  Method.
[4] 前記工程 (a)で得られた少なくとも上記一般式（3)で表される ω—フルォロスルホ- ル化合物、及び副生成物である下記一般式 (5) FSO O-CFY-R -SO F (5) [4] At least the ω-fluorosulfur compound represented by the general formula (3) obtained in the step (a) and the following general formula (5) which is a by-product FSO O-CFY-R -SO F (5)
2 f 2  2 f 2
(R及び Yは上記一般式（1)と同じである。 )  (R and Y are the same as in the above general formula (1).)
f  f
で表されるスルホ-ルフルオリド化合物を含む反応混合物を、  A reaction mixture containing a sulfol fluoride compound represented by
1)アルカリ金属塩、アルカリ土類金属塩、又はルイス塩基と接触させて、該反応混合 物中の上記一般式（5)で表されるスルホニルフルオリドィ匕合物を、上記一般式（3)で 表される ω—フルォロスルホ-ル化合物に変換し、  1) The sulfonylfluoride conjugate represented by the general formula (5) in the reaction mixture is brought into contact with an alkali metal salt, an alkaline earth metal salt, or a Lewis base, and ) Is converted to a ω-fluorosulfol compound represented by
2)次いで、 1)の操作で得られた、上記一般式（3)で表される ω—フルォロスルホニル 化合物を、工程 (b)に使用する、  2) Then, the ω-fluorosulfonyl compound represented by the general formula (3) obtained by the operation of 1) is used in the step (b),
請求項 3に記載の方法。  The method of claim 3.
[5] 前記工程 (a)で得られた、少なくとも上記一般式（3)で表される ω—フルォロスルホ ニル化合物、及び副生成物である上記一般式（5)で表されるスルホニルフルオリド化 合物を含む反応混合物から、 [5] At least the ω-fluorosulfonyl compound represented by the general formula (3) obtained in the step (a) and the sulfonyl fluoride represented by the general formula (5) as a by-product From the reaction mixture containing the compound
3)上記一般式（3)で表される ω—フルォロスルホ-ルイ匕合物を分離除去し、 3) Separate and remove the ω-fluorosulholi-luid conjugate represented by the general formula (3),
4)その結果得られた反応残渣中の上記一般式（5)で表されるスルホ-ルフルオリド 化合物を、アルカリ金属塩、アルカリ土類金属塩、又はルイス塩基と接触させて、上 記一般式（3)で表される ω—フルォロスルホ-ルイ匕合物に変換し、 4) The sulfol fluoride compound represented by the above general formula (5) in the resulting reaction residue is brought into contact with an alkali metal salt, an alkaline earth metal salt, or a Lewis base to obtain the above-mentioned general formula ( 3) converted to ω-fluorosulho-rui-dani compound represented by
5)次いで、上記工程 4)で得られた、上記一般式（3)で表される ω—フルォロスルホ- ル化合物を、前記工程 (b)に使用する、  5) Next, the ω-fluorosulfur compound represented by the general formula (3) obtained in the above step 4) is used in the above step (b),
請求項 3に記載の方法。  The method of claim 3.
[6] 前記工程 (a' )で使用される酸化剤が SO又は発煙硫酸である、請求項 2に記載の [6] The method according to claim 2, wherein the oxidizing agent used in the step (a ′) is SO or fuming sulfuric acid.
3  Three
方法。  Method.
[7] 前記工程 (a' )で得られた、少なくとも上記一般式（3 ' )で表される ω—フルォロスル ホニル化合物、及び副生成物である下記一般式（5' )  [7] At least the ω-fluorosulfonyl compound represented by the general formula (3 ′) obtained in the step (a ′) and the following general formula (5 ′) which is a by-product
FSO 0 (CF ) SO F (5，）  FSO 0 (CF) SO F (5,)
2 2 m 2  2 2 m 2
(mは上記一般式（1 ' )と同じである。 )  (m is the same as in the above general formula (1 ′).)
で表されるスルホ-ルフルオリド化合物を含む反応混合物を、  A reaction mixture containing a sulfol fluoride compound represented by
1 ' )アルカリ金属塩、アルカリ土類金属塩、又はルイス塩基と接触させて、該反応混 合物中の上記一般式（5 ' )で表されるスルホニルフルオリドィ匕合物を、上記一般式（3 ' )で表される ω—フルォロスルホ-ル化合物に変換し、 1 ′) The sulfonylfluoride compound represented by the above general formula (5 ′) in the reaction mixture is contacted with an alkali metal salt, an alkaline earth metal salt, or a Lewis base, and Expression (3 ') To the ω-fluorosulfol compound represented by
2 ' )次いで、 1 ' )の操作で得られた上記一般式（3 ' )で表される ω—フルォロスルホ- ルイ匕合物を工程 (b' )に使用する  2 ′) Then, the ω-fluorosulholi- Louis conjugate represented by the general formula (3 ′) obtained by the operation of 1 ′) is used in the step (b ′).
請求項 6に記載の方法。  The method of claim 6.
[8] 前記工程 (a' )で得られた、少なくとも上記一般式（3 ' )で表される ω—フルォロスル ホニル化合物、及び副生成物である上記一般式（5 ' )で表されるスルホニルフルオリ ド化合物を含む反応混合物から、 [8] At least the ω-fluorosulfonyl compound represented by the general formula (3 ′) obtained in the step (a ′), and the sulfonyl represented by the general formula (5 ′) as a by-product From the reaction mixture containing the fluoride compound,
3 ' )上記一般式（3 ' )で表される ω—フルォロスルホ-ルイ匕合物を分離除去し、 4' )その結果得られた反応残渣中の上記一般式（5' )で表されるスルホ-ルフルオリ ド化合物を、アルカリ金属塩、アルカリ土類金属塩、又はルイス塩基と接触させて、上 記一般式（3 ' )で表される ω—フルォロスルホニル化合物に変換し、  3 ′) The ω-fluorosulfurol conjugate represented by the above general formula (3 ′) is separated and removed, and 4 ′) The resulting reaction residue is represented by the above general formula (5 ′) The sulfol fluoride compound is brought into contact with an alkali metal salt, an alkaline earth metal salt, or a Lewis base to convert it into an ω-fluorosulfonyl compound represented by the above general formula (3 ′),
5 ' )次!、で、上記工程 4 ' )で得られた上記一般式（3 ' )で表される ω—フルォロスルホ ニル化合物を、前記工程 (b' )に使用する、  5 ′) Next, the ω-fluorosulfonyl compound represented by the above general formula (3 ′) obtained in the above step 4 ′) is used in the above step (b ′),
請求項 6に記載の方法。  The method of claim 6.
[9] 上記一般式（3 ' )で表される ω—フルォロスルホ-ル化合物とへキサフルォロプロピ レンォキシドをフッ素イオン含有ィ匕合物の存在下、下記一般式 (6) [9] An ω-fluorosulfol compound represented by the above general formula (3 ′) and hexafluoropropylenoxide are present in the presence of a fluoride ion-containing compound of the following general formula (6)
RxO (R20) R1 (6) R x O (R 2 0) R 1 (6)
P  P
(R1は炭素数 1一 5のアルキル基であり、 R2は C H又は C Hである。 pは 0— 10 (R 1 is an alkyl group having 115 carbon atoms, R 2 is CH or CH. P is 0-10
2 4 3 6  2 4 3 6
の整数である。 )  Is an integer. )
で表されるエーテル系溶媒とカルボン酸ジ-トリル系溶媒の混合溶媒存在下で反応 させることを含む、上記一般式 (4' )において n' =0である下記一般式 (4")  Wherein the reaction is performed in the presence of a mixed solvent of an ether-based solvent and a carboxylic acid di-tolyl-based solvent represented by the following general formula (4 ") wherein n '= 0 in the above general formula (4').
CF CF (COF) 0 (CF ) SO F (4")  CF CF (COF) 0 (CF) SO F (4 ")
3 2 m 2  3 2 m 2
(mは上記一般式（1 ' )と同じである。 )  (m is the same as in the above general formula (1 ′).)
で表される酸フルオリド化合物を製造する方法。  A method for producing an acid fluoride compound represented by the formula:
[10] 上記一般式 (6)で表されるエーテル系溶媒とカルボン酸ジ-トリル系溶媒の混合溶 媒中に占める該カルボン酸ジ-トリル系溶媒の質量割合が 30質量％以上 99質量％ 以下である請求項 9記載の方法。 [10] The mass ratio of the carboxylic acid di-tolyl solvent in the mixed solvent of the ether solvent represented by the general formula (6) and the carboxylic acid di-tolyl solvent is 30% by mass to 99% by mass. 10. The method of claim 9, wherein:
[11] 上記一般式 (4")で表される酸フルオリドィ匕合物をカルボン酸塩に変換し、次！、で 該カルボン酸塩を熱分解して、上記一般式（2' )において n' =0である下記一般式（ 2")で表される ω—フルォロスルホ-ルペルフルォロアルキルビュルエーテルを製造 する方法であって、目的生成物である下記一般式（2")で表される ω—フルォロスル ホ-ルペルフルォロアルキルビュルエーテルの生成モル数を r、副生成物として再生 成した上記一般式 (4")で表される酸フルオリドィ匕合物の生成モル数を sとした場合、 [s]Z[r+s]で表される副生成物の生成割合が 0. 1以下で反応を実施することを特徴と する、上記方法。 [11] The acid fluoride conjugate represented by the above general formula (4 ") is converted into a carboxylate, and the following! The carboxylate is thermally decomposed to produce an ω-fluorosulfol-perperfluoroalkylbutyl ether represented by the following general formula (2 ″) wherein n ′ = 0 in the above general formula (2 ′). Wherein r is the number of moles of ω-fluorosul-hole perfluoroalkylbutyl ether represented by the following general formula (2 ″), which is a target product, and the above general formula is regenerated as a by-product. Assuming that the number of moles of the acid fluoride conjugate represented by the formula (4 ") is s, the reaction is performed when the by-product formation ratio represented by [s] Z [r + s] is 0.1 or less. The above method, characterized in that:
CF =CFO (CF ) SO F (2")  CF = CFO (CF) SO F (2 ")
2 2 m 2  2 2 m 2
(mは上記一般式（1 ' )と同じである。 )  (m is the same as in the above general formula (1 ′).)
[12] 上記一般式 (4")で表される酸フルオリドィ匕合物から誘導されるカルボン酸塩が下 記一般式 (7)で表されるカリウム塩であり、かつ、該カルボン酸塩の熱分解を無溶媒 で行う、請求項 11に記載の方法。 [12] The carboxylate derived from the acid fluoride conjugate represented by the above general formula (4 ") is a potassium salt represented by the following general formula (7), and 12. The method according to claim 11, wherein the thermal decomposition is performed without a solvent.
CF CF (CO K) 0 (CF ) SO F (7)  CF CF (CO K) 0 (CF) SO F (7)
3 2 2 m 2  3 2 2 m 2
(mは上記一般式（1 ' )と同じである。 )  (m is the same as in the above general formula (1 ′).)
[13] カルボン酸塩の熱分解を、該カルボン酸塩を固相状態に保ちながら行う、請求項 1[13] The thermal decomposition of the carboxylate is performed while maintaining the carboxylate in a solid state.
1又は 12に記載の方法。 13. The method according to 1 or 12.
[14] 上記一般式（1， )で表される ω—ノ、口ペルフルォロアルキルスルホ-ルフルオリドが 、下記工程 (i)一（iv)により得られる、請求項 2に記載の方法： [14] The method according to claim 2, wherein the ω-no, perfluoroalkylsulfur fluoride represented by the general formula (1) is obtained by the following step (i)-(iv):
(i)下記一般式 (8)  (i) The following general formula (8)
X (CF ) X (8)  X (CF) X (8)
2 m  2 m
(X及び mは上記一般式（1 ' )と同じである。 )  (X and m are the same as in the above general formula (1 ′).)
で表される a , ω—ジハロペルフルォロアルカンをアルカリ金属塩型、アルカリ土類金 属塩型、第 4級アンモ-ゥム塩型、又は第 4級ホスホ-ゥム塩型の何れ力から選ばれ る亜ジチオン酸塩と混合、攪拌して、下記一般式 (9)  A, ω-dihaloperfluoroalkane represented by the following formula: alkali metal salt type, alkaline earth metal salt type, quaternary ammonium salt type, or quaternary phospho-dimethyl salt type Mix and stir with a dithionite selected from any of
X (CF ) SO M (9)  X (CF) SO M (9)
2 m 2  2 m 2
(式中、 Mは、 Ma、 Mb 、第 4級アンモ -ゥムラジカル又は第 4級ホスホ-ゥムラジ  (Wherein, M is Ma, Mb, a quaternary ammo-radical or a quaternary phospho-dimethyl
1/2  1/2
カルであり、 Maはアルカリ金属、 Mbはアルカリ土類金属である。 X及び mは上記一 般式（1 ' )と同じである。） で表される ωーハロペルフルォロアルキルスルフィン酸塩を製造する工程、 Ma is an alkali metal and Mb is an alkaline earth metal. X and m are the same as those in the general formula (1 ′). ) A process for producing an ω-haloperfluoroalkylsulfinate represented by:
(ii)工程 (i)で得られた反応混合物から上記一般式（9)で表される ω -ハロペルフル ォロアルキルスルフィン酸塩を分離する工程、  (ii) separating the ω-haloperfluoroalkylsulfinate represented by the general formula (9) from the reaction mixture obtained in the step (i),
(iii)工程（ii)で得られた上記一般式（9)で表される ω ノヽロペルフルォロアルキルス ルフィン酸塩を塩素化剤で処理して下記一般式（10)  (iii) treating the ω-noperoperfluoroalkyl sulfinate represented by the above general formula (9) obtained in the step (ii) with a chlorinating agent to obtain the following general formula (10)
X (CF ) SO CI ( 10)  X (CF) SO CI (10)
2 m 2  2 m 2
(X及び mは上記一般式（1 ' )と同じである。 )  (X and m are the same as in the above general formula (1 ′).)
で表される ω—ハロペルフルォロアルキルスルホ-ルクロリドを製造する工程、及び A process of producing ω-haloperfluoroalkylsulfol-chloride represented by
(iv)工程（iii)で得られた上記一般式（10)で表される ω—ハロペルフルォロアルキル スルホニルクロリドをフッ素イオン含有ィ匕合物で処理して、上記一般式（1 ' )で表され る ω—ハロペルフルォロアルキルスルホ-ルフルオリドを製造する工程。 (iv) treating the ω-haloperfluoroalkyl sulfonyl chloride represented by the general formula (10) obtained in the step (iii) with a fluoride ion-containing conjugate, ) it expresses in omega - halo pel full O b alkylsulfonyl - the process of manufacturing the Rufuruorido.
[15] 前記工程 (ii)が、工程 (i)の反応で得られた少なくとも上記一般式 (9)で表される ω ーハロペルフルォロアルキルスルフィン酸塩及び副生成物である下記一般式（ 11) [15] The following general method, wherein the step (ii) is at least the ω-haloperfluoroalkyl sulfinic acid salt represented by the general formula (9) and a by-product obtained by the reaction of the step (i). Equation (11)
MO S (CF ) SO M ( 11) MO S (CF) SO M (11)
2 2 m 2  2 2 m 2
(Mは上記一般式（9)と同じであり、 mは上記一般式（1 ' )と同じである。 ) で表されるペルフルォロアルキル α , ω ビススルフィン酸塩を含む反応混合物か ら上記一般式（9)で表される ω—ハロペルフルォロアルキルスルフィン酸塩を抽出分 離する操作を含む、請求項 14に記載の方法。  (M is the same as in the above general formula (9), m is the same as in the above general formula (1 ′).) A reaction mixture containing a perfluoroalkyl α, ω bissulfinate represented by the following formula: 15. The method according to claim 14, comprising an operation of extracting and separating the ω-haloperfluoroalkylsulfinate represented by the general formula (9).
[16] 前記工程 (ii)力 下記工程 (ii 1)及び工程 (ii 2)を含む工程である請求項 14〖こ 記載の方法。 [16] The method according to claim 14, which is a step comprising the following step (ii1) and step (ii2).
(ii 1)前記工程 (i)で得られた少なくとも未反応の上記一般式 (8)で表される ex , ω -ジハ口ペルフルォロアルカン、目的化合物である上記一般式（9)で表される ω -ハ 口ペルフルォロアルキルスルフィン酸塩、及び副生成物である上記一般式（11)で表 されるペルフルォロアルキル α , ω ビススルフィン酸塩を含む反応混合物から、上 記一般式（8)で表される a , ω ジハロペルフルォロアルカンを除去する工程、 (ii 2)上記工程 (ii 1)で得られた少なくとも上記一般式（9)で表される ω—ハロペル フルォロアルキルスルフィン酸塩及び上記一般式（11)で表されるペルフルォロアル キル a , ω ビススルフィン酸塩を含む混合物から、上記一般式（9)で表される ω - ノ、口ペルフルォロアルキルスルフィン酸塩を抽出分離する工程。 (ii 1) at least the unreacted ex, ω-diha-mouth perfluoroalkane represented by the general formula (8) obtained in the step (i), and the compound represented by the general formula (9) From a reaction mixture containing a perfluoroalkylsulfinate represented by the formula ω-c and a perfluoroalkyl α, ω bissulfinate represented by the general formula (11) as a by-product: Removing the a, ω dihaloperfluoroalkane represented by the general formula (8); (ii 2) at least represented by the general formula (9) obtained in the step (ii 1) From a mixture containing an ω-haloperfluoroalkylsulfinate and a perfluoroalkyl a, ωbissulfinate represented by the above general formula (11), ω − represented by the above general formula (9) No. Step of extracting and separating perfluoroalkylsulfinates.
[17] 上記一般式 (9)で表される ω—ハロペルフルォロアルキルスルフィン酸塩を分離除 去した後の反応残渣を塩素化剤で処理する操作により上記一般式 (8)で表される α , ω ジハロペルフルォロアルカン及び Ζ又は上記一般式（10)で表される ω—ハロ ペルフルォロアルキルスルホ-ルクロリドを製造し、これらを工程（i)及び Z又は工程 (iv)に再使用する、請求項 14一 16のいずれか一項に記載の方法。 [17] The ω-haloperfluoroalkylsulfinate represented by the general formula (9) is separated and removed, and then the reaction residue is treated with a chlorinating agent to obtain a compound represented by the general formula (8). Α, ω dihaloperfluoroalkane and Ζ or ω-haloperfluoroalkylsulfur-chloride represented by the above general formula (10) are produced, and these are produced in step (i) and Z or step 17. The method according to any one of claims 14 to 16 for reuse in (iv).
[18] 上記一般式 (9)で表される ω—ハロペルフルォロアルキルスルフィン酸塩を分離除 去した後の、少なくとも上記一般式（11)で表されるペルフルォロアルキル α , ω— ビススルフィン酸塩及び無機沃化物又は無機臭化物から選ばれる少なくとも一方の 無機塩を含有する反応残渣を溶解した水溶液を塩素化剤で処理し、沃素又は臭素 の少なくとも一方と下記一般式（ 12) [18] After separating and removing the ω-haloperfluoroalkylsulfinate represented by the general formula (9), at least the perfluoroalkyl α, represented by the general formula (11) An aqueous solution in which a reaction residue containing at least one inorganic salt selected from ω-bissulfinate and inorganic iodide or inorganic bromide is dissolved is treated with a chlorinating agent, and at least one of iodine or bromine is added to the following general formula (12) )
CIO S (CF ) SO CI (12)  CIO S (CF) SO CI (12)
2 2 m 2  2 2 m 2
(mは上記一般式（1 ' )と同じである。 )  (m is the same as in the above general formula (1 ′).)
で表されるペルフルォロアルキル α , ω—ビススルホ-ルクロリドを生成させ、次い で、当該反応混合物を水難溶性有機溶媒で抽出処理することにより、上記一般式 (8 )で表される , ω ジハロペルフルォロアルカン及び Z又は上記一般式（10)で表 される ω—ハロペルフルォロアルキルスルホ-ルクロリドを製造'分離し、これらを工程 (i)及び Ζ又は工程 (iv)に再使用する、請求項 14一 16のいずれか一項に記載の方 法。  By producing a perfluoroalkyl α, ω-bissulfol-chloride represented by the following formula, and then subjecting the reaction mixture to an extraction treatment with a poorly water-soluble organic solvent, the reaction mixture represented by the general formula (8) ω Dihaloperfluoroalkane and Z or ω-haloperfluoroalkylsulfol-chloride represented by the above general formula (10) are produced and separated, and these are separated in step (i) and Ζ or step (iv). 17. The method according to any one of claims 14 to 16, wherein said method is reused.
[19] 上記一般式 (9)で表される ω—ハロペルフルォロアルキルスルフィン酸塩を分離除 去した後の反応残渣を、塩素化剤で処理することにより上記一般式（ 12)で表される ペルフルォロアルキル α , ω ビススルホ-ルクロリドを製造し、次いで当該ペルフ ルォロアルキル α , ω—ビススルホユルク口リドを沃素又は臭素と反応させて、上記 一般式（8)で表される a , ω ジハロペルフルォロアルカン及び Ζ又は上記一般式（ 10)で表される ω ノヽロペルフルォロアルキルスルホ-ルクロリドを製造、分離し、こ れらを工程 (i)及び Ζ又は工程 (iv)に再使用する、請求項 14一 16のいずれか一項 に記載の方法。 [19] The reaction residue after separation and removal of the ω-haloperfluoroalkylsulfinate represented by the above general formula (9) is treated with a chlorinating agent to give the above general formula (12) A perfluoroalkyl α, ω bissulfol-chloride represented by the formula (1) is produced, and the perfluoroalkyl α , ω-bissulfoyl chloride is reacted with iodine or bromine to obtain a, a ω dihaloperfluoroalkane and Ζ or ω noperoperfluoroalkyl sulfol chloride represented by the above general formula (10) are produced and separated, and these are subjected to step (i) and Ζ or step 17. The method according to any one of claims 14 to 16 for reuse in (iv).
[20] 上記一般式（ 12)で表されるペルフルォロアルキル a , ω ビススルホユルクロリド を沃素又は臭素と反応させることを含む上記一般式 (8)で表される a , ω—ジハロぺ ルフルォロアルカン及び Ζ又は上記一般式（10)で表される ω—ハロペルフルォロア ルキルスルホニルクロリドを製造する方法。 [20] Perfluoroalkyl a, ω bissulfoyl chloride represented by the above general formula (12) A, ω-dihalofluorofluoroalkane represented by the above general formula (8) and ω-haloperfluoro represented by the above general formula (10), which comprises reacting with iodine or bromine. A method for producing lower alkylsulfonyl chloride.
[21] 上記一般式（1 ' )一（5' )、（7)—（12)、（2")、及び (4")で表される化合物におい て、 mは 4一 8の整数である請求項 2及び請求項 6— 20のいずれ力 1項に記載の方 法。 [21] In the compounds represented by the above general formulas (1 ′)-(5 ′), (7)-(12), (2 ″), and (4 ″), m is an integer of 418. The method according to any one of claims 2 and 6-20.
[22] 上記一般式（1 ' )一（5' )、（7)—（12)、（2")、及び (4")で表される化合物におい て、 mは 4一 6の整数である請求項 2及び請求項 6— 20のいずれ力 1項に記載の方 法。  [22] In the compounds represented by the general formulas (1 ′)-(5 ′), (7)-(12), (2 ″), and (4 ″), m is an integer of 4-16. The method according to any one of claims 2 and 6-20.
[23] 上記一般式（2)、（2' )、（4)、及び (4' )で表される化合物において、 n又は nが 0 である請求項 1一 8、 14一 19及び 21— 22のいずれ力 1項に記載の方法。  [23] The compound represented by the above general formulas (2), (2 '), (4) and (4'), wherein n or n is 0. 22. The method according to paragraph 1.
[24] 上記一般式（ 1)、（ 1 ' )、及び (8)—（ 10)で表される化合物にお 、て、 Xが沃素原 子である請求項 1一 8及び 14一 22のいずれか 1項に記載の方法。 [24] The compound according to claim 118, wherein in the compounds represented by the general formulas (1), (1 ') and (8)-(10), X is an iodine atom. A method according to any one of the preceding claims.
[25] 請求項 14に記載の工程 (i)一（iv)を含む、上記一般式（1 ' )で表される ω ハロぺ ルフルォロアルキルスルホ-ルフルオリドを製造する方法。 [25] A method for producing an ω-halogenofluoroalkylsulfur-fluoride represented by the general formula (1 ′), comprising the step (i)-(iv) according to claim 14.
[26] 請求項 15— 19のいずれか 1項に記載の工程を含む、上記一般式（1 ' )で表される ω ノヽロペルフルォロアルキルスルホ-ルフルオリドを製造する方法。 [26] A method for producing ω-noperoperfluoroalkylsulfur fluoride represented by the general formula (1 ′), comprising the step according to any one of claims 15 to 19.
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Publication number Priority date Publication date Assignee Title
JP2006248907A (en) * 2005-03-08 2006-09-21 Daikin Ind Ltd Method for producing fluorine-containing halide
US7399887B1 (en) 2007-08-06 2008-07-15 E. I. Du Pont De Nemours And Company Fluorinated sulfonate surfactants
JP2011203029A (en) * 2010-03-25 2011-10-13 Hitachi-Ge Nuclear Energy Ltd Method of processing fluoride compound

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