WO2003106407A1 - Procede de production de fluorosulfonylalkyle-vinyle ethers contenant du fluor - Google Patents

Procede de production de fluorosulfonylalkyle-vinyle ethers contenant du fluor Download PDF

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Publication number
WO2003106407A1
WO2003106407A1 PCT/JP2003/006440 JP0306440W WO03106407A1 WO 2003106407 A1 WO2003106407 A1 WO 2003106407A1 JP 0306440 W JP0306440 W JP 0306440W WO 03106407 A1 WO03106407 A1 WO 03106407A1
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WIPO (PCT)
Prior art keywords
general formula
vinyl ether
cfo
integer
reaction
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PCT/JP2003/006440
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English (en)
Japanese (ja)
Inventor
杉山　明平
大塚　達也
市原　一義
萬谷　聡哉
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ダイキン工業株式会社
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Application filed by ダイキン工業株式会社 filed Critical ダイキン工業株式会社
Priority to AU2003242416A priority Critical patent/AU2003242416A1/en
Publication of WO2003106407A1 publication Critical patent/WO2003106407A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C313/02—Sulfinic acids; Derivatives thereof
    • 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
    • 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

Definitions

  • the present invention relates to a method for producing a fluorinated fluorosulfonylalkyl vinyl ether, and a method for producing an intermediate of the fluorinated fluorosulfonylalkyl vinyl ether.
  • Fluorinated Full O b sulfonyl alkyl vinyl ether of formula CF2 CFOCF2CF 2 S0 2 F is Ru compounds useful der as industrial raw materials such as an ion-exchange membrane material.
  • a sulfonyl vinyl ether such as the fluorinated fluorosulfonylalkyl vinyl ether
  • hexafluoropropylene oxide is added to FCOCF 2 S0
  • a method is described in which after addition to 2 F, the obtained acid fluoride derivative is thermally decomposed.
  • two or more molecules of hexafluoropropylene oxide are added,
  • CF 2 CFO (CF 2 CF (CF 3) ⁇ ) n CF 2 CF 2 S0 2 is Rukoto give sulfo ether represented by F are possible, the hexa full O b propylene O sulfoxide one molecular addition From the following formula
  • Japanese Patent Application Laid-Open No. 57-28025 describes a method in which a fluorene propylene oxide is added to FCOCF 2 SO 2 F and then thermally decomposed.
  • this method it is possible to obtain the above-mentioned fluorinated fluorosulfonylalkyl pinyl ether, but since the chloropentafluoropropylene oxide used as a raw material cannot be obtained in good yield, Fluorine-containing fluorosulfonyl alkyl vinyl ester One teller cannot be efficiently manufactured at low cost.
  • JP-A-61-30552 and JP-A-10-139745 disclose halogen-terminated vinyl ethers. how to convert halogens S0 2 F group, the JP 1 1 one 2 2 8 4 7 4 No. Gazette, a method for dechlorination with zinc CF 2 C1CFC10CF 2 CF 2 S0 2 F and the like are described ing.
  • the present invention has been made in view of the above situation, and a main object of the present invention is to provide a method capable of producing a fluorine-containing fluorosulfonylalkyl vinyl ether in an industrially advantageous manner with a good yield. That is.
  • Inventors of the present invention have conducted intensive studies in view of the above-mentioned problems, and as a result, have found that by reacting a fluorinated alkyl vinyl ether having a terminal octylogen atom with a dithionite and a neutralizing agent, a vinyl group is obtained. It has been found that a sulfinic acid salt of vinyl ether can be obtained as it is. By chlorinating and fluorinating the obtained sulfinate, it becomes possible to produce the desired fluorinated fluorosulfonylalkyl vinyl ether in a relatively simple process in a high yield. The present invention has been completed here.
  • the present invention provides the following fluorinated fluorosulfonylalkyl vinyl ether PC leakage 440
  • CF 2 CFO (CF 2 CF (CF 3 ) ⁇ ) n CF2 (CF 2 CF2) m CF2S0 2 F (1)
  • CF 2 CFO (CF 2 CF (CF 3 ) 0) n CF 2 (CF 2 CF 2 ) m CF2X (2)
  • CF 2 CFO (CF 2 CF (CF 3 ) ⁇ ) n CF 2 (CF 2 CF 2 ) m CF 2 S0 2 M (3) (where M is Ma or Mb 1/2 and Ma Is an alkali metal, Mb is an alkaline earth metal, m and n are the same as above, a process for producing a vinyl ether sulfinate represented by the following formula:
  • CF 2 CFO (CF 2 CF (CF 3 ) 0) n CF2 (CF 2 CF 2 ) m CF 2 X
  • CF 2 CFO (CF 2 CF (CF 3 ) ⁇ ) n CF 2 (CF2CF2) m CF 2 S0 2 M
  • M is Ma or Mb
  • Ma is an alkali metal
  • Mb is an alkaline earth metal
  • m and n are the same as described above.
  • CF 2 CFO (CF 2 CF (CF 3 ) ⁇ ) n CF 2 (CF 2 CF 2 ) m CF 2 S0 2 M
  • M is Ma or Mb 1/2
  • Ma is an alkali metal
  • Mb is an alkaline earth metal
  • M is an integer of 0-5
  • n is an integer of 0-10.
  • the vinyl ether sulphinate represented by the formula is chlorinated and then fluorinated, a general formula:
  • CF 2 CFO (CF 2 CF (CF 3 ) ⁇ ) n CF2 (CF 2 CF2) m CF 2 S02F
  • CF 2 CFO (CF 2 CF (CF 3 ) ⁇ ) n CF2 (CF2CF2) m CF 2 X (2)
  • CF 2 CFO (CF 2 CF (CF 3 ) 0) n CF2 (CF2CF2) m CF2S0 2 M (3)
  • M is M a or Mb 1/2, the M a is an alkali metal, Mb is force Li earth metals. M and n are the same. Above) Pinirue one Terusurufu represented by And phosphate.
  • the ⁇ -octalogenated pinyl ether of the general formula (2) used as a raw material is a known substance.
  • the fluorine-containing compound represented by) S0 3, C1S0 3 H is reacted with fuming sulfuric acid FOC (CF 2 CF 2) after the m CF 2 X
  • HFP0 hexafluoropropylene oxide
  • the dithionite alkali metal Ru used when Chiosuruhon the ⁇ - halogenated Biel ether of the general formula (2) for example, Li 2 S 2 0 4, Na 2 S 2 0 4, K 2 S 2 0 4, Cs 2 S 2 0 4 or the like can be mentioned, in particular, Na 2 S 2 0 4, etc. K 2 S 2 0 4 is preferred.
  • the amount of dithionite used must be at least 1 mol per 1 mol of the substrate, and preferably about 1 to 5 mol.
  • the neutralizing agent MaHC0 3, Mb 1/2 HC_ ⁇ 3 hydrogen carbonates such as, Ma 2 C_ ⁇ 3, carbonates such as MbC_ ⁇ 3, MAOH, M b E Bruno 2 ⁇ hydroxides such as H And various other bases can be used.
  • Ma indicates an alkali metal
  • Mb indicates an alkaline earth metal.
  • the amount of the neutralizing agent to be used is preferably about 1 to 20 times equivalent, more preferably about 1 to 10 times equivalent to the substrate.
  • the order of the reaction is not particularly limited, and for example, the general formula (2) Reacting the ⁇ -halogenated vinyl ether of the formula (2) with a dithionite and a neutralizing agent at the same time, reacting the ⁇ -halogenated vinyl ether of the general formula (2) with the dithionite, and then reacting with the neutralizing agent.
  • a reaction method can be adopted. The above reaction is usually performed in a solvent.
  • the solvent used in the reaction is not particularly limited, and examples thereof include water, ketones such as acetone, esters such as ethyl acetate, dioxane, acetonitrile, dimethylformamide, dimethylsulfoxide, and tetrahydrofuran. These can be used alone or in combination of two or more.
  • the vinyl ether sulfide of the general formula (3) can be obtained in high yield. Can be obtained.
  • the concentration of the ⁇ -halogenated vinyl ether compound of the general formula (2) in the solvent is not particularly limited, but may be usually about 10 to 80% by mass.
  • the reaction temperature is preferably about ⁇ 20 to 90, more preferably about 0 to 50 ° C. for the reaction with the neutralizing agent and the reaction with the ditite.
  • the reaction time may be set according to the reaction conditions to be actually employed until the desired reaction has progressed sufficiently. Usually, the total time is about 0.5 to 48 hours depending on the reaction conditions. Can be performed within a range.
  • CF 2 CFO (CF 2 CF (CF 3 ) ⁇ ) n CF2 (CF2CF 2 ) m CF2S0 2 M (3)
  • examples of the alkali metal include Na, K, Li, and Cs
  • examples of the alkaline earth metal include Ca and Mg.
  • the vinyl ether sulfinate is a novel substance useful as an intermediate for producing a fluorinated fluorosulfonyl alkyl vinyl ether of the general formula (1).
  • CF 2 CFO (CF 2 CF (CF 3 ) ⁇ ) n CF2 (CF 2 CF2) m CF2S0 2 F (1)
  • the chlorination reaction can be performed according to a conventional method using a known chlorinating agent. Specifically, for example, after dissolving or dispersing the vinyl ether sulfinate of the general formula (3) in water, an organic solvent, or the like, performing a chlorination reaction by adding a chlorinating agent thereto. Can be.
  • the organic solvent used in the decarboxylation reaction may be present as it is during the chlorination reaction, or may be removed.
  • an acid such as hydrochloric acid, sulfuric acid, formic acid, or acetic acid may be contained in the solvent depending on the type of the chlorinating agent used.
  • an acid such as hydrochloric acid, sulfuric acid, formic acid, or acetic acid
  • hydrochloric acid generated by the reaction is contained in water.
  • copper chloride used as the chlorinating agent
  • an aqueous solution containing formic acid can be used as the solvent.
  • the concentration of the acid in these cases is not particularly limited as long as it does not adversely affect the chlorination reaction.
  • the organic solvent can be appropriately selected and used as long as it does not adversely affect the reaction.
  • the chlorinating agent is not particularly limited, and a known chlorinating agent can be used.
  • a known chlorinating agent can be used.
  • chlorine, sulfuryl chloride, copper (II) chloride, etc. are used as chlorinating agents.
  • chlorine is preferably used.
  • chlorination reaction is performed in water using chlorine, the obtained chlorinated product is separated into an organic layer, so that it can be easily collected and industrially implemented.
  • the conditions of 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 a desired chlorinated product is formed.
  • the chlorination reaction may be carried out by supplying chlorine gas into an aqueous solution in which the vinyl ether sulfinate of the general formula (3) is dissolved. Is about 0 to 50 ° C, and the amount of chlorine to be charged is about 1 to 5 mol, preferably about 1.2 to 3 mol, per 1 mol of bierether sulfinate of the general formula (3). .
  • the reaction time varies depending on the specific reaction conditions, but is usually within a range of about 0.5 to 48 hours.
  • the concentration of the pinyl monotersulfinate of the general formula (3) in the aqueous solution is not particularly limited, but may be generally about 0.5 to 50% by mass.
  • CF 2 CFO (CF 2 CF (CF 3 ) ⁇ ) n CF2 (CF 2 CF2) m CF2S02F (1)
  • the fluorination reaction can be performed according to a known method.
  • the chlorinated product and the fluorinating agent may be reacted in a solvent for the fluorination reaction or without a solvent.
  • the solvent is not particularly limited, and may be any solvent that does not participate in the reaction, and examples thereof include organic solvents such as sulfolane, dimethylsulfoxide, and dimethylformamide, and water.
  • the fluorinating agent a known fluorinating agent can be used.
  • NaF, KF and the like can be suitably used.
  • the reaction temperature may be about 20 to 200 ° C
  • the reaction time may be about 0.5 to 48 hours
  • the amount of the fluorinating agent used may be 1 mole of chlorinated product.
  • the amount may be about 1 to 5 moles.
  • concentration of chlorinated substances in the solvent 3/06440
  • the obtained crude compound may be purified by a known method such as extraction, distillation, recrystallization, and column chromatography.
  • the fluorine-containing sulfonylalkyl vinyl ether represented by the general formula (1) obtained by the method of the present invention is a useful substance as a monomer component for a polymer used for an electrolyte membrane or an ion exchange membrane.
  • This electrolyte membrane or ion exchange membrane is used, for example, for an electrolyte membrane of a solid polymer electrolyte fuel cell, a membrane for a lithium battery, a membrane for salt electrolysis, a membrane for water electrolysis, a membrane for hydrohalogen oxyacid electrolysis, and an oxygen concentrator. Used as membrane, humidity sensor membrane, gas sensor membrane, etc.
  • the desired fluorinated fluorosulfonyl ether can be produced at low cost and with high yield by an industrially advantageous method without requiring complicated operations.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production de fluorosulfonylalkyle-vinyle éthers contenant du fluor de formule : CF2=CFO(CF2CF(CF3)O)nCF2(CF2CF2)mCF2SO2F. Dans cette formule, m est un nombre entier compris entre 0 et 5, et n est un nombre entier compris entre 0 et 10. Le procédé de l'invention est caractérisé par la réaction d'un éther vinylique ω halogéné de formule : CF2=CFO(CF2CF(CF3)O)nCF2(CF2CF2)mCF2X. Dans cette formule, X désigne I ou Br, et m et n sont chacun définis ci-dessus, avec un dithionite métallique alcalin et un agent de neutralisation, pour former un sulfinate d'éther vinylique de formule : CF2=CFO(CF2CF(CF3)O)nCF2(CF2CF2)mCF2SO2M. Dans cette formule, M désigne Ma ou Mb1/2 ; Ma désigne un métal alcalin ; Mb désigne un métal alcalino-terreux ; et m et n sont chacun définis ci-dessus). Le procédé de l'invention est également caractérisé par la chloration du sulfinate d'éther vinylique, puis par la fluoration du composé obtenu. Selon ce procédé, les fluorosulfonylalkyle-vinyle éthers contenant du fluor peuvent être produits avantageusement de manière industrielle, et ce, à haut rendement.
PCT/JP2003/006440 2002-06-14 2003-05-23 Procede de production de fluorosulfonylalkyle-vinyle ethers contenant du fluor WO2003106407A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003242416A AU2003242416A1 (en) 2002-06-14 2003-05-23 Process for production of fluorine-containing fluoro- sulfonylalkyl vinyl ethers

Applications Claiming Priority (2)

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JP2002173637A JP4189632B2 (ja) 2002-06-14 2002-06-14 含フッ素フルオロスルホニルアルキルビニルエーテルの製造方法
JP2002-173637 2002-06-14

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AU (1) AU2003242416A1 (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2475477C1 (ru) * 2011-12-09 2013-02-20 Закрытое акционерное общество научно-производственное Объединение "ПиМ-Инвест" (ЗАО НПО "Пим-Инвест") Новый способ получения 2-фторсульфонилтетрафторэтилтрифторвинилового эфира

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005073182A1 (fr) * 2004-02-02 2005-08-11 Daikin Industries, Ltd. Procédé de production de fluorure de sulfonyle insaturé contenant du fluor
EP2651881B1 (fr) * 2010-12-17 2018-06-06 3M Innovative Properties Company Préparation d'oligomères et de co-oligomères d'acides sulfiniques hautement fluorés et de sels de ceux-ci
CN110759805B (zh) * 2018-07-26 2021-12-14 中国科学院上海有机化学研究所 氟烷基碘代物的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57128703A (en) * 1981-02-02 1982-08-10 Tokuyama Soda Co Ltd Treating method of fluorine-containing compound
JPS6130552A (ja) * 1984-07-24 1986-02-12 Asahi Glass Co Ltd 官能基を有するパ−フルオロビニルエ−テルの製造方法
WO1999032439A1 (fr) * 1997-12-22 1999-07-01 Minnesota Mining And Manufacturing Company Procede de preparation de sulfinates fluores

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57128703A (en) * 1981-02-02 1982-08-10 Tokuyama Soda Co Ltd Treating method of fluorine-containing compound
JPS6130552A (ja) * 1984-07-24 1986-02-12 Asahi Glass Co Ltd 官能基を有するパ−フルオロビニルエ−テルの製造方法
WO1999032439A1 (fr) * 1997-12-22 1999-07-01 Minnesota Mining And Manufacturing Company Procede de preparation de sulfinates fluores

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2475477C1 (ru) * 2011-12-09 2013-02-20 Закрытое акционерное общество научно-производственное Объединение "ПиМ-Инвест" (ЗАО НПО "Пим-Инвест") Новый способ получения 2-фторсульфонилтетрафторэтилтрифторвинилового эфира

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AU2003242416A1 (en) 2003-12-31
JP2004018427A (ja) 2004-01-22
JP4189632B2 (ja) 2008-12-03

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