WO2024106331A1 - Procédé de production de chlorure de sulfonyle contenant du fluor et procédé de production de fluorure de sulfonyle contenant du fluor - Google Patents

Procédé de production de chlorure de sulfonyle contenant du fluor et procédé de production de fluorure de sulfonyle contenant du fluor Download PDF

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Publication number
WO2024106331A1
WO2024106331A1 PCT/JP2023/040549 JP2023040549W WO2024106331A1 WO 2024106331 A1 WO2024106331 A1 WO 2024106331A1 JP 2023040549 W JP2023040549 W JP 2023040549W WO 2024106331 A1 WO2024106331 A1 WO 2024106331A1
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fluorine
containing sulfonyl
producing
sulfonyl chloride
fluoride
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PCT/JP2023/040549
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English (en)
Japanese (ja)
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浩一 村田
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Ａｇｃ株式会社
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • C07C329/12—Dithiocarbonic acids; Derivatives thereof
    • C07C329/14—Esters of dithiocarbonic acids
    • C07C329/16—Esters of dithiocarbonic acids having sulfur atoms of dithiocarbonic groups bound to acyclic carbon atoms

Definitions

  • the present invention relates to a method for producing fluorine-containing sulfonyl chlorides and fluorine-containing sulfonyl fluorides.
  • Fluorine-containing sulfonyl halides such as fluorine-containing sulfonyl chlorides and fluorine-containing sulfonyl fluorides, are useful compounds as synthetic raw materials for a variety of applications, such as fluorinated surface treatment agents, medicines, and agricultural chemicals. They are also used as monomer raw materials for cation exchange membranes and polymer electrolyte membranes for solid polymer fuel cells.
  • Fluorine-containing sulfonyl halides are generally produced by introducing a sulfonyl group into perfluorocarbon etc.
  • a method is known in which tetrafluoroethylene is reacted with sulfur trioxide or fuming sulfuric acid, then with hexafluoropropylene oxide, and finally decarbonated to produce a fluorosulfonyl group-containing perfluorovinyl ether.
  • Patent Document 2 Also known are methods for perfluorinating alkanesulfonyl halides as raw materials by electrolytic fluorination (e.g., Patent Document 2) or by reaction with a fluorine-containing gas (e.g., Patent Document 3).
  • JP 2002-528433 A Japanese Patent Application Laid-Open No. 57-164991 WO 02/44138
  • the sulfur trioxide used in the above-mentioned production method is an air pollutant, is highly hygroscopic, and generates heat and smoke when in contact with moisture, and fuming sulfuric acid, which contains sulfur trioxide, is a deleterious substance, and therefore, handling of either of these substances on an industrial scale is discouraged.
  • the production method using a perfluoroalkyl iodide and sodium dithionite has the problem that it is not easy to produce the desired perfluoroalkyl iodide.
  • alkanesulfonyl halides require large-scale equipment, is a complicated process, and has the problem of producing many by-products.
  • the reaction between alkanesulfonyl halides and fluorine-containing gas also requires highly corrosion-resistant reaction equipment, and has other problems, such as the C-S bond being easily broken, resulting in a low yield.
  • the present invention has been made in consideration of these circumstances, and aims to provide a method for producing fluorine-containing sulfonyl chloride and a method for producing fluorine-containing sulfonyl fluoride that are highly safe and versatile and can produce fluorine-containing sulfonyl chloride and fluorine-containing sulfonyl fluoride.
  • the present invention is based on the discovery that fluorine-containing sulfonyl chlorides and fluorine-containing sulfonyl fluorides can be synthesized in a simple and safe manner by using a specific fluorine-containing dithiocarbonate ester as a raw material.
  • [4] The method for producing a fluorine-containing sulfonyl chloride according to any one of [1] to [3], wherein Rf is a fluoroalkyl group having 1 to 10 carbon atoms.
  • [5] The method for producing a fluorine-containing sulfonyl chloride according to [3] or [4], wherein M is lithium, sodium or potassium.
  • [6] The method for producing a fluorine-containing sulfonyl chloride according to any one of [3] to [5], wherein the radical reaction is carried out using irradiation light including light with a wavelength of 210 to 600 nm.
  • [7] The method for producing a fluorine-containing sulfonyl chloride according to any one of [3] to [5], wherein the radical reaction is carried out using an organic peroxide as a radical initiator in an amount of 0.01 to 1 mol per 1 mol of Rf-CO-SC( ⁇ S)OR.
  • the manufacturing method of the present invention makes it possible to manufacture fluorine-containing sulfonyl chlorides and fluorine-containing sulfonyl fluorides in a highly safe and versatile manner.
  • the method for producing a fluorine-containing sulfonyl chloride of the present invention is a method for producing a fluorine-containing sulfonyl chloride represented by the general formula (2): Rf-SO 2 Cl (wherein Rf is the same as above) by reacting a dithiocarbonate represented by the general formula (1): Rf-SC( ⁇ S)OR (wherein Rf is a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms which may contain an ether bond and which may contain either or both of a chlorine atom and a hydrogen atom; and R is a linear or branched alkyl group having 1 to 20 carbon atoms which may contain an aromatic ring ) with chlorine in the presence of water.
  • fluorine-containing sulfonyl chloride Rf-SO 2 Cl
  • the reactants are easily available, highly versatile compounds, and the method is relatively safe, and Rf-SO 2 Cl can be produced easily.
  • Rf is a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms, which may contain an ether bond, and may contain either or both of a chlorine atom and a hydrogen atom. From the viewpoints of availability and ease of production, the number of carbon atoms in the perfluoroalkyl group is 1 to 20, preferably 1 to 15, and more preferably 1 to 10.
  • perfluoroalkyl group examples include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, an undecafluoropentyl group, and a tridecafluorohexyl group, and the like, and the perfluoroalkyl group may be linear or branched.
  • the carbon chain of a compound is linear or branched.
  • the perfluoroalkyl group in the present invention may contain an ether bond, and may have some of the fluorine atoms substituted with either or both of chlorine atoms and hydrogen atoms.
  • Examples include a 1-heptafluoropropoxytetrafluoroethyl group, a 2-(1,2-dichlorotrifluoroethoxy)tetrafluoroethyl group, a 3-(1,2-dichlorotrifluoroethoxy)hexafluoropropyl group, a 1,1,2,2-tetrafluoroethyl group, and a 4H-perfluorobutyl group.
  • R is a linear or branched alkyl group having 1 to 20 carbon atoms, which may contain an aromatic ring. From the viewpoints of availability and ease of production, the number of carbon atoms in the alkyl group is 1 to 20, preferably 1 to 8, and more preferably 1 to 5. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and the alkyl group may be linear or branched.
  • the alkyl group in R may contain an aromatic ring, for example, an aryl group such as a phenyl group, a tolyl group, or a naphthyl group.
  • the number of carbon atoms in the alkyl group in R does not include the number of carbon atoms in the aromatic ring.
  • Rf in Rf-SO 2 Cl synthesized from Rf-SC( ⁇ S)OR is the same as Rf of Rf-SC( ⁇ S)OR.
  • Rf-SO 2 Cl from Rf-SC( ⁇ S)OR is carried out by reacting it with chlorine in the presence of water.
  • a fluorine-containing sulfonyl chloride can be obtained by a simple method using water and chlorine as reactants to oxidize the divalent sulfur in Rf-SC( ⁇ S)OR to hexavalent sulfur constituting a sulfonyl group.
  • this synthesis is preferably carried out, for example, by dissolving Rf-SC( ⁇ S)OR in a solvent and mixing it with water to prepare a reaction solution, and then introducing chlorine into the solution.
  • the solvent include acetic acid and propionic acid.
  • the amount of water is preferably 0.1 to 10 times, more preferably 0.2 to 8 times, and even more preferably 0.5 to 5 times, in terms of mass ratio, relative to Rf-SC( ⁇ S)OR.
  • the reaction temperature is preferably from room temperature (25° C.) to 80° C., more preferably from 30 to 70° C., and further preferably from 40 to 60° C. From the viewpoint of improving the yield of Rf-SO 2 Cl, it is preferable to carry out the reaction at 40 to 50° C. for 5 to 12 hours, for example.
  • Rf-SC( ⁇ S)OR which is the raw material in the method for producing a fluorinated sulfonyl chloride of the present invention, is not particularly limited, and it can be obtained by a known method.
  • Rf-SC( ⁇ S)OR is preferably a dithiocarbonate obtained by radical reaction of a dithiocarbonate compound represented by general formula (13): Rf-CO-SC( ⁇ S)OR (wherein Rf and R are the same as above), which is produced by reacting an acid halide represented by general formula (11): Rf-COX (wherein Rf is the same as above, and X is a halogen atom) with a dithiocarbonate represented by general formula (12): MSC( ⁇ S)OR (wherein R is the same as above, and M is an alkali metal).
  • Rf-COX a commercially available product corresponding to the desired Rf can be used.
  • M is an alkali metal, and from the viewpoint of versatility, it is preferably lithium, sodium, or potassium.
  • this reaction is preferably carried out in a solvent, for example, hydrocarbons such as hexane, cyclohexane, benzene, toluene, etc., halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, etc.
  • MX precipitates as a solid and can be separated by filtration or the like, preferably by pressure filtration.
  • Rf-CO-SC( ⁇ S)OR is decarbonylated by a radical reaction using light irradiation or a radical initiator to obtain Rf-SC( ⁇ S)OR.
  • light irradiation it is preferable to use light having a wavelength of, for example, 210 to 600 nm, preferably 350 to 500 nm.
  • the solvent in order to prevent the light energy from being absorbed, it is preferable that the solvent has a transmittance of 70% or more, preferably 90% or more, at the wavelength used.
  • the radical initiator may, for example, be an organic peroxide such as dilauroyl peroxide.
  • the amount used is preferably 0.01 to 1 mol, more preferably 0.02 to 0.5 mol, and even more preferably 0.05 to 0.2 mol, per 1 mol of Rf-CO-SC( ⁇ S)OR, from the viewpoint of appropriate reactivity.
  • the radical initiator may be added all at once, or may be added in several portions over a period of time depending on the progress of the reaction.
  • the reaction conditions vary depending on the specific reactants and the type of initiator, but typically the reaction pressure is atmospheric pressure in an inert gas atmosphere, the reaction temperature is preferably 0 to 100° C., and the reaction time is preferably 0.5 to 48 hours.
  • the produced Rf-SC( ⁇ S)OR can be purified and isolated, for example, by distillation. From the viewpoint of production efficiency, it is preferable to use the Rf-SC( ⁇ S)OR thus obtained as a synthetic raw material in the process for producing a fluorinated sulfonyl chloride of the present invention.
  • the method for producing a fluorine-containing sulfonyl fluoride of the present invention is a method for producing a fluorine-containing sulfonyl fluoride represented by general formula (14): Rf-SO 2 F (wherein Rf is the same as above) by reacting the fluorine-containing sulfonyl chloride obtained by the above-mentioned method for producing a fluorine-containing sulfonyl chloride of the present invention with a fluoride.
  • Rf-SO 2 F is the same as Rf of Rf-SO 2 Cl. According to such a production method, Rf-SO 2 F can be obtained from relatively easily available raw materials and through safer operating steps.
  • an alkali metal fluoride preferably sodium fluoride or potassium fluoride
  • this reaction is preferably carried out in a solvent, more preferably a polar organic solvent, such as N-methyl-2-pyrrolidone, sulfolane, dimethylsulfoxide, dimethylformamide, dimethylacetamide, or 1,3-dimethylimidazolidinone.
  • the reaction conditions vary depending on the specific reactants, but usually, the reaction pressure is atmospheric pressure, the reaction temperature is -20 to 100°C, and the reaction time is preferably 0.5 to 48 hours.
  • Rf-SO 2 F When Rf is, for example, 3-(1,2-dichlorotrifluoroethoxy)hexafluoropropyl group, the thus obtained Rf-SO 2 F can be made to give a fluorosulfonyl group-containing perfluorovinyl ether by eliminating chlorine.
  • Fluorosulfonyl group-containing perfluorovinyl ether is useful as a monomer component of fluorine-containing polymers, and is particularly useful as a monomer raw material for cation exchange membranes and polymer electrolyte membranes for solid polymer fuel cells.
  • the production method of the present invention has the advantage that such useful monomer raw materials can be efficiently obtained by a relatively safe method.
  • the present invention will be specifically described below based on examples, but the present invention is not limited to the following examples (synthesis examples).
  • synthesis examples reactions involving compounds highly reactive with oxygen or water were carried out under a nitrogen stream.
  • the yield refers to an isolated yield unless otherwise specified.
  • the yield calculated from the peak area ratio of the NMR spectrum is referred to as the NMR yield.
  • the NMR measurements were performed by 1 H-NMR using tetramethylsilane as an internal standard and 19 F-NMR using trichlorofluoromethane as an internal standard.
  • the IR (infrared absorption) spectrum was measured by a Fourier transform infrared spectrophotometer.
  • the crude product was concentrated and purified by silica gel chromatography (developing solvent: hexane) and distillation (boiling point: 58-60° C. at 25 mmHg) to isolate 4.14 g (14.3 mmol) of C 3 F 7 SC( ⁇ S)OC 2 H 5 (yield 57%).
  • the chlorine gas in the reaction system was purged and distilled to obtain a fraction of 1.39 g.
  • the fraction contained 0.290 g (1.07 mmol) of C 3 F 7 SO 2 Cl, and the distillation residue contained 0.106 g (0.39 mmol) of C 3 F 7 SO 2 Cl (total 1.46 mmol, NMR yield 29%).
  • the pressure was reduced to 300 mmHg and the mixture was heated to 80-90° C., yielding 0.54 g of a fraction.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production de chlorure de sulfonyle contenant du fluor et un procédé de production de fluorure de sulfonyle contenant du fluor qui sont hautement sûrs et polyvalents et permettent d'obtenir du chlorure de sulfonyle contenant du fluor et du fluorure de sulfonyle contenant du fluor.　L'invention concerne un procédé de production de chlorure de sulfonyle contenant du fluor représenté par la formule générale (2) : Rf-SO2Cl (dans laquelle Rf est un groupe fluoroalkyle linéaire ou ramifié ayant de 1 à 20 atomes de carbone, qui peut contenir une liaison éther et un ou les deux atomes de chlore et d'hydrogène), comprenant la réaction d'un ester de dithiocarbonate représenté par la formule générale (1) : Rf-SC(=S)OR (dans laquelle Rf est tel que décrit ci-dessus ; et R est un groupe alkyle linéaire ou ramifié ayant de 1 à 20 atomes de carbone et qui peut contenir un cycle aromatique) avec du chlore en présence d'eau.
PCT/JP2023/040549 2022-11-15 2023-11-10 Procédé de production de chlorure de sulfonyle contenant du fluor et procédé de production de fluorure de sulfonyle contenant du fluor WO2024106331A1 (fr)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006137725A (ja) * 2004-11-15 2006-06-01 Daikin Ind Ltd 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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006137725A (ja) * 2004-11-15 2006-06-01 Daikin Ind Ltd 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

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
L.-Q. HU ET AL: "SYNTHESIS OF PERHALOALKANESLFONYL HALIDES AND THEIR SULFONIMIDE DERIVATIVES.", INORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY, EASTON , US, vol. 32, no. 23, 1 January 1993 (1993-01-01), Easton , US , pages 5007 - 5010, XP000925887, ISSN: 0020-1669, DOI: 10.1021/ic00075a011 *
MORGAN M, BAGCHI PRITHA; FAHRNI CHRISTOPH J.: "Designed To Dissolve: Suppression of Colloidal Aggregation of Cu(I)-Selective Fluorescent Probes in Aqueous Buffer and In-Gel Detection of a Metallochaperone", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, vol. 133, no. 40, 12 October 2011 (2011-10-12), pages 15906 - 15909, XP093171723, ISSN: 0002-7863, DOI: 10.1021/ja207004v *
SALOMON PIERRE, ZARD SAMIR Z.: "A Practical Source of Chlorodifluoromethyl Radicals. Convergent Routes to gem -Difluoroalkenes and -dienes and (2,2-Difluoroethyl)-indoles, -azaindoles, and -naphthols", ORGANIC LETTERS, AMERICAN CHEMICAL SOCIETY, US, vol. 16, no. 11, 6 June 2014 (2014-06-06), US , pages 2926 - 2929, XP093171721, ISSN: 1523-7060, DOI: 10.1021/ol501063a *

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