Patent EA-004498-B1 (EA)
Title: Method for the synthesis of perfluorosulphonamides, perfluorosulphonimides and their salts, and a sulphonation reagent
Inventor: PEVERE VIRGINIE
IPC: C07B61/00
Filed: 1998-05-15
Abstract: 1. A process for perfluorosulphonation characterised in that it consists in contacting a nucleophile whose nucleophilic atom is a nitrogen atom with a reagent comprising by successive or simultaneous addition: sulphonyl chloride; and and an organic base which simultaneously cannot be alkylated and is liposoluble, said base being selected from the group consisting of a hindered dialkylphosphine, trialkylphosphine, phosphonium hydroxide, hindered dialkylamine, trialkylamine or ammonium hydroxide, the organic part of said sulphonyl chloride is perfluorinated on the carbon carried by the sulphur and amount of base at least equal to stoichiometrically necessary to neutralize the hydrohalic acid given off, or taken in excess, equal to the maximum amount stoichiometrically necessary to neutralize the hydrohalic acid given off. 2. A process according to claim 1, wherein said nucleophile is in a neutral or anionic form and has, as associated acid, an acid for which the pKa is at most equal to approximately 7, preferably 6, most equal to 5. 3. A process according to claim 1 and 2, wherein said nitrogen of the nucleophile is connected to an electron-withdrawing group, preferably to a sulphonyl group, the nucleophile is selected preferably from sulphamides of sulphonic acids wherein the sulphur is bonded to an aryl, or sulphamides of sulphonic acids wherein the sulphur is bonded to an aliphatic radical, including alkyl radicals, preferably from sulphamides of sulphonic acids in which the sulphur is bonded to the aliphatic radical having a perfluorinated carbon adjoining the sulphur. 4. A process according to claims 1 to 3, wherein said nucleophile is a salt of a sulphonamide (sulphamide) and of an organic base which cannot be alkylated. 5. A process according to claims 1 to 4, wherein said nucleophile is a sulphonamide in the form of a liposoluble salt with an organic base which cannot be alkylated and is liposoluble. 6. A process according to claims 1 to 5, wherein said non-alkyled organic base is selected from the group consisting of a hindered dialkylphosphine, trialkylphosphine, phosphonium hydroxide, hindered dialkylamine, trialkylamine or ammonium hydroxide. 7. A process according to claims 1 to 6, wherein said non-alkyled organic base which cannot be alkylated and is liposoluble exhibits a high solubility in benzene defined as symbol "s" in the "Handbook of Chemistry and Physics", or defined as symbol "v" in the "Handbook of Chemistry and Physics". 8. A process according to claims 1 to 7, wherein said organic base which cannot be alkylated exhibits a high solubility in benzene defined as symbol "s" in the "Handbook of Chemistry and Physics", or defined as symbol "v" in the "Handbook of Chemistry and Physics". 9. A process according to claims 1 to 8, wherein the pKa of the acid associated with an acid whose pKa is greater than or equal to that of said sulphonamide. 10. A process according to claims 1 to 9wherein the pKA acid which cannot be alkylated and is liposoluble is associated with an acid whose pKa is greater than or equal to that of said sulphonamide. 11. A process according to claims 1 to 10, wherein said nucleophile is a salt of a sulphonamide and of an organic base which cannot be alkylated, said organic base which cannot be alkylated is identical to said organic base which cannot be alkylated and is liposoluble. 12. A process according to claims 1 to 11, wherein the contact is carried out in an organic solvent, preferably in poor polar, having a miscibility of at most 10% by mass with water, mainly at most 5%, preferably at most 2%. 13. A process according to claims 1 to 12, wherein the contact is carried out in an organic solvent which is selected so that said salt is soluble in said solvent to a concentration level of at least 0.05M, preferably of at least 0.2M. 14. A process according to claims 1 to 13, wherein the organic part of said sulphonyl chloride is alike to the organic part of said sulfonamide. 15. A process according to claims 1 to 14, wherein the organic parts of said sulphonyl chloride and of said sulphonamide are alike or different, and are of formula (Rf): -(CX2)p-GEA wherein: the X groups, which are alike or different, represent a fluorine or a radical of formula CnFn+1, with n an integer at most equal to 5,preferably to 2; p represents an integer at most equal to 2; and GEA represents an electron-withdrawing group, whose optional functional groups are inert under the reaction conditions, preferably a fluorine atom or a perfluorated radical of formula CnFn+1, wherein n is an integer at most equal to 8, preferably to 5, and the total carbon number of Rf is between 1 and 15, preferably being between 1 and 10. 16. A process according to claims 1 to 15, wherein said nucleophile compound, the nucleophile atom of which is nitrogen, is a salt of sulphonamide (sulfamide) and organic non alkylated base and said process further comprising, after optional purification and isolation steps, treating with lithium hydroxide or a basic lithium salt. 17. A reagent for carrying out the process according to claims 1 to 16, wherein comprises adding successively or simultaneously: heavy sulfonyl halide (i.e. whose atomic number is not less than that of chlorine), preferably sulphonyl chloride, and advantageously sulphonyl chloride; and an organic base both not capable of alkylation and lipid soluble selected from of a hindered dialkylphosphine, trialkylphosphine, phosphonium hydroxide, hindered dialkylamine, trialkylamine or ammonium hydroxide, and poor polar solvent, wherein the organic part of said sulphonyl halogenide is perfluorinated on the carbon carried by the sulphur atom. 18. The reagent according to claim 17, wherein said poor polar solvent, including a mixture of solvents, is selected from solvents having low solubility in water and not containing chlorinated aliphatic chain. 19. The reagent according to claim 17 and 18, wherein said poor polar solvent is selected from solvents, the polarity of which (Et expressed in kcal per mol) is at most equal to 40 (preferably two significant digits). 20. The reagent according to claim 17 to 19, wherein said poor polar solvent is selected from acid-containing organic compounds (in particular, ethers, esters and even ketones), hydrocarbons (including petroleum fractions), aromatic hydrocarbons halogenated in core. 21. The reagent according to claim 17 to 20, wherein said poor polar solvent is selected from substituted benzenes and hydrocarbons halogenated in core.