NONAFLUORO-1-BUTANESULFONYL CHLORIDE

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a toluene (100 ml) solution of (2-(hydroxymethyl)-1,3-dioxan-2-yl)methyl benzoate (4.76 g, 18.8 mmol), 1,8-diazabicyclo[5.4.0]unedec-7-ene (8.43 ml, 56.4 mmol) was added, cooled on ice and nonafluoro-1-butanesulfonyl chloride (5.06 ml, 28.2 mmol) was added. The mixture was stirred under ice-cool for 15 minutes, and at 40° C. for 20 hours, and further stirred at room temperature for 8 days. The reaction mixture was extracted by adding water and ethyl acetate. The organic layer was washed with a saturated saline solution, dried over magnesium sulfate, and filtrated through silica gel, and then, the filtrate was concentrated. The residue was subjected twice to silica gel column chromatography (elution solvent: n-heptane/ethyl acetate=4/1) to obtain the title compound (2.22 g, yield: 46.4%). was added cool for 15 minutes further stirred at room temperature for 8 days The reaction mixture was extracted by adding water and ethyl acetate The organic layer was washed with a saturated saline solution dried over magnesium sulfate filtrated through silica gel the filtrate was concentrated The residue was subjected twice to silica gel column chromatography (elution solvent: n-heptane/ethyl acetate=4/1)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a toluene (100 ml) solution of (2-(hydroxymethyl)-1,3-dioxan-2-yl)methyl benzoate (4.76 g, 18.8 mmol), 1,8-diazabicyclo[5.4.0]unedec-7-ene (8.43 ml, 56.4 mmol) was added, cooled on ice and nonafluoro-1-butanesulfonyl chloride (5.06 ml, 28.2 mmol) was added. The mixture was stirred under ice-cool for 15 minutes, and at 40° C. for 20 hours, and further stirred at room temperature for 8 days. The reaction mixture was extracted by adding water and ethyl acetate. The organic layer was washed with a saturated saline solution, dried over magnesium sulfate, and filtrated through silica gel, and then, the filtrate was concentrated. The residue was subjected twice to silica gel column chromatography (elution solvent: n-heptane/ethyl acetate=4/1) to obtain the title compound (2.22 g, yield: 46.4%). was added cool for 15 minutes further stirred at room temperature for 8 days The reaction mixture was extracted by adding water and ethyl acetate The organic layer was washed with a saturated saline solution dried over magnesium sulfate filtrated through silica gel the filtrate was concentrated The residue was subjected twice to silica gel column chromatography (elution solvent: n-heptane/ethyl acetate=4/1)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a toluene (100 ml) solution of (2-(hydroxymethyl)-1,3-dioxan-2-yl)methyl benzoate (4.76 g, 18.8 mmol), 1,8-diazabicyclo[5.4.0]unedec-7-ene (8.43 ml, 56.4 mmol) was added, cooled on ice and nonafluoro-1-butanesulfonyl chloride (5.06 ml, 28.2 mmol) was added. The mixture was stirred under ice-cool for 15 minutes, and at 40° C. for 20 hours, and further stirred at room temperature for 8 days. The reaction mixture was extracted by adding water and ethyl acetate. The organic layer was washed with a saturated saline solution, dried over magnesium sulfate, and filtrated through silica gel, and then, the filtrate was concentrated. The residue was subjected twice to silica gel column chromatography (elution solvent: n-heptane/ethyl acetate=4/1) to obtain the title compound (2.22 g, yield: 46.4%). was added cool for 15 minutes further stirred at room temperature for 8 days The reaction mixture was extracted by adding water and ethyl acetate The organic layer was washed with a saturated saline solution dried over magnesium sulfate filtrated through silica gel the filtrate was concentrated The residue was subjected twice to silica gel column chromatography (elution solvent: n-heptane/ethyl acetate=4/1)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: where R1 and R2 are individually chosen from F, CF3, C2F5, C4F9, an aromatic group, or a fluorinated aromatic group. A non-limiting example of the lithium fluorosulfonimides includes lithium bis(fluorosulfonyl)imide (LiN(FSO2)2). Some non-limiting examples of the lithium fluoroalkylsulfonimide salt include lithium bis(trifluoromethylsulfonyl)imide (LiN(CF3SO2)2) and lithium bis(pentafluoroethylsulfonyl)imide (LiN(C2F5SO2)2), both of which are commercially available as HQ-115 and FC-130, respectively, from 3M in St. Paul, Minn. The lithium fluoroalkylsulfonimide salt may also be chosen from lithium [(trifluoromethylsulfonyl)(nonafluorobutylsulfonyl)]imide (CF3SO2N(Li)SO2C4F9), which may be synthesized according to, e.g., the scheme depicted in FIG. 7. This synthesis includes two reactants which were prepared in parallel, namely perfluorobutylsulfonyl fluoride (C4F9SO2F) and lithium N-trimethylsilyl-trifluoromethanesulfonamide salt (CF3SO2N(Li)Si(CH3)3). First, iodoperfluorobutane (C4F9I) was dissolved into a 1:1 (vol/vol) mixture of acetonitrile (CH3CN or “ACN”) and deionized water, and then this mixture was slowly added into an aqueous solution of Na2S2O4 and NaHCO3 at a temperature of about 10° C. The mixture was added such that the molar ratio of C4F9I to Na2S2O4 to NaHCO3 was about 1:3.2:5.5. The reaction was completed after stirring at room temperature for about two days, with the formation of a sodium sulfinate salt (C4F9SO2Na). Deionized water was poured in another flask, cooled down to 0° C. using an ice-salt mixture, and chlorine gas was bubbled through the solution until saturation was reached. The reaction mixture was added slowly to the flask containing the chlorine-saturated water while chlorine gas was still bubbled vigorously throughout the addition. A white precipitate was formed. This mixture was filtered and the white solid was dried in the air at room temperature for one hour. The solid was further purified by sublimation at 60° C. under dynamic vacuum, leaving a white solid perfluorobutylsulfonyl chloride (C4F9SO2Cl). The next step was to stir this chloride with an excess KF in dry acetonitrile at room temperature for 4 days, then the temperature was increased to 90° C. for another 2 days, at which time 19F NMR showed the reaction to be complete. The reaction mixture was filtered through a celite layer, and the product was isolated from filtrate by the addition of excess deionized water. The product, perfluorobutylsulfonyl fluoride (C4F9SO2F), was dried over P2O5 and then distilled under dynamic vacuum at room temperature. may be synthesized was bubbled through the solution until saturation The reaction mixture was added slowly to the flask containing the chlorine-saturated water while chlorine gas was still bubbled vigorously throughout the addition A white precipitate was formed This mixture was filtered the white solid was dried in the air at room temperature for one hour The solid was further purified by sublimation at 60° C. under dynamic vacuum

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: where R1 and R2 are individually chosen from F, CF3, C2F5, C4F9, an aromatic group, or a fluorinated aromatic group. A non-limiting example of the lithium fluorosulfonimides includes lithium bis(fluorosulfonyl)imide (LiN(FSO2)2). Some non-limiting examples of the lithium fluoroalkylsulfonimide salt include lithium bis(trifluoromethylsulfonyl)imide (LiN(CF3SO2)2) and lithium bis(pentafluoroethylsulfonyl)imide (LiN(C2F5SO2)2), both of which are commercially available as HQ-115 and FC-130, respectively, from 3M in St. Paul, Minn. The lithium fluoroalkylsulfonimide salt may also be chosen from lithium [(trifluoromethylsulfonyl)(nonafluorobutylsulfonyl)]imide (CF3SO2N(Li)SO2C4F9), which may be synthesized according to, e.g., the scheme depicted in FIG. 7. This synthesis includes two reactants which were prepared in parallel, namely perfluorobutylsulfonyl fluoride (C4F9SO2F) and lithium N-trimethylsilyl-trifluoromethanesulfonamide salt (CF3SO2N(Li)Si(CH3)3). First, iodoperfluorobutane (C4F9I) was dissolved into a 1:1 (vol/vol) mixture of acetonitrile (CH3CN or “ACN”) and deionized water, and then this mixture was slowly added into an aqueous solution of Na2S2O4 and NaHCO3 at a temperature of about 10° C. The mixture was added such that the molar ratio of C4F9I to Na2S2O4 to NaHCO3 was about 1:3.2:5.5. The reaction was completed after stirring at room temperature for about two days, with the formation of a sodium sulfinate salt (C4F9SO2Na). Deionized water was poured in another flask, cooled down to 0° C. using an ice-salt mixture, and chlorine gas was bubbled through the solution until saturation was reached. The reaction mixture was added slowly to the flask containing the chlorine-saturated water while chlorine gas was still bubbled vigorously throughout the addition. A white precipitate was formed. This mixture was filtered and the white solid was dried in the air at room temperature for one hour. The solid was further purified by sublimation at 60° C. under dynamic vacuum, leaving a white solid perfluorobutylsulfonyl chloride (C4F9SO2Cl). The next step was to stir this chloride with an excess KF in dry acetonitrile at room temperature for 4 days, then the temperature was increased to 90° C. for another 2 days, at which time 19F NMR showed the reaction to be complete. The reaction mixture was filtered through a celite layer, and the product was isolated from filtrate by the addition of excess deionized water. The product, perfluorobutylsulfonyl fluoride (C4F9SO2F), was dried over P2O5 and then distilled under dynamic vacuum at room temperature. may be synthesized was bubbled through the solution until saturation The reaction mixture was added slowly to the flask containing the chlorine-saturated water while chlorine gas was still bubbled vigorously throughout the addition A white precipitate was formed This mixture was filtered the white solid was dried in the air at room temperature for one hour The solid was further purified by sublimation at 60° C. under dynamic vacuum

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: where R1 and R2 are individually chosen from F, CF3, C2F5, C4F9, an aromatic group, or a fluorinated aromatic group. A non-limiting example of the lithium fluorosulfonimides includes lithium bis(fluorosulfonyl)imide (LiN(FSO2)2). Some non-limiting examples of the lithium fluoroalkylsulfonimide salt include lithium bis(trifluoromethylsulfonyl)imide (LiN(CF3SO2)2) and lithium bis(pentafluoroethylsulfonyl)imide (LiN(C2F5SO2)2), both of which are commercially available as HQ-115 and FC-130, respectively, from 3M in St. Paul, Minn. The lithium fluoroalkylsulfonimide salt may also be chosen from lithium [(trifluoromethylsulfonyl)(nonafluorobutylsulfonyl)]imide (CF3SO2N(Li)SO2C4F9), which may be synthesized according to, e.g., the scheme depicted in FIG. 7. This synthesis includes two reactants which were prepared in parallel, namely perfluorobutylsulfonyl fluoride (C4F9SO2F) and lithium N-trimethylsilyl-trifluoromethanesulfonamide salt (CF3SO2N(Li)Si(CH3)3). First, iodoperfluorobutane (C4F9I) was dissolved into a 1:1 (vol/vol) mixture of acetonitrile (CH3CN or “ACN”) and deionized water, and then this mixture was slowly added into an aqueous solution of Na2S2O4 and NaHCO3 at a temperature of about 10° C. The mixture was added such that the molar ratio of C4F9I to Na2S2O4 to NaHCO3 was about 1:3.2:5.5. The reaction was completed after stirring at room temperature for about two days, with the formation of a sodium sulfinate salt (C4F9SO2Na). Deionized water was poured in another flask, cooled down to 0° C. using an ice-salt mixture, and chlorine gas was bubbled through the solution until saturation was reached. The reaction mixture was added slowly to the flask containing the chlorine-saturated water while chlorine gas was still bubbled vigorously throughout the addition. A white precipitate was formed. This mixture was filtered and the white solid was dried in the air at room temperature for one hour. The solid was further purified by sublimation at 60° C. under dynamic vacuum, leaving a white solid perfluorobutylsulfonyl chloride (C4F9SO2Cl). The next step was to stir this chloride with an excess KF in dry acetonitrile at room temperature for 4 days, then the temperature was increased to 90° C. for another 2 days, at which time 19F NMR showed the reaction to be complete. The reaction mixture was filtered through a celite layer, and the product was isolated from filtrate by the addition of excess deionized water. The product, perfluorobutylsulfonyl fluoride (C4F9SO2F), was dried over P2O5 and then distilled under dynamic vacuum at room temperature. may be synthesized was bubbled through the solution until saturation The reaction mixture was added slowly to the flask containing the chlorine-saturated water while chlorine gas was still bubbled vigorously throughout the addition A white precipitate was formed This mixture was filtered the white solid was dried in the air at room temperature for one hour The solid was further purified by sublimation at 60° C. under dynamic vacuum

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a toluene (100 ml) solution of (2-(hydroxymethyl)-1,3-dioxan-2-yl)methyl benzoate (4.76 g, 18.8 mmol), 1,8-diazabicyclo[5.4.0]unedec-7-ene (8.43 ml, 56.4 mmol) was added, cooled on ice and nonafluoro-1-butanesulfonyl chloride (5.06 ml, 28.2 mmol) was added. The mixture was stirred under ice-cool for 15 minutes, and at 40° C. for 20 hours, and further stirred at room temperature for 8 days. The reaction mixture was extracted by adding water and ethyl acetate. The organic layer was washed with a saturated saline solution, dried over magnesium sulfate, and filtrated through silica gel, and then, the filtrate was concentrated. The residue was subjected twice to silica gel column chromatography (elution solvent: n-heptane/ethyl acetate=4/1) to obtain the title compound (2.22 g, yield: 46.4%). was added cool for 15 minutes further stirred at room temperature for 8 days The reaction mixture was extracted by adding water and ethyl acetate The organic layer was washed with a saturated saline solution dried over magnesium sulfate filtrated through silica gel the filtrate was concentrated The residue was subjected twice to silica gel column chromatography (elution solvent: n-heptane/ethyl acetate=4/1)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 9.5 g (43.0 mmol) of methyl 2,4-dichloro-3-hydroxybenzoate in 240 ml of acetonitrile were admixed with 8.6 g (62.2 mmol) of potassium carbonate and then with 9.5 ml (52.8 mmol) of nonafluoro-n-butanesulfonyl chloride. The reaction mixture was stirred at room temperature (RT) for 16 h. For workup, the contents were poured onto ice-water and the mixture was extracted with ethyl acetate. The organic phase was dried and the filtrate was freed of the solvent on a rotary evaporator. The residue was purified by chromatography, which gave 3.5 g of clean product. For workup, the contents were poured onto ice-water the mixture was extracted with ethyl acetate The organic phase was dried the filtrate was freed of the solvent on a rotary evaporator The residue was purified by chromatography, which

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The process according to claim 12, wherein the perfluorobutanesulphonate alkaline salts are solubilised in methanol and treated with gaseous hydrochloric acid to give the corresponding perfluorobutanesulphonic acid which, after treatment with PCl5 is transformed into the corresponding perfluorobutanesulphonyl chloride, the latter reacts with 2,2,2-trifluoroethanol and triethylamine in dichloromethane to give 2,2,2-trifluoroethanol perfluorobutanesulphonate, which is recycled in the reaction at phase a).