A Convenient Route to Tetraalkylammonium Perfluoroalkoxides from Hydrofluoroethers

Hydrofluoroethers are shown to alkylate tertiary amines readily under solvent‐free conditions, affording valuable tetraalkylammonium perfluoroalkoxides bearing α‐fluorines. The reaction of RFCF2OCH3 (RF=CF2CF3, CF2CF2CF3, and CF(CF3)2) with NR1R2R3 produces twenty new α‐perfluoroalkoxides, [(CH3)NR1R2R3][RFCF2O] under mild conditions. These α‐perfluoroalkoxides are easy to handle, thermally stable, and can be used for the perfluoroalkoxylation of benzyl bromides.