Auf dem Wege zu neuen lipophilen, delokalisierten Onium-Fluoriden, -Trimethyldifluorsilikaten und -Perfluoralkoholaten:Synthesen, Eigenschaften, Anwendungen

In this study a range of new sources of fluoride ions with lipophilic and delocalized cations having symmetrical and nonsymetrical C-N-P , C-N-S and C-N-C backbones completely substituted by dialkylamino groups were designed to improve the 'Halex' fluorination process.Reactions of bis(dialkylamino)difluoromethane with N-trimethylsilyltetramethylguanidine and tris(diethylamino)phosphazene led to (Alk2N)2CNC(NMe2)2 Me3SiF2- and (Alk2N)2CNP(NEt2)2 HF2-, respectively. Sulfur tetrachloride reacted with tetramethylguanidine to give tris(tetramethylguanido) chloride. Depending on the reaction conditions sulfur tetrafluoride and (diethylamino)sulphur trifluoride and tetramethylguanidine or N-trimethylsilyltetramethylguanidine afforded the salts with C-N-S backbone with F-, HF2-, Me3SiF2- or Me2SiF3- counter ions. The X-Ray structures of some new salts are discussed.Convenient and scalable methods of perfluoralkoholate [OCF2RF]- preparation via reaction of mono- and bisperfluoroalkylacid fluorides as well as fluorosulfonic acids with CNC-silicates, DFI, (Me2N)2CF2 and TMAF were developed.