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Citation link: http://nbn-resolving.de/urn:nbn:de:gbv:46-diss000105102
00010510.pdf
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Auf dem Wege zu neuen lipophilen, delokalisierten Onium-Fluoriden, -Trimethyldifluorsilikaten und -Perfluoralkoholaten:Synthesen, Eigenschaften, Anwendungen


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Other Titles: On the Way to New Lipophilic Delokalized Onium-fluorides- Trimethyldifluorosilicates and Perfluoroalkoholates: Synthesis, Properties and Application
Authors: Kalinovich, Nataliya 
Supervisor: Röschenthaler, Gerd-Volker
1. Expert: Breunig, Hans, Joahim 
2. Expert: Wöhrle, Dieter
Abstract: 
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.
Keywords: Delocalized Cation, Lipophilic Cation, Halex Process, Naked Fluoride Ion, DFI, Tetramethylammonium Fluoride, MMP, Perfluoroalkoholate, Perfluoralkylester
Issue Date: 31-May-2006
Type: Dissertation
URN: urn:nbn:de:gbv:46-diss000105102
Institution: Universität Bremen 
Faculty: FB2 Biologie/Chemie 
Appears in Collections:Dissertationen

  

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