Elemental fluorination : the synthesis of fluorinated polymers, organometallics and organic molecules
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Liquid-Phase elemental fluorination has been utilized for the synthesis of a wide range of functionalized perfluoropolyethers, functionalized perfluoropentafluoro sulfanyl (SF5) and tetrasulfanyl (SF4) compounds, perfluoronitro compounds, perfluorodibutylmercury and a functionalized perfluorocrown ether. Additionally, a solid-phase fluorination reactor was constructed to afford the fluorination of nitrogencontaining carbon megatubes. An entire series of ethylene glycol based functionalized perfluoropolyether compounds have been synthesized. The masses of the polymeric material range from an average of 1000 up to 1500 amu. The functional groups of the perfluorinated vii difunctional polyethers are di-carboxylic acid, di-carboxylate, di-amide, di-chloride, di-hydride, di-alcohol, di-ethyl thioester, di-cyanoethyl ether, di-hydroxyethyl ester and di-acid chloride all with symetrical end groups. I was was successful in synthesizing an unsymetrical perfluoropolypropylene derivative with functional groups combining di-ol(ketones) and carboxylic acids. These compounds were characterized through mass spectroscopy, 1 H NMR and 19F NMR. Three perfluoropentafluoro sulfanyl methyl esters of increasing length have been synthesized by direct fluorination of the disulfide hydrocarbon analogues. The esters are: SF5CF2COOCH3, SF5(CF2)2COOCH3 and SF5(CF2)3COOCH3. One interesting finding is that SF5(CF2)2COOCH3 displayed an affinity to carry molecular oxygen in both the mass spectrophotometer and the 19F NMR, while the shorter and longer versions did not. Additionally, SF5CF2CF2OCF2CF2SF5 and ClCF2CF2SF4CF2CF2Cl have also been prepared. All compounds were characterized by mass and 19F NMR. The first functionalized perfluorocrown ether, perfluoro-2-chloro-16-crown-5 was prepared, isolated and characterized by mass and fluorine NMR. Two nitroalkanes (nitrobutane and nitrohexane) were also fluorinated and their results reported in this dissertation. Additionally, the liquid-phase elemental fluorination of dibutylmercury was investigated for the first time and reported. Finally, solid-phase fluorination was conducted on the newly discovered nitrogen-containing carbon nanotube material called megatubes. The conditions required to achieve fluorine viii saturation of these tubes is documented and compared to the conditions required for conventional nanotubes. The fluorinated tubes were characterized through gravometric analysis, energy dispersive X-ray analysis and X-ray photoelectron spectroscopy.