The purpose of this thesis was two fold: (i) The synthesis and characterization of SF5 containing dienes. (ii) The characterization of hydro/fluorocarbon compounds containing SF5/S02F groups via their 13C NMR spectra. A new SF5CH2CHBrCH2CF=CF2 was prepared and characterized as a precursor to new dielectric polymers. This new adduct was made from the reaction of pentafluorothio bromide with l,l,2-trifluoro-1,4-pentadiene. A SF5-diene was prepared from the reaction of pentafluorothio chloride with acetylene. This reaction involves a radical addition mechanism. The SF5 group is bonded to the carbon atom carrying the most hydrogens. SF5 - dienes are capable of undergoing different reactions, such as polymerization. Fluorocarbon sulfonyl fluorides (RS02F), which have been synthesized in our lab, were characterized by their 13C NMR spectra. The 13C NMR data of these sulfonyl fluorides show chemical shift values for the methyl and methylene groups next to a fluoroalkyl sulfonyl fluoride group in the 52.8-65.7 ppm range. The spectra showed that the inductive effect of electronegative substituents has a major influence on the 1Jc-F and 1Jc-H coupling. Infrared, 1H, 19F and 13C nuclear magnetic resonance and mass spectra are presented to support the assigned structure for the new compounds, SF5CH=CHCH=CHC1 and SF5CH2CHBrCH2CF=CF2.

Pentafluorosulfur (VI) bromide (SF5Br) adds to olefins of the form CX2=CX2, where X= H or F, with the pentafluorosulfur group usually adding to the carbon with more hydrogens attached to it. This series of compounds was used in an attempt to prepare the corresponding sulfonic acid hydrates of the general formula SF5CX2CX2SO3H·nH2O, in order to have these compounds tested as possible fuel cell electrolytes. The reaction scheme involved reflux of the SF5Br adduct with an equimolar amount of sodium sulfite in 50% ethanol for two days, followed by acidification of the recovered solid material using HCl or H2SO4.

Part I describes the preparation of a number of useful intermediates from the sultone F5SCHCF2OSO2 (1). These intermediates include the following: the ketene F5SC(SO2)=C=O (21), the unique sultone F4S=CCF2OSO2 (23), and various ionic intermediates of the form Y+ [F5SC(SO2F) COX]-. These intermediates play an important role in providing new pathways for preparing fluorosulfonic acid precursors. Fluorosulfonic acids are excellent candidates to improve the efficiency of environmentally safe fuel cells. It was possible to obtain new derivatives of 1 by various reactions of 21, 23 and the ionic intermediates, but it was not possible to introduce an alkyl substituent with either of the intermediates. Part II is concerned with the synthesis of SF5 containing epoxides as possible monomers. When polymerized, materials of high dielectric strength and high chemical resistance should be obtained. The reaction chemistry of one of the epoxides was investigated and it was found that all reactions studied were accompanied by the loss of the SF5 group. Thus, it was not possible to obtain any polymeric materials. Part III deals with the synthetic accessibility of SF$\sb5$ malonic esters and thence of SF$\sb5$ acrylic esters. These compounds should serve as building blocks in the synthesis of SF$\sb5$ containing pyrimidines. The CF3 analogue, 5-trifluoromethyl uracil, is used as an antiviral drug. In order to synthesize either SF5 malonic ester or 2-SF5 acrylic ester an SF5 group has to be introduced at a secondary carbon. A secondary SF$\sb5$ compound could be synthesized (F5SCH (COOC2H5) (CHBrOAc)) but could not be converted to the respective malonic ester F5SCH (COOC2H5) compound. Part IV describes the reactions and preparations of Parts I-III.