Portland State University. Environmental Sciences and Resources Ph. D. Program
Gary L. Gard
Date of Award
Doctor of Philosophy (Ph.D.) in Environmental Sciences and Resources: Chemistry
Environmental Science and Management
3, xi, 172 leaves: ill. 28 cm.
Fluorine compounds, Sulfonic acids
Sulfonyl fluoride systems and their derivatives, RS02F, where R represents hydrocarbon/fluorocarbon moieties continue to be of considerable interest. The incorporation of the sulfonyl fluoride group (S02F) into molecular systems can lead to compounds that are useful as ion-exchange resins, surface active agents, fuel cell electrolytes, and strong sulfonic acids/salts.
Interest in preparing SF5 containing sulfonyl fluorides led to the synthesis of the ᵝ-sultone, SF5CHCF20S02, and its rearranged product. Hydrolysis of the sultone gave SF5CH2S02F which led to the sulfonic acid and salt, SF5CH2S03H•H20 and (SF5CH2S03)2Ca. Esters of the sultone were prepared by reaction of the sultone with fluorinated alcohols in the presence of NaF to give SF5CH(S02F)C(O)OR where R = CH2CF3 and CH(CF3)2.
Polymeric SF5/S02F containing esters were prepared by reaction of allyl esters, RCX(S02F)C(O)OCH2CH=CH2, in ultraviolet light where R = CF3 or SF5 and X= H or F. Fluorinated silver carboxylate salts have been useful in preparing fluoroesters from alkyl iodides. Therefore, a new silver salt, FS02CF2C(0)0Ag was prepared and characterized; its reaction with (CH3)3SiI, HOCH2CH2I and alkyl bromides and iodides are reported.
In addition, new SF5 containing fluoropolymers were synthesized via reaction of fluorinated olefins with SF5Br. Reactions of SF5 containing olefins with CF30Cl, C1F and Cl2 provide reagents that may be of potential use as precursors to sulfonyl fluoride containing systems.
All new compounds were characterized by their respective infrared, nmr and mass spectra.
Terjeson, Robin Joyce, "The Chemistry of Sulfonyl Fluorides: SF5 and/or SO2F Containing Compounds as Precursors to Sulfonic Acids" (1989). Dissertations and Theses. Paper 1241.