SULFONYLAMMONIUM IONS: APPLICATIONS IN MECHANISTIC AND SYNTHETIC ORGANOSULFUR CHEMISTRY

This thesis describes the results obtained from two projects in organosulfur chemistry; both of which involve the use of sulfonylammonium ions. The two projects undertaken involved sulfenes and 3-alkoxysulfonyl trialkylpropanaminium salts ("{3}betylates").;The second project involves the synthesis and reactions of {3}Betylates(3-(Alkoxysulfonyl)propanaminium salts). {3}Betylates are an example of a new type of substrate for aliphatic nucleophilic substitution which enhance the applicability of nucleophilic substitution reactions to problems in organic synthesis by providing a good nucleofuge and phase transfer reagent in one substrate. Unlike their lower homologs, the 2-(alkoxysulfonyl)-ethanimium salts ({2}betylates), the {3}betylates were found to be quite stable to elimination and thus allow clean nucleophilic substitution with a wider variety of nucleophiles. Although {3}betylates are somewhat less reactive than {2}betylates they appear to be able to undergo any reaction characteristics of a {2}betylates. The {3}betylates were synthesized by the reaction of a cyclic sulfonylammonium ion (2,2-dimethylisothiazolidinium 1,1-dioxide fluorosulfate) with alcohols and triethylamine.;The first project describes efforts undertaken to delineate more precisely the reaction mechanisms of sulfenes, a highly reactive species. The reaction mechanism of sulfene was studied by allowing multiexchange to occur with deuterated traps. Methanol-d was used as the trapping agent in benzene-acetonitrile and deuterium oxide as the trap in a buffered deuterium oxide-dimethoxyethane system. The investigations made use of methanesulfonyl chloride and a series of trialkyl(methylsulfonyl)ammonium fluorosulfate salts as starting materials. The multiexchange results were used to deduce aspects of the mechanism. The results obtained showed that nucleophilic catalysis was not a significant path for formation of sulfene from sulfonyl chlorides when triethylamine was used to promote sulfene formation cut that less hindered amines may react with methane sulfonyl chloride via nucleophilic catalysis to some extent.