Date of Award


Degree Type


Degree Name

Doctor of Philosophy


This thesis describes the mechanisms of the reactions of some simple alkenesulfonyl chlorides and 2-substituted ethanesulfonyl chlorides with tertiary amine bases in aqueous and organic media.;Chapter 1 describes the reactions of ethenesulfonyl chloride and trans-1-propene-1-sulfonyl chloride with water in the presence and absence of substituted pyridines. The former reactions are concluded to proceed by S(,N)2' attack of the pyridine based on the sulfonyl chloride to generate ultimately a pyridine betaine and the pyridinium alkenesulfonate. The formation of the alkenesulfonate anion from the alkenesulfonyl chloride by reaction of the pyridine base corresponds to the first well-established example of a vinylogous nucleophilic catalysis mechanism.;Chapter 2 extends the reactions of ethenesulfonyl chloride and pyridinioethanesulfonyl chloride to include the reaction with pyridine and neopentyl alcohol in an organic medium. Evidence is presented indicating that the reaction of ethenesulfonyl chloride with pyridine in this medium also proceeds by the S(,N)2' mechanism.;Chapter 3 reports the results of the reactions of a series of 2-substituted ethanesulfonyl chlorides with pyridine and neopentyl alcohol in an organic medium (nitromethane). Three types of reactions which could be correlated with the nucleofugality of the 2-substituent were observed: (1) elimination of the 2-substituent to generate ethenesulfonyl chloride, which then reacts further to generate a {lcub}2{rcub} betylate and an ethenesulfonate ester; (2) formation of the 2-substituted methylsulfene intermediate, which then reacts to form an ethenesulfonate ester and a 2-substituted ethanesulfonate ester; (3) formation of a 2-substituted ethanesulfonate ester only, generated from the substituted methylsulfene intermediate.;Chapter 4 presents the first synthesis of an alkanesulfonyl chloride bearing a primary hydroxy group, 2-hydroxyethanesulfonyl chloride bearing a primary hydroxy group, 2-hydroxyethanesulfonyl chloride. Several reactions of this sulfonyl chloride, including the tertiary amine promoted alcoholysis reactions in methylene chloride, were investigated. The alcoholysis reactions were concluded to be proceeding by the parallel formation of two reactive intermediates, the unsubstituted beta sultone, and 2-hydroxymethylsulfene. The observed reaction products were then derived by further reaction of these intermediates with the components of the medium.



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