Date of Award

Winter 1985

Project Type

Dissertation

Program or Major

Chemistry

Degree Name

Doctor of Philosophy

Abstract

To investigate the effect of geometry on nucleophilic substitution at sulfur (VI), a search was made for examples of endocyclic substitution. Substrate molecules were synthesized and then treated with strong bases, n-butyllithium or lithium diisopropylamide, in order to deprotonate a nitrogen or carbon so as to create a nucleophile which could attack a sulfonyl sulfur atom intramolecularly with displacement of a leaving group from the latter. The desired substitution was observed in several molecules. Deuterium-labeled substrates were prepared and crossover experiments were run to determine whether or not these reactions were intramolecular. One case involving a four-membered cyclic intermediate or transition state, the reaction of N-methyl-N-phenyl-4-toluenesulfonamide with n-butyllithium, proved to be intramolecular. Another case involving a five-membered cyclic intermediate or transition state, the reaction of 2-aminoaryl arenesulfonates with strong bases, proved to be intramolecular. A third case which had the potential to involve a six-membered cyclic intermediate or transition state, the reaction of 2'-(N-methylaminomethyl)phenyl-4-toluenesulfonate, proved to be intermolecular. No stereochemical investigations were undertaken.

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