"A STUDY OF ENDOCYCLIC NUCLEOPHILIC SUBSTITUTION AT SULFUR(VI) (SULFONA" by DEBRA J. MACINTYRE-ZOLLER

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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