Catalysis of Organic Reactions: Part I: Enhancement of a Solid State Reaction by Proper Orientation within a Crystal. Part II. Micellar Effects on the Stereochemistry and Rate of Aqueous Solvolysis Reactions

Author: Sukenik, Chaim N.

Year: 1976

Degree: Dissertation (Ph.D.)

Advisor: Bergman, Robert G.

Committee Member: Unknown, Unknown

Option: Chemistry

DOI: 10.7907/QB90-WP98

Abstract

Part I. The solid state rearrangement of methyl-p-dimethylaminobenzenesulfonate to the trimethylammoniumbenzenesulfonate zwitterion was studied by a combination of spectroscopic techniques. NMR, Field Desorption Mass Spectrometry, and X-Ray Crystallography were employed to determine the mechanism of this reaction. It was shown to be an intermolecular nucleophilic displacement whose rate is greatly enhanced by the crystallinity of the starting material.

Part II. A study of the effects of micelles on the aqueous solvolysis of alkyl-p-trimethylammoniumbenzenesulfonates revealed that anionic micelles could change the rate and stereochemistry of the solvolysis reaction. The mechanism for the observed rate retardation and induced decrease in stereochemical integrity was probed and a unified mechanistic hypothesis is presented.

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