Stereochemical Aspects of Ionization Processes.
Final scientific rept. 1 Feb 65-30 Jun 70,
WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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The research involved investigations of the amount and stereochemistry of ion-pair return associated with solvolytic reactions of alkyl p-nitrobenzoates and p-toluenesulfonates. One group of experiments involved determining the amount of carboxyl and sulfonate oxygen scrambling associated with ion-pair return. In these studies amounts of oxygen equilibration were compared with the amounts of total return. The objective of these experiments was to determine if oxygen equilibration is a reliable criterion for ion-pair return. The stereochemistry of ion-pair return was investigated for several nonrearranging systems. In these studies rates of racemization of the unsolvolyzed ester were compared with rates of oxygen equilibration. These experiments show that the amount of racemization increases with charge delocalization in the cation. The effect of sodium azide on the amount and stereochemistry of return was determined for solvolysis of several alkyl p-nitrobenzoates. Author
- Organic Chemistry
- Physical Chemistry