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Title: The application of optical activity to the study of some molecular rearrangements
Author: Campbell, Alastair
Awarding Body: University of Surrey
Current Institution: University of Surrey
Date of Award: 1947
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The thesis presents a critical survey of theories of molecular rearrangement and relevant data from the field of optical activity. The bulk of the experimental work deals with a study of the Beckmann, Lossen, Schmidt and Stevens rearrangements. For the first three of these rearrangements (-)alpha-hydratropic acid was used as starting material; being converted in the first case to (-)-acet-alpha-phenylethylamide via the ketone and oxime, in the second case to (-)-alpha-phenylethylamine via the hydroxamic acid, and in the third case to (-)-alpha-phenylethylamine via the azide. In each case the retention of asymmetry of the product was complete. From these findings certain conclusions regarding the reaction mechanism of the rearrangements have been drawn. In the Stevens rearrangement alpha-phenylethylamine was resolved dimethylated and quatermised with phencyl bromide. The product was rearranged and separated into the two diastereoisomeric forms of o-(alpha-phenylethyl)-o-dimethylamino-acetophenone. Attempts were made to determine the dgree of asymmetry of the product and a reaction mechanism has been proposed. The deamination of (-)-alpha-phonylethylamine using nitrous acid has been carried out and the optical consequences of the reaction discussed. Reaction of (-)-methyl hydratropate with Grignard reagents has been found to give optically active carbinols, contrary to published work. Attempts to prepare an optically active acyloin have failed.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available