Date of Award

1997

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Daniel F. Church

Second Advisor

Nickolaus H. Fischer

Abstract

This work discusses the synthesis of bicyclic nitrogen heteorocycles with the emphasis placed on the design and evaluation of a bicyclic nitrone for spin trapping applications. Camphorolactams, 1,7,7-trimethyl-2-aza-bicyclo(2.2.1) heptan-3-one and 1,7,7-trimethyl-3-azabicyclo (2.2.1) heptan-2-one were prepared from camphoric anhydride under Curtius conditions with sodium azide and dimethylformamide. 2-azabicyclo(2.2.1) heptan-3-one was also prepared under Curtius conditions from cis-1,3-cyclopentane-dicarboxylic acid anhydride. N-benzyl-2-azabicyclo (2.2.1) -heptane and N-benzyl-2-azabicyclo (2.2.2) octane were prepared from their aliphatic amine derivatives under Hofmann-Loeffler conditions in low yields. 1,3,3-trimethyl-6-azabicyclo (3.2.1) octane, N-oxide was prepared from its parent amine under sodium tungstate catalyzed oxidation with hydrogen peroxide. The bicyclic nitrone was compared to the most widely used spin trapping agent, phenyl-N-t-butyl nitrone. It proved to be a superior spin trap to phenyl-N-t-butyl nitrone in terms of adduct stability and gas chromato-graphic detection. There is a correlation based on molecular mechanics calculations of enthalpies, between the ring strain associated with these molecules and their reactivity.

ISBN

9780591458497

Pages

134

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