Date of Award
Doctor of Philosophy (PhD)
Daniel F. Church
Nickolaus H. Fischer
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.
Shanklin, Anna Patrice, "Preparation of Strained Nitrogen Heterocycles for Spin Trapping Applications." (1997). LSU Historical Dissertations and Theses. 6447.