Date of Award
Doctor of Philosophy (PhD)
The reactions of part per million (ppm) levels of nitrogen dioxide with cyclohexene have been studied to serve as a model for the reactions that occur between nitrogen dioxide in smoggy air and unsaturated fatty acids in pulmonary lipids. Previous studies done at high nitrogen dioxide levels were confirmed by these studies with nitrogen dioxide at concentrations of 10,000 ppm and higher. These show that nitrogen dioxide reacts with cyclohexene predominantly by addition to the double bond; in the presence of air or oxygen this addition initiates the autoxidation of the alkene. However, at low ppm levels, nitrogen dioxide reacts with this alkene virtually exclusively by abstraction of allylic hydrogen; this unexpected reaction also initiates the autoxidation of the alkene in the presence of oxygen or air, but it leads to the production of nitrous acid rather than an alkene containing a carbon-bound nitro group. In less detailed work, I have confirmed these same results for methyl oleate, linoleate, and linolenate, and have also studied some of the kinetic features of the nitrogen dioxide-initiated autoxidation of these unsaturated fatty acids.
Lightsey, John William, "A Mechanistic Study of Free-Radical Initiation of Alkene Oxidation by Nitrogen Dioxide." (1982). LSU Historical Dissertations and Theses. 3727.