Willcott, Mark Robert2022-06-222022-06-22196913719944https://hdl.handle.net/10657/9857The synthesis of several vinyl cyclopropanes stereospecifically labelled with deuterium is presented. Several new tetrahalovinyl cyclopropanes and tri halovinyl cyclopropanes, which are used as precursors to some of the deuterium labelled vinyl cyclopropanes, are also synthesized. Structure proofs of the deuterated and halogenated vinylcyclopropanes are accomplished by chemical and physical methods, with considerable emphasis being placed on detailed analysis of the 100 MHz nuclear magnetic resonance spectra. Pyrolysis of trans-1-deuterio-2-vinylcyclopropane shows that the reversible, geometrical cis-trans isomerization of the cyclopropyl ring is ca. 40 times faster than the irreversible formation of cyclopentene-d-j at 325[degrees]C. The Arrhenius Equation derived from the kinetic studies of deuterium epimerization on the cyclopropyl ring is: k = 10[raised 14.5[plus-minus]0.1] exp(-48,200[plus-minus]l,600/RT). Interpretation of the time history of the thermolysis of 1 -(cis- and trans-2-deuteriovinyl)-trans,trans-2,3-dideuteriocyclopropane shows unequivocally that the reaction does not follow any simple concerted pathway, but is best described by an intermediate diradical.application/pdfenThis item is protected by copyright but is made available here under a claim of fair use (17 U.S.C. Section 107) for non-profit research and educational purposes. Users of this work assume the responsibility for determining copyright status prior to reusing, publishing, or reproducing this item for purposes other than what is allowed by fair use or other copyright exemptions. Any reuse of this item in excess of fair use or other copyright exemptions requires express permission of the copyright holder.Thesisreformatted digital