Willcott, Mark R.2022-01-262022-01-26197213726725https://hdl.handle.net/10657/8564Bornylene undergoes a retro Diels-Alder reaction to give 1,5,5-trimethylcyclopentadiene and ethylene. The 1,5,5-trimethycyclopentadiene rearranges further to 1.2.3- and 1,2,4-trimethylcyclopentadiene. Two other products identified as 1,2,3-trimethylcyclopentene and 1.2.3-trimethylbicyclo[2.2.l]heptene-2 were also isolated. Thermolysis of two deuterated bornylenes and determination of deuterium distributions in the rearrangement products establishes the intermolecular nature of the methyl migrations. A mechanism for the radical chain process is presented and existing chemical evidence to the contrary is rationalized in terms of this pathway. The cis-trans isomerization of 2-cyano-l-vinylcyclopropane is a unimolecular, first order process. The Arrhenius expression over the temperature range 210.0-258.54[degrees]C is k = 10[raised 14.45[plus-minus].22] exp (-41,060[plus-minus]1,660/RT) From this kinetic study the resonance stabilization of -CH-C[equivalence]N is found to be 7 kcal/mole. The synthesis of 4-exo-methylene spiro[2.4]heptane is outlined. The molecule is unusually sensitive to catalysis and valid kinetic data was not obtained.application/pdfenThis item is protected by copyright but is made available here under a claim of fair use (17 U.S.C. §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