Date of Award
Doctor of Philosophy
Thomas J. Barton
Bicyclo (2.2.2) oct-1-ene 1 was generated by gas phase elimination of trimethylsilyl bromide from 1-bromo-2-(trimethylsilyl)-bicyclo (2.2.2) octane (2). The elimination was effected by passing vapors of 2 over solid-supported tetra-n-butyl ammonium fluoride at room temperature and reduced pressure. Three dimers of 1 were identified by their X-ray crystal structures. A pair of diastereomeric, head-to-head dimers, along with the previously known head-to-tail dimer demonstrate the non-ionic character of the Bredt olefin 1. Attempts to generate bicyclo (2.2.2) octa-1,2-diene are reported;Bicycloalkylidene carbenes are generated in the gas phase and in solution. Factors influencing the fate of these species are discussed. Force field calculations of a series of cyclic and bicyclic vinylidenes are reported and analyzed in the context of ring expansion versus ring contraction. Attempts to synthesize a low temperature, thermal precursor to bicyclic vinylidene are discussed.
Digital Repository @ Iowa State University, http://lib.dr.iastate.edu/
Nathan L. Anderson
Anderson, Nathan L., "The generation and fate of strained, unsaturated, bicyclic hydrocarbons " (1992). Retrospective Theses and Dissertations. 10092.