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Title: Novel routes to 2-substituted-1,3-butadienes by chelotropic extrusion reactions
Author: Maden, David N.
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1993
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2-Substituted-1,3-butadienes are simple dienes generally prepared by elimination or rearrangement reactions under pyrolytic conditions, and are of interest as monomers for polymer synthesis. The most important of these dienes is 2-vinyl-1,3-butadiene ([3]dendralene), the simplest member of a group of acyclic and cyclic cross-conjugated polyolefins known as the dendralenes, which are suitable polyenes for multiple additions of the Diels-Alder type, used to produce large complex polycycles. The work in this thesis concentrates on the novel synthesis of four 2-substituted-1,3-butadienes by chelotropic extrusion reactions via SO2 extrusion from sulpholenes (3-substituted tetrahydrothiophene-1,1-dioxides) and ethene extrusion from 1-substituted cyclohexenes. Such chelotropic extrusion reactions were performed using an efficient and selective technique known as Flash Vacuum Pyrolysis (FVP), which was used to prepare 2-cyanobutadiene via SO2 extrusion and via ethene extrusion from the respective cyano-substituted sulfolene and cyclohexene derivatives, and 2-vinyl-1,3-butadiene and 2-ethynyl-1,3-butadiene by ethene extrusion. Additionally a novel compound 2-phenylethynyl-1,3-butadiene was prepared using both SO2 extrusion from the respective sulfolene derivative and ethene extrusion from the respective cyclohexene derivative. The diene-transmissive nature of this novel compound together with the diene-transmissive nature of 2-cyano-1,3-butadiene was investigated by performing a number of Diels-Alder reactions with cyclic and acyclic dienophiles. Characterisation of all compounds by various analytical techniques including melting point analysis, mass spectroscopy, nuclear magnetic resonance and infrared spectroscopy is also discussed.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available