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Title: Studies on the factors controlling the 1,7-electrocyclisations of diene-conjugated diazoalkanes
Author: Bohill, Mel
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1996
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This work is involved with the 1.7-electrocyclisation reactions of α,β:γ,δ-unsaturated diazoalkanes to give 1H-2,3-benzodiazepines. The objective was to investigate the factors affecting the rates of 1.7-electrocyclisation of these systems. The method used was that of intramolecular competition reactions, where the relative rates of 1.7-electrocyclisation of a range of substitution alkenes was measured against that of a phenyl-substituted alkene as standard. This approach required the development of a versatile synthetic strategy to the 2-(E-2-alkenyl)-6-(E-2-phenylethenyl) benzaldehyde tosylhydrazones, as precursors to the diazoalkanes. A synthetic pathway to the 2-(E-2-alkenyl)-4-phenyl-1H-2,3-benzodiazepines was also necessary to allow unambiguous identification of the products. It was found that olefinic groups with electron-donating substituents were more reactive to 1.7-electrocyclisation and that conjugation reduces the rate of the reaction. Attempts to prepare the corresponding tosylhydrazones with electron-withdrawing substituted olefins proved unsuccessful.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available