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Title: The synthesis of 14-nitro- and 14-amino-codeinone derivatives
Author: McDougall, David James
ISNI:       0000 0001 3623 8422
Awarding Body: University of Glasgow
Current Institution: University of Glasgow
Date of Award: 1975
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The reaction of tetranitromethane with thebaine (4) has been studied and alternative routes to 14beta-amino-derivatives of codeine (2) investigated. The nitration of thebaine with tetranitromethane gave 14beta-nitrocodeinone (53) or its ketal, and a second nitration product whose structure has been identified as 8,14-dihydro-8alpha,10alpha-epidioxy-14beta-nitrothebaine (59). Reaction conditions which preclude or optimise the formation of either product have been found. The structure of the latter product was determined by reduction to either 8,14-dihydro-8alpha,10alpha-dihydroxy-14beta-nitrothebaine (61) or 8,14-dihydro-8alpha,10alpha-epoxy-143-nitrothebaine (65) and by base catalysed hydrolysis to 8,14-dihydro-8B-hydroxy-10-oxo-143-nitrothebaine(55 :R=H). The interconversion of these degradation products has been achieved and their chemistry studied. The cleavage of 8,14-dihydro-8,10-dioxo-14beta-nitrothebaine (64) with alkoxides gave products with unusual spectrometric properties, which have been tentatively identified as the esters (70). Nitryl chloride, dinitrogen tetroxide and nitric acid have been investigated as nitrating agents for thebaine but were found to be unsuitable for the preparation of 14beta-amino-derivatives. The chemistry of the Diels-Alder adducts of C-nitrosocarbonyl-compounds with thebaine, with respect to the preparation of 14beta-amino-derivatives, has been investigated. Acid hydrolysis of these adducts was found to be very dependent upon conditions, yielding a series of N-substituted 14beta-hydroxyamino-derivatives. A preliminary study of the chemistry of these compounds has been undertaken.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available