The Synthesis of 14-Nitro- and 14-Amino-Codeinone Derivatives

McDougall, David James (1975) The Synthesis of 14-Nitro- and 14-Amino-Codeinone Derivatives. PhD thesis, University of Glasgow.

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Abstract

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.

Item Type: Thesis (PhD)
Qualification Level: Doctoral
Keywords: Organic chemistry
Date of Award: 1975
Depositing User: Enlighten Team
Unique ID: glathesis:1975-78697
Copyright: Copyright of this thesis is held by the author.
Date Deposited: 30 Jan 2020 15:01
Last Modified: 30 Jan 2020 15:01
URI: http://theses.gla.ac.uk/id/eprint/78697

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